JP2002169289A - Polymer for photoresist and resin composition for photoresist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoresist resin which can form a fine pattern with excellent homogeneity and high resolution. SOLUTION: The photoresist polymer compound contains at least one kind of monomer unit expressed by formula (I). In the formula, Ra is a hydrogen atom or methyl group and R1 is a hydrogen atom or 1-20C straight-chain hydrocarbon group, branched hydrocarbon group, alicyclic hydrocarbon group, crosslinked alicyclic hydrocarbon group or heterocyclic group which may have substituents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer compound for a photoresist used when performing fine processing of a semiconductor, a resin composition for a photoresist containing the polymer compound, and a method for producing a semiconductor.

[0002]

2. Description of the Related Art A positive photoresist resin used in a semiconductor manufacturing process has a function of exhibiting substrate adhesion and is soluble in an alkali developing solution by being desorbed by an acid generated from a photoacid generator upon exposure. Function is required. Also,
The photoresist resin must also have dry etching resistance. In particular, the use of an excimer laser, ArF, as a light source in the exposure step, and expectations for giga-order semiconductors are increasing. However, since ArF has a wavelength of 193 nm in the deep ultraviolet, the resist material also requires transparency in the ultraviolet region, and a novel monomer has been proposed.

[0003] Among them, polycyclic alicyclic compounds containing a lactone skeleton have recently attracted attention because they have a function of substrate adhesion and are expected to have etching resistance. Among them, Japanese Patent Application Laid-Open No.
There are JP-A-00-26446 and JP-A-2000-159758. However, in the former, the polar group has only a lactone skeleton and is difficult to dissolve in an organic solvent as a resist material. Cyclopentadiene is required, leaving economic problems. In any case, a monomer having a lactone skeleton that has sufficient functions and is economical has not been developed.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel photoresist polymer compound having a good balance between adhesion to a substrate and solubility in an organic solvent and etching resistance. It is in.

Another object of the present invention is to provide a photoresist resin composition capable of forming a fine pattern with high precision, and a method of manufacturing a semiconductor.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that a polymer containing a monomer unit having an alicyclic skeleton having a specific structure in which a lactone ring is condensed is used as a resin for a photoresist. As a result, the present inventors have found that a polymer compound for photoresist having a good balance between adhesion to a substrate, solubility in an organic solvent, and etching resistance can be obtained, and the present invention has been completed.

That is, the present invention provides the following formula (I)

[0008]

Embedded image

(In the above formula, R ^a represents a hydrogen atom or a methyl group, and R ¹ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.) A macrocyclic group, an alicyclic hydrocarbon group, a bridged alicyclic hydrocarbon group, or a heterocyclic group).

The polymer compound for a photoresist comprises at least one monomer unit selected from the formula (I) and the following formulas (IIa) to (IIg):

[0011]

Embedded image

[0012] (In the above formula, R ^a represents a hydrogen atom or a methyl group, R ² and R ³ are the same or different and each represents a hydrogen atom, or a hydrocarbon group having 1 to 8 carbon atoms, R ⁴ ~ ⁶ is
The same or different, each represents a hydrogen atom, a hydroxyl group or a methyl group which may have a protecting group, and R ⁷ and R ⁸ are
The same or different, and each represents a hydrogen atom, a hydroxyl group which may have a protecting group, or -COOR ⁹ , wherein R ⁹ is a t-butyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, or a 2-oxepanyl. R ¹⁰ represents a methyl group or an ethyl group; R ¹¹ and R ¹² are the same or different and represent a hydrogen atom, a hydroxyl group or an oxo group which may have a protecting group, and R ¹³ represents A tertiary hydrocarbon group which may have a substituent, R ¹⁴ to R ¹⁸ are the same or different and each represent a hydrogen atom or a methyl group, R ¹⁹ is a t-butyl group, a 2-tetrahydrofuranyl group, It represents a 2-tetrahydropyranyl group or a 2-oxepanyl group. m is 1-3
And n represents 0 or 1. )) May be included.

Further, in addition to at least one monomer unit selected from the formula (1) or at least one monomer unit selected from the formula (1),
In addition to at least one monomer unit selected from (IIg), the following formulas (IIIa) to (IIIj)

[0014]

Embedded image

(In the above formula, R ^a represents a hydrogen atom or a methyl group, and R ²⁰ and R ²¹ are the same or different and have a hydrogen atom, a hydroxyl group which may have a protecting group, or a protecting group. X represents a carboxyl group which may be protected, and R ²² represents a hydroxyl group, an oxo group or a carboxyl group which may have a protection group, which may have a protection group.
^1-3 are the same or different, -CH ₂ - or -CO-O
Indicates-. R ²³ to ²⁵ are the same or different and each represent a hydrogen atom or a methyl group. R ²⁶ and R ²⁷ are the same or different and each represent a hydrogen atom or a methyl group. R ²⁸ ~ ³² are the same or different, represent a hydrogen atom or a methyl group. R ³³ represents a hydrogen atom or having 1 to 20 carbon atoms which may have a substituent linear hydrocarbons, branched hydrocarbons, alicyclic hydrocarbons, the bridged alicyclic hydrocarbon. ^R34 to ^R37 are the same or different and each represent a hydrogen atom or a methyl group. R ³⁸ represents a hydrogen atom, a hydroxyl group optionally having a protecting group, a hydroxymethyl group optionally having a protecting group, or a carboxyl group optionally having a protecting group. R ³⁹ to ⁵⁶ each represent a hydrogen atom,
It represents a methyl group or an ethyl group. o, p, q and r each represent 0 or 1. )) May be included.

The polymer compound for a photoresist contains 0.1% of a monomer unit having a group containing an alicyclic hydrocarbon ring (excluding the monomer unit represented by the formula (I)).
It is preferable to contain 含 む 50 mol%.

It is preferable that the polymer compound for a photoresist has a solubility parameter value in the range of 19.5 to 24.5 (J / cm ³ ) ^1/2 according to the Fedors method.

The present invention also provides a photoresist resin composition comprising at least the above-mentioned polymer compound for photoresist and a photoacid generator.

The present invention further provides a method for producing a semiconductor, comprising the steps of applying the above-mentioned resin composition for photoresist on a substrate or substrate to form a resist coating film, and exposing and developing to form a pattern. I will provide a.

In this specification, “acryl” and “methacryl” may be collectively referred to as “(meth) acryl”, and “acryloyl” and “methacryloyl” may be collectively referred to as “(meth) acryloyl”.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Polymer for photoresist of the present invention
Compounds are structural units that make up polymer molecules.
At least one monomer selected from the formula (I)
Position (repeating unit) (hereinafter referred to as “monomer unit I”)
May be referred to). This monomer unit
I has a highly hydrophilic lactone ring and carboxyl group.
To provide an adhesion-imparting device that enhances the adhesion to the substrate.
Functions as a knit. In addition, alicyclic carbocycles (cyclo
(Xan ring) to increase etching resistance
It also has the function of Furthermore, the carbon substituted with a norbornene ring
Ruboxyl group (COOR ¹R) which is an ester group of¹To
If a group that is decomposed by acid and becomes alkali-soluble is introduced,
Will also have a desorbing function.

