KR20120033268A - Composition for forming resist lower layer film, polymer, resist lower layer film, process for forming pattern and process for manufacturing semiconductor device - Google Patents

Abstract

PURPOSE: A composition for forming a resist sub layer, polymer, a resist sub layer, a patter forming method, and a semiconductor device manufacturing method are provided to improve the etching speed of a pattern forming process based on a dry etching technique. CONSTITUTION: A composition for forming a resist sub layer includes polymer with a cyclic carbonate structure. A method for forming patterns includes the following: the resist sub layer is formed by applying the composition on a substrate; a resist layer is formed by applying a resist composition on the resist sub layer; the resist layer is exposed by selectively irradiating radiation using a photo mask; the exposed resist layer is developed to form resist patterns; the resist patterns are used as a mask for dry etching the resist sub layer and the substrate to form patterns.

Description

FIELD OF FORMING RESIST LOWER LAYER FILM, POLYMER, RESIST LOWER LAYER FILM, PROCESS FOR FORMING PATTERN AND PROCESS FOR MANUFACTURING SEMICONDUCTOR DEVICE}

The present invention relates to a composition for forming a resist underlayer film, a polymer, a resist underlayer film, a pattern forming method and a method for producing a semiconductor device.

Conventionally, in the manufacture of a semiconductor device, fine processing by a lithography technique using a photoresist composition has been performed. The microfabrication includes the steps of forming a resist film on the substrate, exposing the resist film by irradiation with radiation such as ultraviolet rays, developing the exposed resist film, and etching the substrate using the obtained resist pattern as a protective film. It is processing method to include. In recent years, high integration of semiconductor devices is progressing, and the radiation used tends to be shortened from an KrF excimer laser (248 nm) to an ArF excimer laser (193 nm), and further to EUV (13.5 nm). However, the use of these low-wavelength radiations has a problem in that good fine patterns cannot be formed by the influence of diffuse reflection from the substrate, standing waves, and the like. Therefore, the method of providing a resist underlayer film, such as a bottom anti-reflective coating (BARC), between a resist film and a board | substrate is extensively examined.

As the resist underlayer film, an inorganic resist underlayer film such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon, or an organic resist underlayer film containing a light absorbing material and a high molecular compound is known. While the former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, a sputtering apparatus, etc. for film formation, the latter is advantageous in that no special equipment is required, and a lot of studies have been made. For example, an acrylic resin-type resist underlayer film having a hydroxyl group and a light absorber as a crosslinking reactor described in US Pat. No. 5919599, or a hydroxyl group and a light absorber as a crosslinking reactor described in US Pat. No. 5693691 And novolak resin-type resist underlayer films having the same molecule.

The physical properties required for the composition for forming an organic resist underlayer film include those having a large absorbance with respect to light or radiation, not intermixing with the resist film, and forming a resist underlayer film during application or heat drying. There is no diffusion of low molecules from the composition for the resist into the resist film, and a large dry etching rate compared with the resist. These are described, for example, in Proc. SPIE, Vol. 3678, 174-185 (1999), Proc. .SPIE, Vol. 3678, 800-809 (1999). In addition, the higher the density of semiconductor devices, the higher the resolution, the finer the pattern of a rectangular resist pattern having a finer pattern size can be formed, the better adhesion between the resist underlayer film and the resist film, and the stronger the pattern collapse. It is also required for a composition for forming a resist underlayer film.

In particular, in the current semiconductor device manufacturing process in which the pattern size is advanced, an excellent etching selectivity for the resist film and the substrate can be realized at the time of pattern formation by dry etching, and the resist underlayer makes it possible to resist the pattern collapse. There is a strong demand for development of a film-forming composition and a resist underlayer film having the above characteristics.

US Patent No. 5919599 United States Patent No. 5693691

 Proc. SPIE, Vol. 3678 (1999), p. 174-185  Proc. SPIE, Vol. 3678 (1999), p. 800-809

The present invention has been made on the basis of the above circumstances, and an object thereof is to form a resist underlayer film having a high etching rate at the time of pattern formation by dry etching, achieving an excellent etching selectivity with respect to a resist film, and resisting pattern collapse. To provide a composition for forming a resist underlayer film, a resist underlayer film, a pattern forming method using these, and a method for manufacturing a semiconductor device.

The composition for forming a resist underlayer film of the present invention contains a polymer having a [A] cyclic carbonate structure. When the composition for resist underlayer film formation has a cyclic carbonate structure, the etching rate of the resist underlayer film obtained improves. In addition, since the resist underlayer film has high adhesiveness to the resist film, it is also resistant to pattern collapse.

It is preferable that the polymer (A) has a structural unit (I) represented by the following general formula (1).

In Formula 1, R ¹ is a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, Q ¹ is a divalent linking group, Y is a single bond, a methylene group, linear or branched alkyl having 2 to 10 carbon atoms. A ethylene group, an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 6 to 20 reduced water, or a group formed of these groups, and a part of the hydrogen atoms of the alkylene group, arylene group or heteroarylene group, or All may be substituted and may have an oxygen atom in the carbon chain of the said alkylene group, p is an integer of 0-3, q is 0 or 1, r is an integer of 0-2, X is- CH _2- , -CH ₂ -CH _2- , -O-, -S- or -SO _2- , provided that when r is 2, a plurality of X may be the same or different)

When the polymer (A) has the structural unit (I) represented by the above formula (1), the resist underlayer film obtained from the composition for forming a resist underlayer film further improves the etching rate and is excellent in adhesion to the resist film.

It is preferable that the polymer (A) further has a structural unit (II) represented by the following general formula (2).

(In Formula 2, R <^2> is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, Q <^2> is a bivalent coupling group, R <^3> is a hydrogen atom, a C1-C15 linear or branched alkyl group, carbon number It is an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms or a heteroaryl group of 6 to 20 carbon atoms, and part or all of the hydrogen atoms of the alkyl group, aryl group, aralkyl group or heteroaryl group may be substituted. )

When the polymer (A) further has the structural unit (II) represented by the formula (2), it is possible to form an underlayer film that is excellent in reaction with the crosslinking agent or the crosslinkable group and does not cause intermixing with the resist film.

The polymer (A) has a structural unit represented by the following general formula (1-1) as the structural unit (I), and a structural unit (II-) represented by the following general formula (2-1) as the structural unit (II). It is preferable to have at least 1 type of structural unit selected from the group which consists of 1) and structural unit (II-2) represented by General formula (2-2).

(In Formula (1-1), R ¹ , X, Y, p, q and r have the same meanings as in Formula 1,

In general formula (2-1), R <^4> is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, R <^6> is a C1-C15 alkyl group or a C6-C20 aryl group, and this alkyl group and an aryl group have Some or all of the hydrogen atoms are substituted with a substituent, at least one of the substituents is a group having a hydroxyl group or an amino group,

In formula (2-2), R ⁵ is a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, R ⁷ is a phenyl group, a naphthyl group, an anthryl group or a linear or branched alkyl group having 1 to 15 carbon atoms. Some or all of the hydrogen atoms which this phenyl group, naphthyl group, and anthryl group have may be substituted by substituents other than a hydroxyl group and an amino group, and some or all of the hydrogen atoms which the said alkyl group has are substituted by substituents other than a hydroxyl group and an amino group. At least one of these substituents may be a phenyl group, a naphthyl group, or an anthryl group, provided that some or all of the hydrogen atoms of the phenyl group, naphthyl group, or anthryl group may be substituted with a substituent other than a hydroxyl group and an amino group. )

When the said polymer (A) has structural unit (II-1) which has a hydroxyl group or an amino group, crosslinking reaction with a crosslinking agent is accelerated | stimulated, and the hardness of the resist underlayer film obtained and adhesiveness with respect to a resist film improve. Moreover, by having structural unit (II-2) which has an aromatic ring, the resist underlayer film which is excellent in radiation absorption, such as ArF excimer laser, can be formed.

The polymer (A) has the structural unit (II-1) and the structural unit (II-2) as the structural unit (II), or has the structural unit (II-1), wherein R ⁶ is aryl It is preferable that it is a group. The resist obtained by accelerating crosslinking reaction with a crosslinking agent by having [A] polymer having structural unit (II-1) and (II-2) or having said structural unit (II-1) whose said R <^6> is an aryl group. The hardness of the underlayer film and the adhesion to the resist film are improved, and the radiation of ArF excimer laser and the like is also excellent.

