JPH0973173A - Resist material and resist pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resist material having high transmittance to various radioactive rays including excimer laser and superior dry etching resistance and suppressing cracking at the time of development and the peeling of a pattern by incorporating a specified acidsensitive compd. and an acid generating agent which generates an acid when exposed with radiation. SOLUTION: This resist material contains an acid-sensitive compd. contg. structural units each having an alkali-soluble group protected with a part contg. an alicyclic hydrocarbon group represented by formula I, II, etc., and an acid generating agent which generates an acid when exposed with radiation. The alkali-soluble group is released by the generated acid and makes the acid- sensitive compd. alkali-soluble. In the formulae I, II, each of R1 and R11 is optionally substd. straight chain or branched chain 1-4C alkyl, Z is plural atoms required to complete alicyclic hydrocarbon in combination with C and at least one of R11 's is alicyclic hydrocarbon.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist material, and more specifically 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 novel resist material. Since the pattern forming method according to the present invention is particularly effective in reducing the occurrence of cracks and the peeling of patterns during the development of resist patterns, it can be advantageously used in the manufacture of semiconductor devices such as semiconductor integrated circuits.

[0002]

2. Description of the Related Art In recent years, integration of semiconductor integrated circuits has progressed, and LSIs and VLSIs have been put into practical use. At the same time, the minimum pattern of an integrated circuit has been in the submicron region and has been further miniaturized. . To form a fine pattern, cover the substrate on which the thin film is formed with a resist,
After forming a latent image of a desired pattern by performing selective exposure, it is developed to form a resist pattern, dry etching is performed using this as a mask, and then the resist is removed to use the lithography technique to obtain the desired pattern. Required. The g-line (wavelength 436 nm) and the i-line (wavelength 36
Ultraviolet light of 5 nm) is used, but with the miniaturization of patterns, far ultraviolet light, vacuum ultraviolet light, electron beams, X-rays, and the like having shorter wavelengths have been used as light sources. Particularly recently, excimer laser (K of wavelength 248 nm)
An rF laser (ArF laser having a wavelength of 193 nm) has been attracting attention as a light source, and is expected to be effective for forming a fine pattern. In this specification, when the term “radiation” is used, light from these various light sources, that is, ultraviolet rays, far ultraviolet rays, vacuum ultraviolet rays, electron beams (E
B), X-rays, various laser beams, and the like.

In order to form a submicron pattern using exposure light in the far ultraviolet / vacuum ultraviolet region, which is a shorter wavelength, it is necessary that the resist used has excellent transparency at the wavelength of the exposure light. In addition, it is required to have sufficient dry etching resistance. As such a resist, the present inventors have invented, for example, a radiation-sensitive material characterized by comprising a polymer or copolymer of an acrylic acid ester or an α-substituted acrylic acid ester having an adamantane skeleton in the ester part. Already applied for a patent (see Japanese Patent Application Laid-Open No. 4-39665).
In addition, the inventors of the present invention provide, as a similar resist, a chemically amplified radiation-sensitive material comprising a polymer or copolymer of acrylic acid ester or α-substituted acrylic acid ester having a norbornane skeleton in the ester portion. Invented (see Japanese Patent Application Laid-Open No. 5-257284).

[0004]

SUMMARY OF THE INVENTION The chemically amplified resist and the pattern forming method using the same, which the inventors of the present invention have previously invented, have light from various light sources, particularly wavelengths in the deep ultraviolet and vacuum ultraviolet regions. Not only has high transparency to excimer light, but also excellent dry etching resistance.
However, these resists, when used in thick film,
Even when developing is performed using a developing solution having a high solubility, cracks and pattern peeling easily occur depending on the application conditions applied, and stable patterning characteristics cannot be obtained. Although the exact reason why such a defect is caused is unknown, the alicyclic hydrocarbon portion contained in the skeleton structure of the resist is highly hydrophobic and rigid, so that the resist film is not easily formed during development. It is understood that one of the causes is that the strain applied to the surface becomes large.

Further, as a result of the presence of the alicyclic hydrocarbon moiety as described above, there is also a drawback in that an alkaline 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 structure of the resist has strong hydrophobicity and thus prevents dissolution of the resist in the alkali developing solution. In order to solve the problem associated with the use of an alkaline developer, the present inventors have found that a repeating unit having a protected alkali-soluble group and eliminating the protecting group with an acid makes the compound alkali-soluble. After exposure, a resist containing a polymer or a copolymer containing the above and an acid generator that generates an acid by radiation exposure is developed with a developer containing an aqueous solution or alcohol solution of a specific ammonium compound or morpholine compound. We found a method of forming a resist pattern characterized by
Please refer to the specification of Japanese Patent Application No. 7-23053 filed on Oct. 10).

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

As can be understood from the above description, in improving the chemically amplified resist and the pattern forming method using the same, usually, the approach for improving the resist material itself and the developing solution used in the resist process are improved. There are two approaches taken. The present invention aims to improve the resist material itself in consideration of various conditions.

Accordingly, one object of the present invention is, therefore, to have high transparency to various radiations including excimer light, to have excellent dry etching resistance, to generate cracks during development and to remove patterns. It is an object of the present invention to provide an improved chemically amplified resist which has reduced patterning, that is, exhibits stable patterning characteristics. Another object of the present invention is to provide an improved chemically amplified resist which has good adhesion to a substrate and can faithfully reproduce a pattern corresponding to a mask pattern.

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

[0010]

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

[0011]

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(In the above formula, R _I represents a linear or branched alkyl group having 1 to 4 carbon atoms,
May be substituted or unsubstituted, and Z
Represents a plurality of atoms necessary for completing the alicyclic hydrocarbon group together with the indicated carbon atom)

[0013]

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

[0015]

[Chemical formula 26]

(In the above formula, R _II is as defined above)

[0017]

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

[0019]

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(In the above formula, R _II is as defined above)

[0021]

[Chemical 29]

A structure having an alkali-soluble group protected by R ₁ and Z (wherein R _I and Z are the same as defined above), and the alkali-soluble group is eliminated by an acid to render the compound alkali-soluble. A resist material comprising an acid-sensitive compound containing a unit and an acid generator that generates an acid upon exposure to radiation.

In another of its aspects, the present invention has an alkali-soluble group protected by an alicyclic hydrocarbon group-containing moiety represented by any of the above formulas (I) to (VI), and A resist material containing an acid-sensitive compound containing a structural unit that makes the compound alkali-soluble by leaving the alkali-soluble group by an acid and an acid generator that generates an acid upon exposure to radiation is coated on a substrate to be treated. Then, the resist film on the substrate to be processed is selectively exposed to radiation capable of inducing generation of acid from the acid generator, and after the resist film is post-baked after exposure, the resist film is formed in the exposure step. There is provided a method for forming a resist pattern, which comprises developing a latent image.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the present invention has an alkali-soluble group protected by an alicyclic hydrocarbon group-containing moiety represented by any of the above formulas (I) to (VI). Further, there is provided a resist material comprising an acid-sensitive compound containing a structural unit capable of eliminating the alkali-soluble group by an acid to make the compound alkali-soluble, and an acid generator which generates an acid upon exposure to radiation.

In the above formula (I), R _I is preferably substituted or unsubstituted, 1 to
Straight-chain or branched-chain alkyl groups with 4 carbon atoms, for example methyl or ethyl groups, which are notable in that they become more hydrophobic as the number of carbon atoms increases further. However, there is a problem that the elimination of the group cannot be satisfactorily achieved. Also, when such an alkyl group is substituted, suitable substituents are, for example, halogen, such as chlorine, fluorine, iodine and the like. From the viewpoint of stability of alkali-soluble group,
It is desirable to avoid the use of strongly polar substituents. Moreover, the definition about the alkyl group can be basically similarly 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 one of the main components includes various groups well known in the technical field, but generally, 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, oxazone group, pyrrolidone group, hydroxyoxime group and the like, preferably a carboxylic acid group,
Sulfonic acid groups, amide groups, imide groups, and phenol groups.

Further, in the resist material of the present invention, the above alkali-soluble group is protected by the alicyclic hydrocarbon group-containing portion. The protected alkali-soluble group is preferably a carboxylic acid represented by the following formulas (VII) to (XI):

[0027]

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[0028]

[Chemical 31]

[0029]

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[0030]

[Chemical 33]

[0031]

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(Wherein R _I , R _II and R _III and Z
Are the same as defined above, respectively, and the following formula (XII)
An imide group represented by:

[0033]

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

[0035]

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Where Z is as defined above. The alicyclic hydrocarbon group contained in the alkali-soluble group includes various groups known in the field of chemistry, and those groups may be optionally substituted, Preferably, as described in detail below, it has a plurality of ring structures or a fused ring. The alicyclic hydrocarbon group is particularly preferably
It is adamantane or its derivative.

The acid-sensitive compound used in the present invention, which is sensitive to the acid generated from the acid generator used in combination, can be any compound as long as the conditions described above are satisfied.
It covers a wide range of compounds, from low molecular weight compounds to high molecular weight compounds, and these compounds may be used alone or else may be used as a mixture of two or more compounds. May be. Such acid-sensitive compounds are broadly classified into polymers or copolymers containing the above structural unit as a repeating unit, and low molecular weight non-polymerized compounds. Such an acid-sensitive compound, when it takes the form of a polymer or a copolymer, can have a wide range of molecular weights from low molecular weight to high molecular weight, and is preferably an acrylic acid ester and its derivative, It has repeating units selected from the group consisting of itaconic acid ester and its derivative, fumaric acid ester and its derivative, styrene-substituted compound and its derivative, alone or in combination. When the acid-sensitive compound is in the form of a non-polymerized compound, it is necessary to use an arbitrary alkali-soluble polymer or copolymer in combination with the compound in order to obtain 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 such cases include, but are not limited to, those listed below, including tertiary carbon esters, 3-oxoesters, acetal esters, carboxy ethers, and the like. Also, such additional acid-sensitive compounds may preferably contain alkali-soluble groups as listed below: carboxylic acid groups, sulfonic acid groups, amide groups, imide groups, phenolic groups, acid anhydrides. Group, thiol group, lactone acid 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, hydroxyl group, thioether group and the like.

