JP2010217306A - Pattern forming method and composition for forming flattening film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method capable of suppressing dimensional changes in a resist pattern. <P>SOLUTION: The pattern forming method includes steps of: (1) forming a flattening film by applying a composition for forming a flattening film on a substrate to be processed, where a gap having Dense portion and Flat portion is present; (2) forming a resist film by applying a resist composition on the flattening film; (3) selectively exposing the resist film by irradiating the resist film with radiation; (4) forming a resist pattern by developing the exposed resist film; and (5) forming a predetermined pattern in the flattening film and the substrate by using the resist pattern as a mask. The composition for forming a flattening film contains a predetermined polymer (A), a cross-linking agent (B) and an organic solvent (C). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pattern forming method and a composition for forming a flattened film, and more specifically, a pattern forming method capable of suppressing a dimensional change of a resist pattern and a substrate to be processed such as a semiconductor substrate having unevenness. The present invention relates to a composition for forming a flattened film that can form a flattened film having an etching resistance equal to or less than that of a resist film, has a small density bias, and further has a small amount of sublimation.

  As a method for processing a semiconductor substrate, a dual damascene process has been developed. In the dual damascene process, in forming a dual damascene structure, a substrate to be processed such as a semiconductor substrate having irregularities such as a hole pattern and a trench pattern is relaxed using a planarization film, and then a resist is formed on the planarization film. A method of forming a pattern and forming a predetermined pattern on a substrate to be processed using a resist pattern as a mask is performed (for example, see Patent Documents 1 to 11).

JP 7-316268 A JP 2001-40293 A JP 2000-143937 A JP 2008-65303 A JP 2000-294504 A US Pat. No. 5,915,599 US Pat. No. 5,693,691 JP 2002-190519 A JP 2002-128847 A US Pat. No. 6,686,124 JP 2001-192411 A

  By the way, with high integration and customization of semiconductor elements, steps such as unevenness of a substrate to be processed such as a semiconductor substrate (hereinafter also referred to as “gap”) do not have regular gaps over the entire surface of the substrate. It has become a gap locally. In other words, there is a portion having a dense gap (Dense portion) in a place where the substrate is to be processed, and a substrate having a portion (Flat portion) having almost no gap in another place on the same substrate. . FIG. 1 is a schematic diagram showing a substrate having a local gap. In FIG. 1, the substrate 1 has a local gap so that a dense portion 2 and a flat portion 3 exist. Such a substrate 1 having a gap locally is referred to as a “substrate having a density difference”.

  FIG. 2 is a schematic diagram illustrating an example of a state after a planarization film forming composition is applied on a substrate having a difference in density. When the substrate 1 having a difference in density is planarized using the planarizing film forming composition, the thickness A of the planarizing film 4 on the dense portion 2 is usually thin, and the planarizing film 4 on the flat portion 3 is thin. The film thickness B becomes thick and there is a problem that the flatness is lost. Although this problem is referred to as “rough / dense bias”, there is a demand for a composition for forming a flattened film with less of this coarse / dense bias.

  As a method of reducing the “dense / dense bias”, there is a method of lowering the molecular weight of the resin contained in the planarization film forming composition. However, when the molecular weight of the resin is lowered, a sublimate is generated from the composition for forming a flattening film when forming the flattening film, which is not preferable.

  The present invention has been made in view of such problems of the prior art, and the problem is to suppress dimensional change of the resist pattern using the planarization film forming composition. An object of the present invention is to provide a pattern forming method that can be used. In addition, the problem is to form a flattened film that has the minimum performance (uneven step coverage) as a composition for forming a flattened film and that has an etching resistance equal to or less than that of a resist film. An object of the present invention is to provide a composition for forming a flattened film that can reduce the density bias and further has a small amount of sublimation.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors performed planarization using a composition for forming a planarized film containing a predetermined polymer, a crosslinking agent, and an organic solvent. The present inventors have found that the above problems can be achieved and have completed the present invention. Moreover, it discovered that the said subject could be achieved by containing a predetermined | prescribed polymer, a crosslinking agent, and an organic solvent, and came to complete this invention.

  That is, according to the present invention, the following pattern forming method and planarizing film forming composition are provided.

  [1] A step (1) of forming a planarizing film by applying a planarizing film-forming composition on a substrate to be processed having a gap having a dense part and a flat part, and a resist on the planarizing film A step (2) of applying a composition to form a resist film, a step (3) of selectively exposing the resist film by irradiating the resist film with radiation, and developing the exposed resist film. A step (4) of forming a resist pattern, and a step (5) of forming a predetermined pattern on the planarizing film and the substrate to be processed using the resist pattern as a mask. The composition for forming comprises a polymer (A) having a structural unit (a1) represented by the following general formula (1) and a structural unit (a2) represented by the following general formula (2), and at least two carboxyls Crosslinks with groups (B) and an organic solvent (C), and the polymer (A) has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation column chromatography of 50,000. The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation column chromatography is 1.0 to 1.6. A pattern forming method.

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents a group having an epoxy group. In the general formula (2), R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents an alkyl group having 1 to 20 carbon atoms.

  [2] In the polymer (A), the mass ratio ((a1) / (a2)) of the structural unit (a1) to the structural unit (a2) is 1/1 to 2.5 / 1. The pattern forming method according to [1].

  [3] The pattern forming method according to [1] or [2], wherein the polymer (A) is a polymer composed of only a structural unit derived from at least one of a methacrylic compound and an acrylic compound.

  [4] The pattern forming method according to any one of [1] to [3], which is a method for forming a dual damascene structure.

  [5] The pattern forming method according to [4], wherein the dual damascene structure is formed by a via first method.

  [6] A polymer (A) having a structural unit (a1) represented by the following general formula (1) and a structural unit (a2) represented by the following general formula (2), and having at least two carboxyl groups It contains a crosslinking agent (B) and an organic solvent (C), and the polymer (A) has a polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation column chromatography of 50,000 or more. And the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation column chromatography is 1.0 to 1.6. A composition for forming a planarizing film, which is a coalescence.

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents a group having an epoxy group. In the general formula (2), R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents an alkyl group having 1 to 20 carbon atoms.

  [7] In the polymer (A), the mass ratio ((a1) / (a2)) of the structural unit (a1) to the structural unit (a2) is 1/1 to 2.5 / 1. [6] The flattening film forming composition as described in [6].

  [8] For forming a flattened film according to [6] or [7], wherein the polymer (A) is a polymer composed only of a structural unit derived from at least one of a methacrylic compound and an acrylic compound. Composition.

  According to the pattern forming method of the present invention, there is an effect that a dimensional change of the resist pattern can be suppressed.

