JP5807523B2 - Resist antistatic film laminate and relief pattern manufacturing method - Google Patents

Description

  The present invention relates to a resist antistatic film laminate useful for microfabrication, a relief pattern manufacturing method using the laminate, and an electronic component. The laminate is particularly effective in pattern formation using an electron beam or a charged particle beam.

  In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has rapidly progressed due to advances in lithography technology. For example, high resolution with a dimension width of 50 nm or less is required. Development of resists that meet all requirements of high sensitivity, high resolution, and low line edge roughness (LER) for the fabrication of gate layers in semiconductor integrated circuits and mask pattern processing on glass substrates Is desired.

As a technique for miniaturization, the wavelength of an exposure light source is generally shortened, and in addition to the currently used KrF excimer laser light, ArF, F ₂ , EUV, X-rays, electron beams, and other charged particles Lithography using lines as exposure light has been proposed.

  For example, an electron beam corresponds to a wavelength of 0.005 nm when the acceleration voltage is 50 kV, and has a high resolving power in principle. In many cases, an electron beam is used without using a mask for forming a target pattern. There is an advantage that an arbitrary pattern can be formed by scanning the substrate directly.

However, resist compositions generally have low electrical conductivity, and when charged with an electron beam, a “charge-up phenomenon” occurs in which charges accumulate on the surface or inside of the resist film. If irradiation is continued after the occurrence of charge-up, there has been a problem in that the irradiated electron beam is affected by the charge-up and deviates from the originally intended irradiation position, or the dimension of the relief pattern changes.
The influence of this charge-up phenomenon has hitherto been regarded as a little problem because the machining dimensions are large and the influence is relatively small. However, at the present time when the formation of a fine pattern is required, there has been a problem of affecting the characteristics of the relief pattern and reducing the reliability.

As a means for avoiding the charge-up phenomenon, a method of forming an antistatic film on the resist film has been proposed.
Patent Document 1 proposes a conductive composition for pattern formation containing sulfonated polyaniline and amines and / or quaternary ammonium salts as the antistatic film. Patent Document 2 proposes an antistatic method using a conductive polymer having, as a structural unit, phenylene vinylene having a sulfo group, phenylene vinylene having a sulfo group, or the like. Patent Document 3 proposes an antistatic material containing a water-soluble conductive polymer compound containing an isothianaphthenylene structure having a sulfonic acid or a sulfonate as a repeating unit. Here, the antistatic film is a film used to eliminate the uneven distribution of charges caused by the charge-up phenomenon, and has a lower electric resistance than a normal resist used for microfabrication by using a highly conductive material. It is characterized by having. As a specific numerical value, Patent Document 3 describes that it has a surface resistance of 2 × 10 ⁸ Ω / □ or less.

  On the other hand, as the resist composition, a chemically amplified photosensitive composition using an acid catalytic reaction is used for the purpose of improving sensitivity. Negative-type chemically amplified photosensitive compositions usually contain an acid generator component that generates an acid upon irradiation with light, a crosslinking agent, a basic compound, and the like in a solvent-soluble resin serving as a resist substrate. In such a resist composition, cross-linking occurs between the resin and the cross-linking agent due to the action of the acid generated from the acid generator component by exposure, and the solubility in the developer decreases. In addition, since the acid generated during the crosslinking reaction is catalytically repeated, pattern exposure with a smaller exposure amount is possible. In order to further improve the sensitivity, the acid generator used in the chemically amplified photosensitive composition has been required to have a high acidity of the acid generated (Patent Document 4).

As a solvent-soluble resin serving as a resist substrate, a resist material using a polymer having a weight average molecular weight of about 5000 or more has been used. However, since such a polymer material has a large molecular weight and a wide molecular weight distribution, there is a limit to the reduction in resolving power and LER.
Therefore, development of low molecular weight materials as solvent-soluble materials used in resist compositions has been performed. The low molecular weight material is excellent in resolving power as compared with the high molecular weight material, and can also be expected to reduce LER. Examples of negative resists using such low molecular materials as resist substrates include resists using calix resorcinarene and derivatives thereof (Patent Document 5, Non-Patent Document 1), resists using low molecular polyphenol compound derivatives ( Non-Patent Document 2) and resists using a cyclic polyphenol compound derivative (Patent Document 6).

  Recently, in a negative chemically amplified resist composition, a cationic polymerization type molecular resist has been reported (Non-patent Document 3). The cationic polymerization type molecular resist of Non-Patent Document 3 does not require a conventionally used crosslinking agent because it uses the crosslinkability of an epoxy group. However, since the cationic polymerization type molecular resist of Non-Patent Document 3 does not have a phenolic hydroxyl group, it cannot be developed with an alkali developer mainly used in the production of semiconductor elements. Further, in Non-Patent Document 3, it is described that the cationic polymerization type molecular resist can obtain high sensitivity, high resolution, and low LER, but a step of forming a coating film for pattern formation ( When pre-baking), a dewetting phenomenon occurs, a uniform resist film cannot be formed, and a low LER fine pattern cannot be obtained, and there is a problem in the stability of pattern dimensions. all right.

JP-A-6-3813 JP-A-4-32848 JP 7-41756 A JP 2010-018573 A Japanese Patent Laid-Open No. 10-239843 Japanese Patent Laid-Open No. 11-153863

Journal of Photopolymer Science and Technology Volume 21, Number 3 (2008) 443-449 Chemistry of Materials 2006, 18, 3404-3411 Proc. of SPIE Volume 7273, (2009), 72733E1-10

  In particular, when performing drawing with an electron beam, the inventors use a chemically amplified resist in combination with an antistatic film, the sensitivity changes with the passage of time after drawing, and a desired processing dimension cannot be obtained, or no pattern at all. The knowledge that it may not be formed was obtained. In particular, in the case of the so-called electron beam direct drawing method in which drawing is performed by directly scanning an electron beam on the substrate, the drawing process requires a long time, so the time left from drawing to development is different for each drawing position on the substrate. It was different, and a difference in sensitivity occurred even on one substrate, and it was extremely difficult to obtain a pattern having the dimensions as designed.

The present invention has been made under such circumstances, and avoids a charge-up phenomenon when performing drawing with an electron beam, suppresses a change in sensitivity after drawing of a resist film, and forms a pattern with dimensions as designed. And a resist antistatic film laminate that can obtain a fine relief pattern with high sensitivity, high resolution, and low line edge roughness while having alkali developability, and the resist antistatic film It aims at providing the electronic component using a laminated body.
It is another object of the present invention to provide a method for manufacturing a relief pattern that can obtain a designed pattern without a dimensional error even for a fine pattern.

As a result of intensive research, the inventors have suppressed the sensitivity change after drawing even when a chemically amplified resist and an antistatic film are used in combination by using a specific acid generator described later. It was found that a good relief pattern can be formed.
Furthermore, the inventors introduced a specific crosslinkable group into a specific phenolic compound serving as a resist substrate, and used a resist substrate having crosslinkability and alkali developability, thereby allowing the same phenolic compound and crosslinker to be used. It has been found that the line edge roughness is reduced as compared with the case where the two components are mixed.
The present invention has been completed based on such knowledge.

The present invention provides a support on
(I) Two or more phenolic hydroxyl groups in one molecule, and one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group in the ortho position of the phenolic hydroxyl group in one molecule A sulfonic acid structure represented by —SO ₃ ^— or —SO ₃ —, which is generated directly or indirectly by irradiating an electron beam with one or more phenolic compounds (A) having a molecular weight of 400 to 2500. And having a carbon atom directly bonded to the sulfonic acid structure, an unsaturated hydrocarbon group directly bonded to the sulfonic acid structure, or an aromatic ring directly bonded to the sulfonic acid structure, and directly bonded to the sulfonic acid structure A negative resist composition containing the carbon atom, the unsaturated hydrocarbon group, or the acid generator (B) in which no fluorine atom is bonded to the aromatic ring, A resist film comprising a negative resist composition in which the content of the phenolic compound (A) in the total solid content of the resist composition is 70% by weight or more;
(II) comprising at least an antistatic film,
It is a resist antistatic film laminate.

  In the resist antistatic film laminate according to the present invention, the acid generator (B) is represented by any of the following formulas (1) to (4), which suppresses a sensitivity change after drawing, This is preferable because a low line edge roughness pattern can be obtained with high sensitivity and high resolution.

(In the chemical formula (1), R ¹ may be the same or different, and each independently represents a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, or 3 carbon atoms. -12 cyclic hydrocarbon group, a C1-C12 linear alkoxy group, a C3-C12 branched alkoxy group, a C3-C12 cyclic alkoxy group, a C1-C12 acyl group, C 1-12 sulfide group, hydroxyl group, or halogen atom, R ¹ may be bonded to each other to form a cyclic structure, n is an integer of 0-2, m is 0 R ² may be the same or different and is a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, or an optionally substituted phenyl group. , Or a naphthyl group, and further R ^{2 to} each other directly or through a different atom To form a cyclic structure having 2 to 13 carbon atoms, and R ³ is a hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or 6 to 6 carbon atoms. 14 aryl groups in which a fluorine atom is not bonded to a carbon atom directly bonded to an S atom, an unsaturated hydrocarbon group bonded directly to an S atom, or an aromatic ring directly bonded to an S atom. R ¹ , R ² and R ³ may further have a substituent, and may have an oxygen atom in the carbon skeleton of R ³ .

(In the chemical formula (2), R ⁴ may be the same or different and is a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, or an optionally substituted phenyl group. , A naphthyl group and an anthracene group, and R ⁴ may be bonded to each other directly or via a different atom to form a cyclic structure having 2 to 13 carbon atoms, provided that at least one of R ⁴ is R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and is directly connected to the S atom. The carbon atom to be bonded, the unsaturated hydrocarbon group directly bonded to the S atom, or the aromatic ring directly bonded to the S atom is not bonded with a fluorine atom, and R ⁴ and R ⁵ further have a substituent. In the carbon skeleton of R ^5. (It may have an oxygen atom.)

(In the chemical formula (3), X is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an alkyleneoxy group having 1 to 12 carbon atoms (—R′—O—, where R ′ is R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and S 6 A carbon atom directly bonded to an atom, an unsaturated hydrocarbon group bonded directly to an S atom, or an aromatic ring directly bonded to an S atom, and a fluorine atom not bonded to R ⁶ further has a substituent. And may have an oxygen atom in the carbon skeleton.)

(In the chemical formula (4), R ⁷ is a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or 6 carbon atoms. An aryl group having 12 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and R ⁸ is a linear hydrocarbon group having 1 to 12 carbon atoms and 3 to 12 carbon atoms. A branched hydrocarbon group, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, A fluorine atom is not bonded to a carbon atom directly bonded to the S atom, an unsaturated hydrocarbon group bonded directly to the S atom, or an aromatic ring directly bonded to the S atom, and R ⁷ and R ⁸ are may have a substituent, an oxygen atom to the carbon skeleton of the R ⁸ It may be in.)

  In the resist antistatic film laminate according to the present invention, the phenolic compound (A) has a glass transition temperature (Tg) of 60 ° C. or higher so that a pattern with low sensitivity and high resolution and low line edge roughness can be obtained. It is preferable because it can be obtained.

  In the resist antistatic film laminate according to the present invention, the phenolic compound (A) is one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group. It is preferable to have 3 or more per molecule in terms of high crosslinkability, high sensitivity, high resolution, and a low line edge roughness pattern.

