KR20130111396A - Composition for forming resist lower layer film and process for forming pattern - Google Patents
Composition for forming resist lower layer film and process for forming pattern Download PDFInfo
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- KR20130111396A KR20130111396A KR1020130033362A KR20130033362A KR20130111396A KR 20130111396 A KR20130111396 A KR 20130111396A KR 1020130033362 A KR1020130033362 A KR 1020130033362A KR 20130033362 A KR20130033362 A KR 20130033362A KR 20130111396 A KR20130111396 A KR 20130111396A
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- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
- G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
- G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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Abstract
Description
The present invention relates to a composition for forming a resist underlayer film and a pattern forming method.
In the manufacture of semiconductor devices, a multilayer resist process is used in order to cope with miniaturization of a pattern due to high integration. In this step, first, a resist underlayer film is formed on the substrate to be processed to form a resist underlayer film, and a resist composition is applied on the resist underlayer film to form a resist film. Next, a resist pattern is exposed through a photomask by a reduction projection exposure apparatus (stepper) or the like, and developed with a suitable developer to form a resist pattern. The desired pattern can be formed on the substrate by dry etching the resist underlayer film using the resist pattern as a mask, and further dry etching the substrate under the obtained resist underlayer film pattern as a mask.
As the composition for forming a resist underlayer film, having a high etching selectivity with respect to a resist film can reliably etch a resist underlayer film, and the use of the composition containing polysiloxane is disclosed (Japanese Patent Laid-Open No. 2004-310019). And Japanese Patent Laid-Open No. 2005-018054).
However, the above-mentioned composition has insufficient storage stability, and when the storage period becomes longer, a difference occurs in the film thickness of the resist underlayer film formed even under the same manufacturing conditions. In addition, in the conventional composition, there is a problem that coating defects occur in the resist underlayer film formed due to solids produced by solidifying the polymer component dissolved in the composition during the formation of the resist underlayer film.
This invention is made | formed based on the above circumstances, The objective is the composition for resist underlayer film formation which has the outstanding storage stability and the high coating defect improvement which can suppress generation | occurrence | production of coating defect, and pattern formation using this composition. To provide a way.
According to an aspect of the present invention,
[A] A composition for forming a resist underlayer film containing polysiloxane and [B] solvent,
(B) Resist underlayer film formation containing the organic solvent (Hereinafter, it is also called "(B1) organic solvent") whose solvent is a compound or carbonate compound represented by following General formula (B1), and a standard boiling point is 150.0 degreeC or more. It is a composition for.
(In formula 1, R <1> and R <2> is respectively independently a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 acyl group, R <3> is a hydrogen atom or a methyl group, n is an integer of 1-4, , when n is 2 or more, a plurality of R 3 may be the same or different.)
The composition for forming a resist underlayer film of the present invention includes the above-described specific organic solvent which is a high boiling point component, and thus, in the process of forming a resist underlayer film with excellent storage stability capable of reducing the film thickness change of the resist underlayer film according to the storage of the composition. It has a high coating defect improvement property which can suppress unnecessary evaporation of the solvent, and can suppress solidification of the polymer component dissolved in a composition.
It is preferable that the standard boiling point of (B1) organic solvent is 180 degreeC or more. By making the standard boiling point of the (B1) organic solvent into the said specific range, the said composition can improve storage stability and application | coating defect improvement property.
It is preferable that the content rate of the (B1) organic solvent in the solvent (B) is 1 mass% or more and 50 mass% or less. By making the content rate of the (B1) organic solvent in the solvent (B) into the said specific range, the said composition can improve storage stability and application | coating defect improvement property effectively.
(B1) It is preferable that the static surface tension of an organic solvent is 20 mN / m or more and 50 mN / m or less. By making the static surface tension of the (B1) organic solvent into the said specific range, the said composition can improve the solubility of [A] polysiloxane, and as a result, can improve coating defect improvement.
The solvent (B) preferably further includes an alkylene glycol monoalkyl ether acetate compound (hereinafter also referred to as "(B2) compound") having a (B2) standard boiling point of less than 150.0 ° C. As the solvent [B] further comprises the specific (B2) compound, the composition can improve the solubility of the [A] polysiloxane in the solvent [B], and as a result, further improve the storage stability and the application defect improvement. Can be.