In the chemically amplified resist material, if the structure contains an alicyclic hydrocarbon group, its strong hydrophobicity makes it possible to develop the resist material in an aqueous alkaline solution after exposure. It is considered that dissolution of the exposed area in the alkaline aqueous solution is suppressed. Therefore, as a deprotecting group (a protected alkali-soluble group that can be removed from the resist structure by an acid) to be contained in the resist structure, one having an alicyclic group is used to perform exposure and PEB ( Post-exposure bake; Post Exp
It is preferable that the alicyclic group is removed from the exposed portion by desorbing the alicyclic group by exposure baking). However, since the alicyclic group has a ring structure, the bond angle is fixed, and it is difficult to form a product having a double bond after elimination of the group. Moreover, the elimination reaction did not easily occur. In order to solve this problem, the present inventors, as described above, have an alicyclic group represented by the above formula (I) in a part of the deprotecting group contained in the resist structure and It has been found that it is effective to make the deprotecting group 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 became possible to facilitate the elimination of the group. This is not meant to constrain the invention by the following description, but it is believed that double bonds, which are believed to be formed upon removal of the group, are formed outside the ring where "bond strain" is small. It is expected that it will be possible.

Thus, the resist material having the structure represented by the above formula (I) undergoes an elimination reaction using the protonic acid generated by exposure as a catalyst to generate a carboxylic acid or its analogue, and at the same time The portion of the alicyclic group is removed. Therefore, in the exposed part of the resist material,
The alicyclic group has no effect of inhibiting dissolution, and can be easily dissolved in an alkaline aqueous solution. As a result, the development of the resist material proceeds smoothly, and desired stable patterning characteristics can be obtained.

Further, in the chemically amplified resist in which the alicyclic hydrocarbon group directly forms an ester with the carbon forming the ring structure, the rigidity due to the alicyclic hydrocarbon group should be sufficiently reduced. It seems that you cannot do it. It can be predicted that this is one of the causes of cracks and peeling when strain is likely to occur during development due to an increase in the thickness of the resist film. In order to solve this problem, the present inventors have found that it is effective to introduce the 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 the alicyclic group is included, the ring structure does not directly form an ester, but forms an ester through at least one atom.
In this case, the carbon atom is the most common as an intervening atom, but it is not limited as long as it does 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 made rigid by moving it away from the main chain. It is expected that it has become possible to ease gender.

Thus, the resist material having the structure represented by the above formulas (II) to (VI) causes an elimination reaction by using the protonic acid generated by exposure as a catalyst to form a carboxylic acid or its analogue. , The alicyclic group portion of the exposed portion is removed. For this reason, in the exposed portion of the resist material, the effect of inhibiting dissolution by the alicyclic group is eliminated, and the resist material can be easily dissolved in an aqueous alkaline solution. As a result, the development of the resist material proceeds smoothly, and desired stable patterning characteristics can be obtained. Up to now, the same applies to the case of the resist material having the structure represented by the above formula (I). In addition, with this particular resist material,
Since the alicyclic hydrocarbon group is distant from the main chain as described above, the rigidity of the obtained resist film is reduced, and the influence of strain generated in the resist film during development is reduced. For this reason, cracks and peeling are less likely to occur during development, 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 (wherein a protected alkali-soluble group is eliminated by an acid to become alkali-soluble). What is a "copolymer"?
A chemically amplified resist having a combination of a three-component or multi-component copolymer) or a non-polymerized compound and an acid generator. Hereinafter, such a chemically amplified resist, its preparation, and formation of a resist pattern using the same 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 which is one of the main components is preferably a carboxylic acid group, a sulfonic acid group or an amide group. , A member selected from the group consisting of an imide group and a phenol group,
More preferably, it is a carboxylic acid represented by the above formulas (VII) to (XI), an imide group represented by the following formula (XII), and a phenol group represented by the above formula (XIII).

For example, a carboxylic acid group serving as a protected alkali-soluble group is a unit which produces a carboxylic acid upon elimination of the protecting group from an acid, and examples thereof include t-butyl ester, t-amyl ester, α, α. -A tertiary carbon ester such as dimethylbenzyl ester, an acetal ester such as tetrahydropyranyl ester, a β-oxyketone ester such as 3-oxycyclohexyl ester, and the like.

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

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, An ester formed from an α-oxyalkene or an α-oxycycloalkene, and the like 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 resist. Suitable alicyclic hydrocarbon groups are, for example, those having the following compounds 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 thereof (6) Bicyclohexane and its derivatives (7) Spiro [4,4] nonane and its derivatives (8) Spiro [4,5] decane and its derivatives These compounds have the following structural formulas, respectively. expressed:

[0049]

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In the practice of the present invention, the alicyclic hydrocarbon is preferably one having a plurality of ring structures or a condensed ring as described above, and a monocyclic cyclohexyl group is sufficient. Dry etching resistance cannot be obtained. Also among these compounds,
A condensed ring of adamantane or the like is particularly preferable in order to obtain a dry etching resistance equal to or higher than that of the conventional novolac-based 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 various types and used. The acid-sensitive polymer or copolymer is not limited to those listed below, but preferably, acrylic acid ester and its derivative, itaconic acid ester and its derivative, fumaric acid ester and its derivative, and styrene. It has repeating units (structural units) selected from the group consisting of substitution products and derivatives thereof alone or in combination. Because these repeating units are
This is because it is more advantageous than other polymers or copolymers in terms of preparation of the polymer or copolymer and its coatability.

The acid-sensitive copolymer is not limited to those listed below in combination with the repeating unit as described above, if necessary, but other repeating units such as acrylonitrile may be used. , Olefins, dienes or their derivatives. In the acid-sensitive polymer or copolymer of the present invention,
In order to obtain satisfactory adhesion, it is preferable to use a repeating unit having a strong polarity. In particular, such a polymer or copolymer, in addition to having an alkali-soluble group which is an essential component, if it has a repeating unit which is itself alkali-soluble, a small amount derived from the alkali-soluble group It is expected that development will be possible by the generation of carboxylic acid and the like, which is more preferable.

According to the invention, therefore, the acid-sensitive compound as a component of the resist material is in the form of a copolymer, the repeating units of which, in addition to the structural units mentioned above, are alkali-soluble. A resist material comprising a repeating unit having a group in a side chain and / or an additional protected alkali-soluble group capable of leaving by an acid generated from the acid generator in a side chain is provided. To be done.

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

[0055]

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[0056]

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In the above formula, R may be the same or different and represents hydrogen, halogen or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, and R _I is , A linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted, A represents an acid-eliminating protecting group, and Z represents , Represents a plurality of atoms necessary to complete an alicyclic hydrocarbon group together with the described carbon atom.

The structural unit of the above formula (XIV) has an alicyclic skeleton such as adamantane or norbornane and has a protecting group capable of leaving by an acid generated from an acid generator and an alkali-soluble carboxylic acid group. This is an example of including them in combination. Since an acidic group is present in the structure of the resist, the exposed portion after the exposure is smoothly dissolved into the alkali developing solution. Further, if the content of the acidic group is controlled, development can be performed even with an alkali developer (a 2.38% aqueous solution of tetramethylammonium hydroxide) which is currently standardized. In this case, the content of the unit containing the carboxylic acid in the resist is preferably 5 mol% or more and less than 2 mol%.

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

By the way, the following formula (XIV) or (X
The substituent R _I in V) may be a methyl group, an ethyl group, a halogenated (chlorinated, brominated, etc.) product thereof, and the like, as described above. In addition, the protecting group A which can be removed by an acid is, as described above, a usual protecting group such as a quaternary carbon group or a β-oxyketone group such as t.
-Butyl group, t-amyl group, 3-oxycyclohexyl group and the like. The alicyclic hydrocarbon group completed by Z is preferably adamantane and its derivatives, norbornane and its derivatives, perhydroanthracene and its derivatives, perhydronaphthalene and its Derivatives, tricyclo [5.2.1.0 ^2,6 ] decane and its derivatives, bicyclohexane and its derivatives, spiro [4,4] nonane and its derivatives, spiro [4,5] decane and its derivatives, etc. .

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. The acid-sensitive polymer preferably has the following formula (XVI)
Is a meta (acrylate) polymer represented by

[0062]

[Chemical 40]

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

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

[0065]

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[0066]

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In the above formula, R, A and n are respectively as defined above, and Y is an optional substituent, preferably an alkyl group such as t-butyl group, an ether group such as t-butyl group. Alicyclic groups such as phenoxy group,
For example, adamantyl, norbornyl, cyclohexyl,
Tricyclo [5.2.1.0] decane or the like, or a group represented by the following formula:

[0068]

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

[0070]

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Wherein R ⁴ in substituent D is hydrogen or a substituted or unsubstituted alkyl group such as a methyl group or an ethyl group, and 1 and m are each of any positive value. Represents an integer. Acid-sensitive copolymers that can be advantageously used in the present invention include, but are not limited to the following, more specifically, the following. Note that m and n in the formula are the same as defined above.

[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

[Chemical 51]

[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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The above-mentioned acid-sensitive polymer or copolymer is
If necessary, an alkali-soluble polymer or copolymer,
For example, a novolac resin, a phenol resin, an imide resin, a carboxylic acid-containing resin, and the like may be additionally contained. Furthermore, in carrying out the present invention, instead of the acid-sensitive polymer or copolymer as described above, a low-molecular compound that has not been polymerized (in the present specification, particularly, "non-polymerized compound") Can be used for the same purpose. The non-polymerizable compound used here is an acid-sensitive compound in which the protected alkali-soluble group is eliminated by an acid to become alkali-soluble, as described above, and has the above formulas (I) to (VI) in its molecule. It is not particularly limited as long as it has a protected alkali-soluble group containing the moiety shown and exhibits the described behavior. Generally, 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, and the like, and a part of these skeletons is represented by the formula (I). ~ (V
It is substituted with a group containing the moiety represented by I). When an example of a preferable non-polymerized compound is represented by the general formula,
Although not limited to those listed below, the following compounds are included. In the formula below, R _I , R _II , Z and n are the same as defined above.

[0087]

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[0088]

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[0089]

[Chemical formula 61]

[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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In addition, these non-polymerizable compounds may contain, in addition to the group containing the moiety represented by the above formulas (I) to (VI), other protective groups thereof may be eliminated by an acid, if necessary. Units that generate carboxylic acid and the like, for example, tertiary carbon esters such as t-butyl ester, t-amyl ester, α, α-dimethylbenzyl ester, acetal ester such as tetrahydropyranyl ester, 3-oxycyclohexyl ester, etc. It may have an ester composed of β-oxyketone, and the like.

Since these non-polymerized compounds cannot exhibit the desired resist properties by themselves, it is necessary to use an alkali-soluble polymer or copolymer together. The alkali-soluble polymer or copolymer that can be used here is not limited to those described below, for example, a novolak resin,
Includes phenolic resins, imide resins, carboxylic acid containing resins, and others. The mixing ratio between the non-polymerized compound and the alkali-soluble polymer or copolymer can be changed in a wide range according to the properties of the compound used, the desired resist properties, and other factors.