  In the resist antistatic film laminate according to the present invention, the phenolic compound (A) has a solubility of 5% by weight or more at 23 ° C. in an organic solvent having a boiling point of 80 to 180 ° C. It is preferable that a pattern with low line edge roughness can be obtained with high sensitivity and high resolution.

  In the present invention, it is preferable that the negative resist composition further contains an organic basic compound (C) from the viewpoint of improving the relief pattern shape and improving the temporal stability in the storage state.

The method for producing a relief pattern according to the present invention includes a step of drawing the resist antistatic film laminate according to the present invention with an electron beam,
Removing the antistatic film of the resist antistatic film laminate drawn with an electron beam;
And a step of developing the resist film of the laminate after or simultaneously with the removal of the antistatic film.

  In the method for producing a relief pattern according to the present invention, heat treatment is performed between the step of drawing with the electron beam and the step of developing, so that a pattern as designed can be obtained without dimensional error. To preferred.

  In addition, according to the present invention, it is possible to provide an electronic component having a dimensional error and a pattern as designed.

According to the present invention, a charge-up phenomenon can be avoided, a sensitivity change after electron beam writing of a resist film can be suppressed, a pattern having a dimension as designed can be formed, and high sensitivity can be achieved while having alkali developability. A resist antistatic film laminate capable of obtaining a fine relief pattern with high resolution and low line edge roughness, and an electronic component using the resist antistatic film laminate can be provided.
Further, according to the present invention, it is possible to provide a method for manufacturing a relief pattern that can obtain a designed pattern without a dimensional error even if it is a fine pattern.

It is the schematic which shows an example of the resist antistatic film laminated body of this invention. It is the schematic which shows an example of the manufacturing method of the relief pattern of this invention.

Hereafter, each structure of the resist antistatic film of this invention is demonstrated in detail in order.
Moreover, in the description of the group (atomic group) in this invention, the description which has not described substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “hydrocarbon group” includes not only a hydrocarbon group having no substituent but also a hydrocarbon group having a substituent. The divalent bond of the alkylene group includes a divalent bond from the same carbon atom (for example, —CH ₂ —) as well as a case from a different carbon atom (for example, —CH ₂ CH ₂ —). The hydrocarbon group includes unsaturated hydrocarbons having double bonds, triple bonds, etc. in addition to saturated hydrocarbons. The cyclic structure such as a cycloalkyl group includes monocyclic and condensed polycyclic rings such as bicyclic and tricyclic.

I. Resist Antistatic Film Laminate The resist antistatic film laminate according to the present invention comprises a resist film 20 and an antistatic film 30 on a support 10 as shown in FIG. By laminating an antistatic film on a resist film containing a specific acid generator, the charge build-up phenomenon does not occur in the lithography using an electron beam, so that charge accumulation during electron beam drawing is suppressed. Since the sensitivity change after the electron beam drawing can be suppressed, a fine pattern having a dimension as set can be efficiently formed.
The resist antistatic film laminate according to the present invention comprises a support, a specific resist film, which will be described later, and an antistatic film as essential components, and further layers as necessary. You may have.
Hereinafter, the support, the resist film, and the antistatic film constituting the resist antistatic film laminate will be described in order.

1. Support The support used in the present invention is not particularly limited as long as it can support a resist film, draw the resist film in a predetermined pattern with an electron beam, and develop a fine relief pattern. However, it is appropriately selected depending on the application. The fine relief pattern may be formed as a functional film or a mask for processing the support. For example, in the manufacture of a semiconductor element, a silicon substrate is used as the support, and according to the present invention. After forming the relief pattern, a circuit can be formed in the opening of the relief pattern.
Note that another film may be formed on the support prior to resist coating. For example, when the resist has an adverse effect such as sensitivity reduction or profile deterioration depending on the type of substrate, a thermosetting film or the like is provided on the support to avoid this, and the resist film is provided on the thermosetting film.

  As the support used in the present invention, for example, a silicon substrate can be used for manufacturing a semiconductor element. For so-called photomask fabrication for semiconductor circuit fabrication, a light-shielding film such as Cr, CrON, CrN, MoSi, Ta compound is formed on a light-transmitting substrate such as quartz glass or aluminosilicate glass, MEMS processing Examples thereof include Si and SiO 2 substrates used for the above, substrates such as GaAs, GaN, AlGaAs, InP, InAs, and AlGaSb used for manufacturing compound semiconductors, and substrates such as ITO and MgO as the oxide semiconductors.

2. Resist film The resist film constituting the resist antistatic film laminate of the present invention has two or more phenolic hydroxyl groups in one molecule, and a group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group. A phenolic compound (A) having a molecular weight of 400 to 2500 having one or more substituents selected from 1 in one molecule, and generating an acid directly or indirectly by irradiation with an electron beam; A sulfonic acid structure represented by SO ₃ ^— or —SO ₃ — and a carbon atom directly bonded to the sulfonic acid structure, an unsaturated hydrocarbon group directly bonded to the sulfonic acid structure, or a direct bond to the sulfonic acid structure has an aromatic ring, the carbon atom bonded directly to the acid structure, the unsaturated hydrocarbon group, or said unbound fluorine atom to the aromatic ring acid A negative resist composition containing a crude agent (B), wherein the content of the phenolic compound (A) in the total solid content of the negative resist composition is 70% by weight or more. It consists of a composition.
By using a resist film made of the above specific negative resist composition, a charge-up phenomenon can be avoided, a sensitivity change after electron beam drawing of the resist film can be suppressed, and a pattern with dimensions as designed can be formed. In addition, it is possible to obtain a resist antistatic film laminate that can obtain a fine relief pattern with low sensitivity and high resolution and low line edge roughness while having alkali developability.

By forming a resist film using the specific negative resist composition, the following effects can be estimated as follows.
When a resist film made of a chemically amplified resist composition is irradiated with an electron beam, the acid generator contained in the resist film is decomposed, and the combination of hydrogen ions and the sulfonic acid structure of the acid generator is chemically It is presumed to act as a catalyst for the amplification reaction. In the case of a resist antistatic film laminate, when the acidity of the sulfonic acid structure of the acid generator is stronger than the alkylsulfonic acid contained in the antistatic film described later, the alkylsulfonic acid contained in the antistatic film described later, Or aryl sulfonic acids are relatively weak acids. In this case, it is presumed that hydrogen ions generated in the resist film are taken into the alkylsulfonic acid at the contact portion between the resist film and the antistatic film and the reactivity is lowered (weak acid liberation reaction). Conventionally, acid generators used in chemically amplified resists have high acid acidity. However, such acid generators having high acidity have a weak acid release reaction. The effect is large, and it is presumed that the sensitivity is reduced through deactivation of the generated hydrogen ions.
On the other hand, the acid generator used in the present invention is an acidic generator in which no fluorine atom is bonded to a carbon atom directly bonded to an S atom, an unsaturated hydrocarbon group bonded directly to an S atom, or an aromatic ring directly bonded to an S atom. Since a low degree is selected daringly, there is little or no decrease in the acid concentration due to such a weak acid liberation reaction, and it is estimated that the decrease in sensitivity is small.

In addition, when a large number of components are used in the negative resist composition, a specific component may be easily aggregated or phase-separated due to the compatibility problem of each component. In such a case, a uniform resist film cannot be produced, and the line edge roughness is deteriorated. Further, when a polymer is used as a resist substrate, it is difficult to form a pattern with low line edge roughness because of poor resolution and easy swelling. Further, when a resist composition is prepared by mixing a crosslinking agent with a resist substrate, there is a problem that it is difficult to improve the sensitivity because the content of the crosslinking agent is limited from the viewpoint of compatibility.
On the other hand, the negative resist composition used in the present invention has a relatively low molecular weight specific phenolic compound having a molecular weight of 400 to 2500, a crosslinkable group, a hydroxymethyl group at the ortho position of the phenolic hydroxyl group, A compound substituted with an alkoxymethyl group or the like is used as a resist substrate, and the content of the resist composition of the resist substrate in the solid content is increased. The resist substrate also functions as a cross-linking agent, and the number of components contained in the negative resist composition can be reduced as compared with conventional negative resist compositions. It is estimated that it is possible to improve and obtain a pattern of low line edge roughness with high resolution. Furthermore, it is presumed that a pattern with low line edge roughness can be formed because it has excellent resolving power and hardly swells compared to the case where a polymer is used as a resist substrate.

In the negative resist composition, when an acid is generated from the acid generator (B) by irradiation with an electron beam at the time of forming a resist pattern, the acid acts, and the phenolic compound (A) is an ortho group of phenolic hydroxyl groups. Crosslinks are formed by the presence of one or more substituents selected from the group consisting of a hydroxymethyl group present at the position and an alkoxymethyl group, which makes the alkali insoluble. Therefore, in resist pattern formation, when the resist film made of the negative resist composition is selectively irradiated with an electron beam or heated after irradiation in addition to the electron beam irradiation, the irradiated portion becomes alkali-insoluble, but not irradiated. Since the portion remains alkali-soluble and does not change, a negative resist pattern can be formed by alkali development.
Since the negative resist composition of the present invention is a chemically amplified resist composition as described above, high sensitivity can be achieved. In the negative resist composition of the present invention, since the resist substrate also functions as a crosslinking agent, high sensitivity can be achieved by appropriately adjusting the amount of the crosslinking group, and when the crosslinking agent is mixed with the polyphenol compound. From the point of compatibility, the content of the crosslinking agent is limited, and the problem that it is difficult to improve the sensitivity can be solved.

The negative resist composition used in the present invention comprises a specific phenolic compound (A) and a specific acid generator (B) as essential components, and may contain other components as necessary. It ’s good.
Hereinafter, each component of the negative resist composition will be described in order.

<Phenolic compound (A)>
The phenolic compound (A) used in the present invention has two or more phenolic hydroxyl groups in one molecule, and is selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group. A compound having a molecular weight of 400 to 2500 having one or more substituents in one molecule. By setting the molecular weight of the phenolic compound (A) within the above range, high resolution and low line edge roughness can be achieved.
In the present invention, “phenolic hydroxyl group” means a hydroxyl group directly bonded to an aromatic ring such as benzene.

The phenolic compound (A) used in the present invention may have two or more phenolic hydroxyl groups in one molecule, and the number of phenolic hydroxyl groups in one molecule is not particularly limited. The phenolic compound (A) used in the present invention is preferably selected as appropriate so as to have alkali solubility based on the following.
It is preferable to select and use one having a development rate of 0.5 nm / sec or more with respect to a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution (23 ° C.), and further 1.0 nm / sec or more. It is preferable to select and use a certain one. By setting the alkali development speed of the alkali-soluble resin within the above range, the pattern shape can be improved and the sensitivity can be increased.

  The development rate for an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 2.38 wt% (23 ° C.) is, for example, the above-mentioned phenolic compound (A) alone, for example, a 5 wt% solution. After forming the coating film so that the film thickness after drying becomes 300 nm, it is immersed in an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 2.38% by weight (23 ° C.), and the coating film is completely dissolved. Can be measured and calculated.

  The phenolic compound (A) used in the present invention has at least one substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group in one molecule. Just do it. One or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group function as a crosslinking group for the phenolic compound. In the phenolic compound (A) used in the present invention, one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group are 2 or more per molecule. It is preferable to have three or more in one molecule, and more preferably four or more in one molecule from the viewpoint of increasing the crosslinkability.