  In addition, the planarization film-forming composition of the present invention has the minimum performance (uneven step coverage) as a planarization film-forming composition, and has an etching resistance equal to or less than that of a resist film. A film can be formed, and the effect that the density bias is small and the amount of sublimation is small is also achieved.

It is a schematic diagram which shows the board | substrate which has a gap locally. It is a schematic diagram which shows an example of the state after apply | coating the composition for planarization film formation on the board | substrate with a density difference. It is a schematic diagram which shows 1 process of the formation method of the dual damascene structure using the composition for planarization film formation of this invention. It is a schematic diagram which shows 1 process of the formation method of the dual damascene structure using the composition for planarization film formation of this invention. It is a schematic diagram which shows 1 process of the formation method of the dual damascene structure using the composition for planarization film formation of this invention. It is a schematic diagram which shows 1 process of the formation method of the dual damascene structure using the composition for planarization film formation of this invention. It is a schematic diagram which shows 1 process of the formation method of the dual damascene structure using the composition for planarization film formation of this invention. It is a schematic diagram which shows 1 process of the formation method of the dual damascene structure using the composition for planarization film formation of this invention. It is a schematic diagram which shows 1 process of the formation method of the dual damascene structure using the composition for planarization film formation of this invention. It is a schematic diagram which shows 1 process of the formation method of the dual damascene structure using the composition for planarization film formation of this invention. It is a schematic diagram which shows 1 process of the formation method of the dual damascene structure using the composition for planarization film formation of this invention. It is a schematic diagram which shows 1 process of the formation method of the dual damascene structure using the composition for planarization film formation of this invention.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that modifications, improvements, and the like appropriately added to the embodiments described above fall within the scope of the present invention.

I. Flattening film-forming composition The flattening film-forming composition of the present invention comprises a structural unit (a1) represented by the following general formula (1) (hereinafter also referred to as “structural unit (a1)”) and A polymer (A) having a structural unit (a2) represented by the general formula (2) (hereinafter also referred to as “structural unit (a2)”) (hereinafter also referred to as “polymer (A)”), and at least It contains a crosslinking agent (B) having two carboxyl groups (hereinafter also referred to as “crosslinking agent (B)”) and an organic solvent (C).

In General Formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents a group having an epoxy group. In general formula (2), R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents an alkyl group having 1 to 20 carbon atoms.

1 Polymer (A)
The polymer (A) has a structural unit (a1) and a structural unit (a2), and has a polystyrene-reduced weight average molecular weight (hereinafter also referred to as “Mw”) of 50, measured by gel permeation column chromatography. The ratio (Mw / Mn) of Mw to polystyrene-reduced number average molecular weight (hereinafter also referred to as “Mn”) measured by gel permeation column chromatography is 1.0 to 1.6. The polymer.

  The polymer (A) may be a polymer having a structural unit other than the structural unit (a1) and the structural unit (a2) (hereinafter also referred to as “other structural unit”). However, the structural unit (a1), the structural unit (a2), and other structural units are preferably structural units derived from at least one of a methacrylic compound and an acrylic compound.

(1) Structural unit (a1)
The structural unit (a1) is a structural unit represented by the general formula (1). Of the groups represented by R ¹ in the general formula (1), examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. I-butyl group, t-butyl group and the like. Among these, a methyl group is preferable.

Of the groups represented by R ² in general formula (1), examples of the group having an epoxy group include 2,3-epoxypropyl group, 2-methyl-2,3-epoxypropyl group, 3 , 4-epoxycyclohexylmethyl. Among these, 2,3-epoxypropyl group is preferable.

  Specific examples of monomers constituting the structural unit (a1) include acrylic acid-2,3-epoxypropyl, methacrylic acid-2,3-epoxypropyl, and methacrylic acid-2-methyl-2,3-epoxy. Examples thereof include propyl and 3,4-epoxycyclohexylmethyl methacrylate. Among these, methacrylic acid-2,3-epoxypropyl is preferable.

(2) Structural unit (a2)
The structural unit (a2) is a structural unit represented by the general formula (2). Among the groups represented by R ³ in the general formula (2), examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. I-butyl group, t-butyl group and the like. Among these, a methyl group is preferable.

In the general formula (2), among the groups represented by R ⁴ , examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n- Examples thereof include a butyl group, i-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, and n-octyl group. Among these, a methyl group and a t-butyl group are preferable.

  Specific examples of monomers constituting the structural unit (a2) include methyl acrylate, methyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and n-octyl methacrylate. Etc. Among these, methyl methacrylate and tert-butyl methacrylate are preferable.

  In the polymer (A), the mass ratio ((a1) / (a2)) of the structural unit (a1) to the structural unit (a2) is preferably 1/1 to 2.5 / 1, and 1.5 More preferably, the ratio is / 1 to 2.4 / 1. When the mass ratio ((a1) / (a2)) between the structural unit (a1) and the structural unit (a2) is not within this range, the curability may not be sufficient.

(3) Other structural units Specific examples of other structural units include maleic anhydride.

  In the polymer (A), the ratio of other structural units to the total of the structural units (a1) and (a2) (other structural units / (a1) + (a2)) is 1/1 to 10/1. It is preferable that it is 3 / 1-5 / 1. If the ratio of the other structural unit to the total of the structural unit (a1) and the structural unit (a2) (other structural unit / (a1) + (a2)) is not within this range, the etching resistance may not be preferable. is there.

  The method for preparing the polymer (A) is not particularly limited and can be prepared by a conventionally known polymerization method. For example, the monomer component constituting the structural unit (a1) and the structural unit (a2) can be prepared by polymerizing with a radical polymerization initiator in the presence of a solvent.

  The radical polymerization initiator is not particularly limited, and examples thereof include hydroperoxides, dialkyl peroxides, diacyl peroxides, and azo compounds. Examples of the solvent include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; cycloalkanes such as cyclohexane, cycloheptane and cyclooctane; decalin , Cycloaliphatic hydrocarbons such as norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, hexamethylene dibromide and chlorobenzene; acetic acid Saturated carboxylic acid esters such as ethyl, n-butyl acetate, i-butyl acetate and methyl propionate; ketones such as acetone, 2-butanone, 4-methyl-2-pentanone and 2-heptanone; tetrahydrofuran, dimethoxyethane, Ethers such as diethoxyethane; meta Lumpur, ethanol, 1-propanol, 2-propanol, may be mentioned alcohols such as 4-methyl-2-pentanol. In addition, these solvent may be used individually by 1 type, and may use 2 or more types.

  The polymerization reaction temperature is preferably 40 to 150 ° C, and more preferably 50 to 120 ° C. The reaction time is preferably 1 to 48 hours, and more preferably 1 to 24 hours.

