JP2012088697A - Resist antistatic film laminate, method for forming relief pattern, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist antistatic film laminate, in which a charge-up phenomenon is avoided and changes in the sensitivity of a resist film after exposure are suppressed, and thereby, a fine pattern having dimensions as designed can be formed.SOLUTION: The resist antistatic film laminate includes on a supporting body: (1) a resist film comprising a resist composition containing at least a phenol compound (A) having a molecular weight of 150 to 3000 and an acid generator (B) containing a sulfonic acid structure represented by -SOor -SO- and a carbon atom directly bonded to the sulfonic acid structure or an aromatic ring directly bonded to the sulfonic acid structure, in which no fluorine atom is bonded to the carbon atom or the aromatic ring directly bonded to the sulfonic acid structure; and (2) an antistatic film.

Description

  The present invention relates to a laminate having a laminate structure in which an antistatic film is provided on a resist film containing an acid generator, a pattern forming method using the laminate, and an electronic component. These laminates are particularly effective in pattern formation using electron beams or charged particle beams.

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. 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.

  Among these exposure light sources, lithography using an electron beam is one that is currently being researched and developed for practical use for the purpose of forming fine patterns. An electron beam corresponds to a wavelength of 0.005 nm at an acceleration voltage of 50 kV and has a high resolving power in principle. In many cases, a mask is used to form a target pattern by directly scanning an electron beam on a substrate. There is an advantage that an arbitrary pattern can be formed without using it.

However, since a resist generally used for microfabrication is a highly insulating organic substance, when it is exposed to an electron beam, a “charge-up phenomenon” occurs in which charges accumulate on the surface or inside of the resist film. If exposure is continued after charge-up occurs, there is a problem that the irradiated electron beam is affected by the charge-up and is shifted from the originally intended exposure position, or patterns having different dimensions are formed.
Conventionally, the effect of this charge-up has been relatively less affected due to the large machining size, and has not been regarded as a problem. However, the smaller the processing dimension, the greater the influence, and there was a new problem of affecting the characteristics of electronic parts or relief patterns processed using resist patterns and reducing reliability. . In particular, when a pattern having a thickness of 50 nm or less is formed, a position shift or dimensional change of about several nm causes a serious problem.

As means for avoiding this problem, a plurality of methods for forming an antistatic film on a resist film have been proposed. Patent Document 1 uses a water / IPA solution containing sulfonated polyaniline, and a method of forming an antistatic film by spin coating. Patent Document 2 discloses a polythiophene aqueous solution having sulfonic acid, a polyphenylene vinylene aqueous solution having sulfonic acid, and a sulfonic acid. A method of forming a film by spin coating using each of the polyaniline aqueous solutions having the above, Patent Document 3 proposes a method of forming a film using an aqueous solution containing a polymer having a specific isothianaphthene structure. 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.

  These can be formed without intermixing when spin-coating a water-soluble polymer onto a resist film, and can be removed after exposure either by rinsing with water or development with an aqueous alkaline solution. There are many advantages in constructing. Specifically, a resist film is formed as usual, an antistatic film is formed on the resist film by spin coating, baking and exposure are performed, and then the antistatic film is removed by rinsing and after exposure. A desired pattern is obtained by performing baking (PEB, post exposure bake) and developing, or performing PEB and then simultaneously developing and removing the antistatic film with a developer.

  On the other hand, in order to achieve high sensitivity, in recent years, chemically amplified resists have become the mainstream for both positive and negative resists. This chemically amplified resist uses a catalytic amount of acid generated by exposure to cause a chemical reaction to cause a difference in dissolution rate with respect to the developer to form a pattern.

  When the negative chemically amplified resist layer is heated in the presence of an acid, for example, a phenol compound and a crosslinking agent undergo a crosslinking reaction, the molecular weight increases, and the solubility in a developing solution decreases. On the other hand, the solubility of the positive chemically amplified resist layer in the developer increases in the presence of an acid due to, for example, elimination of an acid dissociable protecting group.

  Conventionally, acid generators used for chemically amplified resists are required to have high acidity of the acid generated from the viewpoint of the reactivity of the acid catalyst (for example, Patent Document 4).

JP-A-6-3813 JP-A-4-32848 JP 7-41756 A JP 2010-018573 A

  The inventors have obtained the knowledge that when a chemically amplified resist is used in combination with an antistatic film, the sensitivity changes with the passage of time after exposure, and a desired processing dimension may not be obtained or a pattern may not be formed at all. It was. In particular, when a direct electron beam is scanned on the substrate, when exposure is performed by a so-called electron beam direct drawing method, the exposure time in the resist layer varies depending on the exposure time from exposure to development for each exposure time. There is a problem that a difference in sensitivity occurs every time and the pattern after development becomes a dimension different from the original setting. In this case, since the amount of dimensional change varies depending on the exposure time until development after exposure, it is extremely difficult to obtain a pattern as designed in the case of an electron beam direct writing method that requires a long time for the exposure process.

  In view of the above circumstances, an object of the present invention is to provide a resist antistatic film laminate capable of forming a fine pattern having dimensions as designed by avoiding a charge-up phenomenon and suppressing a sensitivity change after exposure of the resist film. Provide the body.

The knowledge that chemically amplified resists are easily affected by the external environment, and when exposed to an atmosphere containing alkaline compounds after exposure, the acid generated from the acid generator is neutralized, causing a significant decrease in sensitivity. It was known. However, there has been no detailed study of sensitivity changes after exposure in vacuum in the presence of an antistatic film. As a result of extensive research by the inventor, the inventors have found that in conventional resist compositions, sensitivity changes with the passage of time after exposure in vacuum in the presence of an antistatic film. Specifically, when the pattern is formed with the same exposure amount, the dimension of the finally obtained pattern varies with time. Furthermore, in the case of the so-called electron beam direct drawing method, the pattern is drawn in the order of scanning with the electron beam, so the time taken from the exposure to the development varies depending on the exposure part, and the same dimension on the same substrate is obtained. It was found that even the exposure pattern possessed had different sensitivities depending on the timing of exposure, resulting in a phenomenon that the dimensions of the finally obtained pattern differed. Therefore, paying attention to the acid generator contained in the resist, the sensitivity change after exposure can be achieved even when an antistatic film is laminated on the resist film by using a specific acid generator described later in the resist composition. It was found that a good resist pattern can be formed while suppressing the above.
The present invention has been completed based on such findings.

That is, the resist antistatic film laminate according to the present invention is formed on a support.
(1) a phenol compound having a molecular weight of _{150~3000 (A), - SO 3} - or -SO ₃ - sulfonic acid structure represented by and, the carbon atom bonded directly to the acid structure, coupled directly to the sulfonic acid structure A fluorine atom is bonded to the carbon atom, the unsaturated hydrocarbon group, or the aromatic ring directly bonded to the sulfonic acid structure. A resist film comprising a resist composition containing at least an acid generator (B) that is not present,
(2) At least an antistatic film is provided.

  According to the present invention, a pattern having a processing dimension as set can be obtained with high accuracy by providing an antistatic film, avoiding a charge-up phenomenon, suppressing a sensitivity change after exposure of the resist film.

The resist film used in the present invention is preferably composed of the following negative resist composition or positive resist composition.
<Negative resist composition>
Phenolic compound (A) having a molecular weight of 150 to 3000,
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 directly to the sulfonic acid structure; A compound comprising an aromatic ring to be bonded and having no fluorine atom bonded to the carbon atom, the unsaturated hydrocarbon group, or the aromatic ring directly bonded to the sulfonic acid structure, and having a wavelength of 248 nm or less An acid generator (B ′) that generates an acid directly or indirectly by irradiating the active energy ray of
A negative resist composition containing at least a crosslinking agent (C).
<Positive resist composition>
A phenol compound (Acap) having a molecular weight of 150 to 3000 and at least a portion of the phenolic hydroxyl group protected with an acid-decomposable group; and
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 directly to the sulfonic acid structure; A compound comprising an aromatic ring to be bonded and having no fluorine atom bonded to the carbon atom, the unsaturated hydrocarbon group, or the aromatic ring directly bonded to the sulfonic acid structure, and having a wavelength of 248 nm or less A positive resist composition containing at least an acid generator (B ′) that generates an acid directly or indirectly by irradiating the active energy ray.