  The alkoxymethyl group is preferably an alkoxy group having 1 to 6 carbon atoms, specifically, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, or an n-butoxymethyl group. , Sec-butoxymethyl group, t-butoxymethyl group, various pentyloxymethyl groups, and the like. Among these, as the alkoxymethyl group, a methoxymethyl group and an ethoxymethyl group are preferable because sensitivity is improved.

  As the cross-linking group, in particular, one or more substituents selected from the group consisting of a hydroxymethyl group, a methoxymethyl group, and an ethoxymethyl group at the ortho position of the phenolic hydroxyl group are highly reactive and sensitive. Is preferable from the point that becomes better.

As the phenolic compound (A) used in the present invention, a compound having a molecular weight of 400 to 2500 is selected and used. When the molecular weight is less than the lower limit, the ability to form a resist film and the ability to form a pattern are inferior. On the other hand, when the molecular weight exceeds the upper limit, the solvent used in the resist composition tends to swell, the pattern collapse easily occurs, and the pattern shape may be deteriorated. The molecular weight here refers to the sum of the atomic weights of the atoms constituting the molecule. Moreover, when it is an oligomer which has molecular weight distribution, it represents with the weight average molecular weight using GPC (polystyrene conversion).
In particular, the molecular weight of the phenolic compound (A) used in the present invention is preferably 500 to 2500, and more preferably 600 to 2000 from the viewpoint of film formability and resolution.

The phenolic compound (A) used in the present invention preferably has a glass transition temperature (Tg) of 60 ° C. or higher, more preferably 90 ° C. or higher. When the glass transition temperature is 60 ° C. or higher, a dewetting phenomenon hardly occurs when forming a coating film, and a uniform film is easily obtained. The dewetting phenomenon is a phenomenon in which a spread coating film is dissolved during pre-baking to cause repelling and a film is not formed uniformly.
Usually, as a solvent for a resist composition, when a low boiling point solvent is used, the resist film is dried rapidly and a uniform film cannot be obtained. In order to obtain, a solvent having a boiling point of 90 to 180 ° C. is used. Since the resist film formed by the spin coating method contains a lot of residual solvent, the resist substrate is heated at a temperature of 90 ° C. or higher using a hot plate in order to form a stable resist film except for this solvent ( Pre-bake). However, when a phenolic compound having a glass transition temperature of less than 60 ° C. is used, a dewetting phenomenon of the resist film occurs in the prebaking process, and there is a possibility that a uniform film cannot be obtained.
In contrast, when a phenolic compound having a glass transition temperature of 60 ° C. or higher is used, pre-baking at a high temperature is possible, a uniform film can be obtained, and a resist film excellent in environmental resistance (post coating delay: PCD). Is obtained. Furthermore, it is possible to suppress the dependence of the pattern density on the pattern formation by the electron beam. Further, in the dry etching process after the resist pattern is formed, a pattern having excellent etching resistance (can prevent melting of the pattern due to high temperature during etching) can be obtained.
The glass transition temperature here is measured by a differential scanning calorimeter (DSC).

  Moreover, it is preferable that the phenolic compound (A) used in this invention has the solubility of 5 weight% or more at 23 degreeC with respect to the organic solvent whose boiling point is 80-180 degreeC. In such a case, it is possible to prevent the resist film from being rapidly dried during spin coating, and there is an advantage that a uniform resist film can be obtained. Typical examples of organic solvents having a boiling point of 80 to 180 ° C. include cyclopentanone, propylene glycol monomethyl ether, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl lactate, 2-heptanone, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, and the like. Is mentioned.

  Among them, the phenolic compound (A) used in the present invention has a glass transition temperature (Tg) of 60 ° C. or higher, and 5% by weight or more at 23 ° C. with respect to an organic solvent having a boiling point of 80 to 180 ° C. It is preferable to have the solubility.

  As said phenolic compound (A), the compound represented by following Chemical formula (5) and Chemical formula (7) is mentioned, for example.

In Chemical Formula (5), R ¹¹ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, and a group selected from the group consisting of groups represented by the following chemical formula (6), the R ¹¹ The included aryl group may contain one or more substituents selected from the group consisting of a hydroxyl group, a hydroxymethyl group, and an alkoxymethyl group.

(In the chemical formula (6), R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q is an aryl group or a cycloalkyl group, and m is 1 or 2. Represents.)
R ¹² is each independently a hydrogen atom or a monovalent organic group, and among the plurality of R ¹² , at least two in one molecule are hydrogen atoms. R ¹³ is a group selected from the group consisting of halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, acyl groups, cyano groups, nitro groups, hydroxymethyl groups, and alkoxymethyl groups.
n1 represents an integer of 1 to 3, and n2 represents an integer of 0 to 2. However, a combination satisfying n1 + n2 ≦ 4 is selected from a numerical range of n1 and n2. x1 represents the integer of 3-12.
However, in R ¹¹ and / or R ¹³ , one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group are present in one molecule at the ortho position of the phenolic hydroxyl group.
In addition, the groups represented by the same symbols included in the chemical formula (5) may be the same as or different from each other. ]

(In the chemical formula (7), R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a hydroxymethyl group, or an alkoxymethyl group, or these Represents a group consisting of a combination, a plurality of R ¹⁶ may be bonded to form a ring, a plurality of R ¹⁷ may be combined to form a ring, and a plurality of R ¹⁸ may be combined to form a ring. A plurality of R ¹⁹ may combine to form a ring, and the plurality of R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different from each other.
R ²⁰ and R ²¹ each independently represent a hydrogen atom or a monovalent organic group, and a plurality of R ²⁰ and R ²¹ may be the same as or different from each other. Further, at least two of the plurality of R ²⁰ and R ²¹ are hydrogen atoms. Furthermore, in R ¹⁶ , R ¹⁷ , and / or R ¹⁹ , one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group are present in one molecule at the ortho position of the phenolic hydroxyl group. Have more.
W represents a single bond, an ether bond, a thioether bond, or an alkylene group, a cycloalkylene group, an arylene group, or any combination thereof, which may contain a hetero atom. Plural Ws may be the same or different.
x2 represents a positive integer.
y1 represents an integer of 0 or more. When W is a single bond, y1 is 0.
y2 represents an integer of 0 or more, and y3 represents a positive integer.
z represents an integer of 0 or more.
v represents an integer of 0 or more.
k1 and k4 represent positive integers.
k2, k3, and k5 each independently represents an integer of 0 or more. However, k1 + k2 + z = 5, k3 + v = 3, k4 + k5 = 5, and k2 + k5 ≧ 2 are satisfied. )

In the compound represented by the chemical formula (5), the alkyl group for R ¹¹ is not particularly limited, but an alkyl group having 1 to 18 carbon atoms is preferable. The alkyl group may be linear or branched. For example, methyl group, ethyl group, n-propyl group, n-butyl group, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, hexadecyl group and the like can be mentioned. Moreover, you may have unsaturated bonds, such as a double bond and a triple bond.

  Examples of the substituent that the alkyl group has include a hydroxyl group, an alkoxy group, a halogen atom, and a halogenoalkyl group.

The cycloalkyl group of R ^11, not particularly limited, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like. Further, it may have an unsaturated bond such as a double bond or a triple bond, and may be monocyclic or polycyclic.
As the cycloalkyl group, a cyclohexyl group is preferable.

  The substituent that the cycloalkyl group has is not particularly limited, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, and a halogenoalkyl group.

  The alkyl group having 1 to 5 carbon atoms may be linear or branched. As a linear alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group etc. are mentioned, for example. Examples of the branched alkyl group include i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group and the like.

  The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 2-ethylhexyloxy group.

  Although there is no restriction | limiting in particular as an alkoxyalkyl group, A C1-C8 alkoxyalkyl group is preferable, For example, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group etc. are mentioned.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The halogenoalkyl group is not particularly limited, but is preferably a halogenoalkyl group having 1 to 8 carbon atoms. For example, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, Fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-chloroethyl group, 1-bromoethyl group, 1-fluoroethyl group, 1,2-dichloroethyl group, 1,1,2,2-tetrachloroethyl group, etc. Can be mentioned.

The aryl group of R ^11, is not particularly limited, preferably 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, for example, a phenyl group, a naphthyl group, an anthryl group and the like.

In addition, examples of the substituent that the aryl group has include a hydroxymethyl group, an alkoxymethyl group, a cycloalkyl group, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, and a halogenoalkyl group. Can be mentioned.
Examples of the cycloalkyl group as a substituent that the aryl group has are the same as those described above. The cycloalkyl group may have a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, and an alkoxy group. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, and an i-propyl group. Although there is no restriction | limiting in particular as an alkoxy group, A C1-C8 alkoxy group is preferable, For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, 2-ethylhexyloxy group etc. are mentioned.
The alkyl group having 1 to 5 carbon atoms, the alkoxy group, the alkoxyalkyl group, the halogen atom, the halogenoalkyl group, and the alkoxymethyl group as the substituent that the aryl group has are as described above.

In the chemical formula (6), R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms may be either linear or branched, and among them, a methyl group and an ethyl group are preferable from the viewpoint of etching resistance. When m is 2, two R ¹⁴ and R ¹⁵ may be the same or different.
In the above chemical formula (6), a case where both R ¹⁴ and R ¹⁵ are hydrogen atoms is preferably used.

  Examples of the aryl group of Q in the chemical formula (6) include the same aryl groups as those described above. Examples of the substituent that the aryl group of Q includes are the same as the substituents that the aryl group has, and include one or more substituents selected from the group consisting of a hydroxyl group, a hydroxymethyl group, and an alkoxymethyl group. You can leave. In addition, examples of the cycloalkyl group of Q in the chemical formula (6) include the same cycloalkyl groups as those described above. Examples of the substituent that the cycloalkyl group of Q has are the same as the substituents that the cycloalkyl group has.

The monovalent organic group for R ¹² is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group.
As the alkyl group for R ^12, the same groups as those described above for R ¹¹ can be mentioned. The substituent group of the alkyl group of R ^12, include the same ones of the R ^11.
Further, the cycloalkyl group of R ¹² and the substituent that the cycloalkyl group has can be the same as those of R ¹¹ described above. Furthermore, the aryl group of R ¹² and the substituent that the aryl group has can be the same as those of R ¹¹ described above.

The alkoxymethyl group for R ¹³ is as described above.
As the halogen atom and alkyl group for R ^13, the same groups as those described above for R ¹¹ can be mentioned.
The substituent of the alkyl group as R ¹³ is a cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, carboxy group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group. , Alkoxycarbonyl group, cyano group, nitro group and the like.

The cycloalkyl group of R ¹³ and the substituent that the cycloalkyl group has can be the same as those of R ¹¹ described above. The aryl group of R ^{13 and} the substituent that the aryl group has can be the same as those of R ¹¹ described above.
Examples of the alkoxy group for R ¹³ include the same groups as those described above for R ¹¹ .

The acyl group of R ^13, is not particularly limited, preferably an acyl group having 1 to 8 carbon atoms, e.g., formyl group, acetyl group, propionyl group, butyryl group, valeryl group, a pivaloyl group, include benzoyl group and the like It is done.

  x1 is an integer of 3-12, preferably an integer of 4-12, more preferably an integer of 4-8.

The compound represented by the chemical formula (5) has two or more phenolic hydroxyl groups in one molecule, and is selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group. As long as one or more kinds of substituents are present, the substituents represented by the same reference numerals in the respective repeating units may be the same or different. The positions of OR ¹² and R ¹³ in each repeating unit may be the same or different.

