JP2006091898A - Resist material and resist pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemically amplified resist material capable of suppressing cracking at the time of development and peeling of a pattern. <P>SOLUTION: The resist material contains an acid-sensitive compound containing structural units each having an alkali-soluble group protected with a part containing an alicyclic hydrocarbon group whose carbon atom is bonded to a lower alkyl group and an acid generating agent which generates an acid when exposed to a radiation. The alkali-soluble group is released by the generated acid and makes the acid-sensitive compound alkali-soluble. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resist material. More specifically, the present invention relates to a chemically amplified resist material having high resolution, high sensitivity, and excellent dry etching resistance. The present invention also relates to a method for forming a resist pattern using such a new resist material. Since the pattern forming method according to the present invention is particularly effective in reducing the occurrence of cracks and pattern peeling during development of a resist pattern, it can be advantageously used in the manufacture of semiconductor devices such as semiconductor integrated circuits.

  In recent years, integration of semiconductor integrated circuits has progressed, and LSIs and VLSIs have been put to practical use. At the same time, the minimum pattern of integrated circuits tends to be submicron and further miniaturized. To form a fine pattern, the substrate to be processed on which a thin film is formed is coated with a resist, and a selective exposure is performed to form a latent image of a desired pattern, which is then developed to form a resist pattern, which is then used as a mask for dry etching After that, it is essential to use a lithography technique that obtains a desired pattern by removing the resist. As an exposure source used in this lithography, ultraviolet light of g-line (wavelength 436 nm) and i-line (wavelength 365 nm) is used, but as the pattern becomes finer, far-ultraviolet light having a shorter wavelength, vacuum Ultraviolet light, electron beams, X-rays and the like are used as light sources. Recently, excimer lasers (KrF laser with a wavelength of 248 nm, ArF laser with a wavelength of 193 nm) have attracted attention as a light source, and are expected to be effective for forming fine patterns. In the present specification, when the term “radiation” is used, light from these various light sources, that is, ultraviolet light, far ultraviolet light, vacuum ultraviolet light, electron beam (EB), X-ray, various laser light, etc. Means.

  In order to form a submicron pattern using exposure light in the far ultraviolet / vacuum ultraviolet region, which has a shorter wavelength, it is necessary that the resist used has excellent transparency at the wavelength of the exposure light. Further, it is required to have sufficient dry etching resistance. As such a resist, the present inventors have invented a radiation-sensitive material comprising, for example, a polymer or copolymer of an acrylate ester or an α-substituted acrylate ester having an adamantane skeleton in the ester portion. Have already filed a patent application (see Patent Document 1). The present inventors also provide a chemically amplified radiation-sensitive material comprising a polymer or copolymer of an acrylate ester or α-substituted acrylate ester having a norbornane skeleton in the ester portion as a similar resist. Invented (see Patent Document 2).

Japanese Patent Laid-Open No. 4-39665 JP-A-5-257284

  The chemically amplified resist and the pattern formation method using the same previously invented by the present inventors are highly transparent to light from various light sources, particularly excimer light having wavelengths in the far ultraviolet and vacuum ultraviolet regions. In addition, it has excellent dry etching resistance. However, these resists are prone to cracking and peeling of patterns depending on the conditions of use, such as when they are used in thick films or when developing with a highly soluble developer. It still has the disadvantage that the properties cannot be obtained. Although the exact reason why such a defect is caused is unclear, the alicyclic hydrocarbon portion contained in the resist skeleton structure is strong and rigid, so that the resist film is developed during development. It is understood that one of the causes is that the distortion applied to the film increases.

  Further, as a result of the presence of the alicyclic hydrocarbon moiety as described above, there is also a disadvantage that an alkali developer commonly used in this technical field cannot be used for developing such a chemically amplified resist. That is, it is understood that the alicyclic hydrocarbon portion contained in the resist structure has a strong hydrophobic property and prevents dissolution of the resist in the alkaline developer. In order to solve the problems associated with the use of an alkali developer, the present inventors have a repeating unit having a protected alkali-soluble group and the protecting group is eliminated by an acid to make the compound alkali-soluble. And developing a resist containing a polymer or copolymer containing an acid generator and an acid generator that generates an acid upon exposure to radiation with a developer containing an aqueous solution or alcohol solution of a specific ammonium compound or morpholine compound after exposure. And then filed a patent application (see the specification of Japanese Patent Application No. 7-23053 filed on Feb. 10, 1995).

  Furthermore, the resist as described above usually has poor adhesion to the substrate having the layer to be etched, and the resist film on the substrate may be peeled off from the substrate during development, or a circuit pattern to be baked may be present. When exposure is performed through an exposure mask designed to be shielded from light, a resist pattern having a shape slightly larger than a desired mask pattern may be completed. Therefore, it is desired to provide a resist material that can accurately and faithfully reproduce the resist pattern by the mask pattern.

  As understood from the above description, in improving a chemically amplified resist and a pattern forming method using the resist, usually, an approach for improving the resist material itself and an approach for improving a developer used in the resist process are used. Two approaches have been taken. The present invention is intended to improve the resist material itself in consideration of various conditions and the like.

  Accordingly, one object of the present invention is to have high transparency to various types of radiation including excimer light, to have excellent dry etching resistance, and to reduce generation of cracks and pattern peeling during development. That is, an object of the present invention is to provide an improved chemically amplified resist that exhibits stable patterning characteristics.

  Another object of the present invention is to provide an improved chemically amplified resist having good adhesion to a substrate and capable of faithfully reproducing a pattern corresponding to a mask pattern.

  Another object of the present invention is to provide an improved method of forming a resist pattern which can be developed with a standard alkaline developer using such a chemically amplified resist.

  In one aspect, the present invention provides an alicyclic hydrocarbon group-containing moiety represented by any of the following formulas (I) to (VI):

(Wherein R _I represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted, and Z together with the described carbon atoms Represents multiple atoms required to complete an alicyclic hydrocarbon group)

(In the above formula, R _II may be the same or different and represents a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic alicyclic hydrocarbon group. Where at least one of R _II is an alicyclic hydrocarbon group)

(Wherein R _II is the same as defined above)

(In the above formula, R _III may be the same or different and represents a proton, a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group. Provided that at least one of R _III is an alicyclic hydrocarbon group, and in the formula, at least one of two R _III bonded to a non-double bond carbon atom is 1 to 4 A substituted or unsubstituted linear or branched alkyl group or alicyclic hydrocarbon group having a carbon atom of

(Wherein R _II is the same as defined above)

(In the above formula, R _I and Z are the same as defined above)
An acid-sensitive compound comprising a structural unit that has an alkali-soluble group protected with an acid, and the alkali-soluble group is eliminated by an acid to render the compound alkali-soluble; and an acid generator that generates an acid upon radiation exposure; A resist material comprising: is provided.

In another aspect of the present invention, the present invention has an alkali-soluble group protected with an alicyclic hydrocarbon group-containing moiety represented by any one of the above formulas (I) to (VI), and the alkali-soluble group. A resist material containing an acid-sensitive compound containing a structural unit that causes a group to be eliminated by an acid and render the compound alkali-soluble, and an acid generator that generates an acid by radiation exposure is applied onto a substrate to be treated.
The resist film on the substrate to be processed is selectively exposed to radiation capable of causing the generation of acid from the acid generator, and the post-baking of the resist film after the exposure, the latent image formed in the exposure step Developing,
A method for forming a resist pattern is provided.

  As will be understood from the following detailed description, according to the present invention, by using a chemically amplified resist as described above, and particularly in combination with such a resist, a specific ammonium compound or morpholine compound. By using an aqueous solution or an alcohol solution as a developer, the compatibility with the resist resin, the solubility is controlled, and stress generated during development is reduced, thereby reducing the occurrence of resist pattern peeling and cracks, Stable patterning characteristics can be obtained. Furthermore, according to the present invention, it is possible to obtain stable patterning characteristics by alleviating distortion generated during development. Furthermore, according to the present invention, the exposure margin is widened, and a stable fine resist pattern can be formed. At that time, the adhesion of the resist to the ground is very good. Further, when exposure is performed through an exposure mask in which a circuit pattern to be printed is shielded from light, it is possible to prevent a positive pattern from being slightly larger than a desired mask pattern.

  As described above, the present invention has an alkali-soluble group protected by an alicyclic hydrocarbon group-containing moiety represented by any one of formulas (I) to (VI), and the alkali-soluble group is an acid. A resist material comprising an acid-sensitive compound containing a structural unit that makes the compound alkali-soluble by desorption, and an acid generator that generates an acid by radiation exposure.

In the above formula (I), R _I is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group or an ethyl group, which may be substituted or unsubstituted. However, this is notable in that the hydrophobicity becomes stronger when the number of carbon atoms is further increased, but disadvantages such as inability to satisfactorily achieve group elimination occur. It is. When such an alkyl group is substituted, suitable substituents are, for example, halogen such as chlorine, fluorine, iodine and the like. In view of the stability of the alkali-soluble group, it is desirable to avoid the use of a highly polar substituent. The definition of the alkyl group can be basically applied to the alkyl group defined by R _II or R _III in other formulas.

  In the resist material according to the present invention, the alkali-soluble group to be contained in the structural unit of the acid-sensitive compound, which is the main component, includes various groups well known in this technical field. Carboxylic acid group, sulfonic acid group, amide group, imide group, phenol group, acid anhydride group, thiol group, lactone acid ester group (α-α, β-dimethyl-γ-butyrolactone group), azalactone group, carbonate group, An oxazone group, a pyrrolidone group, a hydroxyoxime group, and the like, preferably a carboxylic acid group, a sulfonic acid group, an amide group, an imide group, and a phenol group.