  The post-exposure stability is that the acid generator (B) used in the present invention is one or more acid generators selected from the group of compounds represented by any of the following chemical formulas (1) to (4). From the point of view, it is preferable.

(In the chemical formula (1), R ¹ may be the same or different, and each independently represents a hydrogen atom, a linear hydrocarbon group having 1 to 12 carbon atoms, or a branched hydrocarbon group having 3 to 12 carbon atoms. , A C3-C12 cyclic hydrocarbon group, a C1-C12 linear alkoxy group, a C3-C12 branched alkoxy group, a C3-C12 cyclic alkoxy group, a C1-C12 12 is an acyl group having 12 carbon atoms, a sulfide group having 1 to 12 carbon atoms, a hydroxyl group, or a halogen atom, and R ¹ may be bonded to each other to form a cyclic structure, where n is an integer of 0 to 2. 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, an optionally substituted phenyl group, or a naphthyl group. In addition, carbon atoms bonded to each other between R ² directly or through different atoms A cyclic structure having a prime number of 2 to 13 may be formed, and R ³ 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. Te, the carbon atom bonded directly to the S atom, those unsaturated hydrocarbon group directly bonded to the S atom, or an aromatic ring bonded directly to the S atom, a fluorine atom not bonded. the R ^1, R ² and R ³ may further have a substituent, and the carbon skeleton of R ³ may have an oxygen atom.)

(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 optionally substituted phenyl. A 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 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 having an S atom A fluorine atom is not bonded to a directly bonded carbon atom, an unsaturated hydrocarbon group directly bonded to the S atom, or an aromatic ring directly bonded to the S atom, wherein 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), L 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 the carbon skeleton of R ⁶ may have an oxygen atom.)

(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 a carbon number. 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, and R ⁸ is a linear hydrocarbon group having 1 to 12 carbon atoms and 3 to 3 carbon atoms. A branched hydrocarbon group having 12 carbon atoms, 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. In addition, 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, R ⁷ and R ⁸ are , may further have a substituent, an oxygen atom to the carbon skeleton of the R ⁸ It may be in.)

The acid generator (B) has a polymer chain structure, a sulfonic acid structure represented by —SO ₃ ^— or —SO ₃ — on the terminal and / or side chain of the polymer chain, and the sulfonic acid A carbon atom directly bonded to the structure, 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; It is preferable to have a saturated hydrocarbon group or an acid generator structure in which no fluorine atom is bonded to the aromatic ring from the viewpoint of suppressing diffusion of the generated acid, improving resolution, and obtaining a good resist pattern.

  It is preferable that the resist composition used in the present invention further contains an organic basic composition (D) from the viewpoint of improving the resist pattern shape and improving the temporal stability in the storage state.

The method for forming a relief pattern according to the present invention comprises a step of exposing the resist antistatic film laminate according to the present invention in a predetermined pattern with an energy beam selected from the group consisting of electron beam, ion beam, EUV, and X-ray. ,
Removing the antistatic film of the exposed resist antistatic film laminate;
And a step of developing the resist film of the laminate after or simultaneously with the removal of the antistatic layer.

  Further, when a relief pattern is formed using a resist antistatic film laminate having a negative resist film, the resist antistatic film laminate may be subjected to a heat treatment after exposure and before development. desirable.

  According to the present invention, it is possible to efficiently manufacture a fine pattern having a dimension as set with high sensitivity and high resolution.

  Furthermore, according to the present invention, even when drawing on a predetermined pattern with the energy beam without using a mask pattern in the exposure step, there is no change in sensitivity of the resist film after exposure, and a highly accurate relief pattern is manufactured. it can.

  The present invention provides an electronic component manufactured using the resist antistatic film laminate according to the present invention.

  According to the present invention, a resist antistatic film laminate capable of forming a fine pattern by avoiding a charge-up phenomenon and suppressing a sensitivity change after exposure of the resist film, and a relief using the resist antistatic film A pattern manufacturing method and an electronic component using the resist antistatic film can be provided.

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 pattern formation method of this invention.

The present invention will be described in detail below.
In the present invention, “energy beam” means far ultraviolet rays such as KrF excimer laser, ArF excimer laser, and F ₂ excimer laser, electron beam, EUV, X-ray and the like.

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.

<Resist antistatic film laminate>
As shown in FIG. 1, the resist antistatic film laminate according to the present invention is provided with a resist film 20 and an antistatic film 30 described later on a support 10. By stacking an antistatic film on the resist film, it is possible to control the accumulation of charges during exposure in lithography using an electron beam or other charged particle beam as exposure light. A fine pattern having street dimensions can be formed efficiently.
Note that another film may be formed on the support prior to resist coating. The film at this time is not limited to inorganic or organic, and any film forming method can be selected.

The resist antistatic film laminate of the present invention can be produced by the following method.
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 to the support is pre-baked (PAB) and the organic solvent (E) in the resist composition is removed 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 composition for an antistatic film can 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.

  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, Electrically conductive layers, metal bump connections, LIGA (lithography electroforming) parts and molds, precision printing screens or stencils, MEMS and semiconductor package parts, and printed wiring boards that can be processed by ultraviolet (UV) lithography Etc.
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 form a fine relief pattern by supporting a resist film, exposing the resist film on a predetermined pattern, and developing it. It is appropriately selected depending on. 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 used for the resist antistatic film of the present invention contains a specific acid generator described later in a matrix composed of a phenolic compound, and is either a negative resist composition or a positive resist composition. Also good. Although the thickness of a resist film is not specifically limited, Usually, it is 30 nm-500 nm, Preferably it is 40 nm-100 nm.
Hereinafter, the negative resist composition and the positive resist composition will be described in order.

(1) The negative resist composition negative resist composition used in the present invention, the phenolic compound having a molecular weight of _{150~3000 (A), - SO 3} - or -SO ₃ - and includes a sulfonic acid structure represented by, 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 the carbon atom directly bonded to the sulfonic acid structure And an acid generated directly or indirectly by irradiation with an active energy ray having a wavelength of 248 nm or less, comprising a compound having no fluorine atom bonded to the unsaturated hydrocarbon group or the aromatic ring. It contains an acid generator (B) and a crosslinking agent (C).
Hereinafter, the compounds constituting the negative resist composition will be described.

Phenol compound (A)
The phenol compound (A) used in the present invention is a compound having a molecular weight of 150 to 3000. By setting the molecular weight within the above range, it is possible to increase the resolution of the pattern.
In the present invention, the phenolic hydroxyl group includes a phenolic hydroxyl group protected with an acid-decomposable group described later.

The phenol compound (A) used in the present invention preferably has 2 or more phenolic hydroxyl groups in one molecule, more preferably 3 or more phenolic hydroxyl groups from the viewpoint of improving the resolution of the pattern. More preferably, 4 or more per molecule. When there are four or more phenolic hydroxyl groups in one molecule, three-dimensional crosslinking is possible, the pattern strength of the resist film after exposure is improved, and pattern collapse that occurs after development can be suppressed, improving resolution. To do.
Further, the presence of more polar groups in the molecule improves the adhesion due to the interaction between the polar groups and the support. Adhesion with the support also improves the resolution. Especially, the phenol compound (A) which has 4 or more of benzene rings which have a phenolic hydroxyl group in 1 molecule is preferable from the point of the said effect.