In the compound represented by the chemical formula (5), x1 is preferably 4 and n1 is preferably 2 from the viewpoint of obtaining a pattern with high sensitivity, high resolution, and good shape. four, n1 is 2, a 8 4-8 of calix resorcin arene derivatives hydrogen atom of R ^12, and, a hydroxymethyl group in the ortho position R ¹² is a hydrogen atom, and alkoxymethyl It is preferable to have one or more substituents selected from the group consisting of groups in one molecule.
In addition, in the compound represented by the chemical formula (5), x1 is preferably 4 and n1 is preferably 2 from the viewpoint of obtaining a pattern with high sensitivity and high resolving power. x1 is 4, n1 is 2, a 8 0-8 amino calix resorcin arene derivatives hydrogen atom of ^{R 12, and,} in ^{R 11,} a phenolic hydroxyl group, the ortho position of the phenolic hydroxyl group It preferably has an aryl group containing one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group.

On the other hand, in the compound represented by the chemical formula (7), the alkyl group in R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be linear or branched, and is preferably a methyl group, an ethyl group, a propyl group, or butyl. And those having 1 to 10 carbon atoms such as a group, an isobutyl group, a hexyl group, and an octyl group.
The cycloalkyl group for R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be monocyclic or polycyclic. For example, groups having a monocyclo, bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms can be given. The number of carbon atoms is preferably 6 to 30, and particularly preferably 7 to 25. For example, adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol Group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, cyclododecanyl group and the like. These alicyclic hydrocarbon groups may have a substituent.
The aryl group in R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same as R ¹¹ described above.
Further, the hydroxymethyl group or alkoxymethyl group in R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same as described above.
In the compound represented by the chemical formula (7), R ¹⁶ has a value of (x2) when (x2) is an integer of 2 or more.

  Examples of the substituent that the alkyl group, cycloalkyl group, and aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkoxy group (a methoxy group, an ethoxy group, A propoxy group, a butoxy group, etc.), a hydroxymethyl group, or an alkoxymethyl group.

Examples of the monovalent organic group in R ²⁰ and R ²¹ include an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an amide group, and a cyano group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group. For example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl Group, cyclopropyl group, cyclobutyl group, cyclohexyl group, adamantyl group and the like. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. The aralkyl group is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a cumyl group. The alkoxy group in the alkoxy group and the alkoxycarbonyl group is preferably an alkoxy group having 1 to 5 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, and an isobutoxy group.

The alkylene group in W may be linear or branched, and preferably has 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and an isobutylene group.
The cycloalkylene group in W may be monocyclic or polycyclic, and examples of the alkylene group forming the ring include a cycloalkylene group having 3 to 8 carbon atoms (for example, a cyclopentylene group and a cyclohexylene group). be able to.
The alkylene group and cycloalkylene group in W may further have a substituent, and examples of the substituent include an alkyl group (preferably having a carbon number of 1 to 10, for example, methyl group, ethyl group, propyl group, isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc.), alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy Group, ethoxy group, propoxy group, butoxy group, etc.), fluorine atom, chlorine atom, bromine atom, iodine atom and the like.

In addition, an alkylene chain or a cycloalkylene chain includes —O—, —OC (═O) —, —OC (═O) O—, —N (R) —C (═O) —, —N in the alkylene chain. (R) —C (═O) O—, —S—, —SO—, —SO ₂ — may be included. Here, R represents a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 10, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group). Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.
The cyclic arylene group in W is preferably a group having 6 to 15 carbon atoms such as a phenylene group, a tolylene group, and a naphthylene group.

Specific examples of the phenolic compound (A) are shown below, but the present invention is not limited thereto. There are two or more phenolic hydroxyl groups in one molecule, and one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group in the ortho position of the phenolic hydroxyl group in one molecule If present, the phenolic hydroxyl groups in the following specific examples may be protected with organic groups.
In the following formulae, each L is independently a hydrogen atom or one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, and at least one L in one molecule is And one or more substituents selected from the group consisting of a hydroxymethyl group present at the ortho position of the phenolic hydroxyl group and an alkoxymethyl group. Moreover, molecular weight shall satisfy | fill 400-2500.

  The phenolic compound (A) used in the present invention is one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group in the parent compound of the phenolic compound. Can be obtained by introducing. As a method for introducing the substituent functioning as the crosslinking group into the parent compound of the phenolic compound, for example, it can be obtained by reacting a corresponding phenol compound not having a hydroxymethyl group with formaldehyde under a base catalyst. Can do. At this time, in order to prevent side reactions such as gelation, the reaction temperature is preferably 50 ° C. or lower. Various bisphenol derivatives having an alkoxymethyl group can be obtained by reacting a corresponding bisphenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent side reactions such as gelation, the reaction temperature is preferably 100 ° C. or lower.

  The parent compound of the phenolic compound (A) is commercially available from, for example, Honshu Chemical Industry Co., Ltd., Asahi Organic Materials Co., Ltd., and the like, and can be used. It can also be synthesized by condensation of various phenol compounds with various aldehydes and ketones.

In the negative resist composition according to the present invention, the phenolic compound (A) may be used alone or in combination of two or more of the above-described compounds.
However, in the negative resist composition according to the present invention, the phenolic compound (A) preferably has a purity of 90% by weight or more from the viewpoint of improving low line edge roughness. In the phenolic compound (A), the purity of compounds having the same structural formula is more preferably 90% by weight or more, and further preferably 95% by weight or more.
When a compound having the same structural formula and having a high purity is used as the phenolic compound (A), the progress of development becomes uniform, and it is estimated that the line edge roughness is reduced.
However, the phenolic compound (A) has a similar impurity structure to the phenolic compound (A) even when the purity of the compound having the same structural formula is less than 90% by weight, and the compatibility is good. Can be preferably used.

  Therefore, the phenolic compound used in the present invention preferably has no molecular weight distribution. The phenolic compound used in the present invention preferably has a small molecular weight distribution, even if it has a molecular weight distribution. The molecular weight distribution (ratio of weight average molecular weight <Mw> to number average molecular weight <Mn> <Mw> / <Mn> is preferably 1.0 to 1.1.

The content of the phenolic compound (A) is 70% by weight or more, preferably 75% by weight or more, and more preferably 80% by weight or more based on the total solid content of the resist composition. . Moreover, since it contains the acid generator (B) mentioned later at least, it is preferable that an upper limit is 98 weight% or less with respect to the total solid of a resist composition.
In addition, in this invention, solid content means things other than an organic solvent among the components which can be contained in a negative resist composition.

<Acid generator (B)>
The acid generator used in the present invention generates an acid directly or indirectly by irradiating an electron beam, and has a sulfonic acid structure represented by —SO ₃ ^— or —SO ₃ — and the sulfonic acid structure. A carbon atom directly bonded, an unsaturated hydrocarbon group directly bonded to the sulfonic acid structure, or an aromatic ring directly bonded to the sulfonic acid structure, and the carbon atom directly bonded to the sulfonic acid structure, the unsaturated It is a compound in which a fluorine atom is not bonded to a hydrocarbon group or the aromatic ring. By using such an acid generator (B), even when used in combination with an antistatic film described later, it is possible to suppress a change in sensitivity after exposure and to form a fine pattern with a dimension as designed. .

  In the acid generator (B), the carbon atom directly bonded to the sulfonic acid structure refers to the carbon atom represented by a in the following chemical formula (8), for example. The acid generator (B) in which the fluorine atom is not bonded to the carbon atom directly bonded to the sulfonic acid structure means that an acid generator having a structure such as the following chemical formula (8) is not included.

  In the acid generator (B), the unsaturated hydrocarbon group directly bonded to the sulfonic acid structure refers to, for example, an unsaturated hydrocarbon group represented by b or c in the following formula (9). The acid generator (B) in which the fluorine atom is not bonded to the unsaturated hydrocarbon group directly bonded to the sulfonic acid structure means that an acid generator having a structure such as the following chemical formula (9) is not included. means.

  In the acid generator (B), the aromatic ring directly bonded to the sulfonic acid structure refers to an aromatic ring represented by d in the following formula (10), for example. The acid generator (B) in which no fluorine atom is bonded to the aromatic ring directly bonded to the sulfonic acid structure means that an acid generator having a structure such as the following chemical formula (10) is not included.

  The acid generator (B) used in the present invention may have a fluorine atom at a position other than the above. For example, an acid generator having a structure represented by the following formula (11) is suitable for the present invention. Can be used.

  The acid dissociation constant (pKa) of the acid generator (B) used in the present invention is preferably −5.0 to 0.0 (zero), more preferably −4.0 to −1.0. This is because if the acid dissociation constant is smaller than this range, a change in sensitivity tends to occur, and if it is larger than this range, the sensitivity becomes worse.

  Further, the acid generator (B) may be an onium salt type compound or a nonionic type compound.

  The acid generator (B) is represented by the following chemical formulas (1) to (4) because it suppresses the sensitivity change after electron beam drawing of the resist film and enables pattern formation with the dimensions as designed. It is preferable to use at least one selected from the group consisting of compounds.

(In the chemical formula (1), R ¹ may be the same or different, and each independently represents a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, or 3 carbon atoms. -12 cyclic hydrocarbon group, a C1-C12 linear alkoxy group, a C3-C12 branched alkoxy group, a C3-C12 cyclic alkoxy group, a C1-C12 acyl group, C 1-12 sulfide group, hydroxyl group, or halogen atom, R ¹ may be bonded to each other to form a cyclic structure, n is an integer of 0-2, m is 0 R ² may be the same or different and is a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, or an optionally substituted phenyl group. , Or a naphthyl group, and further R ^{2 to} each other directly or through a different atom To form a cyclic structure having 2 to 13 carbon atoms, and R ³ is a hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or 6 to 6 carbon atoms. 14 aryl groups in which a fluorine atom is not bonded to a carbon atom directly bonded to an S atom, an unsaturated hydrocarbon group bonded directly to an S atom, or an aromatic ring directly bonded to an S atom. R ¹ , R ² and R ³ may further have a substituent, and may have an oxygen atom in the carbon skeleton of R ³ .

(In the chemical formula (2), R ⁴ may be the same or different and is a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, or an optionally substituted phenyl group. , A naphthyl group and an anthracene group, and R ⁴ may be bonded to each other directly or via a different atom to form a cyclic structure having 2 to 13 carbon atoms, provided that at least one of R ⁴ is R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and is directly connected to the S atom. The carbon atom to be bonded, the unsaturated hydrocarbon group directly bonded to the S atom, or the aromatic ring directly bonded to the S atom is not bonded with a fluorine atom, and R ⁴ and R ⁵ further have a substituent. In the carbon skeleton of R ^5. (It may have an oxygen atom.)

(In the chemical formula (3), X is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an alkyleneoxy group having 1 to 12 carbon atoms (—R′—O—, where R ′ is R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and S 6 A carbon atom directly bonded to an atom, an unsaturated hydrocarbon group bonded directly to an S atom, or an aromatic ring directly bonded to an S atom, and a fluorine atom not bonded to R ⁶ further has a substituent. And may have an oxygen atom in the carbon skeleton.)

(In the chemical formula (4), R ⁷ is a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or 6 carbon atoms. An aryl group having 12 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and R ⁸ is a linear hydrocarbon group having 1 to 12 carbon atoms and 3 to 12 carbon atoms. A branched hydrocarbon group, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, A fluorine atom is not bonded to a carbon atom directly bonded to the S atom, an unsaturated hydrocarbon group bonded directly to the S atom, or an aromatic ring directly bonded to the S atom, and R ⁷ and R ⁸ are may have a substituent, an oxygen atom to the carbon skeleton of the R ³ It may be in.)