It is preferable that the composition for resist underlayer film formation of this invention contains a [B] crosslinking agent further. Since the composition for forming a resist underlayer film contains a structural unit having a hydroxyl group or an amino group, the crosslinking reaction between the [B] crosslinking agent and the polymer occurs by further including the [B] crosslinking agent, and the intermixing of the resulting resist underlayer film and the resist film is performed. Suppressed.

The crosslinking agent (B) preferably has at least two crosslinking functional groups. Since the crosslinking agent (B) has at least two crosslinking functional groups, the self-condensation of the crosslinking agent and the crosslinking reaction with the polymer [A] are further promoted, so that the hardness of the resist underlayer film formed from the composition is further improved.

It is preferable that the polymer (A) further has a structural unit (III) containing a fluorine atom. When the composition for forming a resist underlayer film contains a polymer containing a fluorine atom, the etching rate of the resulting resist underlayer film is further increased.

The present invention,

Structural unit (I) represented by the following general formula (1-1),

Structural unit (II-1) represented by the following general formula (2-1), and

Structural unit (II-2) represented by the following general formula (2-2)

It includes a polymer having a.

(In Formula (1-1), R ¹ , X, Y, p, q and r have the same meanings as in Formula 1,

In general formula (2-1), R <^4> is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, R <^6> is a C1-C15 alkyl group or a C6-C20 aryl group, and this alkyl group and an aryl group have Some or all of the hydrogen atoms are substituted with a substituent, at least one of the substituents is a group having a hydroxyl group or an amino group,

In formula (2-2), R ⁵ is a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, R ⁷ is a phenyl group, a naphthyl group, an anthryl group or a linear or branched alkyl group having 1 to 15 carbon atoms. Some or all of the hydrogen atoms which this phenyl group, naphthyl group, and anthryl group have may be substituted by substituents other than a hydroxyl group and an amino group, and some or all of the hydrogen atoms which the said alkyl group has are substituted by substituents other than a hydroxyl group and an amino group. At least one of these substituents may be a phenyl group, a naphthyl group, or an anthryl group, provided that some or all of the hydrogen atoms of the phenyl group, naphthyl group, or anthryl group may be substituted with a substituent other than a hydroxyl group and an amino group. )

The said polymer is used suitably as a material of the composition for lower layer film formation of this invention. The polymer contains a structural unit having a hydroxyl group or an amino group and a structural unit having an aromatic ring. Therefore, when the said polymer is used as a material of the composition for lower layer film formation of this invention, the resist underlayer film obtained is excellent in hardness and adhesiveness, and also excellent in radiation absorption, such as ArF excimer laser.

Since the resist underlayer film of this invention was formed using the said composition for forming a resist underlayer film, the etching rate in a dry etching process is excellent. Moreover, since it has high adhesiveness with respect to a resist film, it is strong also in pattern collapse.

The pattern forming method of the present invention,

(1) forming a resist underlayer film by applying the composition for forming a resist underlayer film on a substrate to be processed;

(2) forming a resist film by applying a resist composition on the resist underlayer film;

(3) selectively irradiating the resist film with a photomask to expose the resist film;

(4) developing the exposed resist film to form a resist pattern;

(5) forming a pattern by dry etching the resist underlayer film and the substrate to be processed using the resist pattern as a mask.

Since the resist underlayer film obtained from the said composition for resist underlayer film formation has the characteristics mentioned above, according to the pattern formation method of this invention, finer pattern formation is attained.

In the pattern formation method of this invention, it is preferable that said (3) process is performed by the light of 193 nm wavelength. Since the resist underlayer film formed using the said underlayer film forming composition can prevent the diffuse reflection by the board | substrate of the ArF excimer laser which has a wavelength of 193 nm, it can have a higher resolution and can form a fine pattern simultaneously. .

The manufacturing method of the semiconductor device of this invention,

(1) applying the composition for forming a resist underlayer film of the present invention on a substrate to be processed to form a resist underlayer film;

(2) forming a resist film by applying a resist composition on the resist underlayer film;

(3) selectively irradiating the resist film with a photomask to expose the resist film;

(4) developing the exposed resist film to form a resist pattern;

(5) forming a pattern by dry etching the resist underlayer film and the substrate to be processed using the resist pattern as a mask;

(6) forming an integrated circuit device having the pattern

.

Since the resist underlayer film obtained from the said composition for forming a resist underlayer film has the above characteristics, according to the manufacturing method of the semiconductor device of this invention, the semiconductor device which has a finer pattern can be manufactured.

In the manufacturing method of the semiconductor device of this invention, it is preferable that said (3) process is performed by the light of 193 nm wavelength. Since the resist underlayer film formed using this composition can prevent the diffuse reflection by the board | substrate of ArF excimer laser which has a wavelength of 193 nm, the semiconductor device which has a fine pattern with a higher resolution can be manufactured.

By using the composition for forming a resist underlayer film of the present invention, it is possible to form a resist underlayer film having a high etching rate and realizing an excellent etching selectivity with respect to the resist film. In addition, since the resist underlayer film is excellent in adhesion to the resist film, pattern collapse can be suppressed. As a result, finer pattern formation becomes possible when the said composition for resist underlayer film formation is used.

EMBODIMENT OF THE INVENTION Embodiment of the pattern formation method and the manufacturing method of a semiconductor device using the composition for resist underlayer film formation of this invention, the resist underlayer film, the composition for this resist underlayer film formation are demonstrated below.

<Composition for forming a resist underlayer film>

The resist underlayer film-forming composition contains the polymer [A]. [B] Crosslinking agent may be further contained as a suitable component. Moreover, other arbitrary components may be included in the range which does not impair the effect of this invention. Each component is demonstrated below.

<[A] polymer>

The polymer [A] is a polymer having a cyclic carbonate structure. Since the polymer has a cyclic carbonate structure having a high oxygen atom content, the resist underlayer film formed by using the composition for forming a resist underlayer film containing the polymer [A] has a high etching rate and an excellent etching selectivity with respect to the resist film. Do. Moreover, the adhesiveness with respect to a resist film is also excellent. As a cyclic carbonate structure, group represented by following formula (3) is mentioned, for example.

(In Formula 3, p is an integer of 0 to 3, q is 0 or 1, r is an integer of 0 to 2, X is -CH _2- , -CH ₂ -CH _2- , -O-, -S- or -SO ₂ -with the proviso that when r is 2, a plurality of X's may be the same or different, and "*" is a bond and a part of the hydrogen atoms possessed by the cyclic carbonate group in the above formula (3) Or all may be substituted)

As group represented by the said General formula (3), group represented by following General formula (3-1) and (3-2) is mentioned as a preferable group.

("*" In the formulas (3-1) and (3-2) is a bond)

[A] The polymer preferably has a structural unit (I) represented by the formula (1) having a cyclic carbonate structure, and a structural unit (II) represented by the formula (2), a structural unit containing a fluorine atom ( It is preferable to further have III). In addition, the polymer [A] may have other structural units as long as the effects of the present invention are not impaired. Hereinafter, each structural unit is demonstrated. In addition, [A] polymer may have each structural unit individually by 1 type, and may have 2 or more types.

[Structural Unit (I)]

It is preferable that the polymer (A) has a structural unit (I) represented by the formula (1).

In said Formula (1), R <^1> is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. Q ¹ is a divalent linking group. Y is a group formed by combining a single bond, a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 6 to 20 carbon atoms, or a group thereof. Some or all of the hydrogen atoms which the said alkylene group, arylene group, or heteroarylene group have may be substituted. Moreover, you may have an oxygen atom in the carbon chain of the said alkylene group. p is an integer of 0-3. q is 0 or 1; r is an integer of 0 to 2. X is -CH _2- , -CH ₂ -CH _2- , -O-, -S- or -SO _2- . However, when r is 2, some X may be same or different.

Examples of the divalent linking group represented by Q ¹ include -O-, -S-, -COO-, -OCO-, -NHCOO-, -NHCONH-, -SO _2- , -CO- and the like. . Of these, -COO- is preferred.