The phenol compound (A) used in the present invention preferably has a glass transition temperature (Tg) of 90 ° C. or higher, and more preferably 100 ° C. or higher. When the glass transition temperature is 90 ° C. or higher, a dewetting phenomenon does not easily occur when forming a coating film, and a uniform film is easily obtained. The dewetting phenomenon is a phenomenon in which a spread coating film melts during pre-baking and repelling occurs, so that a film is not uniformly formed.
The glass transition temperature here is measured by a differential scanning calorimeter (DSC).

  Moreover, it is preferable that the said phenol compound (A) has the solubility of 0.5 weight% or more 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 phenol compound (A) used in the present invention has three or more phenolic hydroxyl groups in one molecule, a glass transition temperature (Tg) of 90 ° C. or more, and a boiling point of 80 to 180 ° C. It preferably has a solubility of 0.5% by weight or more with respect to the organic solvent.

  Examples of the phenol compound (A) include compounds represented by the following chemical formula (5) and chemical formula (7). The compound represented by the following chemical formula (5) is preferable from the viewpoint of obtaining a pattern with high sensitivity, high resolution, and good shape.

(In the chemical formula (5), each R ⁹ is independently a hydrogen atom or a group selected from the group consisting of a hydrocarbon group, a cycloalkyl group, an aryl group, and a group represented by the following chemical formula (6).)

(In the chemical formula (6), Q is an aryl group or a cycloalkyl group, m represents 1 or 2.) R ¹⁰ are each independently a hydrogen atom or an organic group, among a plurality of R ¹⁰ At least one is a hydrogen atom. R ¹¹ is a group selected from the group consisting of a halogen atom or a hydrocarbon group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, and a nitro group. 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. 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 ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom, a hydrocarbon group or a cycloalkyl group. A plurality of R ¹² are bonded to form a ring. A plurality of R ¹³ may be combined to form a ring, a plurality of R ¹⁴ may be combined to form a ring, or a plurality of R ¹⁵ may be combined to form a ring. A plurality of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be the same as or different from each other.
R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or an organic group, and a plurality of R ¹⁶ and R ¹⁷ may be the same as or different from each other. Further, at least one of the plurality of R ¹⁶ and R ¹⁷ is a hydrogen atom.
W represents a group consisting of a single bond, an alkylene group, a cycloalkylene group or an arylene group and any combination thereof.
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 hydrocarbon group for R ⁹ 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 hydrocarbon group has include a hydroxyl group, an alkoxy group, a halogen atom, and a halogenoalkyl group.

The cycloalkyl group of R ^9, is 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, a halogenoalkyl group, and a cyano 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 ^9, 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.

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 cycloalkyl group as the substituent of the aryl group include the same cycloalkyl groups that may have the above-described substituent.
The alkyl group having 1 to 5 carbon atoms, the alkoxy group, the alkoxyalkyl group, the halogen atom, and the halogenoalkyl group as the substituent that the aryl group has are as described above for the cycloalkyl group.

The Q aryl group, the cycloalkyl group, and the substituents they have in the above chemical formula (6) can be the same as those in R ⁹ .

As the organic group for R ^10, it is not particularly limited, a hydrocarbon group, a cycloalkyl group, an aryl group.
The hydrocarbon group, cycloalkyl group, aryl group of R ^{10 and} the substituents they have can be the same as those of R ⁹ described above.

As the halogen atom and hydrocarbon group for R ^11, the same groups as those described above for R ⁹ can be used.
The hydrocarbon group as R ¹¹ has 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, Examples include an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group.

The cycloalkyl group which may have a substituent for R ^11, the aryl group which may have a substituent, and the alkoxy group may be the same as those for R ⁹ described above.
The acyl group of R ^11, 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.

As long as the compound represented by the chemical formula (5) has two or more phenolic hydroxyl groups, the substituents represented by the same symbols in the respective repeating units may be the same or different. The positions of OR ¹⁰ and R ¹¹ in each repeating unit may be the same or different. Moreover, the number of n1 and n2 in each repeating unit may be the same or different. For example, in the compound represented by the chemical formula (5), when x1 is 4, all the repeating units may be the same as the following chemical formula (8), or all the repeating units may be the same as the following chemical formula (9). The repeating unit may be different.

In the compound represented by the chemical formula (5), x1 is preferably 4 and n1 is preferably 2 or 3 from the viewpoint of obtaining a pattern with high sensitivity and high resolution and good shape. x1 is 4, n1 is 2, and it is preferably a calix resorcinarene derivative having 2 to 8 hydrogen atoms out of 8 R ¹⁰ . Furthermore, it is preferable that a hydrogen atom of the eight R ¹⁰ is calix resorcin arene derivative is 2-4, among others, in one of the hydrogen atoms of the two R ¹⁰ in the repeating unit of the formula (5), The other is an organic group, and a calix resorcinarene derivative having four hydrogen atoms in one molecule is preferable from the viewpoint of achieving high sensitivity while using a high concentration developer.

On the other hand, in the compound represented by the chemical formula (7), the hydrocarbon group in R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be linear or branched, preferably a methyl group, an ethyl group, a propyl group, Examples thereof include those having 1 to 10 carbon atoms such as a butyl group, an isobutyl group, a hexyl group, and an octyl group.
The cycloalkyl group in R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ 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.

  Examples of the substituent that the hydrocarbon group or cycloalkyl group may have include a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxy group (methoxy group, ethoxy group, propoxy). Group, butoxy group, etc.).

Examples of the organic group in R ¹⁶ and R ¹⁷ 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.

When at least one phenolic hydroxyl group in one molecule is present, the phenol compound (A) protects the phenolic hydroxyl group of a compound (maternal compound) serving as a mother nucleus such as a polyhydric phenol compound with an organic group. Also good.
Although the specific example of the mother nucleus compound of a phenol compound (A) is shown below, this invention is not limited to these. The phenolic hydroxyl groups in the following specific examples may be protected with an organic group as long as one or more phenolic hydroxyl groups in one molecule are present.

  The mother compound of the phenol 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 phenol compound (A) may be used alone or in combination of two or more of the compounds described above. For example, the compound represented by the chemical formula (5) and the compound represented by the chemical formula (7) may be used in combination, or all repeating units such as the compound represented by the chemical formula (8) may be used. May be used in combination with a compound having different repeating units such as the compound represented by the chemical formula (9).

The molecular weight of the phenol compound (A) is 150 to 3000.
When the phenol compound (A) is a compound represented by the chemical formula (5), the molecular weight is preferably 300 to 2000, and more preferably 400 to 1500.
Moreover, when the said phenol compound (A) is a compound represented by the said Chemical formula (7), molecular weight becomes like this. Preferably it is 300-2500, More preferably, it is 400-2000.

It is preferable that content of the said phenol compound (A) is 50 to 95 weight% with respect to the total solid, More preferably, it is 60 to 90 weight%.
In addition, in this invention, solid content means things other than a solvent among the components contained in a resist composition. When the content of the phenol compound is less than the above range, the content of the acid generator and the crosslinking agent is excessively increased, and the uniformity of the crosslinking reaction is lowered, so that the profile and the resolution are deteriorated. When the content of the phenol compound is more than the above range, the content of the generator and the crosslinking agent becomes too small, and the crosslinking reaction does not proceed sufficiently, so that the sensitivity is lowered and the resolution is remarkably deteriorated.

Acid generator (B)
The acid generator used in the present invention includes a sulfonic acid structure represented by —SO ₃ ^— or —SO ₃ —, a carbon atom directly bonded to the sulfonic acid structure, and an unsaturated bond directly bonded to the sulfonic acid structure. A compound in which a fluorine atom is not bonded to a hydrocarbon group or an aromatic ring directly bonded to the sulfonic acid structure, and an acid is directly or indirectly irradiated with an active energy ray having a wavelength of 248 nm or less. It is a generated compound.
The acid generator may be an onium salt compound or a nonionic compound.