Here, the “substituent” of R ^{1 to} R ^{8 and the} like in the above chemical formulas (1) to (4) is a hydrocarbon group such as an alkyl group, a hydrocarbon group containing a hetero atom such as an alkoxy group or an acyl group, Alternatively, any of a group not containing a carbon atom such as a hydroxyl group or a sulfide group may be used. The “substituent” may be either a functional group having reaction activity or a mere residue having no reaction activity.
The size of the “substituent” is not particularly limited, but it is desirable that the substituent is not too large compared to the portion of the basic structure to which the substituent is bonded. For example, the total number of atoms other than hydrogen among the atoms constituting the substituent is preferably not more than the total number of atoms other than hydrogen among the atoms constituting the portion of the basic structure to which the substituent is bonded.

Examples of the linear hydrocarbon group having 1 to 12 carbon atoms of R ¹ in the chemical formula (1) include a methyl group, an ethyl group, a propyl group, an n-butyl group, a hexyl group, and an octyl group. It may have an unsaturated bond such as a heavy bond or a triple bond, and may have a substituent such as a hydroxyl group, an alkoxy group, a halogen atom, or a halogenoalkyl group.

Examples of the branched hydrocarbon group having 3 to 12 carbon atoms of R ¹ include a sec-butyl group, i-butyl group, 2-ethylhexyl group, and the like, and an unsaturated bond such as a double bond or a triple bond may be used. You may have, You may have substituents, such as a hydroxyl group, an alkoxy group, a halogen atom, and a halogenoalkyl group.

Examples of the cyclic hydrocarbon group having 3 to 12 carbon atoms of R ¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like, which may be either monocyclic or polycyclic, It may have an unsaturated bond such as a double bond or a triple bond, and may have a substituent.

  The substituent that the cyclic hydrocarbon group has is not particularly limited, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, a halogenoalkyl group, and a cyano group. It is done.

  The C1-C5 alkyl group as a substituent which a cyclic hydrocarbon group has may be either linear or branched. As a linear alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group etc. are mentioned, for example. Examples of the branched alkyl group include i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group and the like.

Examples of the linear alkoxy group having 1 to 12 carbon atoms of R ^1, for example, a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Examples of the branched alkoxy group having 3 to 12 carbon atoms for R ¹ include a 2-ethylhexyloxy group and a t-butoxy group.

Examples of the cyclic alkoxy group having 3 to 12 carbon atoms of R ¹ include a phenoxy group, a cyclohexyloxy group, a benzyloxy group, and a 1-naphthyloxy group.

Examples of the acyl group having 1 to 12 carbon atoms of R ¹ include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, pivaloyl group, benzoyl group and the like.

The sulfide group having 1 to 12 carbon atoms of R ^1, for example, methyl sulfide group, ethyl sulfide group, and a phenyl sulfide group.

Examples of the halogen atom for R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The R ¹ bonded to each other to form a cyclic structure is not particularly limited, and examples thereof include an alkylene group having 1 to 12 carbon atoms, such as a methylene group, an ethylene group, and a propylene group. And may have a substituent such as a hydroxyl group, an alkoxy group, a halogen atom, or a halogenoalkyl group.

The linear hydrocarbon group having 1 to 12 carbon atoms and the branched hydrocarbon group having 3 to 12 carbon atoms of R ² can be the same as R ¹ .

Examples of the optionally substituted phenyl group or naphthyl group substituent of R ² include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, a halogenoalkyl group, and a cyano group. Etc.
The alkyl group having 1 to 5 carbon atoms may be linear or branched. As a linear alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group etc. are mentioned, for example. Examples of the branched alkyl group include i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group and the like.

The cyclic structure having a carbon number of 2 to 13 bound directly or via an heteroatom with one another by R ² to each other is not particularly limited, for example, the following formula as an acid generator having the ring structure (B) (12) What can be represented.

Examples of the hydrocarbon group having 1 to 12 carbon atoms and the cyclic hydrocarbon group having 3 to 12 carbon atoms of R ³ include those similar to R ¹ . However, those in which a fluorine atom is bonded to a carbon atom directly bonded to an S atom are excluded.

Examples of the aryl group having 6 to 14 carbon atoms of R ³ include a phenyl group, a naphthyl group, and an anthryl group.
Moreover, as a substituent which an aryl group has, a cycloalkyl group, a C1-C5 alkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, a halogenoalkyl group etc. are mentioned. However, the case where a fluorine atom is bonded to an aromatic ring directly bonded to an S atom is excluded.

R ³ may have an oxygen atom in the carbon skeleton, or may have an oxygen atom as a substituent. Examples of such a compound include those having an ether bond, those having a carbonyl group, those having an ester bond, and specifically include a methoxyethyl group, an ethoxyethyl group, a methoxyphenyl group, an acetylethyl group, An acetylphenyl group, an ethoxycarbonylmethyl group, a phenoxycarbonylmethyl group, etc. are mentioned.

  Examples of the compound represented by the chemical formula (1) include diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium benzenesulfonate, and diphenyl-2. , 4,6-trimethylphenyl-p-toluenesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate, and the like.

In the above chemical formula (2), R ⁴ may be the same as R ² except that it may be an anthracene group which may be substituted.
In the chemical formula (2), R ⁵ may be the same as R ³ .

  Examples of the compound represented by the chemical formula (2) include bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, and bis (4-t-butyl). Phenyl) iodonium 10-camphorsulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, bis (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, bis (4-trifluoromethylphenyl) ) Iodonium benzenesulfonate, bis (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate, and the like.

  In said chemical formula (3), as a C1-C12 alkylene group of X, a methylene group, ethylene group, a propylene group etc. are mentioned, for example, Substitution, such as a hydroxyl group, an alkoxy group, a halogen atom, a halogenoalkyl group, is mentioned It may have a group.

Examples of the arylene group having 6 to 12 carbon atoms of X include a phenylene group and a naphthylene group, and include a cycloalkyl group, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, and a halogen atom. And may have a substituent such as a halogenoalkyl group.
R ⁶ may be the same as R ³ described above.

  Examples of the compound represented by the chemical formula (3) include N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N -(10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2. 2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenes) Phonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) naphthylimide and the like. Can be mentioned.

In the above chemical formula (4), straight-chain hydrocarbon group having 1 to 12 carbon atoms of ^{R 7,} a branched hydrocarbon group having 3 to 12 carbon atoms, cyclic hydrocarbon group having 3 to 12 carbon atoms similarly to ^{R 1} Can be.

The aryl group having 6 to 12 carbon atoms R ^7, for example, a phenyl group, a naphthyl group, and the like.
Moreover, as a substituent which an aryl group has, a cycloalkyl group, a C1-C5 alkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, a halogen atom, a halogenoalkyl group etc. are mentioned.

Examples of the heteroaryl group having 3 to 12 carbon atoms for R ⁷ include a pyridyl group and a quinolyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms of R ⁷ include a benzyl group, a phenethyl group, and a naphthylmethyl group.
R ⁸ can be the same as R ³ and R ⁷ described above.

  Examples of the compound represented by the chemical formula (4) include α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino). Examples include -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile, α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile, and the like.

In the chemical formula (1) to the chemical formula (4), R ³ , R ⁵ , R ⁶ , and R ⁸ are each a steric group that is a cyclic hydrocarbon group, an aryl group, a heteroaryl group, or an aralkyl group. The bulky structure is preferable because the diffusibility of the generated acid can be suppressed and a pattern with high resolution can be obtained.

These acid generators (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
Although the compounding quantity of an acid generator (B) is not specifically limited, 1-40 weight part is normally used with respect to 100 weight part of said phenolic compounds (A). Above all, a uniform resist film can be created, the storage stability of the negative resist composition can be improved, the sensitivity change after electron beam drawing can be suppressed, and a pattern with low line edge roughness can be obtained with high sensitivity and high resolution. From the viewpoint, the acid generator (B) is preferably 1 to 30 parts by weight, and more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the phenol compound (A).

<Organic basic compound (C)>
The negative resist composition used in the present invention preferably further uses an organic basic compound (C) in order to improve the resist pattern shape, stability over time in storage conditions, and the like. The organic basic compound (C) can be selected from any known organic basic compounds.
Examples of the organic basic compound (C) include nitrogen-containing organic compounds, such as nitrogen-containing compounds having a nitrogen atom, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. It is not limited to these. These nitrogen-containing organic compounds include compounds containing polar groups such as ether bonds, carbonyl bonds, ester bonds, carbonate bonds, sulfide bonds, sulfone bonds, and the like, ester groups, acetal groups, cyano groups, alkoxy groups, A compound containing a polar group such as a hydroxyl group as a substituent is also preferably used.

  Examples of the nitrogen-containing organic compound include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine, cyclohexylamine; -N-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, methyl-n-dodecyl Di (cyclo) alkylamines such as amine, di-n-dodecylmethylamine, cyclohexylmethylamine, dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri- n-hexylamine, tri-n-heptylamine, tri-n- Tri (cyclo) alkylamines such as cutylamine, tri-n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine, tricyclohexylamine; monoethanolamine, Alkanolamines such as diethanolamine and triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine , Aromatic amines such as tribenzylamine, 1-naphthylamine; ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylene Amine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4- Aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) ) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1 -Methylethyl] benzene, polyethyleneimine, 2,2- (phenylimino) diethanol, polyallylamine, N- (2 Dimethylaminoethyl) acrylamide polymer, tris (2-acetoxyethyl) amine, tris (2-pivaloyloxyethyl) amine, tris (2-t-butoxycarbonyloxyethyl) amine, tris [2- (2- Oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (t-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (2-methoxyethoxy) ethyl] amine, N- [2- (methylsulfonyl) ethyl] diethanolamine, N- [2- (methylsulfonyl) ethyl] bis (2-acetoxyethyl) amine, N- [2- (methylsulfonyl) ethyl] bis (2-formyloxy) Ethyl) amine, N- [2- (methylsulfonyl) ethyl] bi (2-methoxyethyl) amine, 3,3 ′-[2- (methylsulfonyl) ethyl] iminodipropionic acid dimethyl, N- (tetrahydrofurfuryl) bis [2- (methylsulfonyl) ethyl] amine, 3- Examples include t-butyl [bis (2-methoxyethyl) amino] propionate, t-butyl 3- [bis (2-acetoxyethyl) amino] propionate, and the like.

  Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. Can be mentioned.

  Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea. Etc.

  Examples of the nitrogen-containing heterocyclic compound include imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, 2-phenylbenzimidazole, 4,5-diphenylimidazole, 2,4,5-trimethyl. Imidazoles such as phenylimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, Pyridines such as nicotinic acid, nicotinic amide, quinoline, 8-oxyquinoline, acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpipe Razine, 1,4-diazabicyclo [2.2.2] octane, 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2 -(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2- (methoxymethoxy) ethyl] morpholine, 4- [2- (2-methoxyethoxy) methoxy] ethyl] morpholine 1- (2 ', 3' -Dihydroxypropyl) -2-methylimidazole, 1,3-di (2'-methyl-1'-imidazolylmethyl) benzene, 1-benzyl-2-methylimidazole, 1-benzylimidazole, acetic acid 2- (1H -Benzimidazol-1-yl) ethyl, 2- (2-phenyl-1H-benzimidazol-1-yl) ethyl acetate, 3- (2- Enyl-1H-benzimidazol-1-yl) methyl propionate, 1- [2- (1,3-dioxolan-2-yl) ethyl] 1H-benzimidazole, 4- (1H-benzimidazol-1-yl) Examples include butyronitrile, t-butyl 3-morpholinopropionate, t-butyl 3-piperidinopropionate, 1-ethylcyclopentyl 3-piperidinopropionate, 1-ethyl 2-norbornyl 3-piperidinopropionate, and the like. It is done.