As a C2-C10 linear or branched alkylene group which Y represents, for example, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group Etc. can be mentioned. Among the methylene groups and these, methylene groups, ethylene groups, propylene groups, butylene groups and pentylene groups are preferable.

Examples of the arylene group having 6 to 20 carbon atoms represented by Y include phenylene group, methylphenylene group, methoxyphenylene group, nitrophenylene group, 1,4-naphthylene group, 2,6-naphthylene group and the like. have.

As a hetero arylene group which said Y represents, a pyridine diyl group, a quinolinediyl group, a quinoxaline diyl group, etc. are mentioned, for example.

As structural unit (I) represented by the said General formula (1), the structural unit represented with the following general formula etc. are mentioned, for example.

In the formula, R ¹ has the same meaning as in formula (1).

Among them, the structural unit (I) represented by the general formula (I-1) is preferable.

As a monomer which provides a structural unit (I), 4- (1, 3- dioxa-2-oxo) cyclopentyl (meth) acrylate etc. are mentioned, for example.

It is preferable that it is 5 mol% or more and 60 mol% or less, and, as for the content rate of a structural unit (I) in a polymer (A), it is more preferable that it is 10 mol% or more and 50 mol% or less. By making the content rate of a structural unit (I) into the said specific range, the resist underlayer film obtained from the said composition for resist underlayer film formation is excellent in the etching rate and the etching selectivity with respect to a resist film.

[Structural Unit (II)]

It is preferable that the polymer (A) further has a structural unit (II) represented by the formula (2). The polymer (A) further improves the reactivity with the crosslinking agent or the crosslinkable group by further having not only the structural unit (I) but also the structural unit (II). In addition, the resist underlayer film formed from the composition for forming a resist underlayer film hardly causes intermixing with the resist film.

In said Formula (2), R <^2> is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. Q ² is a divalent linking group. R ³ is a linear or branched alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a heteroaryl group having 6 to 20 carbon atoms. Some or all of the hydrogen atoms of this alkyl group, aryl group, aralkyl group or heteroaryl group may be substituted.

Examples of the divalent linking group represented by Q ² include the same groups as those exemplified as the divalent linking group represented by Q ^{1 in} Formula 1 above. Of these, -COO- is preferred.

As a C1-C15 linear or branched alkyl group which R <^3> represents, for example, a methyl group, an ethyl group, a propyl group, n-butyl group, i-butyl group, n-pentyl group, i-pentyl group, n -Hexyl group, i-hexyl group, etc. are mentioned.

As a C6-C20 aryl group which R <^3> represents, a phenyl group, a naphthyl group, etc. are mentioned, for example. Among these, a phenyl group is preferable.

As a C7-20 aralkyl group which R <^3> represents, a benzyl group, a phenylene ethyl group, a naphthalene methyl group, etc. are mentioned, for example.

As a heteroaryl group of the reduced number 6-20 which R <^3> represents, a pyridyl group, a quinolidinyl group, a pyrazyl group, etc. are mentioned, for example.

As a substituent which one part or all part of the hydrogen atom of the said alkyl group, aralkyl group, aryl group, or heteroaryl group may be substituted, a hydroxyl group or an amino group is preferable, and a hydroxyl group is more preferable.

[A] The polymer is a group consisting of the structural unit (II-1) represented by the formula (2-1) and the structural unit (II-2) represented by the formula (2-2) as the structural unit (II). It is preferable to have at least 1 type of structural unit chosen from. Since structural unit (II-1) contains at least one hydroxyl group or an amino group as a substituent, the reactivity with the crosslinking agent or crosslinkable group of a [A] polymer is accelerated | stimulated. In addition, since the structural unit (II-2) has a phenyl group, a naphthyl group, or an anthryl group, the resist underlayer film formed from the composition for forming a resist underlayer film has radiation absorbing properties such as KrF excimer laser, ArF excimer laser, and DUV fluorine laser. This is excellent.

In said general formula (2-1), R <^4> is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. R ⁶ is an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 20 carbon atoms. Some or all of the hydrogen atoms which the said alkyl group and the aryl group have are substituted by the substituent, and at least one of the said substituents is group which has a hydroxyl group or an amino group. As a substituent other than the group which has a hydroxyl group and an amino group, a halogen atom, a C1-C10 alkyl group, a C3-C10 cycloalkyl group, etc. are mentioned.

As said C1-C15 alkyl group, the group similar to the group illustrated as a C1-C15 linear or branched alkyl group represented by said R <^3> is mentioned.

Examples of the aryl group having 6 to 20 carbon atoms include the same groups as the groups exemplified as the aryl group having 6 to 20 carbon atoms represented by R ³ .

In said Formula (2-2), R <^5> is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. R ⁷ is a phenyl group, a naphthyl group, an anthryl group or a linear or branched alkyl group having 1 to 15 carbon atoms. Some or all of the hydrogen atoms which the said phenyl group, naphthyl group, and anthryl group have may be substituted by substituents other than a hydroxyl group and an amino group. In addition, some or all of the hydrogen atoms which the said alkyl group has are substituted by substituents other than a hydroxyl group and an amino group, At least one of these substituents is a phenyl group, a naphthyl group, or an anthryl group. However, some or all of the hydrogen atoms which the said phenyl group, naphthyl group, or anthryl group have may be substituted by substituents other than a hydroxyl group and an amino group. As a substituent other than a hydroxyl group and an amino group, a halogen atom, a C1-C10 alkyl group, a C3-C10 cycloalkyl group, etc. are mentioned.

As a C1-C15 linear or branched alkyl group represented by said R <^7> , the group similar to the group illustrated as a C1-C15 linear or branched alkyl group represented by said R <^3> is mentioned.

As the polymer (A), the structural unit (II) has a structural unit (II-1) and a structural unit (II-2), or the structural unit (II) has a structural unit (II-1), It is more preferable that said R <^6> is an aryl group.

As said structural unit (II-1), the structural unit represented by the following general formula (2-1-1), (2-1-2), and (2-1-4) is preferable.

In the formula, R ² has the same meaning as in formula (2).

As said structural unit (II-2), the structural unit represented with the following general formula is preferable.

In the formula, R ² has the same meaning as in formula (2).

As a monomer which provides a structural unit (II), for example, 3- (1-oxa-2-oxo) cyclopentyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and the like.

It is preferable that it is 30 mol% or more and 95 mol% or less, and, as for the content rate of structural unit (II) in a polymer, it is more preferable that it is 40 mol% or more and 90 mol% or less. By making the content rate of a structural unit (II) into the said specific range, the reactivity with the crosslinking agent or crosslinkable group of a [A] polymer can be improved.

The content of the structural unit (II-1) in the polymer (A) is preferably 10 mol% or more and 80 mol% or less, and more preferably 20 mol% or more and 70 mol% or less. As content rate of a structural unit (II-2), it is preferable that they are 0 mol% or more and 50 mol% or less, and it is more preferable that they are 20 mol% or more and 40 mol% or less. By setting the content rate of the structural units (II-1) and (II-2) in the specific range, the resist underlayer obtained from the composition for forming a resist underlayer film while being excellent in reactivity with the crosslinking agent or crosslinkable group of the polymer [A]. It is possible to improve the radiation absorption rate of the film. Moreover, as a polymer [A], what has both a structural unit (II-1) and (II-2) at the said specific content rate is preferable.

[Structural Unit (III)]

Structural unit (III) is a structural unit containing a fluorine atom. As structural unit (III), the structural unit represented by following General formula (4) is preferable.

(In Formula 4, R ⁸ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R ⁹ is a C1-C6 linear or branched alkyl group having a fluorine atom, or C3 having a fluorine atom. To a monovalent alicyclic group of 20, provided that some or all of the hydrogen atoms of the alkyl group and the alicyclic group may be substituted)

As a C1-C6 linear or branched alkyl group which has a fluorine atom represented by said R <^9> , a part or all of the hydrogen atoms which a methyl group, an ethyl group, n-propyl group, n-butyl group, etc. have, for example, are fluorine. The group substituted by the atom etc. are mentioned.

As a C3-C20 monovalent alicyclic group which has a fluorine atom represented by said R <^9> , For example, a cyclopentyl group, a cyclopentyl propyl group, a cyclohexyl group, a cyclohexylmethyl group, a cycloheptyl group, a cyclooctyl group, cyclooctyl The group etc. which the one part or all part of the hydrogen atom which the methyl group etc. have were substituted by the fluorine atom are mentioned.