R ¹ shown in the formula (I), which is the monomer unit I, represents a substituent such as a methyl, ethyl, propyl, butyl, pentyl, hexyl group or a substituted hydroxyethyl or hydroxybutyl group. A linear hydrocarbon group which may be contained, i-propyl, s-butyl, t-
Branched hydrocarbon groups such as butyl group, cyclopentyl,
Alicyclic hydrocarbon groups such as cyclohexyl group, bridged alicyclic hydrocarbon groups such as adamantyl, norbornyl, tricyclodecanyl, decahydronaphthyl group, 2-tetrahydrofuranyl, 2-tetrahydropyranyl, 2-oxepanyl A heterocyclic group such as a group is preferable. Further, when R ¹ is a hydrogen atom, the wettability with respect to alkali development is improved, and R ¹ is a group capable of leaving by an acid, for example, t-butyl, 2-tetrahydrofuranyl, 2-tetrahydropyranyl, -Oxepanyl group and the like are preferable.

As a typical example of the formula (I), [1-1] 2- (meth) acryloyloxy-7-carboxy-4-oxatricyclo [4.2.1.
0 ^3,7 ] nonan-5-one (R ^a = H or CH ₃ , R ¹ = carboxylic acid group) [1-2] 2- (meth) acryloyloxy-7-methoxycarbonyl-4-oxatricyclo [ 4.2.
1.0 ^3,7 ] nonan-5-one (R ^a = H or CH ₃ , R ¹
= Methyl group) [1-3] 2- (meth) acryloyloxy-7-ethoxycarbonyl-4-oxatricyclo [4.2.
1.0 ^3,7 ] nonan-5-one (R ^a = H or CH ₃ , R ¹
= Ethyl group) [1-4] 2- (meth) acryloyloxy-7-isopropoxycarbonyl-4-oxatricyclo [4.
2.1.0 ^3,7 ] nonan-5-one (R ^a = H or C
H ₃ , R ¹ = isopropyl group) [1-5] 2- (meth) acryloyloxy-7-t
-Butyroxycarbonyl-4-oxatricyclo [4.
2.1.0 ^3,7 ] nonan-5-one (R ^a = H or C
H ₃ , R ¹ = t-butyl group) [1-6] 2- (meth) acryloyloxy-7-
(1-Methyl-1-adamantylethoxy) carbonyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one (R ^a = H or CH ₃ , R ¹ = 1-methyl- 1
-Adamantylethyl group) [1-7] 2- (meth) acryloyloxy-7- (2-
Tetrahydropyranyloxy) carbonyl-4-oxatricyclo [4.2.1.0 ^3,7] nonan-5-one (R ^a = H or CH _3, R ¹ = 2- tetrahydropyranyl group) and the like But are not limited to these.

As a method for producing the monomer represented by the above formula (I), cyclopentadiene and the following formula (4)

[0025]

Embedded image

A norbornene skeleton is formed by the Diels-Alder reaction with the derivative from maleic anhydride shown in the above, and then the double bond of the norbornene skeleton is epoxidized with hydrogen peroxide in the presence of a catalyst such as tungstic acid. The epoxy group is formed by the following formula (5) by a ring-closing reaction with carboxylic acid.

[0027]

Embedded image

Is formed. Further, it is reacted with acryl chloride or methacryl chloride in the presence of a dehydrochlorinating agent such as triethylamine to obtain the monomer of the formula (I).

In a preferred embodiment of the present invention, the above formula (I)
And at least one monomer unit (repeating unit) selected from the formulas (IIa) to (IIg) (hereinafter, may be referred to as “monomer unit II”). Contains.

In the monomer unit II, the compound represented by the formula (II)
A typical example as a) is [2-1] 1- (1- (meth) acryloyloxy-1-
Methylethyl) adamantane (R^a= H or CH_Three, R^Two
= R^Three= CH_Three, R^Four= R^Five= R⁶= H) [2-2] 1-hydroxy-3- (1- (meth) acryloyl
Iloxy-1-methylethyl) adamantane (R^a=
H or CH_Three, R^Two= R^Three= CH_Three, R^Four= OH, R^Five= R⁶
= H) [2-3] 1- (1-ethyl-1- (meth) acryloyl
Oxypropyl) adamantane (R^a= H or CH_Three, R
^Two= R^Three= CH_TwoCH_Three, R^Four= R^Five= R⁶= H) [2-4] 1-hydroxy-3- (1-ethyl-1- (me
TA) acryloyloxypropyl) adamantane (R^a
= H or CH_Three, R^Two= R^Three= CH_TwoCH_Three, R^Four= OH, R
^Five= R⁶= H) [2-5] 1- (1- (meth) acryloyloxy-1-)
Methylpropyl) adamantane (R^a= H or CH_Three, R
^Two= CH_Three, R^Three= CH_TwoCH_Three, R^Four= R^Five= R⁶= H) [2-6] 1-hydroxy-3- (1- (meth) acryloyl
Iloxy-1-methylpropyl) adamantane (R^a
= H or CH_Three, R^Two= CH_Three, R^Three= CH_TwoCH_Three, R^Four=
OH, R^Five= R⁶= H) [2-7] 1- (1- (meth) acryloyloxy-1,
2-dimethylpropyl) adamantane (R^a= H or C
H_Three, R^Two= CH_Three, R^Three= CH (CH_Three)_Two, R^Four= R ^Five= R
⁶= H) [2-8] 1-hydroxy-3- (1- (meth) acryloyl
Yloxy-1,2-dimethylpropyl) adamantane
(R^a= H or CH_Three, R^Two= CH_Three, R^Three= CH (CH_Three)
_Two, R^Four= OH, R^Five= R⁶= H) [2-9] 1,3-dihydroxy-5- (1- (meth) a
Acryloyloxy-1-methylethyl) adamantane
(R^a= H or CH_Three, R^Two= R^Three= CH_Three, R^Four= R^Five= O
H, R⁶= H) [2-10] 1,3-dihydroxy-5- (1-ethyl-1)
-(Meth) acryloyloxypropyl) adamantane
(R^a= H or CH_Three, R^Two= R^Three= CH_TwoCH_Three, R ^Four= R^Five
= OH, R⁶= H) [2-11] 1,3-dihydroxy-5- (1- (meth) a
Acryloyloxy-1-methylpropyl) adamantane
(R^a= H or CH_Three, R^Two= CH_Three, R^Three= CH_TwoCH_Three,
R^Four= R^Five= OH, R⁶= H) [2-12] 1,3-dihydroxy-5- (1- (meth) a
(Cryloyloxy-1,2-dimethylpropyl) adama
Tan (R^a= H or CH_Three, R^Two= CH_Three, R^Three= CH
(CH_Three)_Two, R^Four= R^Five= OH, R⁶= H).