  The Mw of the polymer (A) is 50,000 or more, preferably 55,000 or more, and more preferably 60,000 or more. If Mw is less than 50,000, the amount of sublimation may not be sufficiently suppressed, or the flatness may be insufficient. In addition, Mw of a polymer (A) can be normally controlled by making the usage-amount of a radical polymerization initiator into 3 mass% or less of a monomer component.

  Moreover, ratio (Mw / Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) of a polymer (A) is 1.0-1.6, and is 1.2-1.6. It is preferable that it is 1.3-1.5. When Mw / Mn is not in this range, the amount of sublimation may not be sufficiently suppressed, or flatness may be insufficient. In addition, Mw / Mn of the polymer (A) can be suppressed by performing reprecipitation after the completion of the polymerization reaction.

2 Crosslinking agent (B)
The crosslinking agent (B) is a crosslinking agent having at least two carboxyl groups and is a component for obtaining a planarized film by curing the planarized film forming composition of the present invention. As such a crosslinking agent (B), specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,4 -Benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, etc. can be mentioned.

  The amount of the crosslinking agent (B) used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and 5 to 15 parts per 100 parts by mass of the polymer (A). The part by mass is particularly preferred.

3 Organic solvent (C)
Examples of the organic solvent (C) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether; ethylene glycol monomethyl ether Ethylene glycol monoalkyl ether acetates such as acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl Ether, diethylene glycol di-n-butyl ether Diethylene dialkyl ethers; triethylene glycol dimethyl ether, triethylene glycol dialkyl ethers such as triethylene glycol diethyl ether;

  Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n -Propylene glycol dialkyl ethers such as propyl ether and propylene glycol di-n-butyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Propylene glycol such as Roh alkyl ether acetates;

  Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate, n-butyl lactate, i-butyl lactate; methyl formate, ethyl formate, n-propyl formate, i-propyl formate, n-formate Butyl, i-butyl formate, n-amyl formate, i-amyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-acetate -Amyl, n-hexyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, i-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate Aliphatic carboxylic acid esters such as i-propyl butyrate, n-butyl butyrate and i-butyl butyrate;

  Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , Ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3 -Other esters such as methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate;

  Aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; N-methylformamide, N , N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone and other amides; γ-butyrolactone and other lactones. In addition, (C) organic solvent may be used individually by 1 type, and may use 2 or more types.

  The content ratio of the organic solvent (C) is preferably such an amount that the solid content concentration of the composition for forming a flattened film is 5 to 80% by mass, and more preferably 5 to 40% by mass. The amount is preferably 10 to 30% by mass, particularly preferably. If the solid content concentration of the composition for forming a flattened film is less than 5% by mass, a sufficient film thickness cannot be obtained, and etching may not be possible. On the other hand, if it exceeds 80% by mass, the polymer (A) may be precipitated because the solubility is not sufficient.

4 Other ingredients (D)
Moreover, the composition for planarization film formation of this invention may contain components (D) other than a polymer (A), a crosslinking agent (B), and an organic solvent (C). Examples of the other component (D) include an acid generator, a crosslinking agent other than the crosslinking agent (B) (hereinafter also referred to as “other crosslinking agent”), a binder resin, a radiation absorber, a surfactant, and storage stability. Agents, antifoaming agents, and adhesion aids.

(1) Acid generator An acid generator is a component which generates an acid by exposure or heating. By containing such an acid generator, the crosslinking reaction is promoted, so that there is an advantage that the film formation is performed efficiently. In the present specification, an acid generator that generates an acid upon exposure is referred to as a “photoacid generator”, and an acid generator that generates an acid upon heating is referred to as a “thermal acid generator”. Moreover, a photo-acid generator and a thermal acid generator can also be used together as an acid generator.

(Photoacid generator)
Specific examples of photoacid generators include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium naphthalene. Sulfonate, diphenyliodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) Iodonium n-dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium 1 - camphorsulfonate, bis (4-t- butylphenyl) iodonium naphthalene sulfonate, bis (4-t- butylphenyl) iodonium hexafluoroantimonate,

  Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium hexafluoroantimonate, 4 -Hydroxyphenyl phenyl methylsulfonium p-toluenesulfonate, 4-hydroxyphenyl benzyl methylsulfonium p-toluenesulfonate,

  Cyclohexyl methyl 2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldicyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoro Lome Sulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldiethyl Sulfonium trifluoromethanesulfonate,

  1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxynaphthalene-1- Yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane Sulfonate, 1- (4- (1-methoxyethoxy) naphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4- (2-methoxyethoxy) naphthalene 1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxycarbonyloxynaphthalen-1-yl) tetrahydrothio Phenium trifluoromethanesulfonate, 1- (4-n-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate,

  1- (4-i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, (4-t-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4- (2-tetrahydrofuranyloxy) naphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4- (2-Tetrahydropyranyloxy) naphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-benzyloxy) tetrahydrothiophenium trifluoro Methanesulfonate, 1- (naphthyl acetamide methyl) onium salt photoacid generators such as tetrahydrothiophenium trifluoromethanesulfonate;

  Halogen-containing compound-based photoacid generators such as phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine, 1-naphthylbis (trichloromethyl) -s-triazine; 2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,3,4-naphthoquinonediazide-4-sulfonic acid ester of 2,3,4,4′-tetrahydroxybenzophenone or 1, Diazoketone compound photoacid generators such as 2-naphthoquinonediazide-5-sulfonic acid ester; sulfone compound photoacid generators such as 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenylsulfonyl) methane Benzoin tosylate, pyrogallol Lith (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2,2,1] hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide Examples include sulfonic acid compound photoacid generators such as trifluoromethanesulfonate and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate.

  Among these, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium naphthalenesulfonate, bis (4-t -Butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-t-butyl) Phenyl) iodonium 10-camphorsulfonate, bis (4-tert-butylphenyl) iodoni Arm naphthalene sulfonate is preferred. In addition, a photo-acid generator may be used individually by 1 type, and may use 2 or more types.

(Thermal acid generator)
Specific examples of the thermal acid generator include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl sulfonates. In addition, a thermal acid generator may be used individually by 1 type, and may use 2 or more types.

  The content of the acid generator is preferably 0.01 to 200 parts by mass and more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer (A). If the content is less than 0.01 parts by mass, the acid generated may be too small to obtain a sufficient effect. On the other hand, if it exceeds 200 parts by mass, there is too much acid, so that the equilibrium of film formation does not proceed easily, and the film formation efficiency may be reduced.

(2) Other crosslinking agents As other crosslinking agents, polynuclear phenols and various commercially available curing agents can be used. Moreover, these can also be used together.