As structural unit (III), the structural unit represented by following General formula (4-1), (4-2), etc. are mentioned, for example.

(In formulas (4-1) and (4-2), R ⁹ has the same meaning as in formula (4).)

As a monomer which provides a structural unit (III), For example, trifluoromethyl (meth) acrylate, 2,2,2- trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, Perfluoro n-propyl (meth) acrylate, perfluoro i-propyl (meth) acrylate, perfluoro n-butyl (meth) acrylate, perfluoro i-butyl (meth) acrylate, perfluoro T-butyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2- (1,1,1,3,3,3-hexafluoro) propyl (meth) acrylate, 1- ( 2,2,3,3,4,4,5,5-octafluoro) pentyl (meth) acrylate, 1- (2,2,3,3,4,4,5,5-octafluoro) Hexyl (meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 1- (2,2,3,3,3-pentafluoro) propyl (meth) acrylate, 1- (2,2, 3,3,4,4,4-heptafluoro) penta (meth) acrylate, 1- (3,3,4,4,5,5,6,6,7,7,8,8,9, 9,10,10,10-heptadecafluoro) decyl (meth) acrylate, 1- (5-trifluoromethyl-3,3,4,4,5,6,6,6-octafluoro) Hexyl (meth) acrylate etc. are mentioned.

It is preferable that they are 1 mol% or more and 40 mol% or less, and, as for the content rate of the structural unit (III) in a polymer, it is more preferable that they are 5 mol% or more and 30 mol% or less.

[[A] polymer synthesis method]

The polymer (A) can be produced, for example, by polymerizing a monomer providing each of the predetermined structural units in a suitable solvent using a radical polymerization initiator.

As a radical initiator used for the said superposition | polymerization, azobisisobutyronitrile (AIBN), 2,2'- azobis (4-methoxy-2, 4- dimethylvaleronitrile), 2,2'- azobis ( 2-cyclopropyl propionitrile), 2,2'- azobis (2,4-dimethylvaleronitrile), 2,2'- azobis (2-methylpropionitrile), etc. are mentioned. These initiators can also be used in mixture of 2 or more type.

As a solvent used for the said superposition | polymerization, for example,

alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane;

Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane;

Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene;

Halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, hexamethylene dibromide and chlorobenzene;

Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate;

Ketones such as acetone, 2-butanone, 4-methyl-2-pentanone and 2-heptanone;

Ethers such as tetrahydrofuran, dimethoxyethanes and diethoxyethanes;

Alcohol, such as methanol, ethanol, 1-propanol, 2-propanol, and 4-methyl- 2-pentanol, etc. are mentioned. These solvents may be used alone or in combination of two or more thereof.

As reaction temperature in the said superposition | polymerization, 40 degreeC-150 degreeC and 50 degreeC-150 degreeC are preferable normally. As reaction time, 1 hour-48 hours and 1 hour-24 hours are preferable normally.

As a polystyrene reduced weight average molecular weight (Mw) by the gel permeation chromatography (GPC) method of polymer (A), 1,000-100,000 are preferable, 2,000-50,000 are more preferable, 3,000-30,000 are especially preferable. When the Mw of the polymer [A] is less than 1,000, there is a possibility that the intermixing resistance of the film is lowered. On the other hand, when Mw exceeds 100,000, there exists a tendency for the in-plane uniformity of an underlayer film to fall.

The ratio (Mw / Mn) of the polystyrene reduced number average molecular weight (Mn) by the MPC of the polymer (A) and the GPC method is usually 1 to 3, preferably 1 to 2.5.

<[B] crosslinking agent>

The crosslinking agent [B] used in the composition for forming a resist underlayer film of the present invention is a compound which forms a bond with a compound composition such as resin or other crosslinkable molecules by the action of heat or acid. [B] As a crosslinking agent, the polyfunctional (meth) acrylate compound, an epoxy compound, the hydroxymethyl group substituted phenol compound, the compound which has an alkoxyalkylated amino group, etc. are mentioned, for example.

As a polyfunctional (meth) acrylate compound, for example, trimethylolpropane tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) Acrylate, ethylene glycol (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentyl Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanate There may be mentioned the rate of di (meth) acrylate and the like.

As an epoxy compound, a novolak-type epoxy resin, a bisphenol-type epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, etc. are mentioned, for example.

As a hydroxymethyl group substituted phenolic compound, 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene [2,6-bis (hydroxymethyl) -p-cresol] etc. are mentioned.

Examples of the compound having an alkoxyalkylated amino group include a plurality of activities in one molecule such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylolated benzoguanamine, and (poly) methylolurea The compound which is the nitrogen containing compound which has a methylol group, in which at least one of the hydrogen atoms of the hydroxyl group of this methylol group was substituted by alkyl groups, such as a methyl group and a butyl group, etc. are mentioned. In addition, the compound which has the alkoxyalkylated amino group may be a mixture which mixed several substituted compounds, and although the thing containing the oligomer component formed by partial self-condensation exists, these can also be used. Of these, compounds having an alkoxyalkylated amino group are preferred. Especially, methylolated melamine and methylolated glycoluril are more preferable.

As the crosslinking agent (B), one having at least two crosslinking forming functional groups is more preferable. In the present invention, the "crosslinking forming functional group" is not particularly limited as long as it is a functional group having crosslinking reactivity with the polymer [A]. For example, a glycidyl ether group, glycidyl ester group, glycidylamino group, and methoxy Methyl group, ethoxymethyl group, benzyloxymethyl group, acetoxymethyl group, benzoyloxymethyl group, formyl group, acetyl group, vinyl group, isopropenyl group, dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group And morpholinomethyl groups. As the compound having the aforementioned crosslinking functional group, methoxymethylated glycoluril or methoxymethylated melamine is preferable, and hexamethoxymethylated melamine and tetramethoxymethylated glycoluril are particularly preferable.

In addition, these [B] crosslinking agents can be used individually by 1 type or in combination of 2 or more type.

The crosslinking agent (B) may cause a crosslinking reaction by self-condensation, but when a crosslinking functional group is present in the [A] polymer, it may cause a crosslinking reaction with these crosslinking functional groups. In addition, when the structural unit (II) represented by the formula (2) in the polymer [A] has a hydroxyl group or an amino group, the crosslinking functional group and the hydroxyl group or the amino group of the crosslinking agent may cause a crosslinking reaction.

The content rate of the crosslinking agent (B) is suitably set so that the lower layer film formed by the composition for resist underlayer film forming may fully be hardened | cured. Specifically, the content ratio of the [B] crosslinking agent is usually 0.001 to 100 parts by mass, preferably 0.01 to 50 parts by mass, and preferably 0.1 to 30 parts by mass based on 100 parts by mass of the polymer [A] contained in the resist underlayer film-forming composition. It is more preferable that it is a mass part. If it is less than 0.001 mass part, there exists a possibility that the hardness of the resist underlayer film obtained may become inadequate. On the other hand, when it exceeds 100 mass parts, a crosslinking reaction may arise between the crosslinking agent in a resist underlayer film, and a resist film.

<Other optional ingredients>

The composition for resist underlayer film formation may contain [C] crosslinking catalyst, [D] solvent, [E] surfactant, [F] storage stabilizer, etc. as other arbitrary components. Each component is explained in full detail below.

([C] crosslinking catalyst)

As the composition for forming a resist underlayer film, various amine compounds, phenol resins, amino resins, mercaptan-based compounds, hydrazides, polyphenols, polybasic acids, photoacid generators, or thermal acid generators can be used as the crosslinking catalyst. Especially, the light or thermal acid generator which hardly affects productivity or the optical characteristic of a residual catalyst is preferable.

In the present invention, a compound represented by the following formula is preferable.

([D] solvent)

The resist underlayer film-forming composition usually contains the solvent [D]. The solvent [D] is not particularly limited as long as it can dissolve at least the above-mentioned [A] polymer, the [B] crosslinking agent and other optional components added as necessary. Examples of the solvent [D] include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, mixed solvents thereof, and the like.