The acid generator used in the chemically amplified resist of the present invention in combination with the acid-sensitive polymer or copolymer or non-polymerized compound as described above is generally used in resist chemistry. The acid generator may be a substance that generates a protonic acid upon irradiation with radiation such as ultraviolet rays, far ultraviolet rays, vacuum ultraviolet rays, electron beams, X-rays, and laser light. 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 formula: Ar-N ₂ ⁺ X ^- in (the above formula, Ar is a substituted or unsubstituted aromatic group, such as a phenyl group, or an alicyclic group, and X is halogen such as Cl, Br, I or F,
BF ₄ , BF ₆ , PF ₆ , AsF ₆ , SbF ₆ , CF ₃
SO _3, represents and ClO ₄ or an organic sulfonic acid anion) (2) iodonium salt represented by the following formula:

[0098]

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(In the above formula, Ar and X are the same as defined above.) (3) Sulfonium salt represented by the following formula:

[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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(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 or the like, R ¹ , R ² and R ³ are phenyl groups or the like, and tBu is a t-butyl group) (4) A sulfonate represented by the following formula:

[0107]

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(In the above formula, Ar and R are the same as defined above.) (5) Oxazole derivative represented by the following formula:

[0109]

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(In the above formula, X has the same meaning 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 derivatives:

[0111]

[Chemical 76]

(In the above formula, X has the same definition as described above, provided that one of the -CX ₃ groups may be a substituted or unsubstituted aryl group or alkenyl group) (7) it is disulfone _{derivatives: Ar-SO 2 -SO 2 -Ar} ( in the above formula, Ar are as defined above) (8) imide represented by the formula compound:

[0113]

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(In the above formula, X has the same meaning as defined above.) (9) Others such as oxime sulfonate, diazonaphthoquinone and benzoin tosylate. More specifically, some examples of these acid generators are the following compounds. Triphenylsulfonium hexafluoroantimonate:

[0115]

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Triphenylphosphonium hexafluorophosphate:

[0117]

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Diphenyliodohexafluorophosphate:

[0119]

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Benzoin tosylate:

[0121]

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In carrying out the present invention, a chemically amplified resist is prepared from the above-mentioned acid-sensitive compound and acid generator. For example, such a resist can be prepared in the form of a resist solution according to a conventional method using a technique generally used in resist chemistry. For example, when the acid-sensitive compound constituting the resist is a polymer or a copolymer as described above, the selected monomer for forming the polymer or the copolymer is a suitable polymerization initiator. Polymerization can be carried out in the presence, and then an acid generator can be added to the resulting polymer or copolymer solution to give 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):

[0123]

[Chemical formula 82]

MAIB (Dimethyl-2,2-azoisobisbutyrate):

[0125]

[Chemical 83]

In the preparation of the chemically amplified resist, the amount of the acid generator added to the acid sensitive compound can be varied over a wide range, and is generally about 1 to 30% by weight.
It is preferably about 1 to 15% by weight. Further, the solvent used for preparing such a resist solution can be variously changed depending on the type of the resist, coating conditions, and other factors, but preferably, for example, cyclohexane, propylene glycol monomethyl ether acetate (PGMEA). , An organic solvent such as ethyl lactate.

The method for forming a resist pattern according to the present invention can be carried out through various arbitrary steps, but preferably it can be carried out as follows. First, the solution of the chemically amplified resist prepared as described above is applied on the substrate to be processed. The substrate to be processed used here may be any substrate normally used in semiconductor devices and other devices, and specifically, silicon, oxide film, polysilicon, nitride film, aluminum, etc. may be mentioned. You can These substrates may or may not have the circuitry already built. In some cases, these substrates are preferably pretreated with an adhesion promoter such as hexamethyldisilazane (HMDS) in order to improve the adhesion to the resist.

The coating of the resist solution can be carried out by using a conventional coating device such as a spin coater, a dip coater, a roller coater or the like. Although the thickness of the formed resist film can be widely varied depending on factors such as the use of the resist film, it is usually about 0.3 to 2.
The range is 0 μm. Then, if necessary, before selectively exposing to radiation, the resist film formed in the above step is prebaked at a temperature of about 60 to 150 ° C., preferably about 60 to 100 ° C. for about 60 to 180 seconds. .
For this prebaking, a heating means such as a hot plate can be used.

If a top coat film (protective film) is further formed on the resist film, for example,
A top coat film can be obtained by applying a solution of an olefin resin onto a resist film by spin coating and performing baking at a temperature of about 100 ° C. After forming the resist film and optionally prebaking, the resist film is selectively exposed to radiation by 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. As the exposure condition, an appropriate condition can be selected each time. As a result of this selective exposure, an acid is generated from the acid generator contained in the resist film.

Then, the resist film after exposure is subjected to post-exposure baking (PEB) to cause an acid-catalyzed elimination reaction of the protective group. This post-exposure bake can be performed in the same manner as the previous pre-bake. For example, the baking temperature is about 60-150 ° C, preferably about 100-15.
0 ° C. When a top coat film is used in combination, after the post-exposure bake and before the development, it is removed by, for example, an organic solvent.

After the post-exposure bake is completed, the post-exposure resist film is liquid-developed by a conventional method. As the developer used here, an appropriate one can be arbitrarily selected from developers commonly used in this technical field. A particularly preferred developer is the above-cited JP-A-7
As proposed in -23053,
Ammonium compounds of the formula as developers:

[0132]

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(Wherein R ₁ , R ₂ , R ₃ and R ₄ are respectively
Which may be the same or different and represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms), a morpholine compound of the following formula:

[0134]

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A developing solution containing an aqueous solution or an alcohol solution of a mixture thereof. Preferred examples of the ammonium compound as the developer are not limited to those listed below, but include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), and tetrapropylammonium hydroxide (TPAH). ), Tetrabutylammonium hydroxide (TBAH), and the like.

These developers are dissolved in water or in alcohols such as methanol, etal and isopropyl alcohol to prepare a developing solution. Although the concentration of the dissolving developer can vary widely,
Generally, it will be in the range of about 0.1 to 15% by weight, preferably about 0.1 to 10% by weight. The development time is not particularly limited, but is generally about 1 to 1.
It is in the range of 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 can be understood from the above description and the following examples, in the present invention, the chemically amplified resist material is represented by the formulas (I) to (VI) in the structure thereof.
1 of carbon atoms having an alicyclic group and constituting the ring skeleton
By using a compound having a deprotecting group having a moiety in which each is substituted with an appropriate lower alkyl group or a compound having a deprotecting group whose ring skeleton is ester-bonded through one or more other atoms, Solubility increases and development progresses smoothly, so peeling and cracking of the resist film can be reduced and stable patterning characteristics can be obtained, or the rigidity due to alicyclic hydrocarbon groups can be reduced. In addition, stable patterning characteristics can be obtained.

The deprotecting group used in the present invention has been found to be particularly effective in a chemical resist consisting of an alicyclic unit and a deprotecting unit, but it can be satisfied in the case of other resists. It is possible to exert an effect. As described above, examples of the resist having a particularly remarkable effect include alicyclic groups such as adamantane and its derivatives, norbornane and its derivatives, tricyclo [5.2.1.0 ^2,6 ] decane and its derivatives. And a resin containing:

[0139]

Next, the present invention will be described with reference to some embodiments. It should be understood that the following embodiments are merely examples and the present invention is not limited thereto. Example 1 2-Methyladamantyl methacrylate monomer and t-butyl monomer acrylate were charged into a polymerization vessel at a ratio of 4: 6 to prepare a 2 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN (azoisobutyronitrile), was added to this 1,4-dioxane solution in an amount of 5 mol%, and the mixture was heated to 80 ° C.
Was allowed to polymerize for about 8 hours. After completion of the polymerization, n-
Purification was performed using hexane as a precipitant. A 2-methyladamantyl methacrylate / t-butyl acrylate copolymer represented by the following formula was obtained.

[0140]

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The obtained 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 above, 15% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate, was added and dissolved in cyclohexanone. The obtained resist solution was applied on a silicon substrate pretreated with hexamethyldisilazane (HMDS) to a film thickness of 0.
Spin coated at 7μm and 100 ℃ on a hot plate
And prebaked for 100 seconds.

After the completion of prebaking, the obtained resist film was changed to KrF excimer stepper (manufactured by Nikon Corporation, NA = 0.4).
In step 5), a pattern of KrF laser light having a wavelength of 248 nm was selectively exposed. Then, the resist film after exposure is exposed to 6 ° C. at 130 ° C.
PEB (bake after exposure) was performed for 0 second. Then, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 21.2 mJ / cm ² , and the resolution is 0.275 μm L & S (line and space).
Met. Example 3 The procedure described in Example 2 above was repeated. However, in this example,
As the developing solution, a tetrabutylammonium hydroxide (TBAH) aqueous solution having the same concentration (0.27N) was used instead of the 0.27N TMAH aqueous solution. The same satisfactory resist pattern as in the case of Example 2 above is Eth = 2
It was obtained at a resolution of 0.275 μm L & S at 8.6 mJ / cm ² . Example 4 (Comparative Example) The procedure described in Examples 1 and 2 was repeated. However, in this example, for comparison, the composition ratio (m: n) is represented by the following formula by the method described in Example 1 above, the composition ratio (m: n) is 53:47, the weight average molecular weight (Mw) is 3830, and the dispersity ( Mw /
Mn) adamantyl methacrylate / t-butyl acrylate copolymer with 2.1:

[0143]

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Was prepared. A resist process was carried out as described in Example 2 above using the resulting copolymer, but no pattern was obtained. Example 5 2-Methyladamantyl acrylate monomer was charged into a polymerization vessel to prepare a 2 mol / L toluene solution. A polymerization initiator, AIBN, was added to this toluene solution in an amount of 2 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, methanol was used as a precipitant for purification. A 2-methyladamantyl acrylate polymer represented by the following formula (where n is the number of repeating units necessary for obtaining the following molecular weight) was obtained.

[0145]

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The obtained polymer had a weight average molecular weight (M
w) is 8950, and dispersity (Mw / Mn) is 1.8.
Met. Example 6 To the 2-methyladamantyl acrylate polymer prepared in Example 5 above was added 15% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate,
Dissolved in cyclohexanone. The obtained resist solution was spin-coated on a silicon substrate pretreated with hexamethyldisilazane (HMDS) to a thickness of 0.7 μm, and prebaked on a hot plate at 100 ° C. for 100 seconds.