A typical example of the above formula (IIb) is [2-13] 1-t-butoxycarbonyl-3- (meth) acryloyloxyadamantane (R ^a = H or CH ₃ , R
^{7 = R 8 = H, R} 9 = t- butyl group) [2-14] 1,3-bis (t-butoxycarbonyl) -5
-(Meth) acryloyloxyadamantane ( ^Ra = H
Or ^{_{CH 3, R 7 = CO-}} O-C (CH 3) 3, R 8 = H,
R ⁹ = t-butyl group) [2-15] 1-t-butoxycarbonyl-3-hydroxy-5- (meth) acryloyloxyadamantane ( ^Ra
= H or ^{_{CH 3, R 7 = OH,}} R 8 = H, R 9 = t- butyl group) [2-16] 1- (2-tetrahydropyranyloxy) -3- (meth) acryloyloxy adamantane ( R ^a = H or CH ₃ , R ⁷ = R ⁸ = H, R ⁹ = 2-tetrahydropyranyl group) [2-17] 1,3-bis (2-tetrahydropyranyloxycarbonyl) -5- (meta ) acryloyloxyadamantane (R ^a = H or CH _3, R ⁷ = 2- tetrahydropyranyloxy ^{group, R 8 = H, R 9} = 2- tetrahydropyranyl group) [2-18] 1- (2- tetrahydropyranyloxy carbonyl) -3-hydroxy-5- (meth) acryloyloxy adamantane (R ^a = H or ^{_{CH 3, R 7 = OH,}} R 8
= H, R ⁹ = 2-tetrahydropyranyl group).

A typical example of the above formula (IIc) is [2-19] 2- (meth) acryloyloxy-2-methyladamantane (R ^a = H or CH ₃ , R ¹⁰ = CH ₃ , R ¹¹
= R ¹² = H) [2-20] 1-hydroxy-2- (meth) acryloyloxy-2-methyladamantane (R ^a = H or CH ₃ , R
¹⁰ = CH ₃ , R ¹¹ = 1-OH, R ¹² = H) [2-21] 5-hydroxy-2- (meth) acryloyloxy-2-methyladamantane ( ^Ra = H or CH ₃ , R
¹⁰ = CH ₃ , R ¹¹ = 5-OH, R ¹² = H) [2-22] 1,3-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane ( ^Ra = H or C
_{^{H 3, R 10 = CH 3}} , R 11 = 1-OH, R 12 = 3-OH) [2-23] 1,5- dihydroxy-2- (meth) acryloyloxy-2-methyl-adamantane (R ^a = H or C
_{^{H 3, R 10 = CH 3}} , R 11 = 1-OH, R 12 = 5-OH) [2-24] 1,3- dihydroxy-6 (meth) acryloyloxy-6-methyl-adamantane (R ^a = H or C
_{^{H 3, R 10 = CH 3}} , R 11 = 1-OH, R 12 = 3-OH) [2-25] 2- ( meth) acryloyloxy-2-ethyl adamantane (R ^a = H or CH _3, R ¹⁰ = CH ₂ CH ₃ ,
R ¹¹ = R ¹² = H) [2-26] 1-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane (R ^a = H or CH ₃ , R
_{^{10 = CH 2 CH 3, R}} 11 = 1-OH, R 12 = H) [2-27] 5- hydroxy-2- (meth) acryloyloxy-2-ethyl adamantane (R ^a = H or CH _3, R
_{^{10 = CH 2 CH 3, R}} 11 = 5-OH, R 12 = H) [2-28] 1,3- dihydroxy-2- (meth) acryloyloxy-2-ethyl adamantane (R ^a = H or C
_{^{H 3, R 10 = CH 2}} CH 3, R 11 = 1-OH, R 12 = 3-
OH) [2-29] 1,5-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane (R ^a = H or C
_{^{H 3, R 10 = CH 2}} CH 3, R 11 = 1-OH, R 12 = 5-
OH) [2-30] 1,3-dihydroxy-6- (meth) acryloyloxy-6-ethyladamantane ( ^Ra = H or C
_{^{H 3, R 10 = CH 2}} CH 3, R 11 = 1-OH, R 12 = 3-
OH).

A typical example of the above formula (IId) is [2-31] t-butyl (meth) acrylate (R ^a = H or CH ₃ , R ¹³ = t-butyl group).

A typical example of the above formula (IIe) is [2-32] 2-tetrahydropyranyl (meth) acrylate (R ^a = H or CH ₃ , m = 2) [2-33] 2-tetrahydrofuranyl ( (Meth) acrylate (R ^a = H or CH ₃ , m = 1).

A typical example of the above formula (IIf) is [2-34] β- (meth) acryloyloxy-γ-butyrolactone (R ^a = H or CH ₃ , R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷
= R ¹⁸ = H) [2-35] β- (meth) acryloyloxy-α, α-dimethyl-γ-butyrolactone (R ^a = H or CH ₃ , R ¹⁴
= R ¹⁵ = CH ₃ , R ¹⁶ = R ¹⁷ = R ¹⁸ = H) [2-36] β- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone (R ^a = H or CH ₃ , R ¹⁷
= R ¹⁸ = CH ₃ , R ¹⁴ = R ¹⁵ = R ¹⁶ = H) [2-37] β- (meth) acryloyloxy-α, α, β
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 14 = R 15}} = R 16 = CH 3, R 17 = R 18 = H) [2-38] β- ( meth) acryloyloxy-beta, gamma, gamma
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 16 = R 17}} = R 18 = CH 3, R 14 = R 15 = H) [2-39] β- ( meth) acryloyloxy-.alpha., alpha,
β, γ, γ-pentamethyl-γ-butyrolactone ( ^Ra
= H or CH ₃ , R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = R ¹⁸ = C
H _3).

A typical example of the above formula (IIg) is [2-40] 5-t-butoxycarbonylnorbornene (R
¹⁹= T-butyl group, n = 0) [2-41] 9-t-butoxycarbonyltetracyclo
[6.2.1.1^3,6. 0^2,7] Dodeca-4-ene (R¹⁹
= T-butyl group, n = 1) [2-42] 5- (2-tetrahydropyranyloxycarbo)
Nyl) norbornene (R ¹⁹= T-butyl group, n = 0) and the like, but are not limited thereto.
No.

The polymer compound for a photoresist of the present invention comprises, in addition to the monomer unit I, or the monomer units I and II, at least one selected from the monomer units represented by the formulas (IIIa) to (IIIh). Species of monomer unit (repeating unit) (hereinafter referred to as “monomer unit III”)
May be included).

As a typical example of the above formula (IIIa), [3-1] 1-hydroxy-3- (meth) acryloyloxyadamantane (R ^a = H or CH ₃ , R ²⁰ = OH, R
^{21 = R 22 = H) [} 3-2] 1,3- dihydroxy-5- (meth) acryloyloxy adamantane (R ^a = H or CH _3, R ²⁰ = R
^{21 = OH, R 22 = H} ) [3-3] 1- carboxy-3- (meth) acryloyloxy adamantane (R ^a = H or CH _3, R ²⁰ = COO
H, R ²¹ = R ²² = H) [3-4] 1,3-dicarboxy-5- (meth) acryloyloxyadamantane (R ^a = H or CH ₃ , R ²⁰ = R
^{21 = COOH, R 22 = H} ) [3-5] 1- carboxy-3-hydroxy-5- (meth) acryloyloxy adamantane (R ^a = H or C
^{_{H 3, R 20 = COOH,}} R 21 = OH, R 22 = H) [3-6] 1- ( meth) acryloyloxy-4-oxo-adamantane (R ^a = H or _{^{CH 3, R 20 = R 21}} = H, R
²² = 4-oxo group) [3-7] 3-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane (R ^a = H or CH ₃ , R
^{20 = 3-OH, R 21} = H, R 22 = 4- oxo group) [3-8] 7-hydroxy-1- (meth) acryloyloxy-4-oxo-adamantane (R ^a = H or CH _3, R
²⁰ = 7-OH, R ²¹ = H, R ²² = 4-oxo group).