As an alcoholic solvent, for example

Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, tert- Pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol , sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec- tetradecyl alcohol, sec-heptadecyl alcohol, green Monoalcohol solvents such as furyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

Propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4- Polyhydric alcohol solvents such as 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Polyhydric alcohol partial ether solvents such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like.

Examples of the ether solvent include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, and the like.

As a ketone solvent, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n- Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, aceto And acetophenone may be mentioned.

As the amide solvent, for example, N, N'-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide , N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone and the like.

Examples of the ester solvent include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate and n-acetic acid Butyl, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cycloacetate Hexyl, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol mono-n-butyl ether, propylene acetate monomethyl ether, propylene acetate Recol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetate glycol, methoxytriglycol acetate, ethyl propionate, propionate n -Butyl, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like. .

As a hydrocarbon solvent, for example

aliphatic such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane Hydrocarbon solvents;

Benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n Aromatic hydrocarbon solvents, such as amyl naphthalene, etc. are mentioned.

Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether, and cyclohexanone are preferable. These organic solvents may be used independently and may use 2 or more types together.

([E] surfactant)

Surfactant can be added in order to improve the applicability | paintability of the said composition for resist underlayer film formation, reduce application | coating nonuniformity, and developability of a radiation irradiation part. As an example of a preferable surfactant, a nonionic surfactant, a fluorine-type surfactant, and a silicone type surfactant are mentioned.

As a nonionic surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; (Meth) acrylic acid type copolymers etc. are mentioned. Examples of the (meth) acrylic acid copolymers include polyflow No. 57, copper No. 95 (manufactured by Kyowa Co., Ltd.), and the like.

As the fluorine-based surfactant, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 Fluoro ethers such as 1,2,2-tetrafluorobutyl) ether and hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether; Sodium perfluorododecyl sulfonate; Fluoroalkanes such as 1,1,2,2,8,8,9,9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane; Sodium fluoroalkylbenzenesulfonates; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodides; Fluoroalkyl polyoxyethylene ethers; Perfluoroalkyl polyoxyethanols; Perfluoroalkyl alkoxylates; Fluorine-based alkyl esters and the like.

Commercially available products of these fluorine-based surfactants include F-Top EF301, 303, and 352 (above, manufactured by Shin Akita Kasei Co., Ltd.), MegaPack F171, 172, 173 (manufactured by Dainippon Ink, Inc.), fluoride FC430, 431 (more than, Sumitomo 3M Corporation), Asahi Guard AG710, Suplon S-382, SC-101, 102, 103, 104, 105, 106 (above, Asahi Glass Co., Ltd.), FTX-218 (manufactured by Neos) Can be.

As an example of a silicone type surfactant, SH200-100cs, SH28PA, SH30PA, ST89PA, SH190 (above, Toray Dow Corning Silicone Co., Ltd.), organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned, for example. .

In the case of using the surfactant (E), the amount is preferably 0.001 parts by mass or more and 10 parts by mass or less, and more preferably 0.005 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymer [A]. The coating property of the composition for resist underlayer film formation can be optimized by making the usage-amount of [E] surfactant into 0.001 mass part or more and 10 mass parts or less.

<Preparation of the composition for forming a resist underlayer film>

The composition for forming a resist underlayer film includes the above-mentioned [A] polymer, [B] crosslinking agent which is a suitable component, [C] crosslinking catalyst added as needed, [D] solvent, and [E] surfactant. It is prepared by mixing uniformly. Usually, the composition for forming a resist underlayer film is preferably produced and used in a state in which it is dissolved or dispersed in a suitable solvent.

When preparing the composition for forming a resist underlayer film as a solution state, the solid content concentration, that is, the ratio of the total amount of the above-mentioned [A] polymer, the [B] crosslinking agent which is a suitable component, and the [C] crosslinking catalyst added as necessary, is It can be set to arbitrary concentrations according to the purpose of use, the film thickness value required, and the like. 0.5-50 mass% is preferable, and 1-40 mass% is more preferable. More preferably, it is 1.5-35 mass%. The solution of the composition for forming a resist underlayer film thus prepared may be used after being filtered using a Millipore filter or the like having a pore size of about 0.2 to 0.5 µm.

<Polymer>

The polymer is a structural unit represented by the structural unit (I) represented by the general formula (1-1), the structural unit (II-1) represented by the general formula (2-1) and the general formula (2-2) ( II-2). The polymer contains a structural unit having a hydroxyl group or an amino group and a structural unit having an aromatic ring. Therefore, when this polymer is used as a material of the composition for forming an underlayer film of the present invention, the resulting resist film promotes crosslinking reaction with a crosslinking agent, and is excellent in hardness and adhesiveness, and also excellent in radiation absorption such as an ArF excimer laser. Therefore, this polymer is used suitably as a material of the composition for lower layer film formation of this invention. In addition, about this polymer, the description about the polymer [A] of the said composition for resist underlayer film formation is applicable.

<Resist Underlayer Film>

Since the resist underlayer film is formed using a composition for forming a resist underlayer film containing a polymer having a [A] cyclic carbonate structure, the resist underlayer film has a high etching rate, and has an excellent etching selectivity for the resist film and the substrate. have. Moreover, the adhesiveness with respect to a resist film is also excellent. In addition, since the polymer [A] has a structural unit having an aromatic ring, the resist underlayer film is excellent in radiation absorption such as an ArF excimer laser and can be preferably used as an antireflection film. In addition, since the polymer [A] has a hydroxyl group or an amino group, the crosslinking reaction with the [B] crosslinking agent is promoted, and the intermixing resistance of the resulting resist underlayer film is improved. Such a resist underlayer film can be suitably used for technical applications requiring high resolution.

The film thickness of the resist underlayer film is usually 5 nm or more and 200 nm or less, and in order to increase patterning property, 10 nm or more and 100 nm or less are preferable.

<Method for producing resist underlayer film>

As a specific manufacturing method of the said resist underlayer film, a coating film is formed by apply | coating this composition for resist underlayer film formation on the surface of a board | substrate or another underlayer film, etc., for example, and heat-processing this coating film, or a latent photo-acid generator When it contains, the method of hardening by irradiating an ultraviolet light and heat-processing is mentioned. As the substrate, for example, an insulating film made of silicon oxide, silicon nitride, silicon oxynitride, polysiloxane, or the like, coated with a low dielectric insulating film such as black diamond (manufactured by AMAT), silk (manufactured by Dow Chemical), or LKD5109 (manufactured by JSR) An interlayer insulating film such as a wafer can be used. In addition, as this board | substrate, patterned board | substrates, such as a wiring groove (trench) and a plug groove (via), can also be used.

As a method of apply | coating the composition for resist underlayer film forming, a well-known method is mentioned, For example, a spin coating method, a roll coating method, an immersion method, etc. are mentioned. In addition, the heating temperature of the coating film formed is 50-450 degreeC normally.

<Pattern forming method>

The pattern forming method of the present invention comprises the steps of (1) applying a composition for forming a resist underlayer film on a substrate to be processed to form a resist underlayer film (hereinafter also referred to as "step 1"), and (2) a resist on the resist underlayer film A process of applying a composition to form a resist film (hereinafter also referred to as "step 2"), and (3) exposing the resist film to selective radiation through a photomask (hereinafter referred to as "step 3"). "," (4) developing the exposed resist film to form a resist pattern (hereinafter also referred to as "step 4"), and (5) using the resist pattern as a mask for the resist underlayer film and the And a process of forming a pattern by dry etching the substrate to be processed (hereinafter, also referred to as "step 5").

Hereinafter, each of these steps will be described sequentially.

[Step (1)]

In this step (1), a resist underlayer film is formed on the substrate using the composition for forming a resist underlayer film. Thereby, the board | substrate with a resist underlayer film in which the resist underlayer film was formed on the board | substrate can be obtained. As said board | substrate, the thing similar to what was illustrated by the manufacturing method of a resist underlayer film can be used.

Furthermore, another underlayer film (hereinafter also referred to as "underlayer film") different from the resist underlayer film obtained by using the composition for forming a resist underlayer film of the present invention may be previously formed on the substrate. This underlayer film is a film to which antireflection function, coating film flatness, and high etching resistance to fluorine-based gases such as CF ₄ are imparted. This underlayer film can be formed by a conventionally well-known method using the material marketed by brand names, such as "NFC HM8005" (made by JSR Corporation) and "NFC CT08" (made by JSR Corporation).