  These organic basic compounds (C) can be used alone or in combination of two or more. The compounding quantity of an organic basic compound (C) is 0.01-10 weight part with respect to 100 weight part of said phenolic compounds (A), Preferably it is 0.1-5 weight part. If it is less than 0.01 part by weight, the effect of the addition cannot be obtained. On the other hand, when it exceeds 10 parts by weight, the sensitivity is lowered and the developability of the unexposed part tends to deteriorate.

<Other ingredients>
Since the negative resist composition of the present invention uses the specific phenolic compound (A), it is not necessary to contain a phenolic compound having no hydroxymethyl group or alkoxymethyl group. A phenolic compound that does not fall under the phenolic compound (A) of the present application, such as a phenolic compound that does not have a hydroxymethyl group or an alkoxymethyl group, may be included within a range that does not impair the effects of the present invention, but has a low line edge. It is preferably not included from the viewpoint of roughness.
Moreover, since the negative resist composition of the present invention uses the specific phenolic compound (A), it is not necessary to separately include a conventionally used crosslinking agent. However, it may be added in a small amount within the range where the effects of the present invention are not impaired, and the resolution may be improved along with an increase in sensitivity or an increase in pattern strength. The content of such a crosslinking agent can be 10% by weight or less, more preferably 5% by weight or less, based on the total solid content of the resist composition. Such a crosslinking agent is preferably not included from the viewpoint of low line edge roughness.

The crosslinking agent that does not correspond to the specific phenolic compound (A) is not particularly limited, and may be arbitrarily selected from known crosslinking agents used in conventional chemically amplified negative resist compositions. Can be used. For example, 4,4′-methylenebis [2,6-bis (hydroxymethyl)] phenol (MBHP), 4,4′-methylenebis [2,6-bis (methoxymethyl)] phenol (MBMP), 2,3- Dihydroxy-5-hydroxymethylnorbornane, 2-hydroxy-5,6-bis (hydroxymethyl) norbornane, cyclohexanedimethanol, 3,4,8 (or 9) -trihydroxytricyclodecane, 2-methyl-2-adaman Examples thereof include aliphatic cyclic hydrocarbons having a hydroxyl group and / or a hydroxyalkyl group such as butanol, 1,4-dioxane-2,3-diol, and 1,3,5-trihydroxycyclohexane, or oxygen-containing derivatives thereof.
Further, a glycoluril-based crosslinking agent may be used that uses melamine-based crosslinking agent, urea-based crosslinking agent, alkyleneurea-based crosslinking agent, or glycoluril.

Moreover, you may add the oligomer or polymer component for improving the performance of a resist film within the range which does not impair the effect of this invention to the negative resist composition of this invention. By adding an oligomer or polymer component and introducing a network structure in the resist film, resolution may be improved by improving pattern strength, and pattern shape (line edge roughness) may be improved. The content of such an oligomer or polymer component is preferably 5% by weight or less, more preferably 3% by weight or less, based on the total solid content of the resist composition.
The oligomer or polymer component is derived from a novolak resin, a polyhydroxystyrene derivative, acrylic acid or methacrylic acid, which is an alkali developable resin conventionally used in negative resist compositions for i-line, KrF, and ArF. An acrylic copolymer. These oligomer or polymer components may have a reactive functional group.
The weight average molecular weight of the oligomer or polymer component is preferably 2000 to 30000, and more preferably 2000 to 20000. The weight average molecular weight here refers to a polystyrene equivalent value measured by a GPC (gel permeation chromatography) method.

  In the negative resist composition of the present invention, as long as the effect of the present invention is not impaired, an additive having a miscibility, for example, an additional resin for improving the performance of the resist film, in order to improve coatability. These surfactants, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, and the like can be added and contained as appropriate.

<Preparation of negative resist composition>
The negative resist composition used in the present invention is usually prepared by uniformly mixing the above-described phenolic compound (A), acid generator (B), and other additives as required in an organic solvent. Is done.

As the organic solvent, those generally used as solvents for chemically amplified resists can be used. For example, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethylene glycol dimethyl ether, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide N- methylpyrrolidone, tetrahydrofuran and the like are preferred, it is possible to use these solvents singly or in combination. Further, isopropyl alcohol, ethyl alcohol, methyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, isobutyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-methoxyethanol , 2-ethoxyethanol, 1-ethoxy-2-propanol, 1-methoxy-2-propanol and other alcohols, and toluene, xylene and other aromatic solvents may be contained. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, cyclohexanone, cyclopentanone, 1-ethoxy-2-propanol, and ethyl lactate, which have the highest solubility of the acid generator in the resist component, are used as safety solvents. Certain propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and mixed solvents thereof are preferably used.
The amount of the solvent in the resist composition is not particularly limited, and is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. Generally, the solvent is used so that the solid content concentration of the resist composition is preferably in the range of 0.5 to 20% by weight, more preferably 0.5 to 15% by weight.

3. Antistatic film As the antistatic film used in the present invention, a known conductive compound having a sulfonic acid structure (for example, conductive compounds described in Patent Documents 1 to 3) can be used, and the conductive compound is used as a solvent. After melting, the resist antistatic film laminate is formed on the resist film formed on the support by the manufacturing method of the resist antistatic film laminate. By stacking the antistatic film, the charge-up phenomenon is prevented, and there is no pattern displacement or dimensional error, and a desired resist pattern can be obtained.

  The conductive compound used for the antistatic film of the present invention is not particularly limited as long as it has a sulfonic acid structure. For example, sulfonated polyaniline having a structural unit represented by the following chemical formula (15), or the following chemical formula (16) And those having an isothianaphthenylene structure shown in FIG.

(In the chemical formula (15), R ³⁰ may be the same or different and each independently represents a hydrogen atom, a methoxy group, a methyl group, an ethyl group, a hydroxy group, or —SO ₃ M, and the Ms are the same. And each independently represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium cation, and k represents an arbitrary value of 0 to 1.)

(In the chemical formula (16), R ³¹ may be the same or different and each independently represents a hydrogen atom, a linear or branched saturated or unsaturated alkyl having 1 to 20 carbon atoms, alkoxy or alkyl. Ester group, halogen, —SO ₃ M, nitro group, cyano group, primary to tertiary amino group, trihalomethyl group, phenyl group and substituted phenyl group, M may be the same or different, Each independently represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium cation.)

Although the weight average molecular weight of the said electroconductive compound is not specifically limited, The thing of 2000-100000 is used normally.
The weight average molecular weight is determined by gel permeation chromatography (GPC) using polystyrene as a standard product.

The solvent used when applying the conductive compound on the resist film is not particularly limited, and a solvent that dissolves the resist film and does not affect the resist film can be appropriately selected.
For example, in addition to water, alcohols such as methanol, ethanol, propanol, and isopropanol; ketones such as acetone and methyl isobutyl ketone; cellosolves such as methyl cellosolve, ethyl cellosolve, and ethyl cellosolve acetate; methylpropylene glycol, ethylpropylene glycol, and the like Propylene glycols; Amides such as dimethylformamide and dimethylacetamide; Pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone are preferably used. Each of these may be used alone, or a plurality of solvents may be mixed at an arbitrary ratio.

  The conductive compound solution may contain an arbitrary component as long as it does not interfere with the conductivity of the antistatic film. For example, an amine or a quaternary ammonium salt is used to adjust the pH of the conductive compound solution. It may be added.

  The ratio of the conductive compound to the solvent is usually 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight with respect to 100 parts by weight of the solvent. This is because if the proportion of the conductive compound is less than the above range, pinholes are generated in the formed antistatic film or the conductivity is poor, and if it exceeds the above range, the flatness of the antistatic film is deteriorated.

  The thickness of the antistatic film is not particularly limited, but is usually 20 nm to 100 nm, preferably 20 nm to 60 nm.

4). Method for Producing Resist Antistatic Film Laminate The method for producing a resist antistatic film laminate according to the present invention is not particularly limited, and can be produced by a conventionally known method.
For example, first, a resist film is formed on a support. Usually, the resist film is formed by applying a resist composition. The coating method is not particularly limited as long as the resist composition can be uniformly coated on the support, and various methods such as a spray method, a roll coating method, a slit coating method, and a spin coating method can be used. Can be used.

  Next, the resist composition applied on the substrate is pre-baked (PAB) to remove the organic solvent to form a resist film. The prebaking temperature may be appropriately determined depending on the components of the resist composition, the blending ratio, the type of the organic solvent, and the like, and is usually 70 to 160 ° C., preferably 90 to 130 ° C., and the prebaking time is usually from 30 seconds. About 15 minutes.

  Next, the antistatic film composition is applied onto the resist film formed on the support to form a laminate. The coating method is not particularly limited as long as it can uniformly apply the antistatic film composition, and various methods such as a spray method, a roll coating method, a slit coating method, and a spin coating method are used. be able to. However, in order not to cause intermixing with the resist composition, the composition for the antistatic film uses water or a mixture of lower alcohol as the solvent, so the apparatus for applying the antistatic film composition is a resist composition. It is better to separate it from what you are applying.

  Next, if necessary, the coating film of the antistatic film composition may be baked. The baking conditions are appropriately determined depending on the composition of the antistatic film composition to be used, the temperature is usually 60 to 200 ° C., preferably 60 to 130 ° C., and the time is usually about 30 seconds to 15 minutes.

II. Manufacturing method of relief pattern The manufacturing method of the relief pattern according to the present invention,
The step of drawing the resist antistatic film laminate according to the present invention with an electron beam, the step of removing the antistatic film of the resist antistatic film laminate drawn with an electron beam, and after removing the antistatic film or And a step of developing the resist film of the laminated body simultaneously with the removal. According to the method for manufacturing a relief pattern according to the present invention, there is no dimensional error even for a fine pattern, and a pattern as designed can be obtained.
Hereinafter, each step will be described with reference to FIG.

(I) Step of drawing resist antistatic film laminate according to the present invention in a predetermined pattern with an electron beam As shown in FIG. 2 (a), this step is performed by first using an electron beam drawing apparatus. The resist film 20 is selectively exposed by drawing by direct irradiation. The acceleration voltage and current value may be set arbitrarily. In this step, acid is generated from the acid generator (B) in the electron beam irradiation section 21 of the resist film (FIG. 2B).

When drawing in a predetermined pattern with an electron beam, it takes time to draw, and there may be a large difference in the elapsed time after drawing between the part drawn at the beginning of this process and the part drawn at the end. is there. In this case, there arises a problem that a desired resist pattern cannot be obtained due to a change in sensitivity of the electron beam irradiation portion 21 of the resist film 20.
On the other hand, when the resist antistatic film laminate of the present invention is used, a desired resist pattern can be obtained because the stability of the electron beam irradiation part is high and the change in sensitivity after electron beam drawing is small.