As a typical example of the above formula (IIIb), [3-9] 1- (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one (R ^a = H or CH ₃ , R ²³ = R ²⁴ = R ²⁵ = H, X ¹ =
X ³ = —CH ₂ —, X ² = —CO—O— (the left side is the side of the carbon atom to which R ⁴¹ is bonded) [3-10] 1- (meth) acryloyloxy-4,7-dioxa Tricyclo [4.4.1.1 ^3,9 ] dodecane-
5,8-dione (R ^a = H or _{^{CH 3, R 23 = R 24}} = R 25
^{= H, X 1 = -CO-} O- ( left bonded to the carbon atom side of the ^{R 23), X 2 = -CO} -O- ( carbon atoms side the left is bonded to R ^24), X _{^{3 = -CH 2 -) [3-11}} ] 1- ( meth) acryloyloxy-4,8-dioxatricyclo [4.4.1.1 ^{3, 9]} dodecane -
5,7-dione (R ^a = H or _{^{CH 3, R 23 = R 24}} = R 25
= H, X ¹ = —O—CO— (the left side is the carbon atom side to which R ²³ is bonded), X ² = —CO—O— (the left side is the carbon atom side to which R ²⁴ is bonded), X _{^{3 = -CH 2 -) [3-12}} ] 1- ( meth) acryloyloxy-5,7-dioxatricyclo [4.4.1.1 ^{3, 9]} dodecane -
4,8-dione (R ^a = H or _{^{CH 3, R 23 = R 24}} = R 25
= H, X ¹ = —CO—O— (the left side is the carbon atom side to which R ²³ is bonded), X ² = —O—CO— (the left side is the carbon atom side to which R ²⁴ is bonded), X ³ = -CH ₂ -).

As a typical example of the above formula (IIIc), [3-13] 2- (meth) acryloyloxy-4-oxa
Tricyclo [4.2.1.0^3,7Nonan-5-one
(R^a= H or CH_Three, R²⁶= R²⁷= H) [3-14] 2- (meth) acryloyloxy-2-methyl
-4-oxatricyclo [4.2.1.0^3,7] Nonan
-5-one (R^a= H or CH_Three, R²⁶= CH_Three, R ²⁷=
H).

As a typical example of the above formula (IIId), [3-15] α- (meth) acryloyloxy-γ-butyrolactone (R ^a = H or CH ₃ , R ²⁸ = R ²⁹ = R ³⁰ = R ³¹
= R ³² = H) [3-16] α- (meth) acryloyloxy-α-methyl-γ-butyrolactone (R ^a = H or CH ₃ , R ²⁸ = CH
₃ , R ²⁹ = R ³⁰ = R ³¹ = R ³² = H) [3-17] α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone (R ^a = H or CH ₃ , R ²⁹
= R ³⁰ = CH ₃ , R ²⁸ = R ³¹ = R ³² = H) [3-18] α- (meth) acryloyloxy-α, β, β
-Trimethyl-γ-butyrolactone (R ^a = H or C
H ₃ , R ²⁸ = R ²⁹ = R ³⁰ = CH ₃ , R ³¹ = R ³² = H) [3-19] α- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone (R ^a = H Or CH ₃ , R ³¹
= R ³² = CH ₃ , R ²⁸ = R ²⁹ = R ³⁰ = H) [3-20] α- (meth) acryloyloxy-α, γ, γ
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 28 = R 31}} = R 32 = CH 3, R 29 = R 30 = H) [3-21] α- ( meth) acryloyloxy-beta, beta,
γ, γ-tetramethyl-γ-butyrolactone (R ^a = H
Or CH ₃ , R ²⁹ = R ³⁰ = R ³¹ = R ³² = CH ₃ , R ²⁸ =
H) [3-22] α- (meth) acryloyloxy-α, β,
β, γ, γ-pentamethyl-γ-butyrolactone ( ^Ra
= H or CH ₃ , R ²⁸ = R ²⁹ = R ³⁰ = R ³¹ = R ³² = C
H _3).

As a representative example of the above formula (IIIe), [3-23] (meth) acrylic acid (R ^a = H or CH ₃ , R ³³
= H) [3-24] Methyl (meth) acrylate (R ^a = H or C
H ₃ , R ³³ = methyl group) [3-25] Ethyl (meth) acrylate (R ^a = H or C
H ₃ , R ³³ = ethyl group) [3-26] Isopropyl (meth) acrylate (R ^a = H or CH ₃ , R ³³ = isopropyl group) [3-27] n-butyl (meth) acrylate (R ^a = H or CH ₃ , R ³³ = n-butyl group) [3-28] Cyclohexyl (meth) acrylate (R ^a = H
Or CH ₃ , R ³³ = cyclohexyl group) [3-29] Decahydronaphthyl (meth) acrylate (R ^a
= H or CH ₃ , R ³³ = decahydronaphthyl group) [3-29] norbornyl (meth) acrylate (R ^a = H or CH ₃ , R ³³ = norbornyl group) [3-30] (meth) acrylic acid Isobornyl (R ^a = H or CH ₃ , R ³³ = isobornyl group) [3-31] Adamantyl (meth) acrylate (R ^a = H or CH ₃ , R ³³ = adamantyl group) [3-32] (meth) Dimethyl adamantyl acrylate (R
^a = H or CH ₃ , R ³³ = dimethyladamantyl group) [3-33] Tricyclo (meth) acrylate [5.2.1.
0 ^2,6 ] decyl (R ^a = H or CH ₃ , R ³³ = tricyclo [5.2.1.0 ^2,6 ] decyl group) [3-34] Tetracyclo (meth) acrylate [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodecyl (R ^a = H or CH ₃ , R
³³ = tetracyclo [4.4.0.1 ^2,5 . The 1 ^7,10] substituent dodecyl) R ^33, hydroxyl group, a hydroxymethyl group, a carboxyl group, such as an oxo group.

[3-35] Maleic anhydride is a typical example of the above formula (IIIf).