Although the formation method of this resist underlayer film is not specifically limited, For example, it hardens | cures by exposing and / or heating the coating film formed by apply | coating the composition for resist underlayer film formation on a to-be-processed substrate by well-known methods, such as a spin coating method. Can be formed. Examples of the radiation used for this exposure include visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, molecular rays, ion beams, and the like. Moreover, although the temperature at the time of heating a coating film is not specifically limited, It is preferable that it is 90-550 degreeC, More preferably, it is 90-450 degreeC, More preferably, it is 90-300 degreeC. Although the film thickness of the underlayer film is not particularly limited, it is usually 5 nm or more and 200 nm or less, and in order to improve patterning property, it is preferable that they are 10 nm or more and 100 nm or less.

[Step (2)]

In this step (2), a resist film is formed on the resist underlayer film obtained in step (1) using the resist composition. As the resist composition used in this step (2), for example, a positive or negative chemically amplified resist composition containing a photoacid generator, a positive resist composition containing an alkali-soluble resin and a quinonediazide-based photosensitive agent, Examples of suitable resist compositions include alkali-soluble resins and crosslinking agents.

Moreover, although solid content concentration of a resist composition is not specifically limited, For example, it is preferable that it is 5-50 mass%.

Moreover, as a resist composition, the thing filtered using the filter of about 0.2 micrometer of pore diameters can be used preferably. Moreover, in the pattern formation method of this invention, you may use the resist composition which is a commercial item as it is as such a resist composition.

The method of applying the resist composition is not particularly limited, and for example, can be applied by conventional methods such as spin coating. In addition, when apply | coating a resist composition, the quantity of the resist composition apply | coated so that the obtained resist film may become a predetermined | prescribed film thickness is adjusted.

The resist film can be formed by volatilizing a solvent (that is, a solvent contained in the resist composition) in the coating film by prebaking the coating film formed of the resist composition. Although the temperature at the time of prebaking is adjusted suitably according to the kind of resist composition to be used, etc., It is preferable that it is 30-200 degreeC, More preferably, it is 50-150 degreeC. Moreover, another film can also be provided on the surface of this resist film.

[Step (3)]

In this step (3), the resist film obtained in the step (2) is selectively irradiated with a radiation through a photomask to expose the resist film. The radiation used in this step (3) is appropriately selected from visible rays, ultraviolet rays, far ultraviolet rays, X rays, electron beams, gamma rays, molecular rays, ion beams and the like depending on the type of acid generator used in the resist composition. In particular, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), Kr ₂ excimer laser (147 nm), ArKr excimer laser (134 nm), extreme ultraviolet rays (13.5 nm etc.) etc. are mentioned as a suitable example.

Moreover, there is no restriction | limiting in particular also about the method of exposing, It can carry out according to the method performed by conventionally well-known pattern formation. Moreover, the liquid immersion exposure method can also be used.

[Step (4)]

In this step (4), a resist pattern is formed by developing the resist film exposed in step (3) using a developer. The developing solution used for image development can be suitably selected according to the kind of resist composition used. In the case of a positive chemically amplified resist composition or a positive resist composition containing an alkali-soluble resin, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, Diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1 Alkaline aqueous solution, such as 8-diazabicyclo [5.4.0] -7-undecene and 1, 5- diazabicyclo [4.3.0] -5-nonene, can be used. Moreover, these alkaline aqueous solution may be a thing which added the water-soluble organic solvent, such as alcohol, such as methanol and ethanol, and surfactant suitably.

In addition, in the case of the negative chemical amplification resist composition and the negative resist composition containing alkali-soluble resin, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethyl, for example, 1st amines, such as amine and n-propylamine, 2nd amines, such as diethylamine and di-n-butylamine, 3rd amines, such as triethylamine and methyldiethylamine, dimethylethanolamine, triethanolamine, etc. Aqueous solutions of alkalis such as quaternary ammonium salts such as alcohol amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and piperidine can be used.

In the step (4), a predetermined resist pattern corresponding to the photomask can be formed by performing development with the developer, followed by washing and drying.

In this step (4), postbaking is preferably performed before development (that is, after exposure in step (3)) in order to improve resolution, pattern profile, developability, and the like. Do. Although the temperature of this postbaking is suitably adjusted according to the kind etc. of the resist composition used, it is preferable that it is 50-200 degreeC, More preferably, it is 80-150 degreeC.

[Step (5)]

In this step (5), the resist underlayer film and the substrate are dry-etched using the resist pattern formed in the step (4) as a mask (etching mask) to form a pattern. When the substrate on which the underlayer film is formed is used, the underlayer film is dry-etched together with the resist underlayer film and the substrate. The said dry etching can be performed using a well-known dry etching apparatus. Further, as the source gas at the time of dry etching, it differs depending on the elemental composition of the etched, but O _2, CO, gas containing oxygen atoms such as CO _2, He, N _2, an inert gas such as Ar, Cl _2, BCl may use chlorine-based gas, a gas such as H _2, NH _3, such as _4. In addition, these gases can also be mixed and used.

The resist underlayer film obtained from the composition for forming a resist underlayer film has a high etching rate as described above, and is excellent in adhesiveness with a resist film. Therefore, since it is strong against pattern collapse, according to the pattern formation method of this invention, a finer pattern can be formed.

<Method for Manufacturing Semiconductor Device>

The manufacturing method of the semiconductor device in this invention,

(1) a step of forming a resist underlayer film by applying the composition for forming a resist underlayer film of the present invention on a substrate to be processed (hereinafter also referred to as "step 1");

(2) forming a resist film by applying a resist composition on the resist underlayer film (hereinafter also referred to as "step 2"),

(3) exposing the resist film to radiation by selectively irradiating the resist film through a photomask (hereinafter also referred to as "step 3");

(4) developing the exposed resist film to form a resist pattern (hereinafter also referred to as "step 4"),

(5) forming a pattern by dry etching the resist underlayer film and the substrate to be processed using the resist pattern as a mask (hereinafter also referred to as "step 5");

(6) a step of forming an integrated circuit element (hereinafter also referred to as "step 6").

Each process is demonstrated sequentially below. The said process 1-process 5 are the same as the process 1-process 5 in the pattern formation method mentioned above.

[Process (6)]

In this step (6), an integrated circuit is formed by a conventionally known method using the substrate on which the pattern is formed.

[Example]

Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The measuring method of various physical property values is shown below.

[Weight average molecular weight (Mw), number average molecular weight (Mn)]

Monodisperse polystyrene under analytical conditions with a flow rate of 1.0 mL / min, an elution solvent, tetrahydrofuran, and a column temperature of 40 ° C using a GPC column (2 G2000HXL, 1 G3000 HXL, 1 G4000 HXL) manufactured by Tosoh Corporation. Was measured by gel permeation chromatography (GPC).

¹³ C-NMR Analysis

¹³ C-NMR analysis for determining the fluorine atom content (mass%) of the polymer was measured using a nuclear magnetic resonance apparatus ("JNM-ECX400" manufactured by Nippon Denshi Co., Ltd.).

<Synthesis of polymer [A]>

Polymers (A-1) to (A-6) and (a-1) to (a-6) were synthesized using the compounds (M-1) to (M-12) represented by the following formulas. In addition, the compound used for the synthesis | combination of the polymer (R-1)-(R-2) for resist compositions mentioned later was also shown below.

Example 1

7.00 g (31 mol%) (M-1), 6.63 g (31 mol%) (M-3), 6.37 g (38 mol%) (M-5), dimethyl 2,2'- in a 200 mL flask. 0.55 g of azobis (2-methylpropionate) and 40 g of propylene glycol monomethyl ether were added, followed by stirring at 80 ° C. for 5 hours under nitrogen to conduct a polymerization reaction. After completion of the polymerization, the polymerization solution was cooled to 30 ° C. or lower by water cooling, and then charged into a solution of 300 g of methanol: water (mass ratio 9: 1) to precipitate the polymer. After removing the supernatant solution, 60 g of methanol was added to the precipitated polymer and the polymer was washed. After the supernatant was removed, it was dried at 50 ° C. for 17 hours to obtain a polymer (A-1) (amount 12.8 g, yield 64%). This copolymer had Mw of 21,600 and Mw / Mn of 2.2. ^As a result of ¹³ C-NMR analysis, the contents of (M-1), (M-3) and (M-5) were 32 mol%, 31 mol% and 37 mol%, respectively.