  In the resist material of the present invention, the alkali-soluble groups as described above are protected by the alicyclic hydrocarbon group-containing portion. Such protected alkali-soluble groups are preferably carboxylic acids represented by the following formulas (VII) to (XI):

Wherein R _I , R _II and R _III and Z are the same as defined above,
Imide group represented by the following formula (XII):

(Wherein Z is the same as defined above) or a phenol group represented by the following formula (XIII):

(Wherein Z is the same as defined above)
It is.

  Further, the alicyclic hydrocarbon group contained in the alkali-soluble group includes various groups known in the chemical field, and these groups may be optionally substituted, Preferably, as will be described in detail below, it has a plurality of ring structures or has a condensed ring. The alicyclic hydrocarbon group is particularly preferably adamantane or a derivative thereof.

  The acid-sensitive compound used in the present invention, which is sensitive to the acid generated from the acid generator used in combination, is from a low molecular weight compound to a high molecular weight compound as long as the described conditions are satisfied. A wide range of compounds are included, and these compounds may be used alone or else a mixture of two or more compounds may be used. Such acid-sensitive compounds are broadly classified into polymers or copolymers containing the structural unit as a repeating unit, and low molecular weight non-polymerized compounds. Such an acid sensitive compound can have a wide range of molecular weights from low to high molecular weight when it takes the form of a polymer or copolymer, and is preferably an acrylic ester and its derivatives, It has repeating units selected from the group consisting of itaconic acid esters and derivatives thereof, fumaric acid esters and derivatives thereof, styrene-substituted products and derivatives thereof, alone or in combination. In addition, when the acid-sensitive compound is in the form of a non-polymerized compound, it is necessary to use any alkali-soluble polymer or copolymer in combination with the compound in order to obtain the desired resist characteristics. It is.

  The acid sensitive compounds of the present invention can additionally have one or more similar acid sensitive compounds in combination therewith. Suitable additional acid sensitive compounds in this case include, but are not limited to, those listed below, tertiary carbon esters, 3-oxo esters, acetal esters, carboxy ethers, and the like. Also, such additional acid sensitive compounds can preferably contain alkali soluble groups as listed below: carboxylic acid groups, sulfonic acid groups, amide groups, imide groups, phenol groups, acid anhydrides. Group, thiol group, lactone ester group (α-α, β-dimethyl-γ-butyrolactone group), azalactone group, carbonate group, oxazone group, pyrrolidone group, hydroxyoxime group, nitrile group, nitro group, aldehyde group, acetyl group Groups, hydroxyl groups, thioether groups, etc.

  In a chemically amplified resist material, if the structure contains an alicyclic hydrocarbon group, due to its strong hydrophobicity, at the stage of developing the resist material with an aqueous alkaline solution after exposure, It is considered that dissolution in an alkaline aqueous solution is suppressed. Accordingly, as a deprotecting group to be included in the resist structure (a protected alkali-soluble group that can be removed from the resist structure by an acid), an element having an alicyclic group is used for exposure and PEB ( It is preferable to remove the alicyclic group from the exposed portion by desorption by post exposure baking (Post Exposure Baking). However, since the alicyclic group has a ring structure, the angle of bonding is fixed, and it is difficult to form a product having a double bond after elimination of the group. In addition, the elimination reaction did not easily occur.

  In order to solve this problem, the present inventors have an alicyclic group represented by the above formula (I) in a part of the deprotecting group contained in the resist structure as described above, and It has been found that it is effective to convert the deprotecting group into an ester structure by introducing a moiety in which one of the carbon atoms constituting the ring skeleton is substituted with an appropriate lower alkyl group. That is, by making the deprotecting group an ester structure, it is possible to facilitate the elimination of the group. Although this is not intended to limit the present invention according to the following explanation, a double bond that is considered to be formed at the time of elimination of a group is formed outside a ring with a small “bond distortion”. It is expected that it is derived from the fact that this is possible.

  Thus, the resist material having the structure represented by the above formula (I) generates a carboxylic acid or the like by using the proton acid generated by the exposure as a catalyst to generate a carboxylic acid or the like, and the alicyclic type in the exposed portion. The radical part is removed. For this reason, in the exposure part of a resist material, the dissolution prohibition effect by an alicyclic group is lose | eliminated, and it becomes possible to melt | dissolve easily in aqueous alkali solution. As a result, the development of the resist material proceeds smoothly, and the desired stable patterning characteristics can be obtained.

  In addition, in a chemically amplified resist in which an alicyclic hydrocarbon group directly forms an ester with carbon forming a ring structure, the rigidity resulting from the alicyclic hydrocarbon group cannot be sufficiently reduced. Conceivable. It can be predicted that this is a cause of cracks and peeling when the resist film becomes thick, for example, when distortion is likely to occur during development. In order to solve this problem, the present inventors have found that it is effective to introduce a deprotection structure represented by the above formulas (II) to (VI) into the resist structure as described above. It was. That is, in this deprotected structure, although an alicyclic group is included, the ring structure does not directly form an ester, but forms an ester via at least one atom. The atoms to be interposed in this case are most commonly carbon atoms, but are not limited as long as they do not impair the elimination function, such as oxygen, nitrogen or sulfur. Although this is not intended to limit the present invention by the following description, it is a deprotecting group that does not form an ester directly with the ring structure, and the alicyclic hydrocarbon group is stiffened by moving away from the main chain. It is expected that it will be possible to relax the sex.

  In this way, the resist material having the structure represented by the above formulas (II) to (VI) generates a carboxylic acid or the like by using the proton acid generated by the exposure as a catalyst to generate a carboxylic acid or the like, and the exposed portion. The part of the alicyclic group is removed. For this reason, in the exposure part of a resist material, the dissolution prohibition effect by an alicyclic group is lose | eliminated, and it becomes possible to melt | dissolve easily in aqueous alkali solution. As a result, the development of the resist material proceeds smoothly, and the desired stable patterning characteristics can be obtained. So far, the same applies to the resist material having the structure represented by the above formula (I). In addition, in this specific resist material, since the alicyclic hydrocarbon group is separated from the main chain as described above, the rigidity of the resulting resist film is reduced, and the influence of the distortion generated in the resist film during development is reduced. Get smaller. For this reason, cracks and peeling during development are less likely to occur, and as a result, stable patterning characteristics can be obtained.

  As described above, the chemically amplified resist according to the present invention is an acid-sensitive compound, preferably a polymer or copolymer (here, “copolymer”) in which a protected alkali-soluble group is eliminated by an acid and becomes alkali-soluble. The term “union” refers to a chemically amplified resist having a combination of a three-component copolymer or a multi-component copolymer) or a non-polymerized compound and an acid generator. Hereinafter, such chemically amplified resists, their preparation, and formation of resist patterns using them will be described in detail with reference to preferred embodiments thereof. It should be understood that the present invention is not limited only to the embodiments described below.

  In the chemically amplified resist according to the present invention, the protected alkali-soluble group contained in the structural unit of the acid-sensitive compound as the main component is preferably a carboxylic acid group, a sulfonic acid group, an amide group, an imide group. And a member selected from the group consisting of phenol groups, and more preferably, a carboxylic acid represented by the above formulas (VII) to (XI), an imide group represented by the following formula (XII), and the formula ( XIII).

  For example, a carboxylic acid group as a protected alkali-soluble group is a unit in which the protecting group is eliminated by an acid to generate a carboxylic acid, such as t-butyl ester, t-amyl ester, α, α-dimethylbenzyl. Examples thereof include tertiary carbon esters such as esters, esters composed of acetals such as tetrahydropyranyl esters, esters composed of β-oxyketones such as 3-oxycyclohexyl esters, and the like.

  Protecting groups for these carboxylic acid groups and other alkali-soluble groups are not limited to those listed below, but preferably are tertiary hydrocarbon groups such as t-butyl groups, or β An oxyketone group such as a 3-oxocyclohexyl group, a cyclic β-hydroxyketone group such as a mevalonic lactone group.

  The acid-sensitive compound used in the chemically amplified resist of the present invention is preferably an ester formed from trialkylcarbinol, an ester formed from acetal, an ester formed from β-oxyketone, α-oxy Esters formed from alkenes or α-oxycycloalkenes, etc. can be included in the structural unit.

  The alicyclic hydrocarbon group contained in the alkali-soluble group includes various groups known in the field of chemically amplified resists. An example of a suitable alicyclic hydrocarbon group is one having the following compound as a skeleton.

(1) adamantane and its derivatives (2) norbornane and its derivatives (3) perhydroanthracene and its derivatives (4) perhydronaphthalene and its derivatives (5) tricyclo [5.2.1.0 ^2,6 ] decane and Derivatives (6) Bicyclohexane and its derivatives (7) Spiro [4,4] nonane and its derivatives (8) Spiro [4,5] decane and its derivatives

  Each of these compounds is represented by the following structural formula:

  In practicing the present invention, the alicyclic hydrocarbon preferably has a plurality of ring structures or has a condensed ring as described above, and a cyclohexyl group or the like that is a single ring is sufficient for dry etching. Cannot gain resistance. Of these compounds, a condensed ring such as adamantane is particularly preferable in order to obtain dry etching resistance equal to or higher than that of a conventional novolak resist.

  In the chemically amplified resist according to the present invention, the acid-sensitive compound contained therein can preferably take the form of a polymer or a copolymer. The acid-sensitive polymer or copolymer used here can be arbitrarily selected from a wide variety. The acid-sensitive polymer or copolymer is not limited to those listed below, but is preferably an acrylate ester and derivatives thereof, an itaconic acid ester and derivatives thereof, a fumarate ester and derivatives thereof, and styrene. It has a repeating unit (structural unit) selected from the group consisting of a substituent and a derivative thereof alone or in combination. This is because these repeating units are more advantageous than other polymers or copolymers in terms of preparation of the polymer or copolymer and its coatability.