(Ii) Step of removing the antistatic layer of the resist antistatic film laminate drawn with an electron beam After the electron beam drawing, the antistatic film 30 is removed. This is usually performed by rinsing with pure water, and the rinsing time is about 30 seconds to 10 minutes. There is no restriction on the use of a rinse solution other than pure water, and any of the developer solutions conventionally used for developing resists can be suitably used.
In this step, the antistatic film 30 is removed, and the resist antistatic film laminate is as shown in FIG. Note that this step does not have to be performed after the step (i) of drawing with the electron beam. In the developing step (iii) described later, the antistatic film is removed simultaneously with the formation of the resist pattern using a developer. You may go.

(Iii) developing the resist film of the laminate from which the antistatic layer has been removed

Next, the support is developed using an alkaline developer to remove the non-irradiated part of the electron beam (FIG. 2 (d)).
Examples of the developing method include a spray method, a slit method, a liquid piling method, a dipping method, and a shaking dipping method.
Examples of the alkali developer of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldimethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide An aqueous solution of an alkali such as a quaternary ammonium salt such as choline, or a cyclic amine such as pyrrole or piperidine can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution. Among these alkaline developers, a quaternary ammonium salt is preferable, and an aqueous solution of tetramethylammonium hydroxide and choline is more preferable.

  When a tetramethylammonium hydroxide (TMAH) aqueous solution is used as the alkaline developer, the concentration of the tetramethylammonium hydroxide aqueous solution is preferably 0.1% to 5%, more preferably 0.5%. It is ˜3%, and particularly preferably 1.19% to 2.38%. 2.38% concentration of tetramethylammonium hydroxide aqueous solution is generally most readily available in the semiconductor industry. In addition, when the concentration of the tetramethylammonium hydroxide aqueous solution is less than 0.1%, the developer is neutralized by carbon dioxide in the air, and the sensitivity fluctuates, making it difficult to stably obtain a product. Become.

  After the development treatment, a rinsing treatment is performed, and the alkali developer on the substrate and the resist composition dissolved by the alkali developer are washed away and dried to obtain a resist pattern.

  It is preferable to perform a heat treatment (post-exposure bake (PEB)) between the step (i) for drawing with the electron beam and the step (iii) for developing. By heating, the difference in solubility between the electron beam irradiated portion and the unirradiated portion of the resist film is increased. The conditions for the PEB treatment are usually 70 to 160 ° C., preferably 90 to 130 ° C., and about 0.1 to 15 minutes.

  The resist antistatic film laminate according to the present invention is suitable for a microlithography process for manufacturing miniaturized electronic components such as for forming a gate layer of a semiconductor integrated circuit and for processing a mask pattern formed on a glass substrate. Can be used.

  The present invention also provides an electronic component, at least part of which is manufactured using the resist antistatic film laminate according to the present invention. Examples of the electronic component according to the present invention include a MEMS (micro electromechanical device) component, a micro mechanical component, a microfluidic component, a μ-TAS (micro preanalyzer) component, an inkjet printer component, a microreactor component, Examples include an electrically conductive layer, a metal bump connection portion, a LIGA (lithography electroforming) component and a die, a precision printing screen or stencil, a MEMS and semiconductor package component, and a printed wiring board.

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

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
In addition, the structure and physical properties in the production examples were confirmed using the following apparatuses.
Measurement was performed using MALDI-TOF MS (REFLEX II manufactured by BRUKER) under the following conditions (matrix: 1,8,9-trihydroxyanthracene).
¹ H-NMR: JEOL JNM-LA400WB, manufactured by JEOL Ltd.
High performance liquid chromatography (HPLC) was performed using the following conditions (temperature: 40 ° C., flow rate: 0.5 mL / min, column: VP-ODS (4.7 mm × 150 mm), detection using LC-10ADvp manufactured by Shimadzu Corporation. Measurement was performed using a container SPD-M10Avp, mobile phase: acetonitrile / water.

(Phenolic compounds)
<Synthesis Example 1>
5. A phenolic compound represented by the following chemical formula (17) (maternal compound: Pre-1) (TekOC-4HBPA: Honshu Chemical Industry Co., Ltd.) in a solution consisting of 20 mL of 10% by weight aqueous potassium hydroxide and 20 mL of ethanol. 3 g (10 mmol) was added and stirred and dissolved at room temperature. To this solution, 7.0 mL (80 mmol) of 37% formalin aqueous solution was slowly added at room temperature. Furthermore, after stirring at 40 ° C. for 24 hours under a nitrogen atmosphere, the mixture was poured into 200 mL of water in a beaker. While cooling this in an ice bath, a 2.0 wt% acetic acid aqueous solution was slowly added until the pH reached 5.0. The precipitate was filtered off, sufficiently washed with water, and dried to obtain a mixture of phenolic compounds into which hydroxymethyl groups were introduced. Purification was performed by high performance liquid chromatography to obtain 5.8 g of phenolic compound 1 (A-01) represented by the following chemical formula (18).
The structure of the obtained phenolic compound 1 (A-01) was confirmed by ¹ H-NMR spectrum and MALDI-TOF MS. The glass transition temperature was determined by differential scanning calorimetry. The analysis results are shown in Table 1.

<Synthesis Example 2>
In Synthesis Example 1, in the same manner as in Synthesis Example 1, except that 3.5 g (10 mmol) of 9,9-bis (4-hydroxyphenyl) fluorene was used instead of using the phenolic compound (Pre-1). The phenolic compound 3 (A-03) represented by the following chemical formula (19) was synthesized. As a result, 3.9 g of a white compound was obtained.
The structure of the obtained phenolic compound 2 (A-02) was confirmed by ¹ H-NMR spectrum and MALDI-TOF MS. The glass transition temperature was determined by differential scanning calorimetry. The analysis results are shown in Table 1.

<Synthesis Example 3>
In the synthesis example 1, instead of using the phenolic compound (Pre-1), a phenolic compound (Pre-3) represented by the following chemical formula (20) (TEOC-DF: Asahi Organic Materials Co., Ltd.) 4. A phenolic compound 3 (A-03) represented by the following chemical formula (21) was synthesized in the same manner as in Synthesis Example 1 except that 5 g (10 mmol) was used. As a result, 4.3 g of a white compound was obtained.
The structure of the obtained phenolic compound 3 (A-03) was confirmed by ¹ H-NMR spectrum and MALDI-TOF MS. The glass transition temperature was determined by differential scanning calorimetry. The analysis results are shown in Table 1.

<Synthesis Example 4>
5.7 g (1.0 mmol) of the phenolic compound 3 (A-03) represented by the chemical formula (21) was added to 250 mL of methanol, and dissolved by heating with stirring. To this solution was added 0.25 mL of concentrated sulfuric acid, and the mixture was heated to reflux for 15 hours. After completion of the reaction, the reaction solution was cooled and 1.0 g of potassium carbonate was added. After concentrating the solution, 300 mL of ethyl acetate was added. This solution was washed three times with water and concentrated to obtain 4.9 g of a white compound of phenolic compound 4 (A-04) represented by the following chemical formula (22).
The structure of the obtained phenolic compound 4 (A-04) was confirmed by ¹ H-NMR spectrum and MALDI-TOF MS. The glass transition temperature was determined by differential scanning calorimetry. The analysis results are shown in Table 1.

<Synthesis Example 5>
Under a nitrogen atmosphere, 11.0 g (0.1 mol) of resorcinol was dissolved in 400 mL of ethanol in a 300 mL three-necked flask. To this was added 10.2 mL (0.1 mol) of benzaldehyde, and then 20 mL of concentrated hydrochloric acid was slowly added dropwise and reacted at 75 ° C. for 12 hours. After the reaction, the reaction solution is cooled in an ice bath, the precipitated crystals are filtered off, washed with distilled water until neutral, dried, and a pale yellow phenolic compound represented by the following chemical formula (23) ( 9.2 g of Pre-5) was obtained.
In Synthesis Example 1, instead of using the phenolic compound (Pre-1), 0.8 g (1 mmol) of the phenolic compound (Pre-05) represented by the following chemical formula (23) was used, and the 37% formalin aqueous solution A phenolic compound 5 (A-05) represented by the following chemical formula (24) was synthesized in the same manner as in Synthesis Example 1 except that the addition amount was 0.7 mL (8 mmol) and the reaction temperature was changed to 5 ° C. . As a result, 0.7 g of a pale yellow compound was obtained.
The structure of the obtained phenolic compound 5 (A-05) was confirmed by ¹ H-NMR spectrum and MALDI-TOF MS. The glass transition temperature was determined by differential scanning calorimetry. The analysis results are shown in Table 1.

<Evaluation of solvent solubility of phenolic compounds>
The phenolic compounds (A-01 to A-05) obtained in Synthesis Examples 1 to 5 above were added to typical resist solvents shown below at a concentration of 1 wt% or 5 wt% at 23 ° C. and stirred. Went. A sample dissolved at a concentration of 5 wt% at 23 ° C. was evaluated as “◎”, a sample dissolved at a concentration of 1 wt% was evaluated as “◯”, and an insoluble sample was evaluated as “X”. The results are shown in Table 2.
D-1: Propylene glycol monomethyl ether D-2: Propylene glycol monomethyl ether acetate D-3: Cyclopentanone

(Acid generator)
<Acid generator (P-1)>
The acid generator (P-1) represented by the following chemical formula (25) was obtained from Wako Pure Chemical Industries, Ltd. under the product name Diphenyl-2,4,6-Trimethylphenylsulfone p-toluenesulfonate.

<Acid generator (P-2)>
The acid generator (P-2) represented by the following chemical formula (26) was obtained from Toyo Gosei Co., Ltd. under the product name TPS-TIPBS.

<Acid generator (P-3)>
The acid generator (P-3) represented by the following chemical formula (27) was obtained from Wako Pure Chemical Industries, Ltd. under the product name WPAG-567.

<Acid generator (P-4)>
The acid generator (P-4) represented by the following chemical formula (28) was obtained from Midori Chemical Co., Ltd. under the product name DPI-201.

<Acid generator (P-5)>
The acid generator (P-5) represented by the following chemical formula (29) was obtained from Midori Chemical Co., Ltd. under the product name NAI-101.

<Acid generator (P-6)>
The acid generator (P-6) represented by the following chemical formula (30) was obtained from Midori Chemical Co., Ltd. under the product name PAI-101.

<Acid generator (P-7)>
0.72 g (4 mmol) of sodium benzenesulfonate was dissolved in 20 ml of dichloromethane and 10 mL of water, and 1.27 g (4 mmol) of diphenyliodonium chloride was added thereto, and this suspension solution was added at room temperature (23 ° C.) under a nitrogen atmosphere. Stir for 12 hours. After stirring, the dichloromethane phase was separated, and the remaining aqueous phase was further extracted with dichloromethane three times. The obtained dichloromethane was combined, dried over sodium sulfate and dried. The obtained crystals were dissolved in a small amount of dichloromethane and dropped into diethyl ether, the precipitated crystals were filtered, the obtained crystals were dissolved again in dichloromethane, and a small amount of diethyl ether was added and left to stand for recrystallization. . The obtained crystal was filtered and dried to obtain a white acid generator (P-7) compound represented by the following chemical formula (31).

The purity and structure of the obtained acid generator (P-7) were confirmed from the ¹ H-NMR spectrum.
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 7.29-7.33 (m, 4H, Aromatic-H), 7.51-7.55 (t, 4H, aromatic-H) ), 7.58-7.60 (dd, 2H, aromatic-H), 7.65-7.69 (t, 2H, aromatic-H), 8.24-8.26 (d, 2H, aromatic- H)

<Acid generator (P-8)>
In the synthesis of the acid generator (P-7), a compound represented by the following chemical formula (32) is used according to the synthesis method except that 0.88 g (4 mmol) of sodium 3-nitrobenzenesulfonate is used instead of sodium benzenesulfonate. A white acid generator (P-8) compound was obtained.