[Example 2]

7.00 g (31 mol%) (M-1), 6.63 g (31 mol%) (M-3), 6.37 g (38 mol%) (M-5), dimethyl 2,2'- in a 200 mL flask. 0.55 g of azobis (2-methylpropionate) and 40 g of propylene glycol monomethyl ether were added and stirred at 80 ° C. for 5 hours under nitrogen. Thereafter, 0.23 g (1 mol%) of dimethyl 2,2'-azobis (2-methylpropionate) was further added, the temperature was raised to 90 ° C for reaction for 1 hour, and the polymerization was terminated. After completion of the polymerization, a post-treatment was not carried out to obtain a solution containing the polymer (A-2). This copolymer had Mw of 23,400 and Mw / Mn of 2.3. In addition, the concentration of the solution was 33.3%.

[Examples 3 to 6 and Comparative Examples 1 to 6]

The polymers (A-3) to (A-6) and (a-1) to (a) were prepared in the same manner as in the synthesis method of Example 2, except that the type and amount of each component to be blended were as described in Table 1. -6) was synthesized. Mw and Mw / Mn of the obtained polymer are shown together in Table 1.

<Production of Polymer for Resist Film Formation>

Synthesis Example 1

18.60 g (15 mol%) of compound (M-9), 6.20 g (35 mol%) of compound (M-10) and 25.20 g (50 mol%) of compound (M-12) are dissolved in 100 g of 2-butanone. Then, a monomer solution in which 1.86 g of dimethyl 2,2'-azobis (2-methylpropionate) was further dissolved was prepared. A 500 mL three-necked flask with 50 g of 2-butanone was purged with nitrogen for 30 minutes, heated to 80 ° C. while stirring the reactor, and the prepared monomer solution was added to the dropping funnel over 3 hours using a dropping funnel. It dripped. The dropping start was taken as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After completion of the polymerization, the polymerization solution was cooled by water to 30 ° C. or lower, and charged into 1,000 g of methanol to precipitate white powder. The white powder separated by filtration was dispersed in 200 g of methanol, washed as a slurry, and then filtered twice. It dried at 50 degreeC for 17 hours, and obtained the copolymer of white powder (amount 39 g, yield 78%). This copolymer had Mw of 6,300 and Mw / Mn of 1.4. This copolymer is referred to as polymer (R-1).

Synthesis Example 2

17.69 g (40 mol%) of compound (M-9), 5.35 g (10 mol%) of compound (M-11) and 26.96 g (50 mol%) of compound (M-12) are dissolved in 100 g of 2-butanone. Then, a monomer solution in which 1.99 g of dimethyl 2,2'-azobis (2-methylpropionate) was further dissolved was prepared. A 500 mL three-necked flask with 50 g of 2-butanone was purged with nitrogen for 30 minutes, heated to 80 ° C. while stirring the reactor, and the prepared monomer solution was added to the dropping funnel over 3 hours using a dropping funnel. It dripped. The dropping start was taken as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After completion of the polymerization, the polymerization solution was cooled by water to 30 ° C. or lower, and charged into 1,000 g of methanol to precipitate white powder. The white powder separated by filtration was dispersed in 200 g of methanol, washed as a slurry, and then filtered twice. It dried at 50 degreeC for 17 hours, and obtained the copolymer of white powder (amount 41 g, yield 82%). This copolymer had Mw of 6,100 and Mw / Mn of 1.4. This copolymer is referred to as polymer (R-2).

<Preparation of the composition for forming a resist underlayer film>

Each component ([B] crosslinking agent, [C] bridge | crosslink which comprises the composition for lower layer film formation other than polymer (A-1)-(A-6) and (a-1)-(a-6) manufactured above Catalyst, [D] solvent and other optional components).

[B] crosslinking agent

Compounds represented by the following formulas (B-1) and (B-2)

[C] crosslinking catalyst

Compound represented by the following formula (C-1)

[D] solvent

(D-1): propylene glycol monomethyl ether

(D-2): propylene glycol monomethyl ether

(D-3): cyclohexanone

[E] surfactants

FTX-218 (manufactured by Neos)

<Preparation of the composition for forming a resist underlayer film>

Example 7

100 parts by mass of the polymer (A-1), 20 parts by mass of the crosslinking agent (B-1), 3 parts by mass of the crosslinking catalyst (C-1), 1,800 parts by mass of the solvent (D-1) and 1,800 parts by mass of the solvent (D-2) By mixing, a composition for forming a resist underlayer film (T-1) was prepared.

[Examples 8 to 19 and Comparative Examples 7 to 19]

Except having performed the kind and compounding quantity of each component to mix | blend as described in Table 2, it carried out similarly to Example 7, and manufactured the composition for resist underlayer film formation (T-2)-(T-26). In Example 19 and Comparative Example 19, the amount of the surfactant shown in Table 2 was added.

<Formation of resist underlayer film>

[Examples 20 to 32 and Comparative Examples 20 to 32]

Each of the resist underlayer film forming compositions prepared in Examples and Comparative Examples was applied to the surface of an 8-inch silicon wafer by spin coating, and baked at 205 ° C. for 60 seconds on a hot plate to form a resist underlayer film having a thickness of 90 nm. Formed. The film thickness of the resist underlayer film was calculated using a lithography simulator (trade name "Prolith", manufactured by KLA Tencor Co., Ltd.) to obtain a second minimum value of the reflectance. The refractive index and the attenuation coefficient of the resist underlayer film were measured according to the following evaluation method. The results are shown in Table 3.

As shown in Table 3, in the refractive index and the attenuation coefficient with respect to the laser of wavelength 193 nm, the resist underlayer film of the Example showed the value equivalent to a comparative example, and it turned out that it fully satisfies the general requirement as an antireflection film.

<Formation of resist pattern>

[Manufacture of a radiation sensitive resin composition]

70 parts by mass of the polymer (R-1), 30 parts by mass of the polymer (R-2), 4 parts by mass of triphenylsulfonium nonafluoro-n-butanesulfonate as an acid generator, 4-butoxy-1-naphthyl 5 parts of tetrahydrothiophenium nonafluoro-n-butanesulfonate, 0.9 parts by mass of Nt-amyloxycarbonyl-4-hydroxypiperidine as an acid diffusion control agent, and 1,250 parts of propylene glycol monomethyl ether acetate as a solvent To this, 520 parts by mass of cyclohexanone was mixed to prepare a radiation sensitive resin composition (P-1).

[Formation of resist underlayer film]

Each of the resist underlayer film-forming compositions prepared in Examples and Comparative Examples was applied to the surface of an 8-inch silicon wafer by spin coating, and baked at 205 ° C. for 60 seconds on a hot plate to form a resist underlayer having a thickness of 90 nm. A film was formed.

[Formation of resist film]

The radiation sensitive composition (P-1) adjusted above was apply | coated by spin coating on this resist underlayer film, and it baked at 120 degreeC for 60 second on the hotplate, and formed the photoresist film of 120 nm in thickness. At this time, intermixing of the resist and the anti-reflection film was not observed.

[Formation of resist pattern]

The silicon wafer to which the obtained resist underlayer film forming composition and the radiation sensitive composition were apply | coated was exposed through the mask pattern using ArF excimer laser exposure apparatus (brand name "NSRS306C", the Nikon Corporation make). Thereafter, PEB was performed at 115 ° C. for 60 seconds, followed by developing at 25 ° C. for 30 seconds with a 2.38% aqueous tetramethylammonium hydroxide solution (hereinafter also referred to as “TMAH aqueous solution”), washing with water, and drying to obtain a positive type. A resist pattern was formed and the pattern collapse dimension was measured in accordance with the following evaluation method. The radiation sensitive resin composition used and the result are shown in Table 4 (Examples 33-45 and Comparative Examples 33-45).

<Evaluation method>

Refractive Index and Attenuation Coefficient

A refractive index and attenuation coefficient at wavelength 193 nm were measured using a spectroscopic ellipsometer.