After the completion of prebaking, the obtained resist film was changed to KrF excimer stepper (manufactured by Nikon Corporation, NA = 0.4).
In step 5), a pattern of KrF laser light having a wavelength of 248 nm was selectively exposed. Then, the resist film after exposure is exposed to 6 ° C. at 130 ° C.
PEB (bake after exposure) was performed for 0 second. Then, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 32 mJ / cm ² , and the resolving power is 0.
It was 30 μm L & S. Example 7 2-Methyladamantyl methacrylate and 3-oxocyclohexyl methacrylate were charged in a polymerization container 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, methanol was used as a precipitant for purification. A 2-methyladamantyl methacrylate / 3-oxocyclohexyl methacrylate copolymer represented by the following formula was obtained.

[0148]

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

After completion of the prebaking, the obtained resist film was changed to KrF excimer stepper (manufactured by Nikon Corporation, NA = 0.4).
In step 5), a pattern of KrF laser light having a wavelength of 248 nm was selectively exposed. Then, the resist film after exposure is exposed to 150 ° C.
PEB (bake after exposure) was performed for 0 second. Then, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 9.6 mJ / cm ² , and the resolution was 0.275 μm L & S. Example 9 4-Methyladamantyl Methacrylate Monomer and 3-oxo-1,1-Dimethylputyl Monomer Methacrylate 4:
It was charged into a polymerization vessel at a ratio of 6 to obtain a 2 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to this dioxane 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 n-hexane as a precipitating agent. 2 represented by the following formula
Methyl adamantyl methacrylate / 3-oxo-1,
A 1-dimethylbutyl methacrylate copolymer was obtained.

[0151]

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The obtained 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 above, 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate, was added to cyclohexanone. Dissolved. The obtained resist solution was spin-coated on a silicon substrate pretreated with hexamethyldisilazane (HMDS) to a film thickness of 0.7 μm,
Prebaked at 100 ° C. for 100 seconds on a hot plate.

After the completion of prebaking, the obtained resist film was changed to KrF excimer stepper (manufactured by Nikon Corporation, NA = 0.4).
In step 5), a pattern of KrF laser light having a wavelength of 248 nm was selectively exposed. Then, the resist film after exposure is exposed to 6 ° C. at 130 ° C.
PEB (bake after exposure) was performed for 0 second. Then, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 32 mJ / cm ² , and the resolving power is 0.
325 μm L & S. Example 11 4 -Methyl adamantyl methacrylate and methyl 3-methacryloyloxybutyrate methacrylate 4: 4
It was charged into a polymerization vessel at a ratio of 6 to obtain a 2 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to this dioxane solution in an amount of 2 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. 2 represented by the following formula
A methyl adamantyl methacrylate / 3-methacryloyloxybutyric acid methyl methacrylate copolymer was obtained.

[0154]

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

After the completion of prebaking, the obtained resist film was changed to KrF excimer stepper (manufactured by Nikon Corporation, NA = 0.4).
In step 5), a pattern of KrF laser light having a wavelength of 248 nm was selectively exposed. Then, the resist film after exposure is exposed to 6 ° C. at 130 ° C.
PEB (bake after exposure) was performed for 0 second. Then, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 29 mJ / cm ² , and the resolving power is 0.
It was 30 μm L & S. Example 13 The procedure described in Example 11 above was repeated, and the composition ratio (m: n) was represented by the following formula: 55:45, the weight average molecular weight (Mw) was 11520, and the dispersity (Mw / M).
n) 2.38 2-methyladamantyl methacrylate / 2-hydroxyethyl methacrylate copolymer:

[0157]

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Was prepared. Next, 15% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate, was added to the 2-methyladamantyl methacrylate / 2-hydroxyethyl methacrylate copolymer prepared as described above and dissolved in cyclohexanone.
The obtained resist solution was treated with hexamethyldisilazane (H
0.7μm film thickness on silicon substrate pre-treated with MDS)
Spin coat at 10 ° C on a hot plate at 100 ° C
Prebaked for 0 seconds.

After the completion of prebaking, the obtained resist film was changed to KrF excimer stepper (manufactured by Nikon Corporation, NA = 0.4).
In step 5), a pattern of KrF laser light having a wavelength of 248 nm was selectively exposed. Then, the resist film after exposure is exposed to 6 ° C. at 130 ° C.
PEB (bake after exposure) was performed for 0 second. Then, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 12 mJ / cm ² , and the resolving power is 0.
325 μm L & S. Example 14 2-Methylcyclohexyl methacrylate and 3-oxocyclohexyl methacrylate were charged into a polymerization vessel 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, methanol was used as a precipitant for purification. A 2-methylcyclohexyl methacrylate / 3-oxocyclohexyl methacrylate copolymer represented by the following formula was obtained.

[0160]

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

After the completion of prebaking, the obtained resist film was changed to KrF excimer stepper (manufactured by Nikon Corporation, NA = 0.4).
In step 5), a pattern of KrF laser light having a wavelength of 248 nm was selectively exposed. Then, the resist film after exposure is exposed to 6 ° C. at 130 ° C.
PEB (bake after exposure) was performed for 0 second. Then, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 7.2 mJ / cm ² , and the resolution was 0.275 μm L & S. Example 16 2-Methyladamantylmethacrylate / 3-oxocyclohexylmethacrylate copolymer prepared in Example 7 above with 5% by weight of acid generator, represented by the formula 2
-Oxocyclohexylmethylcyclohexylsulfonium trichlorosulfonate:

[0163]

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Was added and dissolved in cyclohexanone.
The obtained resist solution was treated with hexamethyldisilazane (H
0.7μm film thickness on silicon substrate pre-treated with MDS)
Spin coat at 10 ° C on a hot plate at 100 ° C
Prebaked for 0 seconds. After the completion of prebaking, the obtained resist film was exposed to an ArF exposure device (manufactured by Nikon Corporation, NA = 0.
At 55), selective exposure was performed to an ArF laser beam pattern having a wavelength of 193 nm. Subsequently, the resist film after exposure was PEB (post-exposure bake) at 130 ° C. for 60 seconds. Then, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 6 mJ / cm ² , and the resolving power is 0.
It was 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):

[0165]

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2% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate, was added to and dissolved in cyclohexanone. The obtained resist solution was spin-coated on a silicon substrate pretreated with hexamethyldisilazane (HMDS) to a thickness of 0.7 μm, and prebaked on a hot plate at 100 ° C. for 100 seconds. After completion of the pre-baking, the obtained resist film was irradiated with a KrF excimer stepper (manufactured by Nikon Corporation, NA = 0.45) at a wavelength of 248.
The pattern was selectively exposed to a pattern of a KrF laser beam of nm. Next, the exposed resist film is PEB at 130 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is 0.27
N tetramethylammonium hydroxide (TMA
H) The solution was developed for 60 seconds with an aqueous solution, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy E of the irradiation dose in this example
th is 82 mJ / cm ² , and resolution is 0.325 μm.
It was L & S. Example 18 Polyvinylphenol represented by the following formula, wherein the 2-methyladamantyl acrylate polymer prepared in the above Example 5, weight average molecular weight (Mw) = 8950 and dispersity = 1.8, weight average molecular weight (Mw) = 5150 And dispersity = 2.8:

[0167]

[Chemical 96]

20% by weight was added to the above, 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 on a silicon substrate pretreated with hexamethyldisilazane (HMDS) to a thickness of 0.7 μm, and prebaked on a hot plate at 100 ° C. for 100 seconds.

After completion of the prebaking, the obtained resist film was changed to KrF excimer stepper (manufactured by Nikon Corporation, NA = 0.4).
In step 5), a pattern of KrF laser light having a wavelength of 248 nm was selectively exposed. Then, the resist film after exposure is exposed to 110 ° C. for 6 minutes.
PEB (bake after exposure) was performed for 0 second. Then, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 8.9 mJ / cm ² , and the resolution was 0.325 μm L & S. Example 19 The same polyvinylphenol used in Example 18 above,
Weight average molecular weight (Mw) = 5150 and dispersity = 2.
1-adamantylcarboxylic acid 2-methyladamantyl ester represented by the following formula:

[0170]

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Was added at a rate of 30% 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 on a silicon substrate pretreated with hexamethyldisilazane (HMDS) to a thickness of 0.7 μm, and prebaked on a hot plate at 100 ° C. for 100 seconds.

After the completion of prebaking, the obtained resist film was changed to KrF excimer stepper (manufactured by Nikon Corporation, NA = 0.4).
In step 5), a pattern of KrF laser light having a wavelength of 248 nm was selectively exposed. Then, the resist film after exposure is exposed to 110 ° C. for 6 minutes.
PEB (bake after exposure) was performed for 0 second. Then, the resist film was developed with a 0.27N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 11 mJ / cm ² , and the resolving power is 0.
It was 35 μm L & S. Example 20 Represented by the following formula and having a composition ratio (m: n) of 5: 5,
Then, a copolymer having a weight average molecular weight (Mw) of 23000 was prepared.

[0173]

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2% by weight of the copolymer, triphenylsulfonium triflate (TPS), was added to this copolymer.
SO ₃ CF ₃ ) was added and dissolved in ethyl lactate (EL) so that the copolymer concentration was 15% by weight. The obtained resist solution was spin-coated on a silicon substrate pretreated with hexamethyldisilazane (HMDS), and prebaked on a hot plate at 100 ° C. for 1 minute. Film thickness 1.
A resist film of 0 μm was obtained.

After completion of the prebaking, the obtained resist film is formed into an ArF excimer laser contact aligner (NA = NA).
0.55) was selectively exposed to a pattern of ArF laser light having a wavelength of 193 nm. Then, the resist film immediately after the exposure is
PEB (post-exposure bake) for 60 seconds on a 0 ° C. hot plate. After that, the resist film was developed for 60 seconds with MMD-3, an alkaline developer manufactured by Tokyo Ohka Kogyo Co., Ltd., and rinsed with pure water for 30 seconds. A resist pattern according to the mask size used for exposure was obtained without causing cracking or peeling of the pattern. Resolution is 0.50 μm L & S
(Line and space). 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, having a composition ratio (m: n) of 5: 5 and a weight average molecular weight (Mw) of 14,000 was prepared.

[0176]

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0.50 μm L & S (line and
Although a resist pattern was obtained with the resolution of (space), cracks were generated around the pattern. Example 22 The procedure described in Example 20 above was repeated. However, in this example, the composition ratio (m: n) represented by the following equation is 5:
5, and a copolymer having a weight average molecular weight (Mw) of 18,000 was prepared.