  In addition, the acid-sensitive copolymer may be combined with the above-described repeating units as necessary, and is not limited to those listed below, but other repeating units such as acrylonitrile, olefin, You may prepare using a diene or these derivatives.

  In order to obtain satisfactory adhesion in the acid-sensitive polymer or copolymer of the present invention, it is preferable to use a repeating unit having a strong polarity. In particular, such a polymer or copolymer has a repeating unit that is alkali-soluble in addition to having an alkali-soluble group that is an essential constituent element, and a small amount derived from the alkali-soluble group. It is expected to be developable by the formation of carboxylic acid and the like, which is more preferable.

  Therefore, according to the present invention, the acid-sensitive compound as one component of the resist material is in the form of a copolymer, and the repeating unit has an alkali-soluble group side by side in addition to the structural unit described above. There is provided a resist material comprising a repeating unit in a chain and / or a repeating unit in the side chain having an additional protected alkali-soluble group removable by an acid generated from the acid generator.

  The copolymer of the resist material can preferably have a structural unit represented by the following formula (XIV) or (XV).

In the above formula, Rs may be the same or different and each represents hydrogen, halogen or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms;
R _I represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted,
A represents an acid-removable protecting group, and Z represents the atoms necessary to complete the alicyclic hydrocarbon group with the described carbon atoms.

  The structural unit of the formula (XIV) contains an alicyclic skeleton such as adamantane or norbornane, and contains a protective group that is eliminated by an acid generated from an acid generator and an alkali-soluble carboxylic acid group. This is an example. Since acidic groups are present in the resist structure, the exposed portion after exposure is smoothly dissolved in an alkaline developer. Further, if the content of the acidic group is controlled, development is possible even with a currently standardized alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution). In this case, the content of the carboxylic acid-containing unit in the resist is desirably 5 mol% or more and less than 2 mol%.

  The structural unit of the above formula (XV) has an alicyclic skeleton such as adamantane and norbornane, and is a protective group that is eliminated by an acid generated from an acid generator, which is also an ordinary protective group that is eliminated by an acid (However, when lithography using an ArF excimer laser with a wavelength of 193 nm is intended, it is preferable that an aromatic ring is not included in the protective group), and an alkali-soluble carboxylic acid group is combined. This is an example. In such a resist structure, even if no desorption occurs, the resist can be dissolved in alkali, so that there is an effect that the exposed portion after exposure is smoothly dissolved in the alkali developer.

By the way, the substituent R _I in the following formula (XIV) or (XV) is a methyl group, an ethyl group, or a halogenated (chlorinated, brominated, etc.) thereof, as described above. be able to. Further, the protecting group A that can be removed by an acid is an ordinary protecting group as described above, for example, a quaternary carbon group or a β-oxyketone group such as a t-butyl group, a t-amyl group, or a 3-oxycyclohexyl group. And so on. The alicyclic hydrocarbon group completed by Z is preferably adamantane and derivatives thereof, norbornane and derivatives thereof, perhydroanthracene and derivatives thereof, perhydronaphthalene and derivatives thereof, as shown in the general formula. Derivatives, tricyclo [5.2.1.0 ^2,6 ] decane and derivatives thereof, bicyclohexane and derivatives thereof, spiro [4,4] nonane and derivatives thereof, spiro [4,5] decane and derivatives thereof, and the like. .

  The acid-sensitive polymer or copolymer useful in the present invention will be described more specifically with reference to the case where the alkali-soluble group is a carboxylic acid as follows.

  The acid-sensitive polymer is preferably a meth (acrylate) polymer represented by the following formula (XVI).

In the above formula,
R represents a proton (hydrogen), a halogen, a substituted or unsubstituted alkyl group such as a methyl group or an ethyl group, a methylol group,
A corresponds to the moiety of the above formulas (I) to (VI), for example, a protecting group, preferably a quaternary carbon group or a β-oxyketone group such as a t-butyl group, a t-amyl group, or 3-oxycyclohexyl. Represents an alicyclic hydrocarbon group protected with a group or the like, preferably adamantyl, norbornyl, cyclohexyl, tricyclo [5.2.1.0] decane and the like, and n represents any positive integer.

  The acid-sensitive copolymer is preferably a meta (acrylate) copolymer represented by the following formulas (XVII) and (XVIII). In addition, a meth (acrylate) ternary copolymer can also be comprised according to this.

In the above formula,
R, A and n are each the same as defined above;
Y is an optional substituent, preferably, for example, an alkyl group, such as a t-butyl group, an ether group, such as a phenoxy group, an alicyclic group, such as adamantyl, norbornyl, cyclohexyl, tricyclo [5.2.1. .0] decane or the like, or a group of the following formula:

Wherein R ¹ , R ² and R ³ each represent hydrogen, a substituted or unsubstituted alkyl group or alkylene group, such as a methyl group, an ethyl group, a methylene group, etc., and B is Any substituent, preferably, for example, a carboxyl group or a group of the formula:

Wherein R ⁴ in the substituent D is hydrogen or a substituted or unsubstituted alkyl group such as a methyl group or an ethyl group, and l and m each represent any positive integer. .

  Specific examples of the acid-sensitive copolymer that can be advantageously used in the present invention include, but are not limited to, the following. In addition, m and n in a formula are respectively the same as the said definition.

  The acid-sensitive polymer or copolymer described above additionally contains an alkali-soluble polymer or copolymer, for example, a novolak resin, a phenol resin, an imide resin, a carboxylic acid-containing resin, or the like, if necessary. You may do it.

Furthermore, in the practice of the present invention, instead of the acid-sensitive polymer or copolymer as described above, a low molecular weight compound that is not polymerized (in the present specification, in particular, “non-polymerized compound” and Can be used for the same purpose. As described above, the non-polymerized compound used here is an acid-sensitive compound in which a protected alkali-soluble group is eliminated by an acid and becomes alkali-soluble, and the compounds represented by the formulas (I) to (VI) in the molecule. It is not particularly limited as long as it has a protected alkali-soluble group containing the represented moiety and exhibits the described behavior. In general, such a non-polymerized compound has an alicyclic ring skeleton, a ring skeleton of an aromatic ring such as a benzene ring, an alkyl skeleton, etc., and a part of these skeletons is represented by the formula (I) It is substituted with a group containing a moiety represented by (VI). Examples of preferred non-polymerized compounds are represented by the general formula, but include the following compounds, although not limited to those listed below. In the following formula, R _I , R _II , Z and n are the same as defined above.

  In addition, these non-polymerized compounds may be used in addition to a group containing a moiety represented by the above formulas (I) to (VI), as well as other carboxylic acids when other protecting groups are eliminated by an acid. Units such as t-butyl ester, t-amyl ester, tertiary carbon esters such as α, α-dimethylbenzyl ester, esters composed of acetals such as tetrahydropyranyl ester, β- such as 3-oxycyclohexyl ester, etc. You may have ester which consists of oxy ketone, and others.

  Since these non-polymerized compounds cannot exhibit the desired resist characteristics by themselves, it is necessary to use an alkali-soluble polymer or copolymer in combination. The alkali-soluble polymer or copolymer that can be used here is not limited to those described below, but examples thereof include novolak resins, phenol resins, imide resins, carboxylic acid-containing resins, and the like. Include. The mixing ratio of the non-polymerized compound and the alkali-soluble polymer or copolymer can be changed in a wide range depending on the characteristics of the compound used, the desired resist characteristics, and other factors.

  The acid generator used in combination with the acid-sensitive polymer or copolymer or non-polymerized compound in the chemically amplified resist of the present invention is an acid generator generally used in resist chemistry. An agent, that is, a substance that generates protonic acid upon irradiation with radiation such as ultraviolet rays, far ultraviolet rays, vacuum ultraviolet rays, electron beams, X-rays, and laser beams. Suitable acid generators in the practice of the present invention include, but are not limited to, those listed below.

(1) Diazonium salt represented by the following formula:
Ar-N ₂ ⁺ X ^-
(In the above formula,
Ar represents a substituted or unsubstituted aromatic group such as a phenyl group or an alicyclic group, and X represents a halogen such as Cl, Br, I or F, BF ₄ , BF ₆ , PF ₆ , AsF ₆ , SbF ₆ , CF ₃ SO ₃ , ClO ₄ or organic sulfonate anion, etc.)

(2) An iodonium salt represented by the following formula:

  (In the above formula, Ar and X are the same as defined above)

(3) A sulfonium salt represented by the following formula:

(In the above formula, R, R ¹ , R ² , R ³ , Ar and X are the same as defined above, for example, R is a methyl group, etc., and R ¹ , R ² and R ³ are phenyl. And tBu is a t-butyl group)

(4) Sulfonic acid ester represented by the following formula:

  (In the above formula, Ar and R are as defined above)

(5) Oxazole derivatives represented by the following formula:

(In the above formula, X is as defined above, provided that one of the —CX ₃ groups may be a substituted or unsubstituted aryl group or alkenyl group)

(6) s-triazine derivative represented by the following formula:

(In the above formula, X is as defined above, provided that one of the —CX ₃ groups may be a substituted or unsubstituted aryl group or alkenyl group)

(7) Disulfone derivatives represented by the following formula:
Ar—SO ₂ —SO ₂ —Ar
(In the above formula, Ar is the same as defined above)

(8) Imide compound represented by the following formula:

  (In the above formula, X is the same as defined above)

(9) Others such as oxime sulfonate, diazonaphthoquinone, benzoin tosylate and the like.