As a representative example of the above formula (IIIg), [3-36] 4-oxatricyclo [35.1.0 ^2,6 ] decane-8-en-5-one (R ³⁶ = R ³⁷ = H , O = p =
0, q = 1) [3-37] 3-oxatricyclo [35.1.0 ^2,6 ] decane-8-en-4-one (R ³⁴ = R ³⁵ = H, o = q =
0, p = 1) [3-38] 5-oxatricyclo [6.2.1.0 ^2,7 ]
Undecane-9-en-6-one ^{(R 36 = R 37 = H} , o
= P = 0, q = 2) [3-39] 4-oxatricyclo [6.2.1.0 ^2,7 ]
Undecane-9-en-5-one ^{(R 34 = R 35 = R} 36 =
R ³⁷ = H, o = 0, p = q = 1) [3-40] 4-oxapentacyclo [6.34.1 ^9,12 .
0 ^2,6 . 0 ^8,13] pentadecane-10-ene-5-one ^{(R 36 = R 37 = H} , o = 1, p = 0, q = 1) [3-41] 3- oxa penta cyclo [6.34. ^19,12 .
0 ^2,6 . 0 ^8,13 ] pentadecane-10-en-4-one (R ³⁴ = R ³⁵ = H, o = 1, p = 1, q = 0) [3-42] 5-oxapentacyclo [6.6. 1.1
^10,13 . 0 ^2,7 . 0 ^9,14 ] hexadecane-11-ene-6
-One (R ³⁶ = R ³⁷ = H, o = 1, p = 0, q = 2) [3-43] 4-oxapentacyclo [6.6.1.1
^10,13 . 0 ^2,7 . 0 ^9,14 ] hexadecane-11-ene-5
- one ^{(R 34 = R 35 = R} 36 = R 37 = H, o = 1, p = q
= 1).

As a typical example of the above formula (IIIh), [3-44] norbornene (R ³⁸ ＨH, r = 0) [3-45] 5-hydroxy-2-norbornene (R ³⁸ ＯO
H, r = 0).

As a representative example of the above formula (IIIi), [3-46] 4- (meth) acryloyloxy-6-oxabicyclo [3.2.1] octan-7-one (R ^a = H
Or CH ₃ , R ³⁹ = R ⁴⁰ = R ⁴¹ = R ⁴² = R ⁴³ = R ⁴⁴ = R
⁴⁵ = R ⁴⁶ = R ⁴⁷ = H) [3-47] 4- (meth) acryloyloxy-4-methyl-6-oxabicyclo [3.2.1] octan-7-one ( ^Ra = H or CH ₃ , R ³⁹ = R ⁴⁰ = R ⁴² = R ⁴³ = R ^{44
= R 45 = R 46 = R} 47 = H, R 41 = CH 3) [3-48] 4- ( meth) acryloyloxy-5-methyl-6-oxabicyclo [3.2.1] octane-7 on (R ^a = H or _{^{CH 3, R 39 = R 40}} = R 41 = R 43 = R 44
^{= R 45 = R 46 = R} 47 = H, R 42 = CH 3) [3-49] 4- ( meth) acryloyloxy-4,5-dimethyl-6-oxabicyclo [3.2.1] octane -
7- ON (R ^a = H or _{^{CH 3, R 39 = R 40}} = R 43 = R 44
= R ⁴⁵ = R ⁴⁶ = R ⁴⁷ = H, R ⁴¹ = R ⁴² = CH ₃ ).

As a typical example of the above formula (IIIj), [3-50] 6- (meth) acryloyloxy-2-oxabicyclo [2.2.2] octan-3-one (R ^a = H
Or CH ₃ , R ⁴⁸ = R ⁴⁹ = R ⁵⁰ = R ⁵¹ = R ⁵² = R ⁵³ = R
⁵⁴ = R ⁵⁵ = R ⁵⁶ = H) [3-51] 6- (meth) acryloyloxy-6-methyl-2-oxabicyclo [2.2.2] octan-3-one ( ^Ra = H or CH _{^{3, R 48 = R 49 =}} R 50 = R 52 = R 53
= R ⁵⁴ = R ⁵⁵ = R ⁵⁶ = H, R ⁵¹ = CH ₃ ) [3-52] 6- (Meth) acryloyloxy-1-methyl-2-oxabicyclo [2.2.2] octane-3- on (R ^a = H or _{^{CH 3, R 48 = R 49}} = R 51 = R 52 = R 53
^{= R 54 = R 55 = R} 56 = H, R 50 = CH 3) [3-53] 6- ( meth) acryloyloxy-1,6-dimethyl-2-oxabicyclo [2.2.2] octane -
3-one (R ^a = H or _{^{CH 3, R 48 = R 49}} = R 52 = R 53
= R ⁵⁴ = R ⁵⁵ = R ⁵⁶ = H, R ⁵⁰ = R ⁵¹ = CH ₃ ) and the like, but are not particularly limited thereto.

The photoresist resin composition of the present invention comprises
It contains the polymer compound for photoresist of the present invention and a photoacid generator.

Examples of the photoacid generator include conventional or known compounds which efficiently generate an acid upon exposure to light, such as diazonium salts, iodonium salts (eg, diphenyliodohexafluorophosphate), and sulfonium salts (eg, triphenylsulfonium). Hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium methanesulfonate, etc.), sulfonic acid ester [for example, 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1
-Benzoylmethane, 1,2,3-trisulfonyloxymethylbenzene, 1,3-dinitro-2- (4-phenylsulfonyloxymethyl) benzene, 1-phenyl-1- (4-methylphenylsulfonyloxymethyl)
-1-hydroxy-1-benzoylmethane, etc.], oxathiazole derivatives, s-triazine derivatives, disulfone derivatives (eg, diphenyldisulfone), imide compounds, oxime sulfonates, diazonaphthoquinone, benzoin tosylate, and the like. These photoacid generators can be used alone or in combination of two or more.

The amount of the photoacid generator used can be appropriately selected according to the strength of the acid generated by light irradiation, the ratio of each monomer unit in the polymer compound, and the like. For example, based on 100 parts by weight of the polymer compound 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, more preferably about 2 to 20 parts by weight.

The resin composition for a photoresist includes an alkali-soluble component such as an alkali-soluble resin (eg, a novolak resin, a phenol resin, an imide resin, and a carboxyl group-containing resin), a coloring agent (eg, a dye), and an organic solvent. (Eg, hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, mixed solvents thereof, and the like). May be.

After coating the photoresist resin composition on a substrate or substrate and drying, the coating film (resist film) is exposed to light through a predetermined mask (or further baked after exposure). The fine pattern can be formed with high precision by forming a latent image pattern and then developing.

As the substrate or substrate, a silicon wafer,
Examples include metal, plastic, glass, and ceramic. The application of the resin composition for a photoresist can be performed using a conventional application means such as a spin coater, a dip coater, and a roller coater. The thickness of the coating film is, for example, about 0.1 to 20 μm, and preferably about 0.3 to 2 μm.

Light of various wavelengths, for example, ultraviolet rays, X-rays, etc. can be used for the exposure. For semiconductor resists, g-rays, i-rays, excimer lasers (eg, XeC
1, KrF, KrCl, ArF, ArCl, etc.) are used. Exposure energy is, for example, 1 to 1000 m
J / cm ² , preferably about 10 to 500 mJ / cm ² .

An acid is generated from the photoacid generator by light irradiation,
By this acid, for example, a protective group (leaving group) such as a carboxyl group of the alkali-soluble unit of the polymer compound is rapidly eliminated, and a carboxyl group or the like contributing to solubilization is generated. Therefore, a predetermined pattern can be accurately formed by development with water or an alkali developing solution.