[0178]

[Chemical 100]

A resist pattern corresponding to the mask size used for exposure was obtained without causing pattern cracking or peeling. The resolution was 0.50 μm L & S (line and space). Example 23 The procedure described in Example 20 above was repeated. However, in this example, the composition ratio (m: n) represented by the following equation is 5:
5, and a copolymer having a weight average molecular weight (Mw) of 11,000 was prepared.

[0180]

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A resist pattern corresponding to the mask size used for exposure was obtained without causing pattern cracking or peeling. The resolution was 0.50 μm L & S (line and space). Example 24 The procedure described in Example 20 above was repeated. However, in this example, the composition ratio (m: n) represented by the following equation is 5:
5, and a copolymer having a weight average molecular weight (Mw) of 8000 was prepared.

[0182]

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A resist pattern corresponding to the mask size used for exposure was obtained without causing cracks or peeling of the pattern. The resolution was 0.50 μm L & S (line and space). Example 25 The procedure described in Example 20 above was repeated. However, in this example, the composition ratio (m: n) represented by the following equation is 5:
5, and a copolymer having a weight average molecular weight (Mw) of 9000 was prepared.

[0184]

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A resist pattern corresponding to the mask size used for exposure was obtained without causing cracks or peeling of the pattern. The resolution was 0.50 μm L & S (line and space). Example 26 The procedure described in Example 20 above was repeated. However, in this example, the composition ratio (m: n) represented by the following equation is 5:
5, and a copolymer having a weight average molecular weight (Mw) of 7800 was prepared.

[0186]

[Chemical 104]

A resist pattern according to the mask size used for exposure was obtained without causing cracks or peeling of the pattern. The resolution was 0.50 μm L & S (line and space). Example 27 The procedure described in Example 20 above was repeated. However, in this example, the composition ratio (m: n) represented by the following equation is 5:
5, and a copolymer having a weight average molecular weight (Mw) of 6500 was prepared.

[0188]

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A resist pattern corresponding to the mask size used for exposure was obtained without cracking or peeling of the pattern. The resolution was 0.50 μm L & S (line and space). Example 28 The procedure described in Example 20 above was repeated. However, in this example, the composition ratio (m: n) represented by the following equation is 5:
5, and a copolymer having a weight average molecular weight (Mw) of 16000 was prepared.

[0190]

[Chemical formula 106]

A resist pattern corresponding to the mask size used for exposure was obtained without causing cracks or peeling of the pattern. The resolution was 0.60 μm L & S (line and space). Example 29 The procedure described in Example 20 above was repeated. However, in this example, the composition ratio (m: n) represented by the following equation is 5:
5, and a copolymer having a weight average molecular weight (Mw) of 12,500 was prepared.

[0192]

[Chemical formula 107]

A resist pattern according to the mask size used for exposure was obtained without causing cracks or peeling of the pattern. The resolution was 0.50 μm L & S (line and space). Example 30 The procedure described in Example 20 above was repeated. However, in this example, the composition ratio (m: n) represented by the following equation is 5:
5, and a copolymer having a weight average molecular weight (Mw) of 18000 was prepared, and a far ultraviolet light contact aligner was used as an exposure source instead of the ArF excimer laser contact aligner.

[0194]

Embedded image

A resist pattern corresponding to the mask size used for exposure was obtained without causing cracks or peeling of the pattern. The resolution was 0.50 μm L & S (line and space). Example 31 The procedure described in Example 20 above was repeated. However, in this example, the composition ratio (m: n) represented by the following equation is 5:
5, and a copolymer having a weight average molecular weight (Mw) of 17500 was prepared, and a far-ultraviolet light contact aligner was used as an exposure source instead of the ArF excimer laser contact aligner.

[0196]

[Chemical 109]

A resist pattern corresponding to the mask size used for exposure was obtained without causing cracks or peeling of the pattern. The resolution was 0.55 μm L & S (line and space). Example 32 The procedure described in Example 20 above was repeated. However, in this example, the composition ratio (m: n) represented by the following equation is 5:
5, and a copolymer having a weight average molecular weight (Mw) of 9500 was prepared.

[0198]

Embedded image

A resist pattern corresponding to the mask size used for exposure was obtained without causing cracks or peeling of the pattern. The resolution was 0.60 μm L & S (line and space). Example 33 2-Methyl-2-adamantyl methacrylate monomer and methacrylate monomer were charged in a polymerization container at a ratio of 7: 3,
A 1 mol / L 1,4-dioxane solution was prepared. This one
A polymerization initiator, AIBN (azoisobutyronitrile), was added to the 4-dioxane solution in an amount of 20 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. A 2-methyl-2-adamantyl methacrylate / methacrylic acid copolymer represented by the following formula was obtained.

[0200]

[Chemical 111]

The obtained 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 2-Methyl methacrylate prepared in Example 33 above
2-adamantyl / methacrylic acid copolymer with 2% by weight of an acid generator, triphenylsulfonium triflate (T
PSSO ₃ CF ₃ ) was added and dissolved in propylene glycol monomethyl ether acetate (PGMEA). The obtained resist solution was applied to a silicon substrate pretreated with hexamethyldisilazane (HMDS) to give a film thickness of 0.4.
It was spin coated with a thickness of μm and prebaked on a hot plate at 120 ° C. for 60 seconds.

After the completion of prebaking, the obtained resist film was irradiated with an ArF excimer exposure device (NA = 0.55) at a wavelength of 1.
The pattern was selectively exposed to a 93 nm ArF laser beam pattern. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is 0.11
Develop with an 8 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and further deionize with pure water.
Rinse for 0 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 21.5 mJ / cm ² , and the resolution is 0.
It was 175 μm L & S (line and space). Example 35 The procedure described in Example 34 above was repeated. However, in this example, as the exposure apparatus, a KrF excimer stepper (NA = 0.45) is used instead of the ArF excimer exposure apparatus,
Selective exposure was performed with a KrF laser beam having a wavelength of 248 nm. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern.
The threshold energy Eth of the irradiation dose in this example is 1.4.
8 mJ / cm ² with a resolution of 0.275 μm L & S
(Line and space). Example 36 2-Methyl-2-adamantyl methacrylate monomer, t-butyl methacrylate methacrylate and methacrylic acid monomer were charged in a polymerization container at a ratio of 8: 7: 5 to prepare a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to this 1,4-dioxane solution in an amount of 20 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. A 2-methyl-2-adamantyl methacrylate / t-butyl methacrylate / methacrylic acid copolymer represented by the following formula was obtained.

[0203]

[Chemical 112]

The obtained copolymer had a composition ratio (l: m:
n) is 50:29:21 and the weight average molecular weight (Mw) is 7
800, and the dispersity (Mw / Mn) was 2.20. Example 37 2-Methyl methacrylate prepared in Example 36 above
To a 2-adamantyl / t-butyl methacrylate / methacrylic acid copolymer, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added and dissolved in propylene glycol monomethyl ether acetate (PGMEA). . The obtained resist solution was applied to a silicon substrate pretreated with HMDS to give a film thickness of 0.4.
It was spin coated with a thickness of μm and prebaked on a hot plate at 120 ° C. for 60 seconds.

After the completion of prebaking, the obtained resist film was irradiated with an ArF excimer exposure device (NA = 0.55) at a wavelength of 1.
The pattern was selectively exposed to a 93 nm ArF laser beam pattern. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is 0.11
It was developed for 60 seconds with an 8 wt% TMAH aqueous solution, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 1.4 mJ / cm ² , and the resolution was 0.170 μmL & S (line and space). Example 38 The procedure described in Example 37 above was repeated. However, in this example, as the exposure apparatus, a KrF excimer stepper (NA = 0.45) is used instead of the ArF excimer exposure apparatus,
Selective exposure was performed with a KrF laser beam having a wavelength of 248 nm. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern.
The threshold energy Eth of the irradiation dose in this example is 14.
4 mJ / cm ² and resolution is 0.250 μm L & S
(Line and space). Example 39 2-Methyl-2-adamantyl methacrylate monomer and itaconic acid monomer were charged to a polymerization vessel at a ratio of 9: 1.
A 1 mol / L 1,4-dioxane solution was prepared. This one
A polymerization initiator, AIBN, was added to the 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 precipitating agent. 2-methylmethacrylate represented by the following formula
A 2-adamantyl / itaconic acid copolymer was obtained.

[0206]

[Chemical 113]

The obtained copolymer had a composition ratio (m: n) of 88:12, a weight average molecular weight (Mw) of 6,700 and a dispersity (Mw / Mn) of 2.18. Example 40 2-Methyl methacrylate prepared in Example 39 above
2-adamantyl / itaconic acid copolymer with 2% by weight of acid generator, triphenylsulfonium triflate (TP
SSO ₃ CF ₃ ) was added and dissolved in ethyl lactate (EL). The obtained resist solution was spin-coated on a silicon substrate pretreated with HMDS to a film thickness of 0.4 μm, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After the completion of prebaking, the obtained resist film was irradiated with an ArF excimer exposure device (NA = 0.55) at a wavelength of 1.
The pattern was selectively exposed to a 93 nm ArF laser beam pattern. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is 0.11
It was developed for 60 seconds with an 8 wt% TMAH aqueous solution, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 2.8 mJ / cm ² , and the resolution was 0.175 μmL & S (line and space). Example 41 The procedure described in Example 40 above was repeated. However, in this example, as the exposure apparatus, a KrF excimer stepper (NA = 0.45) is used instead of the ArF excimer exposure apparatus,
Selective exposure was performed with a KrF laser beam having a wavelength of 248 nm. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern.
The threshold energy Eth of the irradiation dose in this example is 25.
0 mJ / cm ² with a resolution of 0.275 μm L & S
(Line and space). Example 42 2-Methyl-2-adamantyl methacrylate monomer and vinylbenzenesulfonic acid monomer were charged into a polymerization vessel at a ratio of 8: 2 to prepare a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AI, is added to the 1,4-dioxane solution.
BN was added in an amount of 20 mol% and polymerized at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. A 2-methyl-2-adamantyl methacrylate / vinylbenzenesulfonic acid copolymer represented by the following formula was obtained.