  Specific examples of polynuclear phenols include dinuclear phenols such as 4,4′-biphenyldiol, 4,4′-methylenebisphenol, 4,4′-ethylidenebisphenol, and bisphenol A; 4,4 ′, 4 ′ Trinuclear phenols such as '-methylidenetrisphenol, 4,4'-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol; polyphenols such as novolak Etc. Among these, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, novolak, and the like are preferable. In addition, polynuclear phenols may be used individually by 1 type, and may use 2 or more types.

  As commercially available curing agents, specifically, 2,3-tolylene diisocyanate, 2,4-tolylene diisocyanate, 3,4-tolylene diisocyanate, 3,5-tolylene diisocyanate, 4,4 Diisocyanates such as' -diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate; hereinafter referred to as “Epicoat 812”, 815, 826, 828, 834, 836, 871, 1001, 1004, 1007, 1009, 1031 (Oilized Shell Epoxy, Inc.), “Araldite 6600”, 6700, 6800, 502, 6071, 6084 6097, 6099 (above, manufactured by Ciba Geigy), "DER331", 332, 333, 661, the 644, the 667 (manufactured by Dow Chemical Co.) epoxy compounds such as;

  "Cymel 300", 301, 303, 350, 370, 771, 325, 327, 703, 712, 701, 272, 202, "My Coat 506", 508 ( As described above, melamine type curing agents such as Mitsui Cyanamid Co., Ltd .; “Cymel 1123”, 1123-10, 1128, “My Coat 102”, 105, 106, 130 (above, Mitsui Cyanamid Co., Ltd.) Benzoguanamine-based curing agents, such as “Cymel 1170”, 1172 (above, manufactured by Mitsui Cyanamid), glycoluril-based curing agents such as “Nikalac N-2702” (manufactured by Sanwa Chemical), and the like. Among these, melamine type curing agents, glycoluril type curing agents and the like are preferable. In addition, a hardening | curing agent may be used individually by 1 type, and may use 2 or more types.

  The content of the other crosslinking agent is preferably 0.01 to 200 parts by mass, and more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer (A). If the content is less than 0.01 parts by mass, the crosslinking efficiency may not be sufficient. On the other hand, if it exceeds 200 parts by mass, the etching resistance may decrease.

(3) Binder resin As the binder resin, various thermoplastic resins and thermosetting resins can be used. Specific examples of the thermoplastic resin include polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-1-hexene, poly-1-heptene, poly-1-octene, poly-1-decene, Α-olefin polymers such as poly-1-dodecene, poly-1-tetradecene, poly-1-hexadecene, poly-1-octadecene, and polyvinylcycloalkane; poly-1,4-pentadiene, poly-1,4 Non-conjugated diene polymers such as hexadiene and poly-1,5-hexadiene; α, β-unsaturated aldehyde polymers; poly (methyl vinyl ketone), poly (aromatic vinyl ketone), poly (cyclic vinyl ketone) ), Etc .; (meth) acrylic acid, α-chloroacrylic acid, (meth) acrylate, (meth) acrylic acid Polymers of α, β-unsaturated carboxylic acids or derivatives thereof such as tellurium and (meth) acrylic acid halides; α, β-unsaturated polymers of poly (meth) acrylic anhydride and maleic anhydride Polymers of saturated carboxylic acid anhydrides; Polymers of unsaturated polybasic carboxylic acid esters such as methylenemalonic acid diester and itaconic acid diester;

  Polymers of diolefin carboxylic acid esters such as sorbic acid ester and muconic acid ester; Polymers of α, β-unsaturated carboxylic acid thioesters such as (meth) acrylic acid thioester and α-chloroacrylic acid thioester; ) Polymers of (meth) acrylonitrile such as acrylonitrile and α-chloroacrylonitrile or derivatives thereof; Polymers of (meth) acrylamide or derivatives thereof such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide; Polymers of metal compounds; Polymers of vinyloxy metal compounds; Polyimines; Polyethers such as polyphenylene oxide, poly-1,3-dioxolane, polyoxirane, polytetrahydrofuran, polytetrahydropyran; Polysulfides; Polysulfonamides Polypeptides; Polyamides such as nylon 66 and nylon 1 to nylon 12; Polyesters such as aliphatic polyester, aromatic polyester, alicyclic polyester, and polycarbonate; Polyureas; Polysulfones; Polyazines; Polyamines Polyaromatic ketones, polyimides, polybenzimidazoles, polybenzoxazoles, polybenzothiazoles, polyaminotriazoles, polyoxadiazoles, polypyrazoles, polytetrazoles, polyquinoxalines, polytriazines Polybenzoxazinones; polyquinolines; polyanthrazolins and the like.

  The thermosetting resin is a component that cures by heating and becomes insoluble in a solvent, and has an action of preventing intermixing between the planarizing film and the resist film (upper layer film) formed thereon. . Specific examples of thermosetting resins include thermosetting acrylic resins, phenol resins, urea resins, melamine resins, amino resins, aromatic hydrocarbon resins, epoxy resins, alkyd resins. Etc. Among these, urea resins, melamine resins, and aromatic hydrocarbon resins are preferable.

  In addition, binder resin may be used individually by 1 type and may use 2 or more types. The content of the binder resin is preferably 10 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass of the polymer (A).

(4) Radiation absorber Examples of the radiation absorber include oil-soluble dyes, disperse dyes, basic dyes, methine dyes, pyrazole dyes, imidazole dyes, hydroxyazo dyes, and the like; bixin derivatives, norbixin , Stilbene, 4,4′-diaminostilbene derivatives, coumarin derivatives, pyrazoline derivatives, and other fluorescent whitening agents; hydroxyazo dyes, trade names “Tinuvin 234”, 1130 (above, manufactured by Ciba Geigy) Agents: aromatic compounds such as anthracene derivatives and anthraquinone derivatives. In addition, a radiation absorber may be used individually by 1 type and may use 2 or more types. The content of the radiation absorber is preferably 10 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass of the polymer (A).

(5) Surfactant A surfactant is a component having an effect of improving coatability, striation, wettability, developability and the like. Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, and polyethylene. Nonionic surfactants such as glycol dilaurate and polyethylene glycol distearate, and “KP341” (manufactured by Shin-Etsu Chemical Co., Ltd.), “Polyflow No. 75”, and No. 95 (above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.),

  "F Top EF101", EF204, EF303, EF352 (above, manufactured by Tochem Products), "Megafac F171", F172, F173 (above, manufactured by Dainippon Ink and Chemicals), "Florade FC430 FC431, FC135, FC93 (above, manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S382, SC101, SC102, SC103, SC104, SC104, SC106 (above, Asahi Glass Co., Ltd.). In addition, surfactant may be used individually by 1 type and may use 2 or more types. The content of the surfactant is preferably 5 parts by mass or less, more preferably 1 part by mass or less, with respect to 100 parts by mass of the polymer (A).