[0056]

The polymer compound for photoresist of the present invention contains a monomer unit having an alicyclic skeleton having a specific structure in which a lactone ring is condensed. A function such as releasability is added, so high etching resistance is expected, and it is necessary for photoresists such as adhesion to substrates, solubility in solvents as resists, and affinity with alkali developers. It has a well-balanced function. Further, by combining with other monomers, it is also possible to further improve the respective functions.

According to the photoresist resin composition and the method for producing a semiconductor of the present invention, since a polymer having the above-mentioned excellent properties is used as a resist, a fine pattern can be formed with high precision. it can.

[0058]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto.

Synthesis Example 1 6.6 g (0.1 mol) of cyclopentadiene, 9.8 g (0.1 mol) of maleic anhydride, and 200 ml of ethyl acetate as a solvent were dissolved in an autoclave, and the solution was poured into an autoclave at 100 ° C.
For 2 hours. After cooling to room temperature, the reaction mixture was placed in a flask equipped with a reflux condenser and a dropping funnel, and 0.2 g of tungstic acid and 3.6 g of water were mixed, and 14.3 g of 30% hydrogen peroxide at a temperature of 50 ° C. ( 0.13 mol) was added dropwise in 10 minutes. The reaction was continued at the same temperature for 5 hours, cooled to room temperature, and washed with water. The organic layer was placed in a rotary evaporator, and the solvent, ethyl acetate, was distilled off. The remaining liquid was mixed with 200 ml of tetrahydrofuran, placed in a flask equipped with a reflux condenser and a dropping funnel, further added with 30.3 g (0.3 mol) of triethylamine, and stirred with 10.5 g (0.1 mol) of methacryl chloride. The solution was added dropwise at room temperature over 30 minutes. Stirring was continued at room temperature for a further 6 hours. When the reaction mixture was analyzed by gas chromatography, the desired 2- (meth) acryloyloxy-7 was obtained.
-Carboxy-4-oxatricyclo [4.2.1.0
^[3,7 ] nonan-5-one was detected in an amount of 14.5 g (0.055 mol). After the reaction mixture was filtered, the target monomer was separated and purified by column chromatography. The target compound was identified by NMR and IR spectra, and the results are shown below. ¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.8 (1
H, ddd), δ 1.9 (3H, s), δ 2.0 (1
H, ddd), δ 2.8 (1H, m), δ 2.9 (1
H, m), δ3.1 (1H, dd), δ3.2 (1H,
dd), δ4.6 (1H, dd), δ4.7 (1H, d
d), δ5.6 (1H, d), δ6.1 (1H, d) FT-IR (NaCl) 2500-3500 cm ⁻¹ , 1
800 cm ⁻¹ , 1730 cm ⁻¹ , 1700 cm ⁻¹ , 16
30 cm ^-1 .

The route of this synthesis is shown below.

[0061]

Embedded image

Synthesis Example 2 6.6 g (0.1 mol) of cyclopentadiene, 17.2 g (0.1 mol) of mono-t-butyl maleate, and 200 ml of ethyl acetate as a solvent were dissolved in an autoclave and heated at 100 ° C. For 2 hours. After cooling to room temperature, the reaction mixture was placed in a flask equipped with a reflux condenser and a dropping funnel, further added with 0.2 g of tungstic acid and mixed, and at a temperature of 50 ° C., 14.3 g of 30% hydrogen peroxide.
(0.13 mol) was added dropwise in 10 minutes. The reaction was continued at the same temperature for 5 hours, cooled to room temperature, and washed with water. The organic layer was placed in a rotary evaporator, and the solvent, ethyl acetate, was distilled off. The remaining liquid is treated with tetrahydrofuran 200m
The mixture was placed in a flask equipped with a reflux condenser and a dropping funnel, 30.3 g (0.3 mol) of triethylamine was further added, and 10.5 g (0.1 mol) of methacryl chloride was stirred at room temperature. It was added dropwise over 30 minutes. Stirring was continued at room temperature for a further 6 hours. When the reaction mixture was analyzed by gas chromatography, the desired 2- (meth)
Acryloyloxy-7-t-butyroxycarbonyl-
4-oxatricyclo [4.2.1.0 ^3,7 ] nonane-
17.5 g (0.054 mol) of 5-one was detected.
After the reaction mixture was filtered, the target monomer was separated and purified by column chromatography. The target is NMR and I
Identification was performed using each spectrum of R, and the results are shown below. ¹ H-NMR (400 MHz, CDCl ₃ ) δ1.3 (9
H, s), δ 1.8 (1H, ddd), δ 1.9 (3
H, s), δ2.0 (1H, ddd), δ2.8 (1
H, m), δ2.9 (1H, m), δ3.1 (1H, d
d), δ3.2 (1H, dd), δ4.6 (1H, d
d), δ4.7 (1H, dd), δ5.6 (1H,
d), δ 6.1 (1H, d) FT-IR (NaCl) 1800 cm ⁻¹ , 1730 cm
^-1 , 1710 cm ^-1 , 1630 cm ^-1 .

The route of this synthesis is shown below.

[0064]

Embedded image

Example 1 Synthesis of polymer compound having the following structure

[0066]

Embedded image

A 10-tube equipped with a reflux pipe, a stirrer and a three-way cock
In a 0 ml round bottom flask, 2.11 g (7.9 mmol) of monomer [1-1] (methacrylate) and monomer [2-
1] (methacrylate) 4.15 g (15.8 mmol)
l), monomer [3-1] (methacrylate) 3.74
g (15.8 mmol) and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and tetrahydrofuran 4
0 g was dissolved. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and under a nitrogen atmosphere,
Stir for 6 hours. The reaction solution was mixed with hexane and ethyl acetate 9:
One mixture was dropped to 500 ml, and the resulting precipitate was separated by filtration for purification. The collected precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 7.12 g of a desired resin. GPC analysis of the recovered polymer showed a weight average molecular weight of 6,300 and a molecular weight distribution of 2.11.
^{In 1} H-NMR (in DMSO-d6) analysis, 1.5-
In addition to 2.5 ppm (broad), 3.1 ppm, 4.
Strong signals were observed around 6 ppm, 4.7 ppm and 12.5 ppm.

Example 2 Synthesis of polymer compound having the following structure

[0069]

Embedded image

[0086] A reflux tube, stirrer, and three-way cock
In a 0 ml round bottom flask, 2.21 g (8.3 mmol) of monomer [1-1] (methacrylate) and monomer [2-
19] (methacrylate) 3.88 g (16.6 mmol)
l), monomer [3-1] (methacrylate) 3.91
g (16.6 mmol) and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and tetrahydrofuran 4
0 g was dissolved. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and under a nitrogen atmosphere,
Stir for 6 hours. The reaction solution was mixed with hexane and ethyl acetate 9:
One mixture was dropped to 500 ml, and the resulting precipitate was separated by filtration for purification. The recovered precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 7.03 g of a desired resin. GPC analysis of the recovered polymer showed a weight average molecular weight of 5,400 and a molecular weight distribution of 1.88.
^{In 1} H-NMR (in DMSO-d6) analysis, 1.5-
In addition to 2.5 ppm (broad), 3.1 ppm, 4.
Strong signals were observed around 6 ppm, 4.7 ppm and 12.5 ppm.