[0209]

[Chemical 114]

The obtained copolymer had a composition ratio (m: n) of 76:24, a weight average molecular weight (Mw) of 6,400, and a dispersity (Mw / Mn) of 2.42. Example 43 2-Methyl methacrylate prepared in Example 42 above
2-adamantyl / vinyl benzenesulfonic acid copolymer 2 wt% of the acid generator, was added triphenylsulfonium triflate (TPSSO ₃ CF _3), was dissolved in ethyl lactate (EL). The obtained resist solution is used for HMD
A silicon substrate pretreated with S was spin-coated with a film thickness of 0.4 μm, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the prebaking, the obtained resist film was exposed to a wavelength of 2 with a KrF excimer stepper (NA = 0.45).
It was selectively exposed to a pattern of 48 nm KrF laser light. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is 0.23
It was developed with a 6% by weight TMAH aqueous solution for 60 seconds and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 12.4 mJ / cm ² , and the resolution was 0.250 μm L & S (line and space). Example 44 2-Methyl-2-adamantyl methacrylate monomer and methacrylic acid amide monomer were charged in a polymerization container at a ratio of 7: 3 to prepare a 1 mol / L 1,4-dioxane solution.
A polymerization initiator, AIBN, was added to this 1,4-dioxane solution in an amount of 20 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. 2-methacrylic acid represented by the following formula
A methyl-2-adamantyl / methacrylic acid amide copolymer was obtained.

[0212]

[Chemical 115]

The obtained copolymer had a composition ratio (m: n) of 75:25, a weight average molecular weight (Mw) of 7,600 and a dispersity (Mw / Mn) of 2.13. Example 45 2-Methyl methacrylate prepared in Example 44 above
To the 2-adamantyl / methacrylic acid amide copolymer, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate (E
L). The obtained resist solution was spin-coated on a silicon substrate pretreated with HMDS to a film thickness of 0.4 μm, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the prebaking, the obtained resist film was subjected to a wavelength of 2 with a KrF excimer stepper (NA = 0.45).
It was selectively exposed to a pattern of 48 nm KrF laser light. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is 0.23
It was developed with a 6% by weight TMAH aqueous solution for 60 seconds and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 24.0 mJ / cm ² , and the resolution was 0.275 μm L & S (line and space). Example 46 2-Methyl-2-adamantyl methacrylate monomer and maleimide monomer were charged in a polymerization container at a ratio of 7: 3,
A 1 mol / L 1,4-dioxane solution was prepared. This one
A polymerization initiator, AIBN, was added to the 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 precipitating agent. 2-methylmethacrylate represented by the following formula
A 2-adamantyl / maleimide copolymer was obtained.

[0215]

Embedded image

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

After the completion of prebaking, the obtained resist film was exposed to a wavelength of 2 with a KrF excimer stepper (NA = 0.45).
It was selectively exposed to a pattern of 48 nm KrF laser light. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is 0.23
It was developed with a 6% by weight TMAH aqueous solution for 60 seconds and rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 30.0 mJ / cm ² , and the resolving power was 0.275 μm L & S (line and space). Example 48 2-Methyl-2-adamantyl methacrylate monomer and itaconic anhydride monomer were charged into a polymerization vessel at a ratio of 8: 2 to prepare a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, is added to the 1,4-dioxane solution in an amount of 20
It was added in an amount of mol% and polymerized at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. A 2-methyl-2-adamantyl methacrylate / itaconic anhydride copolymer represented by the following formula was obtained.

[0218]

[Chemical 117]

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

After the completion of prebaking, the obtained resist film was exposed to a wavelength of 2 with a KrF excimer stepper (NA = 0.45).
It was selectively exposed to a pattern of 48 nm KrF laser light. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is 0.11
It was developed for 60 seconds with an 8 wt% TMAH aqueous solution, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 26.1 mJ / cm ² , and the resolution was 0.275 μm L & S (line and space). Example 50 2-Methyl-2-adamantyl methacrylate and α-acrylic acid- (R)-(+)-β, β-dimethyl-
The γ-butyrolactone monomer was charged into the polymerization vessel at a ratio of 7: 3 to prepare a 1 mol / L 1,4-dioxane solution.
A polymerization initiator, AIBN, was added to this 1,4-dioxane solution in an amount of 20 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. 2-methacrylic acid represented by the following formula
Methyl-2-adamantyl / α-acrylic acid- (R)-
A (+)-β, β-dimethyl-γ-butyrolactone copolymer was obtained.

[0221]

Embedded image

The composition ratio (m: n) of the obtained copolymer was
74:26, weight average molecular weight (Mw) 6200,
And the dispersity (Mw / Mn) was 2.25.Example 51 2-Methyl methacrylate prepared in Example 50 above
2-adamantyl / α-acrylic acid- (R)-(+)-
Double in β, β-dimethyl-γ-butyrolactone copolymer
% Acid generator, triphenylsulfonium triflate
To (TPSSO _ThreeCF_Three) Is added, and ethyl lactate (E
L). The obtained resist solution is subjected to HMDS
Spin film with a thickness of 0.4 μm on a pretreated silicon substrate.
And place the plate on a hot plate for 60 seconds at 120 ° C.
I went to

After the completion of prebaking, the obtained resist film was irradiated with an ArF excimer exposure device (NA = 0.55) at a wavelength of 1.
The pattern was selectively exposed to a 93 nm ArF laser beam pattern. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is set to 2.38.
Development was carried out for 60 seconds with a TMAH aqueous solution of wt%, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 1.9 mJ / cm ² , and the resolution was 0.170 μmL & S (line and space). Example 52 The procedure described in Example 51 above was repeated. However, in this example, as the exposure apparatus, a KrF excimer stepper (NA = 0.45) is used instead of the ArF excimer exposure apparatus,
Selective exposure was performed with a KrF laser beam having a wavelength of 248 nm. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern.
The threshold energy Eth of the irradiation dose in this example is 15.
0 mJ / cm ² and resolution is 0.250 μm L & S
(Line and space). Example 53 2-Methyl-2-adamantyl methacrylate monomer and vinylhydroxyl oxime monomer were charged in a polymerization container at a ratio of 4: 6 to prepare a 1 mol / L 1,4-dioxane solution. A polymerization initiator, A, is added to the 1,4-dioxane solution.
IBN was added in an amount of 20 mol% and polymerized at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. A 2-methyl-2-adamantyl methacrylate / vinylhydroxyl oxime copolymer represented by the following formula was obtained.

[0224]

[Chemical formula 119]

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

After completion of the prebaking, the obtained resist film was subjected to a wavelength of 2 with a KrF excimer stepper (NA = 0.45).
It was selectively exposed to a pattern of 48 nm KrF laser light. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is set to 2.38.
Development was carried out for 60 seconds with a TMAH aqueous solution of wt%, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 34.0 mJ / cm ² , and the resolution was 0.275 μmL & S (line and space). Example 55 2-Methyl-2-adamantyl methacrylate monomer and vinyl carbonate monomer were charged in a polymerization container at a ratio of 1: 9 to prepare a 1 mol / L 1,4-dioxane solution.
A polymerization initiator, AIBN, was added to this 1,4-dioxane solution in an amount of 20 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. 2-methacrylic acid represented by the following formula
A methyl-2-adamantyl / vinyl carbonate copolymer was obtained.

[0227]

Embedded image

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

After completion of the prebaking, the obtained resist film was subjected to a wavelength of 2 with a KrF excimer stepper (NA = 0.45).
It was selectively exposed to a pattern of 48 nm KrF laser light. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is set to 2.38.
Development was carried out for 60 seconds with a TMAH aqueous solution of wt%, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 31.0 mJ / cm ² and the resolution was 0.275 μmL & S (line and space). Example 57 2-Methyl-2-adamantyl methacrylate monomer and vinyl azalactone monomer were charged in a polymerization container at a ratio of 7: 3 to prepare a 1 mol / L 1,4-dioxane solution.
A polymerization initiator, AIBN, was added to this 1,4-dioxane solution in an amount of 20 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. 2-methacrylic acid represented by the following formula
A methyl-2-adamantyl / vinylazalactone copolymer was obtained.

[0230]

[Chemical 121]

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

After the completion of prebaking, the obtained resist film was exposed to a wavelength of 2 with a KrF excimer stepper (NA = 0.45).
It was selectively exposed to a pattern of 48 nm KrF laser light. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is 0.11
It was developed for 60 seconds with an 8 wt% TMAH aqueous solution, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 28.2 mJ / cm ² , and the resolution was 0.250 μm L & S (line and space). Example 59 2-Methyl-2-adamantyl methacrylate monomer and vinyl oxazine monomer were charged in a polymerization container at 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 2
It was added in an amount of 0 mol% and polymerized at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. A 2-methyl-2-adamantyl methacrylate / vinyloxazine copolymer represented by the following formula was obtained.

[0233]

[Chemical formula 122]

The obtained copolymer had a composition ratio (m: n) of 70:30, a weight average molecular weight (Mw) of 11,000 and a dispersity (Mw / Mn) of 1.59. Example 60 2-Methyl methacrylate prepared in Example 59 above
To the 2-adamantyl / vinyloxazine copolymer, 2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added, and ethyl lactate (EL) was added.
Was dissolved. The obtained resist solution was spin-coated on a silicon substrate pretreated with HMDS to a film thickness of 0.4 μm, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the prebaking, the obtained resist film was exposed to a wavelength of 2 with a KrF excimer stepper (NA = 0.45).
It was selectively exposed to a pattern of 48 nm KrF laser light. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is 0.11
It was developed for 60 seconds with an 8 wt% TMAH aqueous solution, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 27.5 mJ / cm ² , and the resolution was 0.250 μm L & S (line and space). Example 61 2-Methyl-2-adamantyl methacrylate monomer and vinylpyrrolidone monomer were charged in a polymerization container at 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 2
It was added in an amount of 0 mol% and polymerized at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. A 2-methyl-2-adamantyl methacrylate / vinylpyrrolidone copolymer represented by the following formula was obtained.

[0236]

[Chemical 123]

The obtained copolymer had a composition ratio (m: n) of 68:32, a weight average molecular weight (Mw) of 9,000 and a dispersity (Mw / Mn) of 1.89. Example 62 2-Methyl methacrylate prepared in Example 61 above
2% by weight of an acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ) was added to a 2-adamantyl / vinylpyrrolidone copolymer and ethyl lactate (EL) was added.
Was dissolved. The obtained resist solution was spin-coated on a silicon substrate pretreated with HMDS to a film thickness of 0.4 μm, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the prebaking, the obtained resist film was subjected to a wavelength of 2 with a KrF excimer stepper (NA = 0.45).
It was selectively exposed to a pattern of 48 nm KrF laser light. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is 0.11
It was developed for 60 seconds with an 8 wt% TMAH aqueous solution, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 30.5 mJ / cm ² , and the resolution was 0.275 μm L & S (line and space). Example 63 2-Methyl-2-adamantyl methacrylate monomer and acrylonitrile monomer were charged into a polymerization vessel 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 2
It was added in an amount of 0 mol% and polymerized at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. A 2-methyl-2-adamantyl methacrylate / acrylonitrile copolymer represented by the following formula was obtained.