II Pattern Forming Method The pattern forming method of the present invention comprises the step of forming the planarizing film forming composition described in “I Composition for planarizing film formation” on a substrate to be processed having a gap having a dense portion and a flat portion. A step (1) of forming a planarized film by coating, a step (2) of forming a resist film by applying a resist composition on the planarized film, and irradiating the resist film with radiation to form a resist film A step (3) of selectively exposing, a step (4) of developing the exposed resist film to form a resist pattern, and using the resist pattern as a mask, a predetermined pattern is formed on the planarizing film and the substrate to be processed. Forming (5). The pattern forming method of the present invention can be suitably used as a method for forming a dual damascene structure.

1 Step (1)
In step (1), the planarizing film-forming composition described in “I. Composition for Forming Flattening Film” is applied onto a substrate to be processed on which a gap having a dense portion and a flat portion is present. Is a step of forming. As the substrate to be processed, for example, an insulating film such as silicon oxide, silicon nitride, silicon oxynitride, polysiloxane, etc., hereinafter all trade names are “black diamond” (manufactured by AMAT), “silk” (manufactured by Dow Chemical) ), An interlayer insulating film such as a wafer coated with a low dielectric insulating film such as “LKD5109” (manufactured by JSR) can be used. As shown in FIG. 1, the substrate 1 to be processed has gaps such as a wiring groove (trench) having a dense portion 2 and a flat portion 3, and a plug groove (via). Therefore, it is preferable to form a planarization film using the composition for planarization film formation of this invention.

  The method for applying the flattening film forming composition is not particularly limited, and a conventionally known method can be employed, for example, a spin coating method. The thickness of the coating film is preferably such that the resulting planarized film has a thickness of 100 to 20000 nm. A flattening film can be formed by applying the flattening film-forming composition and then baking.

  The firing conditions are not particularly limited, but the temperature is preferably 80 to 500 ° C, more preferably 150 to 450 ° C, and particularly preferably 200 to 350 ° C. If the temperature is less than 80 ° C., the crosslinking reaction is unlikely to occur, so that the coating film may not be formed. On the other hand, if it exceeds 500 ° C., the reverse reaction of the crosslinking reaction starts to occur, so that the crosslinking efficiency may be lowered.

  Firing can be usually performed in an inert gas atmosphere or an oxygen-containing atmosphere (oxygen atmosphere). Examples of the inert gas include nitrogen gas, argon gas, helium gas, xenon gas, and krypton gas.

2 Step (2)
Step (2) is a step of forming a resist film by applying a resist composition on the planarizing film. As the resist composition, for example, a positive or negative chemically amplified resist composition containing a photoacid generator, an alkali-soluble resin, and a positive resist composition comprising a quinonediazide-based photosensitizer, an alkali-soluble resin, and There are negative resist compositions comprising a crosslinking agent.

  The solid content concentration of the resist composition is preferably, for example, 5 to 50% by mass. Moreover, as a resist composition, it is preferable to use what was filtered with the filter of the hole diameter of about 0.2 micrometer. In addition, the pattern formation method of this invention can also use a commercially available resist composition as a resist composition as it is.

  As a method for applying the resist composition, for example, a conventional method such as a spin coating method can be appropriately employed. The application amount of the resist composition is adjusted so that a resist film having a desired film thickness can be obtained.

  The resist film can be formed by volatilizing the solvent in the coating film (that is, the solvent contained in the resist composition) by pre-baking the coating film of the resist composition. Although the temperature at the time of prebaking can be suitably set according to the kind etc. of resist composition to be used, it is preferable that it is 30-200 degreeC, and it is still more preferable that it is 50-150 degreeC.

  In the pattern forming method of the present invention, in the step (2), if necessary, an intermediate layer may be further formed on the planarizing film, and a resist film may be formed on the intermediate layer. This intermediate layer has a predetermined function required for supplementing the functions of the planarization film and / or resist film in forming a resist pattern, or for obtaining the functions that they do not have. Is a layer. For example, when the antireflection film is formed as an intermediate layer, the antireflection function of the planarization film can be supplemented.

  This intermediate layer can be formed using an organic compound or an inorganic oxide. Examples of the organic compound include commercially available materials such as “DUV-42”, “DUV-44”, “ARC-28”, and “ARC-29” manufactured by Brewer Science. Alternatively, materials commercially available under trade names such as “AR-3” and “AR-19” manufactured by Rohm and Haas can be used. Examples of the inorganic oxide include materials commercially available under trade names such as “NFC SOG01” and “NFC SOG04” manufactured by JSR, polysiloxane formed by CVD, titanium oxide, alumina oxide, and oxide. Tungsten or the like can be used.

  Examples of the method for forming the intermediate layer include a coating method and a CVD method. Among these, a coating method is preferable. When the coating method is used, there is an advantage that the intermediate layer can be continuously formed after the planarization film is formed.

  The film thickness of the intermediate layer can be appropriately selected according to the function required for the intermediate layer. For example, in a general lithography process, it is preferably 10 to 3000 nm, and preferably 20 to 300 nm. More preferably. If the thickness of the intermediate layer is less than 10 nm, the intermediate layer may be scraped and lost during the etching process of the planarizing film. On the other hand, if it exceeds 3000 nm, there is a possibility that the processing conversion difference becomes large when the resist pattern is transferred to the intermediate layer.

3 Step (3)
Step (3) is a step of selectively exposing the resist film by irradiating the resist film with radiation. In the present specification, “selectively exposing” means exposing through a photomask on which a predetermined mask pattern is formed.

Irradiation can be appropriately selected according to the type of acid generator used in the resist composition. For example, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, γ-rays, molecular beams And ion beam. Among these, far ultraviolet rays are preferable, and in particular, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (wavelength 157 nm), Kr ₂ excimer laser (wavelength 147 nm), ArKr excimer laser (wavelength 134 nm). Extreme ultraviolet rays (wavelength 13 nm, etc.) are more preferable.

4 Step (4)
Step (4) is a step of developing the exposed resist film to form a resist pattern. The developer used for development can be appropriately selected according to the type of resist composition to be used. For example, when using a positive chemically amplified resist composition or a positive resist composition containing an alkali-soluble resin, 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, 1,8-diazabicyclo Alkaline aqueous solutions such as [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene can be used. These alkaline aqueous solutions may be those obtained by adding an appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant.

  In addition, when using a negative chemically amplified resist composition or a negative resist composition containing an alkali-soluble resin, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, etc. Inorganic alkalis; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; dimethylethanolamine, triamine Alcohol amines such as ethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; alkaline aqueous solutions such as cyclic amines such as pyrrole and piperidine can be used.