These acid generators are the following compounds, more specifically, some examples.
Triphenylsulfonium hexafluoroantimonate:

Triphenylphosphonium hexafluorophosphate:

Diphenyliodohexafluorophosphate:

Benzoin tosylate:

In carrying out the present invention, a chemically amplified resist is prepared from the acid-sensitive compound and the acid generator as described above. For example, such a resist can be prepared in the form of a resist solution according to conventional methods using techniques commonly used in resist chemistry. For example, when the acid-sensitive compound constituting the resist is a polymer or copolymer as described above, the selected monomer for forming the polymer or copolymer is used as an appropriate polymerization initiator. It can be polymerized in the presence and then an acid generator can be added to the resulting polymer or copolymer solution to form a resist solution. The polymerization conditions and polymerization initiator used here can be arbitrarily selected from a wide range of commonly used ones. For example, the following can be mentioned as an example of a suitable polymerization initiator.
AIBN (azoisobutyronitrile):

MAIB (dimethyl-2,2-azoisobisbutyrate):

  In the preparation of chemically amplified resists, the amount of acid generator added to the acid sensitive compound can vary over a wide range and is generally about 1-30% by weight, preferably about 1-15% by weight. .

  The solvent used for preparing such a resist solution can be variously changed depending on the type of resist, coating conditions, and other factors. Preferably, for example, cyclohexane, propylene glycol monomethyl ether acetate (PGMEA) is used. Organic solvents such as ethyl lactate.

  Although the method for forming a resist pattern according to the present invention can be carried out through any of various steps, it can be preferably carried out as follows.

  First, a chemically amplified resist solution prepared as described above is applied onto a substrate to be processed. The target substrate used here may be any substrate normally used in semiconductor devices and other devices, and specifically includes silicon, oxide film, polysilicon, nitride film, aluminum, and the like. Can do. These substrates may or may not already have a circuit built in. In some cases, these substrates are preferably pretreated with an adhesion promoter such as hexamethyldisilazane (HMDS) in order to improve adhesion to the resist.

  The resist solution can be applied using a conventional coating apparatus such as a spin coater, a dip coater, or a roller coater. Although the thickness of the resist film to be formed can be widely changed according to factors such as the usage of the resist film, it is usually in the range of about 0.3 to 2.0 μm.

  Then, if necessary, before the selective exposure to radiation, the resist film formed in the above step is pre-baked at a temperature of about 60 to 150 ° C., preferably about 60 to 100 ° C. for about 60 to 180 seconds. . For this pre-baking, for example, a heating means such as a hot plate can be used.

  If a top coat film (protective film) is further applied on the resist film, for example, an olefin resin solution is applied onto the resist film by a spin coating method and baked at a temperature of about 100 ° C. By carrying out, it can be set as a topcoat film.

  After the resist film is formed and optionally pre-baked, the resist film is selectively exposed to radiation with a conventional exposure apparatus. Suitable exposure apparatuses are commercially available ultraviolet (far ultraviolet / vacuum ultraviolet) exposure apparatuses, X-ray exposure apparatuses, electron beam exposure apparatuses, excimer steppers, and the like. Appropriate conditions can be selected for each exposure condition. As a result of this selective exposure, an acid is generated from the acid generator contained in the resist film.

  Next, the exposed resist film is post-exposure baked (PEB) to cause an acid-catalyzed protecting group elimination reaction. This post-exposure bake can be performed in the same manner as the previous pre-bake. For example, the baking temperature is about 60 to 150 ° C, preferably about 100 to 150 ° C. When a top coat film is used in combination, after the post-exposure baking and before development, it is peeled off with an organic solvent, for example.

  After completion of the post-exposure baking, the exposed resist film is subjected to liquid development according to a conventional method. As the developer used here, an appropriate one can be arbitrarily selected from the developers generally used in this technical field. A particularly preferred developer is an ammonium compound of the following formula as a developer, as proposed in JP-A-7-23053 cited above:

(Wherein R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms),
Morpholine compounds of the formula:

Or a developer containing an aqueous solution or an alcohol solution of the mixture. Preferred examples of the ammonium compound as a developer are not limited to those listed below,
Tetramethylammonium hydroxide (TMAH),
Tetraethylammonium hydroxide (TEAH),
Tetrapropylammonium hydroxide (TPAH),
Tetrabutylammonium hydroxide (TBAH),
Etc.

  These developers are dissolved in water, or dissolved in an alcohol such as methanol, etal, isopropyl alcohol or the like to form a developer. The concentration of developer to be dissolved can vary widely, but is generally in the range of about 0.1 to 15% by weight, preferably in the range of about 0.1 to 10% by weight. Although the development time is not particularly limited, it is generally in the range of about 1 to 5 minutes, preferably in the range of about 1 to 3 minutes. As a result of development, the exposed area of the resist film is dissolved and removed, and a desired resist pattern can be obtained. Finally, the obtained resist pattern is also rinsed with pure water according to a conventional method and dried.

  As understood from the above description and the following examples, in the present invention, the chemically amplified resist material has an alicyclic group represented by the above formulas (I) to (VI) in its structure. And a deprotecting group having a moiety in which one of the carbon atoms constituting the ring skeleton is substituted with an appropriate lower alkyl group, or a deprotection in which the ring skeleton is ester-bonded via one or more other atoms By using a compound having a group, the solubility of the exposed portion is increased and development proceeds smoothly, so that peeling and cracking of the resist film can be reduced, and stable patterning characteristics can be obtained. The rigidity resulting from the cyclic hydrocarbon group can be reduced, and stable patterning characteristics can be obtained.

Although the deprotecting group used in the present invention has been found to have a particularly remarkable effect in a chemical resist composed of an alicyclic unit and a deprotecting unit, it has a satisfactory effect in the case of other resists. be able to. In addition, as described above, the resist having particularly remarkable effects includes alicyclic groups such as adamantane and its derivatives, norbornane and its derivatives, tricyclo [5.2.1.0 ^2,6 ] decane and its derivatives. Can be mentioned.

  The invention will now be described with reference to several examples thereof. It should be understood that the following examples are merely examples and do not limit the present invention.

Example 1
A polymerization vessel was charged with 2-methyladamantyl methacrylate monomer and t-butyl monomer allylate in a ratio of 4: 6 to obtain a 2 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN (azoisobutyronitrile), was added to the 1,4-dioxane solution in an amount of 5 mol%, and the mixture was polymerized at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyladamantyl methacrylate / t-butyl acrylate copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 49:51, a weight average molecular weight (Mw) of 6890, and a dispersity (Mw / Mn) of 1.89.

Example 2
To the 2-methyladamantyl methacrylate / t-butyl acrylate copolymer prepared in Example 1, 15% by weight of an acid generator and triphenylsulfonium hexafluoroantimonate were added and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.7 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked at 100 ° C. for 100 seconds on a hot plate.

After completion of pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (Nikon Corporation, NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 130 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The threshold energy Eth of the irradiation dose in this example was 21.2 mJ / cm ² and the resolving power was 0.275 μm L & S (line and space).

Example 3
The procedure described in Example 2 was repeated. However, in this example, a tetrabutylammonium hydroxide (TBAH) aqueous solution having the same concentration (0.27N) was used as the developer instead of the 0.27N TMAH aqueous solution. A satisfactory resist pattern similar to that of Example 2 was obtained with Eth = 28.6 mJ / cm ² and resolving power = 0.275 μm L & S.

Example 4 (Comparative example)
The procedure described in Example 1 and Example 2 was repeated. However, in this example, for comparison, it is represented by the following formula by the method described in Example 1, the composition ratio (m: n) is 53:47, the weight average molecular weight (Mw) is 3830, and the dispersity ( Adamantyl methacrylate / t-butyl acrylate copolymer having Mw / Mn) of 2.1:

Was prepared. A resist process was carried out as described in Example 2 using the obtained copolymer, but no pattern was obtained.

Example 5
A 2-methyladamantyl monomer acrylate was charged into a polymerization vessel to give a 2 mol / L toluene solution. A polymerization initiator, AIBN, was added to the toluene solution in an amount of 2 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using methanol as a precipitant. A 2-methyladamantyl acrylate polymer represented by the following formula (n in the formula is the number of repeating units necessary to obtain the following molecular weight) was obtained.

  The obtained polymer had a weight average molecular weight (Mw) of 8950 and a dispersity (Mw / Mn) of 1.8.

Example 6
15% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate was added to the 2-methyladamantyl acrylate polymer prepared in Example 5 and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.7 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked at 100 ° C. for 100 seconds on a hot plate.

After completion of pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (Nikon Corporation, NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 130 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 32 mJ / cm ² and the resolving power was 0.30 μm L & S.

Example 7
A polymerization vessel was charged with 2-methyladamantyl monomer of methacrylate and 3-oxocyclohexyl monomer of methacrylate at a ratio of 4: 6 to prepare a 2 mol / L toluene solution. A polymerization initiator, AIBN, was added to this toluene solution in an amount of 5 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using methanol as a precipitant. A 2-methyladamantyl methacrylate / 3-oxocyclohexyl methacrylate copolymer represented by the following formula was obtained.

  The obtained copolymer had a composition ratio (m: n) of 49:51, a weight average molecular weight (Mw) of 14400, and a dispersity (Mw / Mn) of 2.30.

Example 8
To the 2-methyladamantyl methacrylate / 3-oxocyclohexyl methacrylate copolymer prepared in Example 7, 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate was added and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.7 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked at 100 ° C. for 100 seconds on a hot plate.

After completion of pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (Nikon Corporation, NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 9.6 mJ / cm ² , and the resolving power was 0.275 μm L & S.

Example 9
A polymerization vessel was charged with 2-methyladamantyl monomer of methacrylate and 3-oxo-1,1-dimethylptyl monomer of methacrylate at a ratio of 4: 6 to obtain a 2 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the dioxane solution in an amount of 5 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyladamantyl methacrylate / 3-oxo-1,1-dimethylbutyl methacrylate copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 47:53, a weight average molecular weight (Mw) of 7420, and a dispersity (Mw / Mn) of 2.40.