[0239]

Embedded image

The obtained 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-Methyl methacrylate prepared in Example 63 above
To the 2-adamantyl / acrylonitrile copolymer, 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 on a silicon substrate pretreated with HMDS to a film thickness of 0.4 μm, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the prebaking, the obtained resist film was exposed to a wavelength of 2 with a KrF excimer stepper (NA = 0.45).
It was selectively exposed to a pattern of 48 nm KrF laser light. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is set to 2.38.
Development was carried out for 60 seconds with a TMAH aqueous solution of wt%, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 38.2 mJ / cm ² , and the resolution was 0.275 μmL & S (line and space). Example 65 2-Methyl-2-adamantyl methacrylate monomer and nitrostyrene monomer were charged into a polymerization vessel at a ratio of 7: 3 to prepare a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, is added to the 1,4-dioxane solution in an amount of 20
It was added in an amount of mol% and polymerized at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. A 2-methyl-2-adamantyl methacrylate / nitrostyrene copolymer represented by the following formula was obtained.

[0242]

Embedded image

The obtained copolymer had a composition ratio (m: n) of 74:26, a weight average molecular weight (Mw) of 14,000 and a dispersity (Mw / Mn) of 1.79. Example 66 2-Methyl methacrylate prepared in Example 65 above
2% by weight in 2-adamantyl / nitrostyrene copolymer
Acid generator, triphenylsulfonium triflate (TPSSO ₃ CF ₃ ), was added and dissolved in cyclohexanone. The obtained resist solution was spin-coated on a silicon substrate pretreated with HMDS to a film thickness of 0.4 μm, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After the completion of prebaking, the obtained resist film was exposed to a wavelength of 2 with a KrF excimer stepper (NA = 0.45).
It was selectively exposed to a pattern of 48 nm KrF laser light. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is set to 2.38.
Development was carried out for 60 seconds with a TMAH aqueous solution of wt%, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 37.5 mJ / cm ² , and the resolving power was 0.275 μmL & S (line and space). Example 67 2-Methyl-2-adamantyl methacrylate monomer and acrolein monomer were charged into a polymerization vessel at a ratio of 1: 1 to prepare a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, is added to the 1,4-dioxane solution in an amount of 20
It was added in an amount of mol% and polymerized at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. A 2-methyl-2-adamantyl methacrylate / acrolein copolymer represented by the following formula was obtained.

[0245]

[Chemical formula 126]

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

After the completion of prebaking, the obtained resist film was irradiated with an ArF excimer exposure device (NA = 0.55) at a wavelength of 1.
The pattern was selectively exposed to a 93 nm ArF laser beam pattern. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is set to 2.38.
Development was carried out for 60 seconds with a TMAH aqueous solution of wt%, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 1.4 mJ / cm ² , and the resolution was 0.170 μmL & S (line and space). Example 69 The procedure described in Example 68 above was repeated. However, in this example, a KrF excimer stepper (NA = 0.45) was used as an exposure device in place of the ArF excimer exposure device, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 21.0.
It was mJ / cm ² and the resolution was 0.250 μm L & S (line and space). Example 70 2-Methyl-2-adamantyl methacrylate monomer and vinyl acetate monomer were charged in a polymerization container at a ratio of 7: 3,
A 1 mol / L 1,4-dioxane solution was prepared. This one
A polymerization initiator, AIBN, was added to the 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 precipitating agent. 2-methylmethacrylate represented by the following formula
A 2-adamantyl / vinyl acetate copolymer was obtained.

[0248]

Embedded image

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

After completion of the prebaking, the obtained resist film was irradiated with an ArF excimer exposure device (NA = 0.55) at a wavelength of 1.
The pattern was selectively exposed to a 93 nm ArF laser beam pattern. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is set to 2.38.
Development was carried out for 60 seconds with a TMAH aqueous solution of wt%, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 2.2 mJ / cm ² , and the resolution was 0.170 μmL & S (line and space). Example 72 The procedure described in Example 71 above was repeated. However, in this example, a KrF excimer stepper (NA = 0.45) was used as an exposure device in place of the ArF excimer exposure device, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 22.0.
It was mJ / cm ² and the resolution was 0.250 μm L & S (line and space). Example 73 Itaconic acid-α-2-methyl-2-adamantyl-β-
Charge methyl monomer into a polymerization vessel and add 1 mol / L of 1,4.
A dioxane solution. A polymerization initiator, AIBN, was added to this 1,4-dioxane solution in an amount of 20 mol%, and 8
Polymerization was carried out at 0 ° C. for about 8 hours. After completion of 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.

[0251]

[Chemical 128]

The obtained polymer had a weight average molecular weight (M
w) is 18,000 and the dispersity (Mw / Mn) is 1.
66. Example 74 Itaconic acid-α-2-methyl-2-adamantyl-β-methyl polymer prepared in Example 73 above was added with 2% by weight of an acid generator, triphenylsulfonium triflate (T.
PSSO ₃ CF ₃ ) was added and dissolved in cyclohexanone. The obtained resist solution was spin-coated on a silicon substrate pretreated with HMDS to a film thickness of 0.4 μm, and prebaked at 120 ° C. for 60 seconds on a hot plate.

After completion of the prebaking, the obtained resist film was irradiated with a wavelength of 1 using an ArF excimer exposure device (NA = 0.55).
The pattern was selectively exposed to a 93 nm ArF laser beam pattern. Next, the exposed resist film is PEB at 150 ° C. for 60 seconds.
(Bake after exposure). After that, the resist film is set to 2.38.
Development was carried out for 60 seconds with a TMAH aqueous solution of wt%, and further rinsed with pure water for 30 seconds. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example was 2.0 mJ / cm ² , and the resolution was 0.175 μmL & S (line and space). Example 75 The procedure described in Example 74 above was repeated. However, in this example, a KrF excimer stepper (NA = 0.45) was used as an exposure device in place of the ArF excimer exposure device, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 28.5.
It was mJ / cm ² and the resolution was 0.275 μm L & S (line and space). Example 76 Bis-2-methyl-2-adamantyl fumarate monomer and fumarate monomer were charged in a polymerization container at a molar ratio of 9: 1 to prepare a 1 mol / L 1,4-dioxane solution.
A polymerization initiator, AIBN, was added to this 1,4-dioxane solution in an amount of 20 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, purification was performed using n-hexane as a precipitating agent. Bis-2 fumarate represented by the following formula
A -methyl-2-adamantyl / fumaric acid copolymer was obtained.

[0254]

[Chemical formula 129]

The obtained 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 Bis-2-methyl-2-adamantyl fumarate / fumaric acid copolymer prepared in Example 76 above was added with 2% by weight of an acid generator, triphenylsulfonium triflate (TP).
SSO ₃ CF ₃ ) was added and dissolved in cyclohexanone. The obtained resist solution was spin-coated on a silicon substrate pretreated with HMDS to a film thickness of 0.4 μm, and prebaked at 120 ° C. for 60 seconds on a hot plate. After the completion of prebaking, the obtained resist film was exposed to ArF excimer exposure apparatus (NA = 0.55) at a wavelength of 193 nm.
A pattern of laser light was selectively exposed. Subsequently, the resist film after exposure was subjected to PEB (post-exposure bake) at 150 ° C. for 60 seconds. After that, the resist film is coated with 0.118% by weight of T
It was developed for 60 seconds with an MAH aqueous solution and further rinsed for 30 seconds with pure water. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 2.8 mJ / cm ² , and the resolution is 0.180 μm.
It was mL & S (line and space). Example 78 The procedure described in Example 77 above was repeated. However, in this example, a KrF excimer stepper (NA = 0.45) was used as an exposure device in place of the ArF excimer exposure device, and selective exposure was performed with KrF laser light having a wavelength of 248 nm. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. The threshold energy Eth of the irradiation dose in this example is 30.5.
It was mJ / cm ² and the resolution was 0.275 μm L & S (line and space). Example 79 2-Methyladamantyl methacrylate and methacrylic acid were charged in a polymerization container at a molar ratio of 9: 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 the mixture was kept 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 with a yield of 44%. The obtained copolymer had a composition ratio of 9: 1 and a weight average molecular weight (Mw) of 9,600. Example 80 To the 2-methyladamantyl methacrylate / methacrylic acid copolymer prepared in Example 79 above, 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate (TPSSbF ₄ ) was added, and the resin content was 15% by weight. It was dissolved in cyclohexanone so that the concentration became%.
The resulting resist solution was spin-coated on a silicon substrate pretreated with HMDS to a film thickness of 0.7 μm.

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

Further, the resist film formed as described above was exposed to a 0.325 μm hole pattern by 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 above was repeated. However, in this example, the addition amount of the acid generator and TPSSbF ₄ was changed from 5% by weight to 2% by weight, and the film thickness of the resist film was 0.7%.
From μm to 0.4 μm, change the exposure equipment from KrF excimer stepper to ArF excimer exposure equipment, wavelength 193 nm (NA
= 0.55). A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. 0.18 μm
The L & S (line and space) pattern was resolved almost 1: 1. Example 82 2-Methyladamantyl methacrylate, t-butyl methacrylic acid and methacrylic acid in a molar ratio of 40: 35: 2.
It was charged into a polymerization vessel at a ratio of 5 to prepare a 1 mol / L 1,4-dioxane solution. A polymerization initiator, AIBN, was added to this 1,4-dioxane solution in an amount of 20 mol%, and the mixture was heated at 80 ° C.
Held for about 7 hours. Then, 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-methyladamantyl methacrylate / t-butyl methacrylic acid / methacrylic acid copolymer was obtained with a yield of 58%. The resulting copolymer had a composition ratio of 50:29:
21, the weight average molecular weight (Mw) was 12000. Example 83 The 2-methyladamantyl methacrylate / t-butyl methacrylic acid / methacrylic acid copolymer prepared in Example 82 above was added with 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate (TPSSbF ₄ ).
Was added and dissolved in cyclohexanone so that the resin content was 15% by weight of the total amount. The obtained resist solution is
A silicon substrate pretreated with MDS was spin-coated with a film thickness of 0.7 μm.