  In step (4), after developing with a developing solution, washing and drying are performed. Further, in order to improve resolution, pattern profile, developability, etc., it is preferable to perform post-baking before developing the resist film. The post-baking temperature can be appropriately adjusted according to the type of resist composition to be used, but is preferably 50 to 200 ° C, and more preferably 80 to 150 ° C.

5 Step (5)
Step (5) is a step of forming a predetermined pattern on the planarizing film and the substrate to be processed using the resist pattern as a mask. The pattern can be formed by performing dry etching, for example. Note that in the case where an intermediate layer is formed over the planarization film, the intermediate layer is also dry-etched together with the planarization film and the substrate to be processed.

A conventionally known dry etching apparatus can be used for the dry etching. The source gas at the time of dry etching is appropriately selected according to the elemental composition of the film to be etched, but includes an oxygen atom gas such as O ₂ , CO, CO ₂ , an inert gas such as He, N ₂ , Ar, A chlorine-based gas such as Cl ₂ or BCl ₃ , a gas of H ₂ or NH ₃ , or the like can be used. In addition, these gases can also be mixed and used.

  Hereinafter, an embodiment in which a dual damascene structure is formed using the pattern forming method of the present invention will be described. As a method for forming the dual damascene structure, for example, a first low dielectric insulating film having a first trench formed in a predetermined pattern shape is embedded in a first trench so that a conductive material is embedded in the first trench. In the second trench of the second low dielectric insulating film having the step of forming the first wiring layer on which the wiring is formed (first wiring forming step) and the second trench formed in a predetermined pattern shape A step of forming a second wiring layer in which a predetermined second wiring is formed by embedding a conductive material (second wiring forming step), and a third low dielectric insulation having a via formed in a predetermined pattern shape Forming a third wiring layer in which a third wiring for connecting the first wiring and the second wiring is formed by embedding a conductive material in the via of the film (third wiring forming process). With the second wiring Simultaneously forming three wires (i.e., at the same time the second trenches and vias filled with a conductive material) and a method. 3 to 12 are schematic views showing one step of a method for forming a dual damascene structure using the planarizing film forming composition of the present invention.

(First wiring formation process)
The first wiring formation step forms a predetermined first wiring by embedding a conductive material in the first trench of the first low dielectric insulating film having the first trench formed in a predetermined pattern shape. It is a process. Specifically, first, a planarizing film is formed on the first low dielectric insulating film of the substrate by the planarizing film forming composition. Next, after forming a resist film on the formed planarization film and forming a resist pattern, using the resist film on which the resist pattern is formed as a mask, as shown in FIG. Is transferred to the planarizing film 4 by etching. Next, as shown in FIG. 4, the planarization film 4 to which the resist pattern 11 has been transferred is used as a mask, and the planarization film 4 is formed on the first low dielectric insulating film 5 disposed under the planarization film 4. The resist pattern 11 is transferred to form the first trench 7. Next, as shown in FIG. 5, the resist film and the planarizing film are removed by plasma ashing. Finally, a predetermined first wiring can be formed by embedding a conductive material in the first trench 7.

  First, the planarizing film 4 is formed on the first low dielectric insulating film 5 of the substrate 1 with the planarizing film forming composition. The type of the first low dielectric insulating film (Low-k film) is not particularly limited as long as the first low dielectric insulating film (Low-k film) is disposed under the planarization film, and for example, an inorganic coating can be used. This inorganic film can be formed of, for example, silicon oxide, silicon nitride, silicon oxynitride, polysiloxane, or the like. In particular, it can be formed from commercially available products such as “black diamond” (manufactured by AMAT), “silk” (manufactured by Dow Chemical), and “LKD5109” (manufactured by JSR).

  The first low dielectric insulating film is, for example, a film formed so as to cover a substrate such as a wafer. The method for forming the first low dielectric insulating film is not particularly limited, and a known method can be used. For example, a coating method (SOD: Spin On Dielectric), a chemical vapor deposition (CVD) method, or the like can be used.

  Next, a resist film 6 is formed on the formed planarizing film 4, a resist pattern 11 is formed on the resist film, and then the resist film 6 on which the resist pattern 11 is formed is used as a mask to form a resist pattern on the resist film 6. 11 is transferred to the planarizing film 4 by etching. Specifically, it can be performed by the method described in “II Pattern Formation Method”.

  Next, using the planarizing film 4 to which the resist pattern 11 has been transferred as a mask, the resist pattern 11 of the planarizing film 4 is transferred to the first low dielectric insulating film 5 disposed under the planarizing film 4. A first trench 7 is formed. The method for transferring the resist pattern of the planarizing film to the first low dielectric insulating film is not particularly limited, and examples thereof include the etching method described above.

Next, the resist film 4 and the planarizing film 6 are removed by plasma ashing. Plasma ashing is a process in which a reactive gas plasma such as oxygen is generated in a gas phase, and organic substances such as a resist film and a planarizing film are decomposed into CO _x and H ₂ O by this plasma and removed. Say.

  The plasma ashing conditions are not particularly limited as long as the resist film and the planarizing film can be removed. For example, the high frequency power applied to the susceptor is preferably 100 to 1000 W, and preferably 100 to 500 W. Is more preferable. The susceptor temperature is preferably 20 to 100 ° C, and more preferably 20 to 60 ° C. In addition, the pressure in the processing container is preferably 1 to 300 mtorr, and more preferably 30 to 100 mtorr.

  The gas used for plasma ashing is not particularly limited as long as the resist film and the planarizing film can be removed, but suppresses an increase in the relative dielectric constant of the first low dielectric insulating film due to plasma ashing. From the viewpoint of being able to be, it is preferably a gas containing at least one selected from the group consisting of nitrogen, hydrogen, ammonia and argon, a mixed gas of nitrogen and hydrogen, a mixed gas of ammonia and argon, ammonia and nitrogen And a mixed gas of hydrogen and hydrogen is particularly preferable.

  Moreover, when using the mixed gas of nitrogen and hydrogen, it is preferable that hydrogen is 20 or less with respect to nitrogen 100 by a volume ratio, and it is still more preferable that hydrogen is 1-10. Moreover, when using the mixed gas of ammonia and argon, it is preferable that argon is 10 or less with respect to 100 ammonia by a volume ratio.

  Finally, a predetermined first wiring 9 is formed by embedding a conductive material in the first trench 7. Examples of the conductive material embedded in the first trench of the first low dielectric insulating film include copper and aluminum. As a method of embedding a conductive material, for example, there is copper electrolytic plating. In this way, a desired first wiring can be formed by embedding the conductive material in the resist pattern.