Example 10
To the 2-methyladamantyl methacrylate / 3-oxo-1,1-dimethylbutyl methacrylate copolymer prepared in Example 9, 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate was added and dissolved in cyclohexanone. . The obtained resist solution was spin-coated at a film thickness of 0.7 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked at 100 ° C. for 100 seconds on a hot plate.

After completion of pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (Nikon Corporation, NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 130 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 32 mJ / cm ² and the resolving power was 0.325 μm L & S.

Example 11
A polymerization vessel was charged with 2-methyladamantyl monomer methacrylate and methyl methacrylate 3-methacryloyloxybutyrate methacrylate in a ratio of 4: 6 to obtain a 2 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the dioxane solution in an amount of 2 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyladamantyl methacrylate / methacryloyl 3-oxybutyric acid methyl methacrylate copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 50:50, a weight average molecular weight (Mw) of 12090, and a dispersity (Mw / Mn) of 1.95.

Example 12
15% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate was added to the 2-methyladamantyl methacrylate / methacryloyl 3-oxybutyric acid methyl methacrylate copolymer prepared in Example 11 and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.7 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked at 100 ° C. for 100 seconds on a hot plate.

After completion of pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (Nikon Corporation, NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 130 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 29 mJ / cm ² and the resolving power was 0.30 μm L & S.

を調製した。 Example 13
By repeating the procedure described in Example 11, the compositional ratio (m: n) is 55:45, the weight average molecular weight (Mw) is 11520, and the dispersity (Mw / Mn) is 2. 38 2-methyladamantyl methacrylate / 2-hydroxyethyl methacrylate copolymers:

Was prepared.

  Next, 15% by weight of an acid generator and triphenylsulfonium hexafluoroantimonate were added to the 2-methyladamantyl methacrylate / 2-hydroxyethyl methacrylate copolymer prepared as described above and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.7 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked at 100 ° C. for 100 seconds on a hot plate.

After completion of pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (Nikon Corporation, NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 130 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 12 mJ / cm ² and the resolving power was 0.325 μm L & S.

Example 14
A polymerization vessel was charged with 2-methylcyclohexyl monomer and 3-oxocyclohexyl monomer in a ratio of 4: 6 to give a 2 mol / L toluene solution. A polymerization initiator, AIBN, was added to this toluene solution in an amount of 5 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using methanol as a precipitant. A 2-methylcyclohexyl methacrylate / 3-oxocyclohexyl methacrylate copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 51:49, a weight average molecular weight (Mw) of 7115, and a dispersity (Mw / Mn) of 1.9.

Example 15
To the 2-methylcyclohexyl methacrylate / 3-oxocyclohexyl methacrylate copolymer prepared in Example 14, 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate was added and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.7 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked at 100 ° C. for 100 seconds on a hot plate.

After completion of pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (Nikon Corporation, NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 130 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 7.2 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 16
The 2-methyladamantyl methacrylate / 3-oxocyclohexyl methacrylate copolymer prepared in Example 7 was added to a 5% by weight acid generator, 2-oxocyclohexylmethylcyclohexylsulfonium trichlorosulfonate represented by the following formula:

Was added and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.7 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked at 100 ° C. for 100 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to an ArF laser beam pattern having a wavelength of 193 nm with an ArF exposure apparatus (Nikon, NA = 0.55). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 130 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 6 mJ / cm ² and the resolving power was 0.20 μm L & S.

Example 17
2-methyladamantyl methacrylate / p-vinylphenol represented by the following formula (composition ratio = 23: 77, weight average molecular weight (Mw) = 6480, dispersity = 3.1):

2% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate was added and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.7 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked at 100 ° C. for 100 seconds on a hot plate.

After completion of pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (Nikon Corporation, NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 130 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 82 mJ / cm ² and the resolving power was 0.325 μm L & S.

Example 18
2-methyladamantyl acrylate polymer prepared in Example 5 above, weight average molecular weight (Mw) = 8950 and dispersity = 1.8, polyvinylphenol represented by the following formula, weight average molecular weight (Mw) = 5150 and dispersion Degree = 2.8:

Was added in a proportion of 20% by weight, and further 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate was added, and the resulting mixture was dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.7 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked at 100 ° C. for 100 seconds on a hot plate.

After completion of pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (Nikon Corporation, NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 110 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 8.9 mJ / cm ² and the resolving power was 0.325 μm L & S.

Example 19
1-adamantylcarboxylic acid 2-methyladamantyl ester represented by the following formula in the same polyvinylphenol as used in Example 18 above, weight average molecular weight (Mw) = 5150 and dispersity = 2.8:

Was added in a proportion of 30% by weight, 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate was added, and the resulting mixture was dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.7 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked at 100 ° C. for 100 seconds on a hot plate.

After completion of pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (Nikon Corporation, NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 110 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 11 mJ / cm ² and the resolving power was 0.35 μm L & S.

Example 20
A copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 23000 was prepared.

To this copolymer, an acid generator of 2% by weight of the copolymer, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate (EL) was added so that the copolymer concentration was 15% by weight. Dissolved. The obtained resist solution was spin-coated on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and pre-baked at 100 ° C. for 1 minute on a hot plate. A resist film having a thickness of 1.0 μm was obtained.

  After completion of pre-baking, the obtained resist film was selectively exposed to an ArF laser light pattern having a wavelength of 193 nm by an ArF excimer laser contact aligner (NA = 0.55). Subsequently, the resist film immediately after the exposure was subjected to PEB (post-exposure baking) for 60 seconds on a hot plate at 150 ° C. Thereafter, the resist film was developed with an alkaline developer MMD-3 manufactured by Tokyo Ohka Kogyo Co., Ltd. for 60 seconds and further rinsed with pure water for 30 seconds. A resist pattern corresponding to the mask size used for the exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.50 μm L & S.

Example 21 (Comparative example)
The procedure described in Example 20 was repeated. However, in this example, for comparison, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 14,000 was prepared.

  Although a resist pattern was obtained with a resolution of 0.50 μm L & S, cracks occurred around the pattern.

Example 22
The procedure described in Example 20 was repeated. However, in this example, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 18000 was prepared.

  A resist pattern corresponding to the mask size used for exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.50 μm L & S.

Example 23
The procedure described in Example 20 was repeated. However, in this example, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 11000 was prepared.

  A resist pattern corresponding to the mask size used for the exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.50 μm L & S.

Example 24
The procedure described in Example 20 was repeated. However, in this example, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 8000 was prepared.

  A resist pattern corresponding to the mask size used for the exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.50 μm L & S.

Example 25
The procedure described in Example 20 was repeated. However, in this example, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 9000 was prepared.

  A resist pattern corresponding to the mask size used for the exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.50 μm L & S.

Example 26
The procedure described in Example 20 was repeated. However, in this example, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 7800 was prepared.

  A resist pattern corresponding to the mask size used for the exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.50 μm L & S.

Example 27
The procedure described in Example 20 was repeated. However, in this example, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 6500 was prepared.

  A resist pattern corresponding to the mask size used for the exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.50 μm L & S.

Example 28
The procedure described in Example 20 was repeated. However, in this example, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 16000 was prepared.

  A resist pattern corresponding to the mask size used for the exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.60 μm L & S.

Example 29
The procedure described in Example 20 was repeated. However, in this example, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 12500 was prepared.

  A resist pattern corresponding to the mask size used for the exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.50 μm L & S.

Example 30
The procedure described in Example 20 was repeated. However, in this example, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 18000 was prepared, and ArF was used as an exposure source. Instead of the excimer laser contact aligner, a deep ultraviolet light contact aligner was used.

  A resist pattern corresponding to the mask size used for the exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.50 μm L & S.

Example 31
The procedure described in Example 20 was repeated. However, in this example, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 17500 is prepared, and ArF is used as an exposure source. Instead of the excimer laser contact aligner, a deep ultraviolet light contact aligner was used.

  A resist pattern corresponding to the mask size used for the exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.55 μm L & S.

Example 32
The procedure described in Example 20 was repeated. However, in this example, a copolymer represented by the following formula and having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 9500 was prepared.

  A resist pattern corresponding to the mask size used for the exposure was obtained without causing cracks or peeling of the pattern. The resolving power was 0.60 μm L & S.

Example 33
The polymerization vessel was charged with 2-methyl-2-adamantyl monomer and methacrylic acid monomer at a ratio of 7: 3 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN (azoisobutyronitrile), was added to the 1,4-dioxane solution in an amount of 20 mol%, and the mixture was polymerized at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / methacrylic acid copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 7: 3, a weight average molecular weight (Mw) of 8500, and a dispersity (Mw / Mn) of 2.10.

Example 34
To the 2-methyl-2-adamantyl methacrylate / methacrylic acid copolymer prepared in Example 33, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and propylene glycol monomethyl ether acetate Dissolved in (PGMEA). The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and pre-baked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to an ArF laser beam pattern having a wavelength of 193 nm with an ArF excimer exposure apparatus (NA = 0.55). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with a 0.118 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 21.5 mJ / cm ² and the resolving power was 0.175 μm L & S.

Example 35
The procedure described in Example 34 was repeated. However, in this example, a KrF excimer stepper (NA = 0.45) was used as the exposure apparatus instead of the ArF excimer exposure apparatus, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 1.48 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 36
A polymerization vessel was charged with 2-methyl-2-adamantyl methacrylate monomer, t-butyl methacrylate monomer and methacrylic acid monomer at a ratio of 8: 7: 5 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / t-butyl methacrylate / methacrylic acid copolymer represented by the following formula was obtained.

  The obtained copolymer had a composition ratio (l: m: n) of 50:29:21, a weight average molecular weight (Mw) of 7800, and a dispersity (Mw / Mn) of 2.20.