By using the acid generator as a resist film, even when an antistatic film is laminated on the resist film, the resist sensitivity after exposure (sensitivity degradation and variation) is small, and the dimensions as set A fine pattern is obtained.
As the above reason, the following is presumed.

In general, when the resist film is irradiated with an electron beam or the like, 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 acts as a catalyst for the chemical amplification reaction. Is done. 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, the alkylsulfonic acid or aryl contained in the antistatic film described later Sulfonic acid is a relatively weak acid. In this case, it is considered that at the contact portion between the resist film and the antistatic film, hydrogen ions generated in the resist film are taken into the alkylsulfonic acid 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 considered that the sensitivity is reduced through deactivation of the generated hydrogen ions.
On the other hand, since the acid generator used in the present invention has no fluorine atom bonded to the carbon atom directly bonded to the S atom, the unsaturated hydrocarbon group directly bonded to the S atom, or the aromatic ring directly bonded to the S atom, The acidity is low, and the decrease in acid concentration due to such a weak acid liberation reaction is 0 or slight, and the sensitivity change is considered to be small.

  In the present invention, the carbon atom directly bonded to the sulfonic acid structure refers to the carbon atom represented by a in the following chemical formula (10), for example. The acid generator (B) in which no fluorine atom is 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 (10) is not included.

  In the present invention, 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 (11). 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 (11) is not included. means.

  In the present invention, the aromatic ring directly bonded to the sulfonic acid structure refers to an aromatic ring represented by d in the following formula (12), for example. The acid generator (B) in which the fluorine atom is not bonded to the aromatic ring directly bonded to the sulfonic acid structure means that, for example, an acid generator having a structure represented by the following chemical formula (12) 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 (13) 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.

  As the acid generator (B), at least one selected from the group consisting of compounds represented by the following chemical formulas (1) to (4) can be used.

In the chemical formula (1), R ¹ may be the same or different, and each independently represents a hydrogen atom, a linear hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, C3-C12 cyclic hydrocarbon group, C1-C12 linear alkoxy group, C3-C12 branched alkoxy group, C3-C12 cyclic alkoxy group, C1-C12 An acyl group, a C1-C12 sulfide group, a hydroxyl group, or a halogen atom. R ¹ may be bonded to each other to form a cyclic structure. n is an integer of 0-2. 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, an optionally substituted phenyl group, or a naphthyl group. Further, R ² may be bonded to each other directly or through a different atom to form a cyclic structure having 2 to 13 carbon atoms. R ³ 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 a carbon atom directly bonded to an S atom, or an S atom A fluorine atom is not bonded to an aromatic ring directly bonded to the ring. 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 .

Here, the “substituent” possessed by R ¹ , R ² , R ³ or the like 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, a hydroxyl group, a sulfide group, or the like Any of the groups containing no carbon atom 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, R ¹ , R ² , R ³ etc.). 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 include a methyl group, an ethyl group, a propyl group, an n-butyl group, a hexyl group, an octyl group, and the like. May have an unsaturated bond 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. And may have a substituent such as a hydroxyl group, an alkoxy group, a halogen atom, or 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 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.

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) (14) 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 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 divalent cyclic structure having 2 to 13 carbon atoms. However, at least one of R ⁴ has an aryl structure. R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group, or an aryl group having 6 to 14 carbon atoms, and is a carbon atom directly bonded to the S atom or an aromatic directly bonded to the S atom. A fluorine atom is not bonded to the ring. R ⁴ and R ⁵ may further have a substituent, and may have an oxygen atom in the carbon skeleton of R ⁵ .

The straight-chain hydrocarbon group having 1 to 12 carbon atoms and the branched hydrocarbon group having 3 to 12 carbon atoms of R ⁴ can be the same as R ¹ described above.

Examples of the arylene group having 6 to 12 carbon atoms of R ⁴ include a phenylene group and a naphthylene 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 the like. You may have substituents, such as an atom and a halogenoalkyl group.

R ⁵ may be the same as R ³ described above.

  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 the chemical formula (3), L can be represented by 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—). , R ′ is an alkylene group having 1 to 12 carbon atoms), and R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and is a carbon atom directly bonded to an S atom Or, a fluorine atom is not bonded to an aromatic ring directly bonded to an S atom. R ⁶ may further have a substituent, and may have an oxygen atom in the carbon skeleton.

  Examples of the alkylene group having 1 to 12 carbon atoms of L include 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. .

  Examples of the arylene group having 6 to 12 carbon atoms of L 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 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. It is a -12 aryl group, a C3-C12 heteroaryl group, or a C7-12 aralkyl group. R ⁸ 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, 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, wherein a fluorine atom is not bonded to a carbon atom directly bonded to an S atom or an aromatic ring directly bonded to an S atom It is. R ⁷ and R ⁸ may further have a substituent, and may have an oxygen atom in the carbon skeleton of R ⁸ .

Linear hydrocarbon group having 1 to 12 carbon atoms of R ^7, branched hydrocarbon group having 3 to 12 carbon atoms, cyclic hydrocarbon group having 3 to 12 carbon atoms be the same as R ¹ it can.

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 may be the same as R ³ 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.

  These acid generators (B) may be used individually by 1 type, may be used in combination of 2 or more types, and the compounding quantity is with respect to 100 parts by weight of the phenol compound (A). Preferably it is 1-40 weight part, More preferably, it is 1-30 weight part, More preferably, it is 5-20 weight part. When the amount is smaller than this range, image formation cannot be performed, and when the amount is larger, a uniform solution is not obtained and the storage stability is lowered.

The acid generator (B) has a polymer chain structure, a sulfonic acid structure represented by —SO ₃ ^— or —SO ₃ — on the terminal and / or side chain of the polymer chain, and the sulfonic acid It has an acid generator structure containing a carbon atom directly bonded to the structure or an aromatic ring directly bonded to the sulfonic acid structure, and no fluorine atom bonded to the carbon atom or aromatic ring directly bonded to the sulfonic acid structure It may be a thing. Hereinafter, the acid generator may be simply referred to as a polymer type acid generator.

In the present invention, the polymer is meant to include those having a low degree of polymerization, that is, oligomers, and the weight average molecular weight is not particularly limited, but those having a molecular weight of 500 to 20000 are usually used.
The weight average molecular weight is determined by gel permeation chromatography (GPC) using polystyrene as a standard product.

  When the polymer type acid generator is used, the diffusion of the acid generator is suppressed in the resist film, so that the resolution is improved and the deterioration of roughness is suppressed.

  The acid generator structure of the polymer-type acid generator is not particularly limited, but is preferably an onium salt-type compound. For example, the anion moiety of the chemical formula (1) or the chemical formula (2) is a terminal of a polymer chain and And / or those bonded to the side chain, and the acid generator structure on the polymer chain may be one type or two or more types.

  The polymer used for the polymer-type acid generator is not particularly limited. For example, it is preferable that the polymer-type acid generator includes a repeating unit to which the anion portion of the acid generator (B) is bonded in terms of suppressing diffusion of the generated acid.

As the repeating unit of the polymer, for example, from a monomer having an ethylenically unsaturated bond such as a repeating unit derived from a (meth) acrylic acid ester, a repeating unit derived from an alicyclic compound, or a repeating unit derived from hydroxystyrene. Examples of the repeated unit to be introduced include one kind or a combination of two or more kinds.
In the present invention, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester.

  Examples of the (meth) acrylic acid ester include those represented by the following chemical formula (15), and examples of the alicyclic compound include those represented by the following chemical formula (16).