  An intermediate layer is formed between the resist film and the planarizing film, or a barrier metal layer 7 is formed on part of the surface of the first low dielectric insulating film 5 and the substrate 1 as shown in FIG. You may do it.

  The intermediate layer is a layer for supplementing functions that are insufficient for the planarization film, the resist film, and both in the formation of the resist pattern. That is, for example, when the planarization film lacks an antireflection function, a film having an antireflection function can be applied to the intermediate layer.

  As the material of the intermediate layer, an organic compound or an inorganic oxide can be appropriately selected depending on a required function. In addition, when a resist film is an organic compound, it is also possible to apply an inorganic oxide to an intermediate | middle layer.

  Commercially available organic compounds for forming the intermediate layer are all trade names, for example, “DUV-42”, “DUV-44”, “ARC-28”, “ARC-29” (hereinafter, Brewer Science). Co., Ltd.), “AR-3”, “AR-19” (above, manufactured by Rohm and Haas), and the like. Examples of the inorganic oxide for forming the intermediate layer include polysiloxane, titanium oxide, alumina oxide, and tungsten oxide. These commercial products are all trade names and include, for example, “NFC SOG01”, “NFC SOG04” (manufactured by JSR).

  As a method for forming the intermediate layer, for example, a coating method, a CVD method, or the like can be used. Among these, it is preferable to use a coating method because an intermediate layer can be continuously formed after the planarization film is formed.

  The thickness of the intermediate layer can be appropriately selected depending on the function required for the intermediate layer, but is preferably 10 to 3000 nm, and more preferably 20 to 300 nm. If the thickness of the intermediate layer is less than 10 nm, the intermediate layer may be scraped off during the etching of the planarizing film. On the other hand, when it exceeds 3000 nm, there is a possibility that a difference in processing conversion may occur remarkably when the resist pattern of the resist film is transferred to the intermediate layer.

  The barrier metal layer is a layer that improves the adhesion between the conductive material embedded in the resist pattern (that is, the first trench formed in the first low dielectric insulating film) and the low dielectric insulating film. Furthermore, it is a layer that prevents diffusion (migration) into the low dielectric insulating film of the conductive material.

  Examples of the material for the barrier metal layer include tantalum, tantalum nitride, titanium, titanium nitride, and ruthenium. Examples of the method for forming the barrier metal layer include a CVD method.

  Note that after the stacking step, it is preferable to remove the conductive material and the barrier metal layer adhering to the surface of the low dielectric insulating film by chemical polishing (CMP) and to planarize the surface of the low dielectric insulating film. .

(Second wiring formation process and third wiring formation process)
In the second wiring formation step and the third wiring formation step, a method similar to the method of forming the first trench in the first wiring formation step can be adopted as the method of forming the second trench and via.

  First, as shown in FIG. 7, after the third low dielectric insulating film 25 and the second low dielectric insulating film 15 are sequentially formed on the first wiring layer 10 formed by the first wiring forming step, A planarizing film 4 and a resist film 6 are sequentially formed on the low dielectric insulating film 15. Next, a resist pattern is formed on the resist film 6 and transferred to the planarizing film 4. The second low dielectric insulating film 15 and the third low dielectric insulating film 25 can be the same low dielectric insulating film as the first low dielectric insulating film 5, and the second low dielectric insulating film and The third low dielectric insulating film can be formed by the same method as the first low dielectric insulating film.

  Next, as shown in FIG. 8, vias 8 are formed in the second low dielectric insulating film 15 and the third low dielectric insulating film 25. The method for forming the via can be performed by a method similar to the method for forming the first trench.

  Next, as shown in FIG. 10, a second trench 17 is formed in the second low dielectric insulating film 15. The method for forming the second trench can be performed in the same manner as the method for forming the first trench. Specifically, as shown in FIG. 9, a planarizing film forming composition is applied onto the second low dielectric insulating film 15, and the second low dielectric insulating film 15 and the third low dielectric insulating film are applied. In addition to planarizing the via 8 formed in 25, the planarizing film 4 is formed on the surface of the second low dielectric insulating film 15. The method for applying the planarization film forming composition is not particularly limited, and examples thereof include a spin coating method, a spray method, and a dip coating method. Next, after a resist film 6 is formed on the planarizing film 4, a resist pattern is formed on the resist film 6, and transferred to the planarizing film 4 by etching. Next, using the planarizing film 4 to which the resist pattern is transferred as a mask, the resist pattern of the planarizing film 4 is transferred to the second low dielectric insulating film 15 disposed under the planarizing film 4. Finally, as shown in FIG. 11, the resist film and the planarizing film are removed by plasma ashing. At this time, the cured flattening film forming composition filling the vias 8 formed in the third low dielectric insulating film 25 is also removed by plasma ashing.

  Finally, as shown in FIG. 12, the second wiring 19 and the third wiring 29 connecting the first wiring 9 and the second wiring 19 are simultaneously formed by embedding a conductive material in the second trench and via. Thus, a dual damascene structure can be formed. Note that the barrier metal layer 12 may be formed before the conductive material is embedded in the second trench and via. Thus, the first wiring layer 10 in which the first wiring 9 is formed, the second wiring layer 20 in which the second wiring 19 is formed, and the third wiring that connects the first wiring 9 and the second wiring 19. The dual damascene structure 40 having the third wiring layer 30 formed with 29 can be manufactured.

  Note that chemical polishing (CMP) can be performed after the conductive material is embedded in the second trench and the via.

  As shown in FIGS. 8 to 10, the dual damascene structure is particularly preferably formed by a via first method in which the trenches 17 are formed after the vias 8 are formed first.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

  [Sublimation amount (ng)]: A planarizing film-forming composition was applied on a silicon wafer having a diameter of 8 inches by a spin coating method to form a coating film of the planarizing film-forming composition. After another silicon wafer having a diameter of 8 inches (hereinafter also referred to as “sublimation amount measurement wafer”) is placed 5 cm above the coating film of the planarizing film-forming composition, the planarizing film-forming composition is applied. The silicon wafer on which the film was formed was placed on a hot plate, heated at 215 ° C. for 60 seconds, and the sublimate generated during the heating was adsorbed on the sublimate measurement wafer. The amount of the sublimate adsorbed on the wafer for measuring the amount of sublimate was measured and used as the amount of sublimate.

  [Coarse / Dense Bias (nm)]: A planarizing film-forming composition was applied by spin coating on a silicon wafer with a diameter of 8 inches having a hole pattern with a depth of 400 nm, a hole diameter of 100 nm, and a pitch of 250 nm. A coating film of the composition for flattening film formation was formed. Next, it was placed on a hot plate and heated at 215 ° C. for 60 seconds. Using the scanning electron microscope, the difference in film thickness between the film thickness of the flattening film having a hole pattern (Dense part) and the film thickness of the flattening film having no hole pattern (Flat part) is obtained. The measured value was used as the density bias.