Example 37
To the 2-methyl-2-adamantyl methacrylate / t-butyl methacrylate / methacrylic acid copolymer prepared in Example 36, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added. , Dissolved in propylene glycol monomethyl ether acetate (PGMEA). The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to an ArF laser beam pattern having a wavelength of 193 nm with an ArF excimer exposure apparatus (NA = 0.55). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with 0.118 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 1.4 mJ / cm ² and the resolving power was 0.170 μm L & S.

Example 38
The procedure described in Example 37 was repeated. However, in this example, a KrF excimer stepper (NA = 0.45) was used as the exposure apparatus instead of the ArF excimer exposure apparatus, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The threshold energy Eth of the irradiation dose in this example was 14.4 mJ / cm ² and the resolving power was 0.250 μm L & S.

Example 39
A 2-methyl-2-adamantyl methacrylate monomer and an itaconic acid monomer were charged into the polymerization vessel at a ratio of 9: 1 to obtain a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / itaconic acid copolymer represented by the following formula was obtained.

  The obtained copolymer had a composition ratio (m: n) of 88:12, a weight average molecular weight (Mw) of 6700, and a dispersity (Mw / Mn) of 2.18.

Example 40
2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added to the 2-methyl-2-adamantyl methacrylate / itaconic acid copolymer prepared in Example 39 to obtain ethyl lactate (EL). Dissolved in. The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to an ArF laser beam pattern having a wavelength of 193 nm with an ArF excimer exposure apparatus (NA = 0.55). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with 0.118 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 2.8 mJ / cm ² and the resolving power was 0.175 μm L & S.

Example 41
The procedure described in Example 40 was repeated. However, in this example, a KrF excimer stepper (NA = 0.45) was used as the exposure apparatus instead of the ArF excimer exposure apparatus, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 25.0 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 42
The polymerization vessel was charged with 2-methyl-2-adamantyl methacrylate monomer and vinylbenzene sulfonic acid monomer at a ratio of 8: 2 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / vinylbenzenesulfonic acid copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 76:24, a weight average molecular weight (Mw) of 6400, and a dispersity (Mw / Mn) of 2.42.

Example 43
To the 2-methyl-2-adamantyl methacrylate / vinylbenzene sulfonic acid copolymer prepared in Example 42, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate ( EL). The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with 0.236 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 12.4 mJ / cm ² and the resolving power was 0.250 μm L & S.

Example 44
A polymerization vessel was charged with 2-methyl-2-adamantyl methacrylate monomer and methacrylamide monomer in a ratio of 7: 3 to prepare a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / methacrylamide copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 75:25, a weight average molecular weight (Mw) of 7600, and a dispersity (Mw / Mn) of 2.13.

Example 45
To the 2-methyl-2-adamantyl methacrylate / methacrylamide copolymer prepared in Example 44, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate (EL ). The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with 0.236 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The threshold energy Eth of the irradiation dose in this example was 24.0 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 46
The polymerization vessel was charged with 2-methyl-2-adamantyl monomer and maleimide monomer in a ratio of 7: 3 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / maleimide copolymer represented by the following formula was obtained.

  The obtained copolymer had a composition ratio (m: n) of 71:29, a weight average molecular weight (Mw) of 8200, and a dispersity (Mw / Mn) of 2.55.

Example 47
To the 2-methyl-2-adamantyl methacrylate / maleimide copolymer prepared in Example 46, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate (EL) was added. Dissolved. The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with 0.236 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 30.0 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 48
A 2-methyl-2-adamantyl methacrylate monomer and an itaconic anhydride monomer were charged into the polymerization vessel at a ratio of 8: 2 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / itaconic anhydride copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 72:28, a weight average molecular weight (Mw) of 8700, and a dispersity (Mw / Mn) of 2.31.

Example 49
To the 2-methyl-2-adamantyl methacrylate / itaconic anhydride copolymer prepared in Example 48, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate (EL ). The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with 0.118 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 26.1 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 50
A polymerization vessel was charged with 2-methyl-2-adamantyl monomer methacrylate and α-acrylic acid- (R)-(+)-β, β-dimethyl-γ-butyrolactone monomer in a ratio of 7: 3, 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / α-acrylic acid- (R)-(+)-β, β-dimethyl-γ-butyrolactone copolymer represented by the following formula was obtained.

  The obtained copolymer had a composition ratio (m: n) of 74:26, a weight average molecular weight (Mw) of 6200, and a dispersity (Mw / Mn) of 2.25.

Example 51
2% by weight of an acid generator in the 2-methyl-2-adamantyl methacrylate / α-acrylic acid- (R)-(+)-β, β-dimethyl-γ-butyrolactone copolymer prepared in Example 50, Triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added and dissolved in ethyl lactate (EL). The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to an ArF laser beam pattern having a wavelength of 193 nm with an ArF excimer exposure apparatus (NA = 0.55). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 1.9 mJ / cm ² and the resolving power was 0.170 μm L & S.

Example 52
The procedure described in Example 51 was repeated. However, in this example, a KrF excimer stepper (NA = 0.45) was used as the exposure apparatus instead of the ArF excimer exposure apparatus, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 15.0 mJ / cm ² and the resolving power was 0.250 μm L & S.

Example 53
A polymerization vessel was charged with 2-methyl-2-adamantyl methacrylate and vinyl hydroxyl oxime monomer in a ratio of 4: 6 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / vinyl hydroxyl oxime copolymer represented by the following formula was obtained.

  The obtained copolymer had a composition ratio (m: n) of 66:44, a weight average molecular weight (Mw) of 6200, and a dispersity (Mw / Mn) of 2.08.

Example 54
To the 2-methyl-2-adamantyl methacrylate / vinylhydroxyloxime copolymer prepared in Example 53, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate (EL ). The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 34.0 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 55
A polymerization vessel was charged with 2-methyl-2-adamantyl methacrylate monomer and vinyl carbonate monomer at a ratio of 1: 9 to form a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / vinyl carbonate copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 82:18, a weight average molecular weight (Mw) of 9300, and a dispersity (Mw / Mn) of 1.99.

Example 56
To the 2-methyl-2-adamantyl methacrylate / vinyl carbonate copolymer prepared in Example 55, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate (EL) Dissolved in. The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 31.0 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 57
A polymerization vessel was charged with 2-methyl-2-adamantyl monomer and vinylazalactone monomer in a ratio of 7: 3 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / vinylazalactone copolymer represented by the following formula was obtained.

  The obtained copolymer had a composition ratio (m: n) of 71:29, a weight average molecular weight (Mw) of 10200, and a dispersity (Mw / Mn) of 1.61.

Example 58
To the 2-methyl-2-adamantyl methacrylate / vinylazalactone copolymer prepared in Example 57, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate (EL ). The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with 0.118 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 28.2 mJ / cm ² and the resolving power was 0.250 μm L & S.

Example 59
A polymerization vessel was charged with 2-methyl-2-adamantyl monomer and vinyl oxazine monomer at a ratio of 7: 3 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / vinyl oxazine copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 70:30, a weight average molecular weight (Mw) of 11000, and a dispersity (Mw / Mn) of 1.59.

Example 60
To the 2-methyl-2-adamantyl methacrylate / vinyl oxazine copolymer prepared in Example 59, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate (EL) Dissolved in. The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with 0.118 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 27.5 mJ / cm ² and the resolving power was 0.250 μm L & S.

Example 61
The polymerization vessel was charged with 2-methyl-2-adamantyl monomer and vinylpyrrolidone monomer at a ratio of 7: 3 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / vinylpyronidone copolymer represented by the following formula was obtained.

  The obtained copolymer had a composition ratio (m: n) of 68:32, a weight average molecular weight (Mw) of 9000, and a dispersity (Mw / Mn) of 1.89.

Example 62
To the 2-methyl-2-adamantyl methacrylate / vinylpyronidone copolymer prepared in Example 61, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate (EL) was added. Dissolved. The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with 0.118 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The threshold energy Eth of the irradiation dose in this example was 30.5 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 63
A polymerization vessel was charged with 2-methyl-2-adamantyl monomer of methacrylic acid and acrylonitrile monomer at a ratio of 1: 1 to prepare a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / acrylonitrile copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 80:20, a weight average molecular weight (Mw) of 6000, and a dispersity (Mw / Mn) of 2.35.

Example 64
2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added to the 2-methyl-2-adamantyl methacrylate / acrylonitrile copolymer prepared in Example 63 and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 38.2 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 65
The polymerization vessel was charged with 2-methyl-2-adamantyl monomer and nitrostyrene monomer at a ratio of 7: 3 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / nitrostyrene copolymer represented by the following formula was obtained.

  The obtained copolymer had a composition ratio (m: n) of 74:26, a weight average molecular weight (Mw) of 14000, and a dispersity (Mw / Mn) of 1.79.

Example 66
To the 2-methyl-2-adamantyl methacrylate / nitrostyrene copolymer prepared in Example 65, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The threshold energy Eth of the irradiation dose in this example was 37.5 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 67
The polymerization vessel was charged with 2-methyl-2-adamantyl monomer and acrolein monomer at a ratio of 1: 1 to give a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / acrolein copolymer represented by the following formula was obtained.

  The obtained copolymer had a composition ratio (m: n) of 70:30, a weight average molecular weight (Mw) of 10,000, and a dispersity (Mw / Mn) of 2.10.

Example 68
To the 2-methyl-2-adamantyl methacrylate / acrolein copolymer prepared in Example 67, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to an ArF laser beam pattern having a wavelength of 193 nm with an ArF excimer exposure apparatus (NA = 0.55). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 1.4 mJ / cm ² and the resolving power was 0.170 μm L & S.