In the chemical formula (15), R ¹⁸ represents a hydrogen atom or a methyl group, A ⁻ represents an anion portion of the acid generator, and A ⁺ represents a cation portion of the acid generator.

In the chemical formula (16), R ¹⁹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a monovalent polar group containing an oxygen atom or a nitrogen atom, A ⁻ is an anion portion of an acid generator, and A ⁺ is an acid. M which shows the cation part of a generating agent represents the integer of 0-2.

  The method for synthesizing the polymer type acid generator is not particularly limited, and for example, the method described in JP-A-2007-197718 can be used.

  These polymer type acid generators may be used alone or in combination of two or more, and the blending amount thereof is based on the phenolic hydroxyl group of the phenol compound (A). The acid generator site of the polymer type acid generator is preferably 1 to 40 mol%, more preferably 1 to 30 mol%, and still more preferably 5 to 20 mol%. When the amount is smaller than this range, image formation cannot be performed, and when the amount is larger, a uniform solution is not obtained and the storage stability is lowered.

Cross-linking agent (C)
The crosslinking agent (C) used in the present invention is not particularly limited, and can be arbitrarily selected from known crosslinking agents used in conventional chemically amplified negative resist compositions. 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 or a hydroxyalkyl group or both thereof, such as butanol, 1,4-dioxane-2,3-diol, 1,3,5-trihumanoxycyclohexane, and oxygen-containing derivatives thereof. .

  In addition, amino group-containing compounds such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea, propylene urea, glycoluril are reacted with formaldehyde or formaldehyde and lower alcohol, and the hydrogen atom of the amino group is hydroxymethyl group or lower alkoxymethyl. And a compound substituted with a group. Of these, those using melamine are melamine-based crosslinking agents, those using urea are urea-based crosslinking agents, those using alkylene ureas such as ethylene urea and propylene urea are alkylene urea-based crosslinking agents, and glycoluril is used. This was called a glycoluril-based crosslinking agent.

  Examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.

  Examples of the urea-based crosslinking agent include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea and the like.

  Examples of the alkylene urea crosslinking agent include mono and / or dihydroxymethylated ethylene urea, mono and / or dimethoxymethylated ethylene urea, mono and / or diethoxymethylated ethylene urea, mono and / or dipropoxymethylated ethylene Ethylene urea crosslinking agents such as urea, mono and / or dibutoxymethylated ethylene urea; mono and / or dihydroxymethylated propylene urea, mono and / or dimethoxymethylated propylene urea, mono and / or diethoxymethylated propylene urea Propylene urea-based crosslinking agents such as mono- and / or dipropoxymethylated propylene urea, mono- and / or dibutoxymethylated propylene urea; 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone 1,3-di (methoxymethyl 4,5-dimethoxy-2-imidazolidinone.

  Examples of the glycoluril-based crosslinking agent include mono, di, tri and / or tetrahydroxymethylated glycoluril, mono, di, tri and / or tetramethoxymethylated glycoluril, mono, di, tri and / or tetraethoxy. Examples include methylated glycoluril, mono, di, tri and / or tetrabutoxymethylated glycoluril.

  These crosslinking agents (C) may be used individually by 1 type, or may be used in combination of 2 or more types, and the compounding quantity is 3-40 weight with respect to 100 weight part of phenol compounds (A). Parts, preferably 3 to 30 parts by weight. When the blending amount of the crosslinking agent (C) is less than 3 parts by weight, crosslinking formation does not proceed sufficiently and a good resist pattern cannot be obtained. On the other hand, if it exceeds 40 parts by weight, the storage stability of the resist coating solution is lowered and the sensitivity is deteriorated with time.

Organic base compound (D)
As the organic base compound (D) used in the present invention, any one of known organic base compounds should be selected and used in order to improve the resist pattern shape, stability over time in storage conditions, and the like. Can do.

  Examples of the organic base compound (D) 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.

  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, polyallylamine, N- (2-dimethylaminoethyl) acrylami 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 acid amide, quinoline, 8-oxyquinoline, acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpi Rajin, 1,4-diazabicyclo [2.2.2] octane, and the like.

  These organic base compounds (D) can be used alone or in combination of two or more. The amount of the organic base compound (D) used is usually 0.01 to 40 mol%, preferably 0.01 to 10 mol%, more preferably 0.000 mol% with respect to the compound that generates an acid upon irradiation with exposure light. 1 to 5 mol%. If it is less than 0.01 mol%, the effect of the addition cannot be obtained. On the other hand, when it exceeds 40 mol%, there is a tendency that sensitivity is lowered and developability of an unexposed portion is deteriorated.

Other components The negative resist composition used in the present invention contains miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, and a dissolution inhibitor. An agent, a plasticizer, a stabilizer, a colorant, an antihalation agent, and the like can be appropriately added and contained.

(Preparation of negative resist composition)
The negative resist composition used in the present invention is usually the above-mentioned phenol compound (A), acid generator (B), cross-linking agent (C), and other additives as required in the organic solvent (E). It is prepared by mixing the agent uniformly.

  As the organic solvent (E), 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, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, propyl pyruvate, N, N-dimethylformamide, Dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, The these solvents singly or in combination can be used. 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 (E), in addition to diethylene glycol dimethyl ether, cyclohexanone, cyclopentanone, 1-ethoxy-2-propanol, and ethyl lactate, the solubility of the acid generator in the resist component is most excellent. Propylene glycol monomethyl ether acetate, which is a safety solvent, and a mixed solvent thereof are preferably used.

  The amount of the solvent in the negative resist composition is not particularly limited, and is appropriately set according to the coating film thickness at a concentration that can be applied to the support. In general, the solvent is used so that the solid content concentration of the negative resist composition is preferably in the range of 0.5 to 20% by weight, more preferably 0.7 to 15% by weight.

(2) Positive resist composition The positive resist composition used in the present invention has a molecular weight of 150 to 3000, a phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group, and- The sulfonic acid structure represented by SO ₃ ^- or -SO _3- and the carbon atom directly bonded to the sulfonic acid structure or the aromatic ring directly bonded to the sulfonic acid structure, and directly bonded to the sulfonic acid structure An acid generator (B) comprising a compound having no fluorine atom bonded to a carbon atom or the aromatic ring, and generating an acid directly or indirectly by irradiation with an active energy ray having a wavelength of 248 nm or less It is characterized by containing. Hereinafter, the compounds constituting the negative resist composition will be described.

Phenol compound (Acap) in which some phenolic hydroxyl groups are protected with acid-decomposable groups
The phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group used in the present invention has an acid-decomposable protecting group dissociated by the action of an acid, and has a solubility in an alkali developer. Increase. It is preferable that two or more phenolic hydroxyl groups protected by an acid-decomposable group have in one molecule of a phenolic compound (Acap) in which the phenolic hydroxyl group is protected by an acid-decomposable group.

  The phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group is obtained by introducing an acid-decomposable group into a part of the phenolic hydroxyl group of the phenol compound (A). it can.

  The acid-decomposable group is eliminated by the acid generated from the acid generator (B) by exposure, and the solubility of the phenol compound (Acap) in which the partial phenolic hydroxyl group is protected with an acid-decomposable group in an alkaline developer. Increase.

The acid-decomposable group is not particularly limited as long as it dissociates in the presence of an acid to generate a phenolic hydroxyl group, and examples thereof include -CG ₃ , -COO-CG ₃ , -CG ₂ -COO-CG _{3 and the} like.
Here, G is each independently R ^<a> or R ^<b> .
Here, R ^a represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group. R ^a may be bonded to each other to form a ring.
R ^b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group.

As the alkyl group for R ^a and R ^b , an alkyl group having 1 to 8 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, or a 2-ethylhexyl group. And octyl group.