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

Further, the resist film formed as described above was exposed with a KrF excimer stepper to a hole pattern of 0.325 μm. 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 above was repeated. However, in this example, the amount of the acid generator and TPSSbF ₄ added was changed from 5% by weight to 2% by weight, and the exposure apparatus was changed from KrF excimer stepper to A.
rF excimer exposure device, wavelength 193 nm (NA = 0.5
5), respectively. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. 0.19 μm L & S
The (line and space) pattern was resolved almost 1: 1. Example 85 2-Methyladamantyl methacrylate, 3-oxocyclohexyl methacrylate and methacrylic acid were charged into a polymerization container at a molar ratio of 50:35:15 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 the mixture was kept 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 a mixed solvent of methanol and water (10: 1), and the precipitate was filtered off. 2-methyladamantyl methacrylate / 3-oxocyclohexyl methacrylate / methacrylic acid copolymer yield 4
Obtained in 3%. The obtained copolymer has a composition ratio of 50 :.
The weight average molecular weight (Mw) was 11,000 at 35:15. Example 86 To the 2-methyladamantyl methacrylate / 3-oxocyclohexyl methacrylate / methacrylic acid copolymer prepared in Example 85 above was added 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate (TPSSbF ₄ ), and the resin was added. The content was dissolved in cyclohexanone so that the content was 15% by weight of the total amount. The resulting resist solution was spin-coated on a silicon substrate pretreated with HMDS to a film thickness of 0.7 μm.

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

Further, the resist film formed as described above was exposed to a 0.325 μm hole pattern by 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 above 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 light pattern used for exposure was obtained without peeling of the pattern. A 0.19 μm L & S (line and space) pattern was resolved approximately 1: 1. Example 88 2-Methylcyclohexyl methacrylate, t-butyl methacrylate and methacrylic acid in a molar ratio of 40: 3.
A polymerization container was charged at a ratio of 5:25, and 1 mol / L of 1,
This was a 4-dioxane solution. A polymerization initiator, AIBN, was added to this 1,4-dioxane solution in an amount of 20 mol%,
Hold 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 n-hexane, and the precipitate was separated by filtration. 2-methylcyclohexyl methacrylate / t
-Butyl methacrylate / methacrylic acid copolymer was obtained with a yield of 63%. The obtained copolymer has a composition ratio of 5
The weight average molecular weight (Mw) is 2100 at 0:29:21.
It was 0. Example 89 The 2-methylcyclohexylmethacrylate / t-butylmethacrylate / methacrylic acid copolymer prepared in Example 88 above contained 5% by weight of an acid generator, triphenylsulfonium hexafluoroantimonate (TPSSbF).
₄ ) was added and dissolved in cyclohexanone so that the resin content was 15% by weight of the total amount. The obtained resist solution was applied onto a silicon substrate pretreated with HMDS to give a film thickness of 0.7.
It was spin-coated with μm.

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

Further, the resist film formed as described above was exposed to a 0.325 μm hole pattern by 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 above was repeated. However, in this example, the amount of the acid generator and TPSSbF ₄ added was changed from 5% by weight to 2% by weight, and the exposure apparatus was changed from KrF excimer stepper to A.
rF excimer exposure device, wavelength 193 nm (NA = 0.5
5), respectively. A desired resist pattern corresponding to the laser light pattern used for exposure was obtained without peeling of the pattern. 0.19 μm L & S
The (line and space) pattern was resolved almost 1: 1.

[0264]

According to the present invention, by using the above chemically amplified resist, and in particular, in combination with such a resist, an aqueous solution or alcohol solution of a specific ammonium compound or morpholine compound is developed. By controlling the compatibility with the resist resin and the solubility to reduce the stress generated during development, the peeling and cracking of the resist pattern can be reduced and stable patterning characteristics can be obtained. You can Furthermore, according to the present invention, stable patterning characteristics can be obtained by relaxing the strain generated during development. Furthermore, according to the present invention, the exposure margin can be widened, and a stable fine resist pattern can be formed. At that time, the adhesion of the resist to the base is very good. It is also possible to prevent the positive pattern from being made slightly larger than the desired mask pattern when exposure is performed through an exposure mask which is designed to shield the circuit pattern to be printed.

Claims (20)

[Claims] 1. An alicyclic hydrocarbon group-containing moiety represented by any of the following formulas (I) to (VI): (In the above formula, R _I represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted, and Z is Represents a plurality of atoms necessary to complete an alicyclic hydrocarbon group) (In the above formula, R _II may be the same or different and is a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic alicyclic hydrocarbon group. Provided that at least one of R _II is an alicyclic hydrocarbon group) (In the above formula, R _II is the same as the above definition.) (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 having a carbon atom of or an alicyclic hydrocarbon group) (In the above formula, R _II is the same as the above definition.) (In the above formula, R _I and Z are the same as defined above.)
An acid-sensitive compound having a structural unit having an alkali-soluble group protected by and having the alkali-soluble group eliminated by an acid to make the compound alkali-soluble, and an acid generator capable of generating an acid upon exposure to radiation. A resist material comprising: 2. 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. . 3. The protected alkali-soluble group is a carboxylic acid group represented by the following formulas (VII) to (XI): Embedded image Embedded image Embedded image Embedded image (Wherein R _I , R _II and R _III and Z are the same as defined above), and an imide group represented by the following formula (XII): (Wherein Z is the same as the above definition) or the following formula (XIII)
Phenol group represented by: (In formula, Z is the same as said definition.) The resist material of Claim 1 or 2 characterized by the above-mentioned. 4. The alicyclic hydrocarbon group contained in the protected alkali-soluble group has a plurality of ring structures or a fused ring.
4. The resist material according to any one of items 3 to 3. 5. The alicyclic hydrocarbon group has the following groups: (1) adamantane and its derivative (2) norbornane and its derivative (3) perhydroanthracene and its derivative (4) perhydronaphthalene and its derivative (5) Tricyclo [5.2.1.0 ^2,6 ] decane and its derivatives (6) Bicyclohexane and its derivatives (7) Spiro [4,4] nonane and its derivatives (8) Spiro [4,5] It is one member selected from decane and its derivative, It is characterized by the above-mentioned.
4. The resist material according to any one of 3 above. 6. The resist material according to claim 1, wherein the acid-sensitive compound is a polymer or a copolymer containing the structural unit as a repeating unit. 7. The repeating unit of the polymer or copolymer is selected from the group consisting of acrylic acid esters and derivatives thereof, itaconic acid esters and derivatives thereof, fumaric esters and derivatives thereof, and substituted styrene and derivatives thereof. The resist material according to claim 6, wherein the resist material is a member. 8. The acid-sensitive compound is a copolymer containing the structural unit as a repeating unit, and the remaining repeating unit of the copolymer has a repeating unit having an alkali-soluble group in a side chain, and / or 7. The resist material according to claim 6, comprising a repeating unit having an additional protected alkali-soluble group capable of being eliminated by an acid generated from the acid generator in a side chain. 9. The copolymer has the following formula (XIV) or (X
Structural unit represented by V): [Chemical 15] (In the above formulas, R may be the same or different and represents hydrogen, halogen or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, and R _I is 1 Represents a linear or branched alkyl group having 4 to 4 carbon atoms, which may be substituted or unsubstituted, A represents an acid-eliminating protecting group, and Z represents
The resist material according to claim 8, further comprising a plurality of atoms necessary for completing the alicyclic hydrocarbon group together with the described carbon atom. 10. The alicyclic hydrocarbon group of the copolymer is
The following groups: (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 its derivatives (6) Bicyclohexane and its derivatives (7) Spiro [4,5] nonane and its derivatives (8) Spiro [4,5] decane and its derivatives The resist material according to claim 9, wherein 11. The method 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. The described resist material. 12. An alicyclic hydrocarbon group-containing moiety represented by any of the following formulas (I) to (VI): (In the above formula, R _I represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted, and Z is Represents a plurality of atoms necessary to complete an alicyclic hydrocarbon group) (In the above formula, R _II may be the same or different and is a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic alicyclic hydrocarbon group. Provided that at least one R _II is an alicyclic hydrocarbon group. (In the above formula, R _II is the same as the above definition.) (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 having a carbon atom of or an alicyclic hydrocarbon group) (In the above formula, R _II is the same as the above definition.) (In the above formula, R _I and Z are the same as defined above.)
An acid-sensitive compound having a structural unit having an alkali-soluble group protected by and having the alkali-soluble group eliminated by an acid to make the compound alkali-soluble, and an acid generator capable of generating an acid upon exposure to radiation. A resist material containing a is coated on a substrate to be processed, the resist film on the substrate to be processed is selectively exposed to radiation capable of causing generation of an acid from the acid generator, and the resist film after exposure is A method of forming a resist pattern, comprising: developing the latent image formed in the exposure step after post-baking. 13. The alkali-soluble group of the resist material is one 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 described pattern forming method. 14. The alicyclic hydrocarbon group of the alkali-soluble group of the resist material has a plurality of ring structures or has a condensed ring.
Or the pattern forming method as described in 13 above. 15. The alicyclic hydrocarbon group of an alkali-soluble group of the resist material has the following groups: (1) adamantane and its derivative (2) norbornane and its derivative (3) perhydroanthracene and its derivative (4) ) Perhydronaphthalene and its derivatives (5) Tricyclo [5.2.1.0 ^2,6 ] decane and its derivatives (6) Bicyclohexane and its derivatives (7) Spiro [4,4] nonane and its derivatives (8) 13. A member selected from spiro [4,5] decane and its derivatives.
Or the pattern forming method as described in 13 above. 16. The acid sensitive compound of the resist material is a polymer or copolymer containing the structural unit as a repeating unit, according to claim 12. Pattern formation method. 17. The acid-sensitive compound is a copolymer containing the structural unit as a repeating unit, and the remaining repeating units of the copolymer have a repeating unit having an alkali-soluble group in a side chain and (or ) A repeating unit having an additional protected alkali-soluble group capable of leaving by an acid generated from the acid generator in a side chain,
The pattern forming method according to claim 16. 18. The structural unit represented by the following formula (XIV) or (XV): Embedded image (In the above formulas, R may be the same or different and represents hydrogen, halogen or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, and R _I is 1 Represents a linear or branched alkyl group having 4 to 4 carbon atoms, which may be substituted or unsubstituted, A represents an acid-eliminating protecting group, and Z represents
18. The pattern forming method according to claim 17, further comprising a plurality of atoms necessary for completing an alicyclic hydrocarbon group together with the described carbon atom. 19. The alicyclic hydrocarbon group of the copolymer is
The following groups: (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 its derivatives (6) Bicyclohexane and its derivatives (7) Spiro [4,5] nonane and its derivatives (8) Spiro [4,5] decane and its derivatives Claim 18
4. The pattern forming method according to 1. 20. The acid-sensitive compound of the resist material is a non-polymerizable compound, and an alkali-soluble polymer or copolymer is used in combination with this compound. The method for forming a pattern according to item 1.