Example 69
The procedure described in Example 68 was repeated. However, in this example, instead of the ArF excimer exposure apparatus, a KrF excimer stepper (NA = 0.45) was used as the exposure apparatus, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 21.0 mJ / cm ² and the resolving power was 0.250 μm L & S.

Example 70
A polymerization vessel was charged with 2-methyl-2-adamantyl monomer and vinyl acetate monomer in a ratio of 7: 3 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A 2-methyl-2-adamantyl methacrylate / vinyl acetate copolymer represented by the following formula was obtained.

  The obtained copolymer had a composition ratio (m: n) of 74:26, a weight average molecular weight (Mw) of 8200, and a dispersity (Mw / Mn) of 1.82.

Example 71
To the 2-methyl-2-adamantyl methacrylate / vinyl acetate copolymer prepared in Example 70, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added and dissolved in cyclohexanone. The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to an ArF laser beam pattern having a wavelength of 193 nm with an ArF excimer exposure apparatus (NA = 0.55). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 2.2 mJ / cm ² and the resolving power was 0.170 μm L & S.

Example 72
The procedure described in Example 71 was repeated. However, in this example, instead of the ArF excimer exposure apparatus, a KrF excimer stepper (NA = 0.45) was used as the exposure apparatus, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 22.0 mJ / cm ² and the resolving power was 0.250 μm L & S.

Example 73
Itaconic acid-α-2-methyl-2-adamantyl-β-methyl monomer was charged into a polymerization vessel to obtain a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using methanol as a precipitant. An itaconic acid-α-2-methyl-2-adamantyl-β-methyl polymer represented by the following formula was obtained.

  The obtained polymer had a weight average molecular weight (Mw) of 18000 and a dispersity (Mw / Mn) of 1.66.

Example 74
To the itaconic acid-α-2-methyl-2-adamantyl-β-methyl polymer prepared in Example 73, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and cyclohexanone was added. Dissolved. The obtained resist solution was spin-coated at a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to an ArF laser beam pattern having a wavelength of 193 nm with an ArF excimer exposure apparatus (NA = 0.55). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 2.0 mJ / cm ² and the resolving power was 0.175 μm L & S.

Example 75
The procedure described in Example 74 was repeated. However, in this example, instead of the ArF excimer exposure apparatus, a KrF excimer stepper (NA = 0.45) was used as the exposure apparatus, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 28.5 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 76
Bis-2-methyl-2-adamantyl monomer of fumarate and monomer of fumarate were charged into a polymerization vessel at a molar ratio of 9: 1 to obtain a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and polymerization was performed at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitant. A bis-2-methyl-2-adamantyl fumarate / fumaric acid copolymer represented by the following formula was obtained.

  The resulting copolymer had a composition ratio (m: n) of 95: 5, a weight average molecular weight (Mw) of 5100, and a dispersity (Mw / Mn) of 2.84.

Example 77
2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added to the bis-2-methyl-2-adamantyl fumarate / fumaric acid copolymer prepared in Example 76 and dissolved in cyclohexanone. did. The obtained resist solution was spin-coated with a film thickness of 0.4 μm on a silicon substrate pretreated with HMDS, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the pre-baking, the obtained resist film was selectively exposed to an ArF laser beam pattern having a wavelength of 193 nm with an ArF excimer exposure apparatus (NA = 0.55). Subsequently, the resist film after exposure was PEB (post-exposure baking) at 150 ° C. for 60 seconds. Thereafter, the resist film was developed with 0.118 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. In this example, the threshold energy Eth of the irradiation dose was 2.8 mJ / cm ² and the resolving power was 0.180 μm L & S.

Example 78
The procedure described in Example 77 was repeated. However, in this example, instead of the ArF excimer exposure apparatus, a KrF excimer stepper (NA = 0.45) was used as the exposure apparatus, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The threshold energy Eth of the irradiation dose in this example was 30.5 mJ / cm ² and the resolving power was 0.275 μm L & S.

Example 79
2-methyladamantyl methacrylate and methacrylic acid were charged into the polymerization vessel at a molar ratio of 9: 1 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and the mixture was held at 80 ° C. for about 7 hours. Then, this reaction system was dissolved in tetrahydrofuran (THF), the obtained solution was put into a large amount of methanol, and the precipitate was separated by filtration. A 2-methyladamantyl methacrylate / methacrylic acid copolymer was obtained in a yield of 44%. The resulting copolymer had a composition ratio of 9: 1 and a weight average molecular weight (Mw) of 9600.

Example 80
To the 2-methyladamantyl methacrylate / methacrylic acid copolymer prepared in Example 79, 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate (TPSSbF ₄ ) was added, so that the resin content was 15% by weight of the total amount. So that it was dissolved in cyclohexanone. The obtained resist solution was spin-coated with a film thickness of 0.7 μm on a silicon substrate pretreated with HMDS.

  The obtained resist film was selectively exposed through a mask to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Immediately after the exposure, the resist film was subjected to PEB (post-exposure baking) for 60 seconds on a hot plate at 150 ° C. Thereafter, the resist film was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The 0.25 μm L & S pattern was resolved approximately 1: 1.

  Further, the resist film formed as described above was exposed to a 0.325 μm hole pattern with a KrF excimer stepper. Also in this case, a 0.325 μm hole resist pattern corresponding to the laser beam pattern used for exposure was obtained.

Example 81
The procedure described in Example 80 was repeated. However, in this example, the addition amount of the acid generator, TPSSbF ₄ is changed from 5 wt% to 2 wt%, the resist film thickness is changed from 0.7 μm to 0.4 μm, and the exposure apparatus is changed to a KrF excimer stepper. To ArF excimer exposure apparatus, wavelength 193 nm (NA = 0.55). A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The 0.18 μm L & S pattern was resolved approximately 1: 1.

Example 82
2-Methyl adamantyl methacrylate, t-butyl methacrylic acid and methacrylic acid were charged into a polymerization vessel at a molar ratio of 40:35:25 to obtain a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and the mixture was held at 80 ° C. for about 7 hours. Thereafter, this reaction system was dissolved in tetrahydrofuran (THF), the obtained solution was put into a large amount of n-hexane, and the precipitate was separated by filtration. 2-methyladamantyl methacrylate / t-butyl methacrylic acid / methacrylic acid copolymer was obtained in a yield of 58%. The resulting copolymer had a composition ratio of 50:29:21 and a weight average molecular weight (Mw) of 12,000.

Example 83
To the 2-methyladamantyl methacrylate / t-butyl methacrylic acid / methacrylic acid copolymer prepared in Example 82, 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate (TPSSbF ₄ ) was added. It dissolved in cyclohexanone so that it might become 15 weight% of the whole quantity. The obtained resist solution was spin-coated with a film thickness of 0.7 μm on a silicon substrate pretreated with HMDS.

  The obtained resist film was selectively exposed through a mask to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Immediately after the exposure, the resist film was subjected to PEB (post-exposure baking) for 60 seconds on a 130 ° C. hot plate. Thereafter, the resist film was developed with 0.17 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The 0.25 μm L & S pattern was resolved approximately 1: 1.

  Further, the resist film formed as described above was exposed to a 0.325 μm hole pattern with a KrF excimer stepper. Also in this case, a 0.325 μm hole resist pattern corresponding to the laser beam pattern used for exposure was obtained.

Example 84
The procedure described in Example 83 was repeated. However, in this example, the addition amount of the acid generator and TPSSbF ₄ is changed from 5 wt% to 2 wt%, and the exposure apparatus is changed from KrF excimer stepper to ArF excimer exposure apparatus, wavelength 193 nm (NA = 0.55). did. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The 0.19 μm L & S pattern was resolved approximately 1: 1.

Example 85
2-Methyladamantyl methacrylate, 3-oxocyclohexyl methacrylate and methacrylic acid were charged in a polymerization vessel at a molar ratio of 50:35:15 to obtain a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and the mixture was held at 80 ° C. for about 7 hours. Thereafter, this reaction system was dissolved in tetrahydrofuran (THF), and the resulting solution was put into a large amount of a mixed solvent of methanol and water (10: 1), and the precipitate was separated by filtration. A 2-methyladamantyl methacrylate / 3-oxocyclohexyl methacrylate / methacrylic acid copolymer was obtained with a yield of 43%. The resulting copolymer had a composition ratio of 50:35:15 and a weight average molecular weight (Mw) of 11,000.

Example 86
To the 2-methyladamantyl methacrylate / 3-oxocyclohexyl methacrylate / methacrylic acid copolymer prepared in Example 85, 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate (TPSSbF ₄ ) was added. It dissolved in cyclohexanone so that it might become 15 weight% of the whole quantity. The obtained resist solution was spin-coated with a film thickness of 0.7 μm on a silicon substrate pretreated with HMDS.

  The obtained resist film was selectively exposed through a mask to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Immediately after the exposure, the resist film was subjected to PEB (post-exposure baking) for 60 seconds on a 130 ° C. hot plate. Thereafter, the resist film was developed with 0.17 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The 0.25 μm L & S pattern was resolved approximately 1: 1.

  Further, the resist film formed as described above was exposed to a 0.325 μm hole pattern with a KrF excimer stepper. Also in this case, a 0.325 μm hole resist pattern corresponding to the laser beam pattern used for exposure was obtained.

Example 87
The procedure described in Example 86 was repeated. However, in this example, the exposure apparatus was changed from a KrF excimer stepper to an ArF excimer exposure apparatus with a wavelength of 193 nm (NA = 0.55). A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The 0.19 μm L & S pattern was resolved approximately 1: 1.

Example 88
2-Methylcyclohexyl methacrylate, t-butyl methacrylate and methacrylic acid were charged into a polymerization vessel in a molar ratio of 40:35:25 to obtain a 1-mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to the 1,4-dioxane solution in an amount of 20 mol%, and the mixture was held at 80 ° C. for about 7 hours. Thereafter, this reaction system was dissolved in tetrahydrofuran (THF), the obtained solution was put into a large amount of n-hexane, and the precipitate was separated by filtration. A 2-methylcyclohexyl methacrylate / t-butyl methacrylate / methacrylic acid copolymer was obtained in a yield of 63%. The resulting copolymer had a composition ratio of 50:29:21 and a weight average molecular weight (Mw) of 21,000.