The cycloalkyl group for R ^a and R ^b may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable. Group, androstanyl group and the like. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The alkenyl group for R ^a and R ^b is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

As the aralkyl group for R ^a and R ^b, an aralkyl group having 7 to 12 carbon atoms is preferable, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

As the aryl group of R ^a and R ^b, an aryl group having 6 to 10 carbon atoms is preferable. For example, a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group, an anthryl group, A 9,10-dimethoxyanthryl group and the like can be mentioned.

Examples of the substituent that R ^a and R ^b may have include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, a carboxy group, a halogen atom, and an alkoxy group. Thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like.

  Although the specific example of an acid-decomposable group is shown below, it is not limited to these.

  Examples of the compound for introducing the acid-decomposable group include, but are not particularly limited to, active carboxylic acid derivative compounds such as acid chlorides, acid anhydrides and dicarbonates having an acid-decomposable group, and alkyl halides.

  The phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group is obtained by converting the mother compound of the phenol compound (A) and the compound having the acid-decomposable group into an amine catalyst such as triethylamine. The reaction can be carried out under normal pressure at 60 ° C. for 6 to 7 hours, reprecipitated in distilled water, washed with distilled water, and dried.

  In the positive resist composition according to the present invention, the phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group may be used alone as one of the above-mentioned compounds, Two or more kinds may be mixed and used.

The molecular weight of the phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group is 150 to 3000.
When the mother nucleus compound of the phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group is a compound represented by the chemical formula (2) of the phenol compound (A), Is preferably 300 to 2000, and more preferably 400 to 1500.
Moreover, when a mother nucleus compound is a compound represented by Chemical formula (4) of the said phenol compound (A), molecular weight becomes like this. Preferably it is 300-2500, More preferably, it is 400-2000.

  The content of the phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group is preferably 50 to 95% by weight, more preferably 60 to 85% by weight.

Acid generator (B)
The acid generator (B) contained in the positive resist composition can be the same as that contained in the negative resist composition.

  These acid generators (B) may be used alone or in combination of two or more, and the blending amount thereof is such that at least a part of the phenolic hydroxyl group is acid-decomposable. Preferably it is 1-40 weight part with respect to 100 weight part of phenol compounds (Acap) protected by the group, More preferably, it is 1-30 weight part, More preferably, it is 5-20 weight part. When the amount is less than this range, image formation cannot be performed, and when the amount is larger, a uniform solution is not obtained and the storage stability is lowered.

Organic base compound (D)
The organic base compound (D) used in the present invention may be the same as that used in the negative resist composition.

Other components The positive resist composition used in the present invention has miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving coating properties, and a dissolution inhibitor. An agent, a plasticizer, a stabilizer, a colorant, an antihalation agent, and the like can be appropriately added and contained.

(Preparation of positive resist composition)
The positive resist composition used in the present invention is usually a phenol compound (Acap) in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group as described above in the solvent (E), and an acid generator (B). And, if necessary, other additives are mixed uniformly. As the solvent (E), those generally used as solvents for chemically amplified resists can be used, and the solvents mentioned in the preparation of the negative resist composition can be used.

  The amount of the solvent in the positive resist composition is not particularly limited, and is appropriately set according to the coating film thickness at a concentration that can be applied to the support. In general, the solvent is used so that the solid content concentration of the positive resist composition is preferably in the range of 0.5 to 20% by weight, more preferably 0.7 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, a sulfonated polyaniline having a structural unit represented by the following chemical formula (17) or a chemical formula (18) Those having an isothianaphthenylene structure may be mentioned.

In chemical formula (17), R ²⁰ 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 M may be the same. They may be different and each independently represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium cation. k represents an arbitrary value from 0 to 1.

In the chemical formula (18), R ²¹ 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. It represents an ester group, a halogen, _-SO 3 M, a nitro group, a cyano group, a primary to tertiary amino group, a trihalomethyl group, a phenyl group and substituted phenyl group. M may be the same or different and 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, 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.

<Relief pattern manufacturing method>
The method for producing a relief pattern according to the present invention includes:
(I) a step of exposing the resist antistatic film laminate according to the present invention in a predetermined pattern with an energy beam selected from the group consisting of an electron beam, an ion beam, EUV, and X-rays;
(Ii) removing the antistatic layer of the exposed resist antistatic film laminate,
(Iii) a step of developing the resist film of the laminate from which the antistatic layer has been removed. According to the pattern forming method of the present invention, it is possible to form a pattern with high resolution, high sensitivity, and good shape.
Hereinafter, each step will be described with reference to FIG.

(I) Step of exposing the resist antistatic film laminate according to the present invention in a predetermined pattern with an energy beam selected from the group consisting of electron beam, ion beam, EUV, and X-ray as shown in FIG. In this step, first, the resist film 20 is exposed by using an electron beam drawing apparatus through a mask having a predetermined pattern shape, or by drawing by direct irradiation with an electron beam or the like not through the mask. , Selectively perform exposure. The acceleration voltage and current value may be set arbitrarily. In this step, acid is generated from the acid generator (B) in the exposed portion 21 of the resist film (FIG. 2B).

When drawing in a predetermined pattern with various energy rays without going through a mask, it takes time to draw, and the post-exposure progress in the part exposed at the beginning of this process and the part exposed at the end There can be large differences in time. In this case, there arises a problem that a desired resist pattern cannot be obtained due to a change in sensitivity of the exposed portion 21 of the resist film 20.
On the other hand, when the resist antistatic film laminate of the present invention is used, stability after exposure is high and sensitivity change after exposure is small. Therefore, a predetermined pattern can be formed with various energy rays without using such a mask. A desired resist pattern can be obtained even when the pattern is drawn.

(Ii) Step of removing the antistatic layer of the exposed resist antistatic film laminate The antistatic film 30 is removed after the exposure. 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. This step does not have to be performed after the exposure step (i). In the developing step (iii) described later, the antistatic film may be removed simultaneously with the formation of the resist pattern using a developer. Good.

(Iii) Step of developing the resist film of the laminate from which the antistatic layer has been removed When the resist film 20 of the resist antistatic film laminate is a negative resist composition, post-exposure heating (Post Exposure Bake, PEB) is performed. Do. The conditions for the PEB treatment are usually 70 to 160 ° C., preferably 90 to 130 ° C., and about 0.1 to 15 minutes.

Next, the support is developed using an alkali developer, and in the case of a negative resist composition film, the portion not exposed to the exposure light is removed (FIG. 2 (d)), and the positive resist composition film is formed. In this case, the exposure light irradiation portion is removed (FIG. 2E).
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.

  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 with a vessel SPD-M10Avp, mobile phase: acetonitrile / water = 5/5).

(Preparation of acid generator)
<Acid generator (P-1)>
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-1) compound represented by the following chemical formula (1-1).

The structure of the obtained acid generator (P-1) was confirmed by high performance liquid chromatography and ¹ H-NMR spectrum.
HPLC (acetonitrile / water = 5/5) retention time: 3.5 minutes
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 7.29 to 7.33 (aromatic-H), 7.51 & 7.53 & 7.55 (t) (aromatic-H), 7. 58-7.60 (aromatic-H), 7.65 & 7.67 & 7.69 (t) (aromatic-H), 8.24 & 8.26 (d) (aromatic-H)

<Acid generator (P-2)>
In the synthesis of the acid generator (P-1), except that 0.88 g (4 mmol) of sodium 3-nitrobenzenesulfonate was used instead of sodium benzenesulfonate, the following chemical formula (1-2) The white acid generator (P-2) compound represented by these was obtained.