Example 3 Synthesis of polymer compound having the following structure

[0072]

Embedded image

A 10 having a reflux pipe, a stirrer and a three-way cock
In a 0 ml round bottom flask, 3.13 g (11.8 mmol) of monomer [1-1] (methacrylate) and monomer [2
-1] (methacrylate) 4.11 g (15.7 mmol)
l), monomer [3-6] (methacrylate) 2.75
g (11.8 mmol) and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and tetrahydrofuran 4
0 g was dissolved. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and under a nitrogen atmosphere,
Stir for 6 hours. The reaction solution was mixed with hexane and ethyl acetate 9:
One mixture was dropped to 500 ml, and the resulting precipitate was separated by filtration for purification. The collected precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 7.12 g of a desired resin. GPC analysis of the recovered polymer showed a weight average molecular weight of 6,300 and a molecular weight distribution of 2.11.
^{In 1} H-NMR (in DMSO-d6) analysis, 1.5-
In addition to 2.5 ppm (broad), 3.1 ppm, 4.
Strong signals were observed around 6 ppm and 12.5 ppm.

Example 4 Synthesis of polymer compound having the following structure

[0075]

Embedded image

A 10-port tube equipped with a reflux tube, stirrer and 3-way cock
In a 0 ml round bottom flask, 6.48 g (20.1 mmol) of monomer [1-5] (methacrylate) and monomer [2
-1] (methacrylate) 3.52 g (13.4 mmol)
l) and initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.0
0 g was added and dissolved in 40 g of tetrahydrofuran.
Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. 500 ml of a 9: 1 mixture of hexane and ethyl acetate
And the resulting precipitate was filtered off to purify. The collected precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 7.27 g of a desired resin. GPC analysis of the recovered polymer showed a weight average molecular weight of 650.
0, molecular weight distribution was 2.14. ¹ H-NMR (D
In the analysis (in MSO-d6), strong signals were observed at 3.1 ppm and 4.6 ppm in addition to 1.5-2.5 ppm (broad).

Example 5 Synthesis of a polymer compound having the following structure

[0078]

Embedded image

[0086] A reflux tube, a stirrer, and a 10-way
In a 0 ml round bottom flask, 6.74 g (20.9 mmol) of monomer [1-5] (methacrylate) and monomer [2
-19] (methacrylate) 3.26 g (13.9 mm
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.)
00 g was added and dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was mixed with a 9: 1 mixture of hexane and ethyl acetate 50.
The mixture was dropped to 0 ml, and the resulting precipitate was separated by filtration for purification. The recovered precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 6.47 g of a desired resin. GPC analysis of the recovered polymer showed a weight average molecular weight of 5
800 and the molecular weight distribution was 1.88. ¹ H-NMR
1.5-2.5 ppm (in DMSO-d6) analysis
In addition to (broad), strong signals were observed at 3.1 ppm and 4.6 ppm.

Example 6 Synthesis of polymer compound having the following structure

[0081]

Embedded image

In a three-necked flask equipped with a stirrer and a reflux tube, 3.0 g (1) of monomer [1-2] (acrylate) was added.
2 mmol), 4.7 g of monomer [2-41] (24 m
mol), 2.3 g of monomer [3-35] (26 mmol)
l) and initiator (V-601 manufactured by Wako Pure Chemical Industries)
0 g was added and dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. The collected precipitate was dried under reduced pressure, dissolved again in 10 g of n-butyl acetate, and the above-mentioned precipitation purification operation was further repeated twice to obtain 7.5 g of a desired resin. GPC analysis of the recovered polymer showed a weight average molecular weight of 700.
0 and the molecular weight distribution was 2.0. ¹ H-NMR (DM
In SO-d6) analysis, in addition to 0.9-3.6 ppm (broad), 1.3 ppm, 1.6 ppm, 1.9 p
pm, 2.6 ppm, 2.8 ppm, 3.2 ppm,
Strong signals were observed at 3.6 ppm and 4.4 ppm.

Example 7 Synthesis of polymer compound having the following structure

[0084]

Embedded image

In a three-necked flask equipped with a stirrer and a reflux tube, 3.1 g (1) of monomer [1-3] (acrylate) was added.
2 mmol), 4.6 g of monomer [2-41] (24 m
mol), 2.3 g of monomer [3-35] (26 mmol)
l) and initiator (V-601 manufactured by Wako Pure Chemical Industries)
0 g was added and dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. The collected precipitate was dried under reduced pressure, dissolved again in 10 g of n-butyl acetate, and the above-mentioned precipitation purification operation was further repeated twice to obtain 7.5 g of a desired resin. GPC analysis of the recovered polymer showed a weight average molecular weight of 710.
0 and the molecular weight distribution was 2.0. ¹ H-NMR (DM
In SO-d6) analysis, in addition to 0.9-3.6 ppm (broad), 1.3 ppm, 1.6 ppm, 1.9 p
pm, 2.6 ppm, 2.8 ppm, 3.2 ppm,
Strong signals were observed at 3.6 ppm and 4.4 ppm.

Example 8 Synthesis of polymer compound having the following structure

[0087]

Embedded image

In a three-necked flask equipped with a stirrer and a reflux tube, 3.2 g (1) of monomer [1-4] (acrylate) was added.
2 mmol), 4.5 g of monomer [2-41] (24 m
mol), 2.3 g of monomer [3-35] (26 mmol)
l) and initiator (V-601 manufactured by Wako Pure Chemical Industries)
0 g was added and dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. The collected precipitate was dried under reduced pressure, dissolved again in 10 g of n-butyl acetate, and the above-mentioned precipitation purification operation was further repeated twice to obtain 7.5 g of a desired resin. GPC analysis of the recovered polymer showed a weight average molecular weight of 700.
0 and the molecular weight distribution was 2.0. ¹ H-NMR (DM
In SO-d6) analysis, in addition to 0.9-3.6 ppm (broad), 1.3 ppm, 1.6 ppm, 1.9 p
pm, 2.6 ppm, 2.8 ppm, 3.2 ppm,
Strong signals were observed at 3.6 ppm and 4.4 ppm.

Comparative Example 1 Synthesis of polymer compound having the following structure

[0090]

Embedded image

[0091] A 10-tube equipped with a reflux pipe, a stirrer and a three-way cock
In a 0 ml round bottom flask, add 2-methacryloyloxy-4-
Oxatricyclo [4.2.1.0 ^3,7 ] nonane-5
1.82 g (8.2 mmol) of monomer [2-
1] (methacrylate) 4.30 g (16.4 mmol)
l), monomer [3-1] (methacrylate) 3.88
g (16.4 mmol) and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were added.
0 g was dissolved. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and under a nitrogen atmosphere,
Stir for 6 hours. The reaction solution was mixed with hexane and ethyl acetate 9:
One mixture was dropped to 500 ml, and the resulting precipitate was separated by filtration for purification. The collected precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 7.12 g of a desired resin. GPC analysis of the recovered polymer showed a weight average molecular weight of 6,700 and a molecular weight distribution of 2.21.
^{In 1} H-NMR (in DMSO-d6) analysis, 1.5-
In addition to 2.5 ppm (broad), 3.1 ppm, 4.
Strong signals were observed around 6 ppm and 4.7 ppm.