Example 89
To the 2-methylcyclohexyl methacrylate / t-butyl methacrylate / methacrylic acid copolymer prepared in Example 88, 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate (TPSSbF ₄ ) was added, and the total amount of the resin content was increased. It was dissolved in cyclohexanone so as to be 15% by weight. The obtained resist solution was spin-coated with a film thickness of 0.7 μm on a silicon substrate pretreated with HMDS.

  The obtained resist film was selectively exposed through a mask to a pattern of KrF laser light having a wavelength of 248 nm with a KrF excimer stepper (NA = 0.45). Immediately after the exposure, the resist film was subjected to PEB (post-exposure baking) for 60 seconds on a 130 ° C. hot plate. Thereafter, the resist film was developed with 0.17 wt% TMAH aqueous solution for 60 seconds, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The 0.25 μm L & S pattern was resolved approximately 1: 1.

  Further, the resist film formed as described above was exposed to a 0.325 μm hole pattern with a KrF excimer stepper. Also in this case, a 0.325 μm hole resist pattern corresponding to the laser beam pattern used for exposure was obtained.

Example 90
The procedure described in Example 89 was repeated. However, in this example, the addition amount of the acid generator and TPSSbF ₄ is changed from 5 wt% to 2 wt%, and the exposure apparatus is changed from KrF excimer stepper to ArF excimer exposure apparatus, wavelength 193 nm (NA = 0.55). did. A desired resist pattern corresponding to the laser beam pattern used for exposure was obtained without causing pattern peeling. The 0.19 μm L & S pattern was resolved approximately 1: 1.

Claims (20)

Alicyclic hydrocarbon group-containing moiety represented by any of the following formulas (I) to (VI):

(Wherein R _I represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted, and Z together with the described carbon atoms Represents multiple atoms required to complete an alicyclic hydrocarbon group)

(In the above formula, R _II may be the same or different and represents a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic alicyclic hydrocarbon group. Where at least one of R _II is an alicyclic hydrocarbon group)

(Wherein R _II is the same as defined above)

(In the above formula, R _III may be the same or different and represents a proton, a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group. Provided that at least one of R _III is an alicyclic hydrocarbon group, and in the formula, at least one of two R _III bonded to a non-double bond carbon atom is 1 to 4 A substituted or unsubstituted linear or branched alkyl group or alicyclic hydrocarbon group having a carbon atom of

(Wherein R _II is the same as defined above)

(In the above formula, R _I and Z are the same as defined above)
An acid-sensitive compound comprising a structural unit that has an alkali-soluble group protected with an acid, and the alkali-soluble group is eliminated by an acid to render the compound alkali-soluble; and an acid generator that generates an acid upon radiation exposure; A resist material comprising:   The resist material according to claim 1, wherein the alkali-soluble group is a member selected from the group consisting of a carboxylic acid group, a sulfonic acid group, an amide group, an imide group, and a phenol group. The protected alkali-soluble group is a carboxylic acid group represented by the following formulas (VII) to (XI):

Wherein R _I , R _II and R _III and Z are the same as defined above,
Imide group represented by the following formula (XII):

(Wherein Z is the same as defined above) or a phenol group represented by the following formula (XIII):

(Wherein Z is the same as defined above)
The resist material according to claim 1, wherein the resist material is a resist material.   The alicyclic hydrocarbon group contained in the protected alkali-soluble group has a plurality of ring structures or has a condensed ring. The resist material described in 1. The alicyclic hydrocarbon group has the following group:
(1) adamantane and its derivatives (2) norbornane and its derivatives (3) perhydroanthracene and its derivatives (4) perhydronaphthalene and its derivatives (5) tricyclo [5.2.1.0 ^2,6 ] decane and (6) Bicyclohexane and derivatives thereof (7) Spiro [4,4] nonane and derivatives thereof (8) One member selected from spiro [4,5] decane and derivatives thereof, The resist material of any one of Claims 1-3.   The resist material according to claim 1, wherein the acid-sensitive compound is a polymer or copolymer containing the structural unit as a repeating unit.   The repeating unit of the polymer or copolymer is a member selected from the group consisting of acrylic acid esters and derivatives thereof, itaconic acid esters and derivatives thereof, fumaric acid esters and derivatives thereof, and styrene-substituted products and derivatives thereof. The resist material according to claim 6, wherein the resist material is characterized.   The acid-sensitive compound is a copolymer containing the structural unit as a repeating unit, and the remaining repeating unit of the copolymer is a repeating unit having an alkali-soluble group in a side chain and / or the acid generator. The resist material according to claim 6, comprising a repeating unit having an additional protected alkali-soluble group which can be removed by an acid generated from the side chain in the side chain. The copolymer is a structural unit represented by the following formula (XIV) or (XV):

(In the above formula, Rs may be the same or different and each represents hydrogen, halogen, or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms;
R _I represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted,
A represents a protecting group removable by an acid, and Z represents a plurality of atoms necessary to complete an alicyclic hydrocarbon group together with the described carbon atom). The resist material according to claim 8. The alicyclic hydrocarbon group of the copolymer has the following group:
(1) adamantane and its derivatives (2) norbornane and its derivatives (3) perhydroanthracene and its derivatives (4) perhydronaphthalene and its derivatives (5) tricyclo [5.2.1.0 ^2,6 ] decane and Derivatives thereof (6) Bicyclohexane and derivatives thereof (7) Spiro [4,4] nonane and derivatives thereof (8) A member selected from spiro [4,5] decane and derivatives thereof Item 10. The resist material according to Item 9.   The resist material according to claim 1, wherein the acid-sensitive compound is a non-polymerized compound, and an alkali-soluble polymer or copolymer is used in combination with the compound. Alicyclic hydrocarbon group-containing moiety represented by any of the following formulas (I) to (VI):

(Wherein R _I represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted, and Z together with the described carbon atoms Represents multiple atoms required to complete an alicyclic hydrocarbon group)

(In the above formula, R _II may be the same or different and represents a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic alicyclic hydrocarbon group. Where at least one of R _II is an alicyclic hydrocarbon group)

(Wherein R _II is the same as defined above)

(In the above formula, R _III may be the same or different and represents a proton, a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group. Provided that at least one of R _III is an alicyclic hydrocarbon group, and in the formula, at least one of two R _III bonded to a non-double bond carbon atom is 1 to 4 A substituted or unsubstituted linear or branched alkyl group or alicyclic hydrocarbon group having a carbon atom of

(Wherein R _II is the same as defined above)

(In the above formula, R _I and Z are the same as defined above)
An acid-sensitive compound comprising a structural unit that has an alkali-soluble group protected with an acid, and the alkali-soluble group is eliminated by an acid to render the compound alkali-soluble; and an acid generator that generates an acid upon radiation exposure; A resist material containing is applied onto the substrate to be processed.
The resist film on the substrate to be processed is selectively exposed to radiation capable of causing the generation of acid from the acid generator, and the post-baking of the resist film after the exposure, the latent image formed in the exposure step Developing,
A method of forming a resist pattern, comprising:   The pattern forming method according to claim 12, wherein the alkali-soluble group of the resist material is a member selected from the group consisting of a carboxylic acid group, a sulfonic acid group, an amide group, an imide group, and a phenol group. .   14. The pattern forming method according to claim 12, wherein the alicyclic hydrocarbon group of the alkali-soluble group of the resist material has a plurality of ring structures or a condensed ring. The alicyclic hydrocarbon group of the alkali-soluble group of the resist material is the following group:
(1) adamantane and its derivatives (2) norbornane and its derivatives (3) perhydroanthracene and its derivatives (4) perhydronaphthalene and its derivatives (5) tricyclo [5.2.1.0 ^2,6 ] decane and Derivatives thereof (6) Bicyclohexane and derivatives thereof (7) Spiro [4,4] nonane and derivatives thereof (8) A member selected from spiro [4,5] decane and derivatives thereof Item 14. The pattern forming method according to Item 12 or 13.   The pattern forming method according to claim 12, wherein the acid-sensitive compound of the resist material is a polymer or a copolymer containing the structural unit as a repeating unit.   The acid-sensitive compound is a copolymer containing the structural unit as a repeating unit, and the remaining repeating unit of the copolymer is a repeating unit having an alkali-soluble group in a side chain and / or the acid generator. The pattern forming method according to claim 16, comprising a repeating unit having an additional protected alkali-soluble group removable from the acid generated in the side chain in the side chain. The copolymer is a structural unit represented by the following formula (XIV) or (XV):

(In the above formula, Rs may be the same or different and each represents hydrogen, halogen, or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms;
R _I represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted,
A represents a protecting group removable by an acid, and Z represents a plurality of atoms necessary to complete an alicyclic hydrocarbon group together with the described carbon atom). The pattern forming method according to claim 17. The alicyclic hydrocarbon group of the copolymer has the following group:
(1) adamantane and its derivatives (2) norbornane and its derivatives (3) perhydroanthracene and its derivatives (4) perhydronaphthalene and its derivatives (5) tricyclo [5.2.1.0 ^2,6 ] decane and Derivatives thereof (6) Bicyclohexane and derivatives thereof (7) Spiro [4,4] nonane and derivatives thereof (8) A member selected from spiro [4,5] decane and derivatives thereof Item 19. A pattern forming method according to Item 18.   The acid-sensitive compound of the resist material is a non-polymerized compound, and an alkali-soluble polymer or copolymer is used in combination with the compound. Pattern forming method.