The structure of the obtained acid generator (P-2) was confirmed by high performance liquid chromatography and ¹ H-NMR spectrum.
HPLC (acetonitrile / water = 5/5) retention time: 3.6 minutes
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 7.51 & 7.53 & 7.55 (t) (aromatic-H), 7.64 to 7.69 (aromatic-H), 8. 01 & 8.03 (d) (aromatic-H), 8.19-8.21 (aromatic-H), 8.24 & 8.26 (d) (aromatic-H) 8.34 (aromatic-H)

<Acid generator (P-3)>
In the synthesis of the acid generator (P-1), except that 0.81-g (4 mmol) of sodium 4-chlorobenzenesulfonate was used instead of sodium benzenesulfonate, the following chemical formula (1-3) The white acid generator (P-3) compound represented by these was obtained.
The structure of the obtained acid generator (P-3) was confirmed by high performance liquid chromatography and ¹ H-NMR spectrum.
HPLC (acetonitrile / water = 5/5) retention time: 3.7 minutes
¹ H-NMR (400 MHz, DMSO-d6, TMS): δ (ppm) 7.36 & 7.38 (d) (aromatic-H) 7.51 & 7.53 & 7.55 (t) (aromatic-H), 7. 58 & 7.60 (d) (aromatic-H), 7.65 & 7.67 & 7.69 (t) (aromatic-H), 8.24 & 8.26 (d) (aromatic-H)

<Acid generator (P-4)>
The acid generator (P-4) represented by the following chemical formula (1-4) was obtained from Midori Chemical Co., Ltd. (product name DPI-201).

<Acid generator (P-5)>
The acid generator (P-5) represented by the following chemical formula (1-5) was obtained from Wako Pure Chemical Industries, Ltd. (product name: Diphenyl-2,4,6-Trimethylphenylsulfonium p-toluenesulfonate).

<Acid generator (P-6)>
As the acid generator (P-6) represented by the following chemical formula (1-6), (product name WPAG-567) was obtained from Wako Pure Chemical Industries, Ltd.

<Acid generator (P-7)>
The acid generator (P-7) represented by the following chemical formula (1-7) was obtained from Midori Chemical Co., Ltd. (product name NAI-101).

<Acid generator (P-8)>
The acid generator (P-8) represented by the following chemical formula (1-8) was obtained from Midori Chemical Co., Ltd. (product name NDI-101).

<Comparative acid generator (RP-1)>
The comparative acid generator (RP-1) represented by the following chemical formula (2-1) 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 (2-2) 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 (2-3) 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 (2-4) 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 (2-5) was obtained from Midori Chemical Co., Ltd. under the product name (NDI-105).

(Preparation of phenolic compounds and crosslinking agents)
<Phenol compound (CRA-01)>
Under a nitrogen atmosphere, 12.4 g (0.1 mol) of 3-methoxyphenol was dissolved in 200 mL of ethanol in a 300 mL three-necked flask. While this was cooled in an ice bath, 13.4 g (0.1 mol) of 2,4-dimethylbenzaldehyde was added, and then 25 mL of concentrated hydrochloric acid was slowly added dropwise and reacted at 70 ° C. for 12 hours. After the reaction, the reaction solution was poured into 500 mL of distilled water, the resulting precipitate (yellow solid) was filtered, washed with distilled water until neutral, and dried. Purification was performed by high performance liquid chromatography to obtain a white compound (calix resorcinarene derivative; CRA-01) represented by the following chemical formula. The structure was confirmed by MALDI-TOF MS and ¹ H-NMR spectrum.

<Phenol compound (A-01)>
A phenol compound (A-01) represented by the following chemical formula was obtained from Asahi Organic Materials Co., Ltd.

<Phenol compound (CRA-02)>
12.4 g (0.1 mol) of resorcinol was dissolved in 200 mL of ethanol. While this was cooled in an ice bath, 12.0 g (0.1 mol) of phenylacetaldehyde was added, and then 25 mL of concentrated hydrochloric acid was slowly added dropwise and reacted at 75 ° C. for 12 hours. After completion of the reaction, the reaction solution was poured into 500 mL of distilled water, and the resulting precipitate (yellow solid) was filtered and washed with distilled water until neutral. The filtered solid was recrystallized from ethanol to obtain a white cyclic compound (CRA-02) (yield 75%) represented by the following chemical formula. The structure was confirmed by MALDI-TOF-MS and ¹ H-NMR spectrum.

<Phenol compound in which phenolic hydroxyl group is protected with an acid-decomposable group (CRA-02P)>
In the reaction vessel, the following calixresorcinarene derivative (CRA-02) 2.0 g (2.36 mmol), acetone 50 mL, potassium carbonate 2.8 g (20 mmol), bromoacetic acid t-butyl ester 18.68 g (9 .44 mmol) was added and the reaction solution was stirred at 75 ° C. for 12 hours. After completion of the reaction, it was poured into 200 mL of 0.1N acetic acid aqueous solution to obtain a white precipitate. The precipitate was filtered off, dissolved in 100 mL of ethyl acetate, and washed twice with 100 mL of distilled water. The ethyl acetate layer was separated, dried over magnesium sulfate, and concentrated to give a phenol compound (CRA-02P) (yield 95%) in which the white phenolic hydroxyl group was protected with an acid-decomposable group. Obtained. ^{From 1} HNMR analysis, the protection ratio for all phenolic hydroxyl groups was 51%.

<Crosslinking agent>
As the cross-linking agent (C-1) represented by the following chemical formula, (product name TM-BIP-A) was obtained from Asahi Organic Materials Co., Ltd.

(Examples 1-9 and Comparative Examples 1-5: Preparation of a negative resist composition)
As shown in Table 1, (CRA-1) or (A-1) as the phenol compound (A), acid generator compounds (P-1) to (P-8) as the acid generator compound (B), and comparative acids Generator compounds (RP-1) to (RP-5), (C-1) as the crosslinking agent (C), tri-n-octylamine (D-1) as the basic compound (D), organic solvent (E) After dissolving in propylene glycol monomethyl ether (E-1) and stirring for 12 hours, it was filtered through a 0.2 μm PTFE filter to prepare a negative resist composition.
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.

(Examples 10 to 11 and Comparative Example 6: Preparation of positive resist composition)
As shown in Table 1, (CRA-02P) as the phenol compound (A), acid generator compounds (P-2) to (P-3) as the acid generator compound (B), and comparative acid generator compound (RP-) 3) Tri-n-octylamine (D-1) as basic compound (D) was dissolved in organic solvent (E) propylene glycol monomethyl ether (E-1), stirred for 12 hours, and then 0.2 μm PTFE. A positive resist composition was prepared by filtration through a filter.
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.

<Manufacture of resist antistatic film laminate and formation of resist pattern>
Using the resist compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 6, resist patterns were prepared and evaluated by the methods shown below. The results are shown in Table 2.

(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 70 nm. .

(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 the drawing is completed, rinsing with pure water is performed for 60 seconds to dissolve and remove the antistatic film layer, followed by baking (PEB) at 110 ° C. for 60 seconds, and a 2.38% TMAH aqueous solution (23 ° C.) for 60 seconds. The film was developed and rinsed with pure water for 60 seconds to form a line and space (L / S) pattern.

<Evaluation>
(1) Sensitivity and resolving power Sensitivity was measured in units of μC / cm ² with the minimum dose at which an L / S pattern of 100 nm 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. The confirmation of the resolution was judged by a length measurement SEM made by Holon. In Examples 1 to 9 and Comparative Examples 1 to 5 using the negative resist composition, the dimensions of the line part were measured, and in Examples 10 to 11 and Comparative Example 6 using the positive resist composition, the dimensions of the space part were measured. .