Comparative Example 2 Synthesis of polymer compound having the following structure

[0093]

Embedded image

[0094] A 10-tube equipped with a reflux pipe, stirrer and three-way cock
In a 0 ml round bottom flask, add 2-methacryloyloxy-4-
Oxatricyclo [4.2.1.0 ^3,7 ] nonane-5
5.60 g (25.2 mmol) of the monomer [2-
1] (methacrylate) 4.40 g (16.8 mmol)
l) and initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.0
0 g was added and dissolved in 40 g of tetrahydrofuran.
Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. 500 ml of a 9: 1 mixture of hexane and ethyl acetate
And the resulting precipitate was filtered off to purify. The recovered precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 7.55 g of a desired resin. GPC analysis of the recovered polymer showed a weight average molecular weight of 690.
0, molecular weight distribution was 2.12. ¹ H-NMR (D
In the analysis (in MSO-d6), strong signals were observed at 3.1 ppm and 4.6 ppm in addition to 1.5-2.5 ppm (broad).

Test Example 1 100 parts by weight of the polymer obtained in Examples 1 to 8 and triphenylsulfonium hexafluoroantimonate 10
Parts by weight and 1,2-propylene glycol monomethyl ether acetate as a solvent, and a polymer concentration of 1
7% by weight of a photoresist resin composition was prepared. The photoresist resin composition was applied to a silicon wafer by spin coating to form a photosensitive layer having a thickness of 1.0 μm. 1 at a temperature of 100 ° C on a hot plate
After pre-baking for 50 seconds, using a KrF excimer laser having a wavelength of 247 nm, the irradiation amount is 30 m through a mask.
After exposure at J / cm ² , post-baking was performed at a temperature of 100 ° C. for 60 seconds. Subsequently, the film was developed with a 0.3 M aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsed with pure water. In each case, a line and space pattern of 0.30 μm was obtained.

Test Example 2 100 parts by weight of the polymer obtained in Comparative Examples 1 and 2 and triphenylsulfonium hexafluoroantimonate 1
0 parts by weight and 1,2-propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a photoresist resin composition having a polymer concentration of 17% by weight.
However, part of the resin did not dissolve, and the function as a photoresist could not be evaluated.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2H025 AA02 AB16 AD03 BE00 BE07 BE10 BF03 BF11 CB43 FA17 4J100 AJ02R AK32R AL03Q AL03R AL08P AL08Q AL08R AR11Q AR11R AR32R BA03Q BA03R BA04Q BA11P BA11R BA15B BC09 BC BC53P BC53Q CA01 CA04 CA06 DA39 JA38

Claims (8)

[Claims] 1. A compound represented by the following formula (I): (In the above formula, Ra represents ^a hydrogen atom or a methyl group,
R ¹ is a hydrogen atom or a carbon atom having 1 to 2 carbon atoms which may have a substituent.
And 0 represents a linear hydrocarbon group, a branched hydrocarbon group, an alicyclic hydrocarbon group, a bridged alicyclic hydrocarbon group, or a heterocyclic group. A) a polymer compound for a photoresist containing at least one monomer unit represented by the formula: 2. The method according to claim 1, wherein the at least one type of monomer represented by the formula (I)
Nomer units and the following formulas (IIa) to (IIg):(In the above formula, R^aRepresents a hydrogen atom or a methyl group,
R^TwoAnd R^ThreeAre the same or different and each represents a hydrogen atom or a carbon atom
Represents a hydrocarbon group of the formulas 1 to 8,^Four~⁶Are the same or different
A hydrogen atom, a hydroxy optionally having a protecting group
A methyl group or a methyl group;⁷And R⁸Are the same or different
A hydrogen atom, a hydroxy optionally having a protecting group
Or —COOR⁹And R⁹Is a t-butyl group, 2-
Tetrahydrofuranyl group, 2-tetrahydropyranyl group
Or a 2-oxepanyl group; ^TenIs a methyl group or d
A tyl group;¹¹And R¹²Are the same or different,
A hydrogen atom, a hydroxyl group which may have a protecting group, or
An oxo group;¹³Is a tertiary carbon which may have a substituent
A hydrogen group;¹⁴~¹⁸Is the same or different and is hydrogen
An atom or a methyl group;¹⁹Is a t-butyl group,
Trahydrofuranyl group, 2-tetrahydropyranyl group or
Represents a 2-oxepanyl group. m represents an integer of 1 to 3
And n represents 0 or 1. ) Selected from at least
2. The photoresist of claim 1, comprising one monomer unit.
High molecular compound for strike. 3. The method of claim 1, wherein at least one of the
Nomer units and the following formulas (IIIa) to (IIIj):(In the above formula, R^aRepresents a hydrogen atom or a methyl group,
R²⁰And R^{twenty one}Are the same or different and are a hydrogen atom, a protecting group
Having a hydroxyl group or a protecting group which may have
Represents an optional carboxyl group;^{twenty two}Has a protecting group
With an optionally substituted hydroxyl, oxo or protecting group
Represents a carboxyl group which may be substituted. X ¹~^ThreeAre the same
Or differently, -CH_Two-Or -CO-O- is shown. R
^{twenty three}~^{twenty five}Are the same or different and each represents a hydrogen atom or a methyl group
Show. R²⁶And R²⁷Are the same or different and each represents a hydrogen atom or
Represents a methyl group. R²⁸~³²Are the same or different,
Represents an element atom or a methyl group. R³³Is a hydrogen atom or substituted
C1-C20 linear hydrocarbon which may have a group, branched
Indicates hydrocarbon, alicyclic hydrocarbon, and bridged alicyclic hydrocarbon
You. R³⁴~³⁷Are the same or different and each represents a hydrogen atom or methyl.
Represents a hydroxyl group. R³⁸Has a hydrogen atom and a protecting group
Hydroxyl group, hydro group which may have a protecting group
Xymethyl group, carboxyl optionally having a protecting group
Represents a group. R³⁹~ ⁵⁶Is a hydrogen atom, a methyl group or
Indicates an ethyl group. o, p, q and r are each 0 or 1
Is shown. At least one monomer selected from
2. The polymer compound for a photoresist according to claim 1, further comprising
object. 4. It comprises at least one monomer unit represented by the formula (I) and at least one monomer unit selected from the formulas (IIa) to (IIg), and further comprises a compound represented by the formula (III)
The polymer compound for a photoresist according to claim 1, comprising at least one type of monomer unit selected from a) to (IIIj). 5. The photoresist composition according to claim 1, comprising at least one monomer unit represented by the formula (I) and 0.1 to 50% of a monomer unit having an alicyclic functional group. Molecular compound. 6. The photoresist according to claim 1, wherein the solubility parameter value according to the Fedors method is in the range of 19.5 to 24.5 (J / cm ³ ) ^1/2 . High molecular compounds. 7. A photoresist resin composition comprising at least the polymer compound for a photoresist according to claim 1 and a photoacid generator. 8. A method for producing a semiconductor, comprising a step of applying the photoresist resin composition according to claim 7 onto a substrate or a substrate to form a resist coating film and forming a pattern through exposure and development.