[Collapse test]

The exposure was performed in the above procedure using a mask having a pattern in which nine 1: 1 line and spaces having a pattern design dimension of 80 nm were arranged. When the exposure amount was increased by 0.5 mJ / cm ² and four of the nine arrayed patterns collapsed, the average value of the remaining five line widths was taken as the collapse dimension. It is evaluated that the shorter the collapse dimension, the more the pattern collapse is suppressed. The scanning electron microscope (brand name "S9380", the Hitachi High-Technologies company) was used for the measurement of the length of a resist pattern.

[Etching Speed]

The obtained solution for forming a resist underlayer film was applied onto a silicon wafer using a spinner. It baked on the hotplate at 205 degreeC for 1 minute, and formed the resist underlayer film. The dry etching rate was measured under conditions using CF ₄ as a dry etching gas. The dry etching rate of the resist underlayer film forming composition when the dry etching rate of the radiation sensitive composition is 1 is shown in Table 5 as a dry etching rate selectivity (Example 46 and Comparative Example 46).

In the examples and comparative examples of the same number shown in Table 4, a resist underlayer film containing different components in the same ratio except that the polymer of [A] was used in Examples and the polymer of Comparative Example having a lactone skeleton in Comparative Examples. The pattern was formed using the resist underlayer film formed from the formation composition. In all the combinations, the resist underlayer film of the Example had a shorter collapsed dimension than the comparative example. When pattern formation was performed using the resist underlayer film obtained from the said resist formation composition, it turned out that pattern collapse can be suppressed compared with a comparative example.

As shown in Table 5, the resist film formed using the resist underlayer film forming composition of the Example has a high etching rate compared with the comparative example. It was found that the resist underlayer film obtained from the resist forming composition having a carbonate structure had a larger etching rate than the comparative example.

By using the composition for forming a resist underlayer film of the present invention, it is possible to form a resist underlayer film having a high etching rate and realizing an excellent etching selectivity with respect to the resist film. In addition, since the resist underlayer film is excellent in adhesion to the resist film and can suppress pattern collapse, finer pattern formation is made possible. The composition for lower layer film formation can fully correspond to the structure of various electronic devices, such as a semiconductor device and a liquid crystal device which require further refinement | miniaturization.

Claims (14)

[A] A composition for forming a resist underlayer film containing a polymer having a cyclic carbonate structure. The composition for forming a resist underlayer film according to claim 1, wherein the polymer [A] has a structural unit (I) represented by the following general formula (1).
<Formula 1>

In Formula 1, R ¹ is a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, Q ¹ is a divalent linking group, Y is a single bond, a methylene group, linear or branched alkyl having 2 to 10 carbon atoms. A ethylene group, an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 6 to 20 reduced water, or a group formed of these groups, and a part of the hydrogen atoms of the alkylene group, arylene group or heteroarylene group, or All may be substituted and may have an oxygen atom in the carbon chain of the said alkylene group, p is an integer of 0-3, q is 0 or 1, r is an integer of 0-2, X is- CH _2- , -CH ₂ -CH _2- , -O-, -S- or -SO _2- , provided that when r is 2, a plurality of X may be the same or different) The composition for forming a resist underlayer film according to claim 2, wherein the polymer [A] further has a structural unit (II) represented by the following formula (2).
<Formula 2>

(In Formula 2, R <^2> is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, Q <^2> is a bivalent coupling group, R <^3> is a hydrogen atom, a C1-C15 linear or branched alkyl group, carbon number It is an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms or a heteroaryl group of 6 to 20 carbon atoms, and part or all of the hydrogen atoms of the alkyl group, aryl group, aralkyl group or heteroaryl group may be substituted. ) The polymer [A] has a structural unit represented by the following general formula (1-1) as the structural unit (I), and is represented by the following general formula (2-1) as the structural unit (II). A composition for forming a resist underlayer film having at least one structural unit selected from the group consisting of structural unit (II-1) and structural unit (II-2) represented by the following general formula (2-2).

(In Formula (1-1), R ¹ , X, Y, p, q and r have the same meanings as in Formula 1,
In general formula (2-1), R <^4> is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, R <^6> is a C1-C15 alkyl group or a C6-C20 aryl group, and this alkyl group and an aryl group have Some or all of the hydrogen atoms are substituted with a substituent, at least one of the substituents is a group having a hydroxyl group or an amino group,
In formula (2-2), R ⁵ is a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, R ⁷ is a phenyl group, a naphthyl group, an anthryl group or a linear or branched alkyl group having 1 to 15 carbon atoms. Some or all of the hydrogen atoms which this phenyl group, naphthyl group, and anthryl group have may be substituted by substituents other than a hydroxyl group and an amino group, and some or all of the hydrogen atoms which the said alkyl group has are substituted by substituents other than a hydroxyl group and an amino group. At least one of these substituents may be a phenyl group, a naphthyl group, or an anthryl group, provided that some or all of the hydrogen atoms of the phenyl group, naphthyl group, or anthryl group may be substituted with a substituent other than a hydroxyl group and an amino group. ) The polymer of claim 4, wherein the polymer [A] has the structural unit (II-1) and the structural unit (II-2) as the structural unit (II), or has the structural unit (II-1), The composition for forming a resist underlayer film wherein R ⁶ is an aryl group. The composition for forming a resist underlayer film according to any one of claims 3 to 5, further comprising [B] a crosslinking agent. The composition for forming a resist underlayer film according to claim 6, wherein the crosslinking agent [B] has at least two crosslinking functional groups. The composition for forming a resist underlayer film according to any one of claims 3 to 7, wherein the polymer (A) further has a structural unit (III) containing a fluorine atom. Structural unit (I) represented by the following general formula (1-1),
Structural unit (II-1) represented by the following general formula (2-1), and
Structural unit (II-2) represented by the following general formula (2-2)
Polymers having

(In Formula (1-1), R ¹ , X, Y, p, q and r have the same meanings as in Formula 1,
In general formula (2-1), R <^4> is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, R <^6> is a C1-C15 alkyl group or a C6-C20 aryl group, and this alkyl group and an aryl group have Some or all of the hydrogen atoms are substituted with a substituent, at least one of the substituents is a group having a hydroxyl group or an amino group,
In formula (2-2), R ⁵ is a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, R ⁷ is a phenyl group, a naphthyl group, an anthryl group or a linear or branched alkyl group having 1 to 15 carbon atoms. Some or all of the hydrogen atoms which this phenyl group, naphthyl group, and anthryl group have may be substituted by substituents other than a hydroxyl group and an amino group, and some or all of the hydrogen atoms which the said alkyl group has are substituted by substituents other than a hydroxyl group and an amino group. At least one of these substituents may be a phenyl group, a naphthyl group, or an anthryl group, provided that some or all of the hydrogen atoms of the phenyl group, naphthyl group, or anthryl group may be substituted with a substituent other than a hydroxyl group and an amino group. ) The resist underlayer film formed from the composition for resist underlayer film forming in any one of Claims 1-8. (1) applying the composition for forming a resist underlayer film according to any one of claims 1 to 8 on a substrate to be formed to form a resist underlayer film;
(2) forming a resist film by applying a resist composition on the resist underlayer film;
(3) selectively irradiating the resist film with a photomask to expose the resist film;
(4) developing the exposed resist film to form a resist pattern;
(5) forming a pattern by dry etching the resist underlayer film and the substrate to be processed using the resist pattern as a mask;
Pattern forming method comprising a. The pattern forming method according to claim 11, wherein the step (3) is performed by light having a wavelength of 193 nm. (1) applying the composition for forming a resist underlayer film according to any one of claims 1 to 8 on a substrate to be formed to form a resist underlayer film;
(2) forming a resist film by applying a resist composition on the resist underlayer film;
(3) selectively irradiating the resist film with a photomask to expose the resist film;
(4) developing the exposed resist film to form a resist pattern;
(5) forming a pattern by dry etching the resist underlayer film and the substrate to be processed using the resist pattern as a mask;
(6) forming an integrated circuit device having the pattern
Method for manufacturing a semiconductor device comprising a. The method for manufacturing a semiconductor device according to claim 13, wherein the step (3) is performed by light having a wavelength of 193 nm.