(2) Post-exposure stability The post-exposure stability defined below was also evaluated.
When the evaluation described above is performed in a short time as much as possible without elapse of time between each process (5 minutes from the end of exposure to PEB and development) and after exposure, it is waited for 3 hours in the vacuum of the exposure machine. When the subsequent processing is performed as usual, there is a difference in the size of the pattern obtained when there is waiting for 3 hours in the exposure machine with the same exposure amount as that obtained when time is taken. When it was small, it was displayed as post-exposure stability. More specifically, exposure is performed using the exposure amount with which a dimension of 100 nm is obtained when development is performed in 5 minutes after exposure, and the dimension obtained by performing development by waiting in a vacuum for 3 hours is subtracted. is there. When the sensitivity changes with the passage of time after exposure, that is, when the dimensions change, in the case of the negative type, dimensions smaller than 100 nm are obtained. The larger the subtraction result, the greater the sensitivity change. The numerical value of the stability after exposure is preferably 0, but if it is not 0, the dimension of the pattern to be formed changes depending on the elapsed time after the electron beam is irradiated to the antistatic film and the resist laminate. Is shown. When the post-exposure stability is not 0 and the numerical value is large, the problem is extremely large in practical use, and the obtained pattern cannot be used as originally intended.

<Summary of results>
From the results shown in Table 2, in Examples 1 to 11, the post-exposure stability was excellent, and a desired pattern could be formed as an antistatic film and a resist laminate. On the other hand, in Comparative Examples 1 to 6 using the comparative acid generators RP-1 to RP-5 as the acid generator, the post-exposure stability is inferior, and the phenomenon that the dimension of the pattern formed changes with the exposure time occurs. did. For this reason, a desired pattern could not be obtained with a desired dimension. In Comparative Examples 1 to 6, a fluorine atom is bonded to the carbon atom directly bonded to the sulfonic acid structure of the acid generator or the aromatic ring directly bonded to the sulfonic acid structure. It is estimated that the degree tends to be stronger.
The resist antistatic film laminate using an acid generator having a higher acidity as in Comparative Examples 1 to 6 is a cross-linking reaction in the case of the negative type, and a place where the elimination reaction of the protecting group occurs in the case of the positive type. The dimensions are small. This suggests that the generated acid has been deactivated. The cause of this is that the generated acid is neutralized by contact with the antistatic film containing a benzenesulfonic acid group. Guessed. Such a phenomenon is presumed to occur because the acid generator used in the comparative example has higher acidity than benzenesulfonic acid, and the benzenesulfonic acid group in the antistatic film behaves as a base. When the concentration of the generated acid decreases due to neutralization, image formation is not sufficiently performed and the size is reduced.
In contrast, the present invention dares to select an acid generator whose acidity is not too high, so that the benzenesulfonic acid group in the antistatic film behaves as a base because the acidity is equal to that of benzenesulfonic acid. Therefore, it is presumed that the generated acid is hardly neutralized and the image formation is performed sufficiently as well as the latent image formed by the electron beam.

DESCRIPTION OF SYMBOLS 1 Resist antistatic film laminated body 10 Support body 20 Resist film 21 Exposed part 30 of resist film Antistatic film 40 Exposure light 41 Exposure range

Claims (9)

On the support,
(1) a phenol compound having a molecular weight of _{150~3000 (A), - SO 3} - or -SO ₃ - sulfonic acid structure represented by and, the carbon atom bonded directly to the acid structure, coupled directly to the sulfonic acid structure A fluorine atom is bonded to the carbon atom, the unsaturated hydrocarbon group, or the aromatic ring directly bonded to the sulfonic acid structure. A resist film comprising a resist composition containing at least an acid generator (B) that is not present,
(2) comprising at least an antistatic film,
Resist antistatic film laminate. On the support,
(1) a resist film comprising the following negative resist composition or positive resist composition;
<Negative resist composition>
Phenolic compound (A) having a molecular weight of 150 to 3000,
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 directly to the sulfonic acid structure; A compound comprising an aromatic ring to be bonded and having no fluorine atom bonded to the carbon atom, the unsaturated hydrocarbon group, or the aromatic ring directly bonded to the sulfonic acid structure, and having a wavelength of 248 nm or less An acid generator (B ′) that generates an acid directly or indirectly by irradiating the active energy ray of
Cross-linking agent (C),
Negative resist composition containing at least <Positive resist composition>
A phenol compound (Acap) having a molecular weight of 150 to 3000 and at least a portion of the phenolic hydroxyl group protected with an acid-decomposable group; and
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 directly to the sulfonic acid structure; A compound comprising an aromatic ring to be bonded and having no fluorine atom bonded to the carbon atom, the unsaturated hydrocarbon group, or the aromatic ring directly bonded to the sulfonic acid structure, and having a wavelength of 248 nm or less Acid generator (B ′) that generates an acid directly or indirectly by irradiating the active energy ray of
At least a positive resist composition (2) containing an antistatic film,
The resist antistatic film laminate according to claim 1. The resist antistatic film laminate according to claim 1 or 2, 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 hydrogen atom, a linear hydrocarbon group having 1 to 12 carbon atoms, or a branched hydrocarbon group having 3 to 12 carbon atoms. , A C3-C12 cyclic hydrocarbon group, a C1-C12 linear alkoxy group, a C3-C12 branched alkoxy group, a C3-C12 cyclic alkoxy group, a C1-C12 12 is an acyl group having 12 carbon atoms, a sulfide group having 1 to 12 carbon atoms, a hydroxyl group, or a halogen atom, and R ¹ may be bonded to each other to form a cyclic structure, where n is an integer of 0 to 2. 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, an optionally substituted phenyl group, or a naphthyl group. In addition, carbon atoms bonded to each other between R ² directly or through different atoms A cyclic structure having a prime number of 2 to 13 may be formed, and R ³ 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. Te, the carbon atom bonded directly to the S atom, in which unbound fluorine atom directly bonded to an unsaturated hydrocarbon group, or an aromatic ring bonded directly to the S atom in S atoms. the 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 optionally substituted phenyl. A 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 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 having an S atom A fluorine atom is not bonded to a directly bonded carbon atom, an unsaturated hydrocarbon group directly bonded to the S atom, or an aromatic ring directly bonded to the S atom, wherein 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), L 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 a carbon number. 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, and R ⁸ is a linear hydrocarbon group having 1 to 12 carbon atoms and 3 to 3 carbon atoms. A branched hydrocarbon group having 12 carbon atoms, 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. In addition, 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, R ⁷ and R ⁸ are , it may further have a substituent, an oxygen atom in the carbon skeleton of the R ³ It may be in.) The acid generator (B) has a polymer chain structure, a sulfonic acid structure represented by —SO ₃ ^— or —SO ₃ — on the terminal and / or side chain of the polymer chain, and the sulfonic acid A carbon atom directly bonded to the structure, 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 resist antistatic film laminate according to any one of claims 1 to 3, which has an acid generator structure in which a fluorine atom is not bonded to a saturated hydrocarbon group or the aromatic ring.   The resist antistatic film laminate according to any one of claims 1 to 4, wherein the negative resist composition or the positive resist composition further contains an organic basic compound (D). Exposing the resist antistatic film laminate according to any one of claims 1 to 5 in a predetermined pattern with an energy beam selected from the group consisting of an electron beam, an ion beam, EUV, and X-rays;
Removing the antistatic film of the exposed resist antistatic film laminate;
And a step of developing the resist film of the laminate after removing the antistatic layer or simultaneously with removing the antistatic layer.   7. The relief pattern formation according to claim 6, wherein the resist antistatic film laminate includes a negative resist film, and the resist antistatic film laminate is exposed to heat and then subjected to heat treatment before development. Method.   The method for forming a relief pattern according to claim 6 or 7, wherein in the exposure step, drawing is performed in a predetermined pattern with the energy beam.   The electronic component manufactured using the resist antistatic film laminated body as described in any one of Claims 1 thru | or 5.

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