The purity and structure of the obtained acid generator (P-8) were confirmed by ¹ H-NMR spectrum.
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 7.51-7.55 (t, 4H, aromatic-H), 7.64-7.69 (m, 3H, aromatic-H ), 8.01-8.03 (d, 1H, aromatic-H), 8.19-8.21 (dd, 1H, aromatic-H), 8.24-8.26 (d, 4H, aromatic- H), 8.34 (m, 1H, aromatic-H)

<Acid generator (P-9)>
In the synthesis of the acid generator (P-7), a compound represented by the following chemical formula (33) is prepared according to the synthesis method except that 0.81 g (4 mmol) of sodium 4-chlorobenzenesulfonate is used instead of sodium benzenesulfonate. A white acid generator (P-9) compound was obtained.

The purity and structure of the obtained acid generator (P-9) were confirmed by ¹ H-NMR spectrum.
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 7.36-7.38 (d, 2H, aromatic-H) 7.51-7.55 (t, 4H, aromatic-H) 7.58-7.60 (d, 2H, aromatic-H), 7.65-7.69 (t, 2H, aromatic-H), 8.24-8.26 (d, 4H, aromatic-H) )

<Comparative acid generator (RP-1)>
The comparative acid generator (RP-1) represented by the following chemical formula (34) was obtained from Midori Chemical Co., Ltd. under the product name DPI-105.

<Comparative acid generator (RP-2)>
The comparative acid generator (RP-2) represented by the following chemical formula (35) was obtained from Midori Chemical Co., Ltd. under the product name TPS-105.

<Comparative acid generator (RP-3)>
The comparative acid generator (RP-3) represented by the following chemical formula (36) was obtained from Midori Chemical Co., Ltd. under the product name TPS-109.

<Comparative acid generator (RP-4)>
The comparative acid generator (RP-4) represented by the following chemical formula (37) was obtained from Midori Chemical Co., Ltd. under the product name TPS-300.

<Comparative acid generator (RP-5)>
The comparative acid generator (RP-5) represented by the following chemical formula (38) was obtained from Midori Chemical Co., Ltd. under the product name NDI-105.

(Examples 1-15 and Comparative Examples 1-5)
As shown in Table 3, (A-01) to (A-05) as the phenol compound (A), acid generator compounds (P-1) to (P-9) as the acid generator compound (B), comparative acid Generator compounds (RP-1) to (RP-5), tri-n-octylamine (C-1) as basic compound (C), organic solvent (D) propylene glycol monomethyl ether (D-1), Add to propylene glycol monomethyl ether acetate (D-2) or cyclopentanone (D-3) in the blending amounts shown in Table 3 to make a uniform solution, and each sample solution is a 0.1 μm Teflon (registered trademark) filter. The negative resist compositions of Examples 1 to 15 and Comparative Examples 1 to 5 were prepared. In addition, the weight part of an acid generator differs because the number of moles of the acid generator used for an Example and a comparative example was match | combined.

<Resist pattern creation and evaluation method>
Using the resist compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 5, a resist pattern was created by the following method and evaluated. The results are shown in Table 4.

(1) Application of resist Each resist composition was uniformly applied on a 6-inch silicon substrate using a spinner, and pre-baked (PAB) at 100 ° C. for 60 seconds to form a resist film having a thickness of 50 nm. . A case where a good resist film was formed was marked with ◯, and a case where a good film formation was difficult due to repelling was marked with x.

(2) Application of antistatic film An antistatic film aquaSAVE57xs manufactured by Mitsubishi Rayon Co., Ltd. was uniformly applied to the substrate after applying the resist composition using a spinner, and baked at 70 ° C. for 90 seconds on the resist film. A resist / antistatic film laminate in which an antistatic film layer having a thickness of 40 nm was formed was obtained.
(3) Formation of resist pattern Drawing was performed on the resist antistatic film laminate using an electron beam drawing apparatus (acceleration voltage 100 KV). After drawing, rinse with pure water for 60 seconds to dissolve and remove the antistatic film layer, then bake treatment (PEB) at 100 ° C. for 60 seconds, and develop with 2.38% TMAH aqueous solution (23 ° C.) for 60 seconds. Then, a rinse process was performed for 60 seconds with pure water to form a line and space (L / S) pattern.

<Evaluation>
(1) Sensitivity, Resolution, Line Edge Roughness Sensitivity and line edge roughness (LER) were measured with a scanning electron microscope (SEM) (manufactured by Holon). Sensitivity was measured in units of μC / cm ² with sensitivity as the minimum dose at which a 100 nm L / S pattern was formed 1: 1. Further, the limit resolution (the line and space are separated and resolved) at the irradiation amount was defined as the resolution. For LER, 500 points of line width were measured for a range of edge of 0.7 μm in the longitudinal direction of a 100 nm L / S pattern, a standard deviation was obtained, and 3σ was calculated.

(2) Line width stability after exposure in vacuum When a resist pattern is formed, a pattern is drawn by an electron beam drawing apparatus, and then in a high vacuum (5.0 × 10 ⁻⁶ Pa) 3 in the electron beam drawing apparatus. A resist pattern was formed by the same method as the above-mentioned “Preparation of resist pattern” except that a step of allowing each resist composition to stand for a period of time was added. An L / S pattern line having a design line width of 100 nm with the same dose as the minimum dose determined by the above-described method of “sensitivity and resolution” using each resist composition before being left for 3 hours under high vacuum. The width was measured. Change in pattern line width obtained with each resist composition after standing for 3 hours under high vacuum is within 1% of the pattern line width obtained with each resist composition before standing for 3 hours under high vacuum Those that are ◯ and those that exceed 1% were rated as x.

<Summary of results>
In the resist antistatic film laminates of Examples 1 to 15 of the present invention, the charge-up phenomenon can be avoided, the sensitivity change after the electron beam drawing of the resist film can be suppressed, and a pattern with the dimensions as designed can be formed. It has been clarified that a fine relief pattern with high sensitivity and high resolution and low line edge roughness can be obtained while having alkali developability.
On the other hand, in the resist antistatic film laminates of Comparative Examples 1 to 5 using an acid generator in which a fluorine atom is bonded to a carbon atom, an unsaturated hydrocarbon group, or an aromatic ring directly bonded to the sulfonic acid structure, exposure is performed. The rear line width stability was poor and the line edge roughness was inferior, and a pattern with the dimensions as designed could not be formed.

DESCRIPTION OF SYMBOLS 1 Resist antistatic film laminated body 10 Support body 20 Resist film 21 Electron beam irradiation part 30 Antistatic film 40 Electron beam 41 Electron beam irradiation range

Claims (8)

On the support,
(I) Two or more phenolic hydroxyl groups in one molecule, and one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group in the ortho position of the phenolic hydroxyl group in one molecule A sulfonic acid structure represented by —SO ₃ ^— or —SO ₃ —, which is generated directly or indirectly by irradiating an electron beam with one or more phenolic compounds (A) having a molecular weight of 400 to 2500. And having a carbon atom directly bonded to the sulfonic acid structure, an unsaturated hydrocarbon group directly bonded to the sulfonic acid structure, or an aromatic ring directly bonded to the sulfonic acid structure, and directly bonded to the sulfonic acid structure A negative resist composition containing the carbon atom, the unsaturated hydrocarbon group, or the acid generator (B) in which no fluorine atom is bonded to the aromatic ring, A resist film comprising a negative resist composition in which the content of the phenolic compound (A) in the total solid content of the resist composition is 70% by weight or more;
(II) comprising at least an antistatic film,
Resist antistatic film laminate. The resist antistatic film laminate according to claim 1, wherein the acid generator (B) is represented by any one of the following formulas (1) to (4).
(In the chemical formula (1), R ¹ may be the same or different, and each independently represents a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, or 3 carbon atoms. -12 cyclic hydrocarbon group, a C1-C12 linear alkoxy group, a C3-C12 branched alkoxy group, a C3-C12 cyclic alkoxy group, a C1-C12 acyl group, C 1-12 sulfide group, hydroxyl group, or halogen atom, R ¹ may be bonded to each other to form a cyclic structure, n is an integer of 0-2, m is 0 R ² may be the same or different and is a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, or an optionally substituted phenyl group. , Or a naphthyl group, and further R ^{2 to} each other directly or through a different atom To form a cyclic structure having 2 to 13 carbon atoms, and R ³ is a hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or 6 to 6 carbon atoms. 14 aryl groups in which a fluorine atom is not bonded to a carbon atom directly bonded to an S atom, an unsaturated hydrocarbon group bonded directly to an S atom, or an aromatic ring directly bonded to an S atom. R ¹ , R ² and R ³ may further have a substituent, and may have an oxygen atom in the carbon skeleton of R ³ .
(In the chemical formula (2), R ⁴ may be the same or different and is a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, or an optionally substituted phenyl group. , A naphthyl group and an anthracene group, and R ⁴ may be bonded to each other directly or via a different atom to form a cyclic structure having 2 to 13 carbon atoms, provided that at least one of R ⁴ is R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and is directly connected to the S atom. The carbon atom to be bonded, the unsaturated hydrocarbon group directly bonded to the S atom, or the aromatic ring directly bonded to the S atom is not bonded with a fluorine atom, and R ⁴ and R ⁵ further have a substituent. In the carbon skeleton of R ^5. (It may have an oxygen atom.)
(In the chemical formula (3), X is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an alkyleneoxy group having 1 to 12 carbon atoms (—R′—O—, where R ′ is R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and S 6 A carbon atom directly bonded to an atom, an unsaturated hydrocarbon group bonded directly to an S atom, or an aromatic ring directly bonded to an S atom, and a fluorine atom not bonded to R ⁶ further has a substituent. And may have an oxygen atom in the carbon skeleton.)
(In the chemical formula (4), R ⁷ is a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or 6 carbon atoms. An aryl group having 12 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and R ⁸ is a linear hydrocarbon group having 1 to 12 carbon atoms and 3 to 12 carbon atoms. A branched hydrocarbon group, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, A fluorine atom is not bonded to a carbon atom directly bonded to the S atom, an unsaturated hydrocarbon group bonded directly to the S atom, or an aromatic ring directly bonded to the S atom, and R ⁷ and R ⁸ are may have a substituent, an oxygen atom to the carbon skeleton of the R ⁸ It may be in.)   The resist antistatic film laminated body of Claim 1 or 2 whose glass transition temperature (Tg) of the said phenolic compound (A) is 60 degreeC or more.   The phenolic compound (A) has at least three substituents in one molecule selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho position of the phenolic hydroxyl group. The resist antistatic film laminated body as described in any one of thru | or 3.   5. The phenolic compound (A) has a solubility of 5 wt% or more at 23 ° C. in an organic solvent having a boiling point of 80 to 180 ° C. 5. 2. The resist antistatic film laminate according to 1.   The resist antistatic film laminate according to any one of claims 1 to 5, wherein the negative resist composition further contains an organic basic compound (C). Drawing the resist antistatic film laminate according to any one of claims 1 to 6 with an electron beam;
Removing the antistatic film of the resist antistatic film laminate drawn with an electron beam;
And a step of developing the resist film of the laminate after or simultaneously with the removal of the antistatic film.   The method for producing a relief pattern according to claim 7, wherein heat treatment is performed between the step of drawing with the electron beam and the step of developing.