  [Evaluation of via embedding property]: Measured by a scanning electron microscope as to whether or not the hole pattern is filled with a flattened film. “×”.

[Etching resistance]: A planarizing film-forming composition was applied on a silicon wafer having a diameter of 8 inches by spin coating to form a planarizing film having a thickness of 300 nm. Thereafter, the planarizing film is etched (pressure: 0.03 Torr, high-frequency power: 300 W, Ar / CF ₄ = 40/100 sccm, substrate temperature: 20 ° C.), and the thickness of the planarized film after the etching process is measured. did. The etching rate (nm / min) was calculated from the relationship between the reduction amount of the film thickness and the processing time. The etching resistance was calculated by the ratio of the etching rate of the flattening film to the etching rate (nm / min) of the coating film formed using methylcyclopentyl methacrylate polymer instead of the flattening film forming composition.

(Synthesis Example 1)
In a separable flask equipped with a thermometer, in a nitrogen atmosphere, 60 parts of methacrylic acid-2,3-epoxypropyl, 40 parts of methyl methacrylate and azoisobutyronitrile as a polymerization initiator are all monomer components 1 mol% with respect to 100 mol% and 200 parts of 3-methoxybutyl acetate as a polymerization solvent were charged and polymerized at 80 ° C. for 6 hours with stirring to obtain a reaction solution. The reaction solution was reprecipitated twice with n-hexane to obtain a polymer (A-1). The weight average molecular weight (Mw) of the obtained polymer (A-1) is 60,000, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5. there were.

(Synthesis Examples 2 to 4 and Comparative Synthesis Examples 1 to 4)
Each polymer was obtained in the same manner as in Synthesis Example 1 except that the polymerization was carried out according to the formulation described in Table 1. The weight average molecular weight (Mw) of the obtained polymer and the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) are also shown in Table 1.

Example 1
10 parts of the polymer (A-1) obtained in Synthesis Example 1 and 1 part of 1,2,4-benzenetricarboxylic acid as the crosslinking agent (B) are described as N-methylpyrrolidone (hereinafter referred to as “NMP”). ) 79 parts and propylene glycol monomethyl ether (hereinafter referred to as “PGME”) 10 parts dissolved in an organic solvent (C) to obtain a mixed solution. The obtained mixed solution was filtered through a membrane filter having a pore size of 0.1 μm to produce a flattened film forming composition. When various measurements were performed using the manufactured composition for planarization film formation, the amount of sublimation was 0.5 ng, evaluation of via embedding was “◯”, and the density bias was 40 nm.

(Examples 2 to 4 and Comparative Examples 1 to 4)
Each flattening film forming composition was produced in the same manner as in Example 1 except that the formulation shown in Table 2 was used. Various measurements were performed using each of the manufactured compositions for forming a flattened film. The evaluation results are shown in Table 3.

  As can be seen from Table 3, when the planarization film forming composition of the present invention is used, a substrate to be processed having a hole pattern in part can be planarized, and the etching resistance is equal to or less than that of the resist film. Further, the generation of sublimates can be suppressed, and further, a flattening film having a small density bias and excellent flatness can be formed.

  The present invention can be suitably used as a material for forming a planarization film in a multilayer resist process suitable for manufacturing a highly integrated circuit element.

1: substrate, 2: dense part, 3: flat part, 4: planarization film, 5: first low dielectric insulating film, 6: resist film, 7: first trench, 8: via, 9: first Wiring: 10: first wiring layer, 11: resist pattern, 12: barrier metal layer, 15: second low dielectric insulating film, 17: second trench, 19: second wiring, 20: second wiring layer, 22, 32: etching stopper layer, 25: third low dielectric insulating film, 29: third wiring, 30: third wiring layer, 40: dual damascene structure, A: film thickness of the flattening film in the dense portion, B: Film thickness of the flattening film in the flat part.

Claims (8)

(1) forming a planarization film by applying a composition for planarization film formation on a substrate to be processed having a gap having a dense part and a flat part;
Applying a resist composition on the planarizing film to form a resist film (2);
Irradiating the resist film with radiation to selectively expose the resist film;
Developing the exposed resist film to form a resist pattern (4);
Using the resist pattern as a mask, forming a predetermined pattern on the planarizing film and the substrate to be processed (5),
A polymer (A) having the structural unit (a1) represented by the following general formula (1) and the structural unit (a2) represented by the following general formula (2): It contains a crosslinking agent (B) having at least two carboxyl groups, and an organic solvent (C).
The polymer (A) has a polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation column chromatography of 50,000 or more, and the weight average molecular weight (Mw) and gel permeation column chromatography. The pattern formation method whose ratio (Mw / Mn) with the number average molecular weight (Mn) of polystyrene conversion measured by chromatography is 1.0-1.6.

In (Formula (1), ^{R 1} represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, ^{R 2} represents a group having an epoxy group. Also, in the general formula (2), R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents an alkyl group having 1 to 20 carbon atoms.)   The mass ratio ((a1) / (a2)) of the structural unit (a1) and the structural unit (a2) in the polymer (A) is 1/1 to 2.5 / 1. The pattern formation method as described.   The pattern forming method according to claim 1, wherein the polymer (A) is a polymer composed of only a structural unit derived from at least one of a methacrylic compound and an acrylic compound.   The pattern formation method according to claim 1, which is a method for forming a dual damascene structure.   The pattern formation method according to claim 4, wherein the dual damascene structure is formed by a via first method. A polymer (A) having a structural unit (a1) represented by the following general formula (1) and a structural unit (a2) represented by the following general formula (2);
A crosslinking agent (B) having at least two carboxyl groups;
An organic solvent (C),
The polymer (A) has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation column chromatography of 50,000 or more, and the weight average molecular weight (Mw) and gel permeation column chromatography. A composition for forming a flattened film, which is a polymer having a ratio (Mw / Mn) of 1.0 to 1.6 with respect to the number average molecular weight (Mn) in terms of polystyrene measured by lithography.

In (Formula (1), ^{R 1} represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, ^{R 2} represents a group having an epoxy group. Also, in the general formula (2), R ³ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, ^{R 4} represents an alkyl group having 1 to 20 carbon atoms.)   The mass ratio ((a1) / (a2)) of the structural unit (a1) and the structural unit (a2) in the polymer (A) is 1/1 to 2.5 / 1. The composition for flattening film formation as described.   The composition for flattening film formation according to claim 6 or 7, wherein the polymer (A) is a polymer composed only of a structural unit derived from at least one of a methacrylic compound and an acrylic compound.

Images