(B2) It is preferable that an alkylene glycol monoalkyl ether acetate compound is a propylene glycol monoalkyl ether acetate compound. By making (B2) a compound into the said specific compound, the said composition can further improve the solubility of [A] polysiloxane with respect to the [B] solvent, As a result, storage stability and coating defect improvement property can be improved further.
Since the said composition for resist underlayer film formation has the property mentioned above, it can use suitably for a multilayer resist process, and can form a resist underlayer film with few coating defects.
It is preferable that the said composition for resist underlayer film formation contains [C] acid diffusion control agent further. By further containing the acid diffusion control agent [C], the composition for forming the resist underlayer film can effectively suppress the diffusion of acid in the resist film generated via the resist underlayer film while maintaining the above effects. As a result, the multilayer resist The shape of the resist pattern formed by a process can be improved.
[C] The acid diffusion control agent is preferably a nitrogen-containing compound. By using the acid diffusion control agent (C) as a nitrogen-containing compound, the composition can more effectively suppress the diffusion, and as a result, the shape of the resist pattern formed by the multilayer resist process can be further improved.
The polysiloxane (A) is preferably a hydrolysis condensate of a compound containing a silane compound represented by the following general formula (i).
(I)
(In Formula i, R A is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a cyano group, and part or all of the hydrogen atoms of the alkyl group. May be substituted with an epoxyalkyloxy group, an acid anhydride group or a cyano group, some or all of the hydrogen atoms of the aryl group may be substituted with a hydroxy group, and X is a halogen atom or -OR B , provided that R is B is a monovalent organic group, a is an integer of 0 to 3, provided that when R A and X are each plural, a plurality of R A and X may be the same or different.)
By making polysiloxane (A) the hydrolysis-condensation product of the said specific compound, the said composition can further improve storage stability and application | coating defect improvement property.
The pattern forming method of the present invention comprises:
(1) forming a resist underlayer film on the substrate to be processed using the composition for forming a resist underlayer film;
(2) forming a resist film on the resist underlayer film using a resist composition;
(3) exposing the resist film by irradiation of exposure light through a photomask;
(4) a step of developing the exposed resist film to form a resist pattern, and
(5) A step of sequentially dry etching the resist underlayer film and the substrate to be processed using the resist pattern as a mask
Respectively.
Since the said composition for resist underlayer film formation has the said characteristic, according to the pattern formation method of this invention, a favorable resist pattern can be formed.
The term "standard boiling point" (hereinafter, also simply referred to as "boiling point") means a boiling point at 1 atm. In addition, "static surface tension" means the surface tension at which the liquid level is stopped. The static surface tension of this specification is the value measured at 25 degreeC by the Wilhelmy method. In addition, "monovalent organic group" means the monovalent group containing at least 1 carbon atom.
As described above, the composition for forming a resist underlayer film of the present invention has excellent storage stability and high coating defect improvement. Therefore, the said composition for resist underlayer film formation and the pattern formation method can be used suitably for the manufacturing process of the semiconductor device which refine | miniaturizes a pattern.
<Composition for forming a resist underlayer film>
The composition for resist underlayer film formation of this invention contains [A] polysiloxane and [B] solvent. Moreover, the said composition for resist underlayer film formation may contain the [C] acid diffusion control agent as a suitable component. Moreover, the said composition for resist underlayer film formation may contain other arbitrary components, unless the effect of this invention is impaired.
Moreover, since the said composition for resist underlayer film forming has high coating defect improvement property, it can use suitably for the multilayer resist process represented by the said pattern formation method etc. mentioned later, and can form a resist underlayer film with few coating defects. have. Hereinafter, each component will be described.
<[A] polysiloxane>
The polysiloxane [A] is not particularly limited as long as it is a polymer having a siloxane bond, but is preferably a hydrolyzed condensate of a compound containing a silane compound represented by the formula (i). The term "hydrolyzed condensate of a compound containing a silane compound" herein refers to a hydrolyzed condensate of the silane compound represented by the formula (i), or a silane compound represented by the formula (i) and a silane compound represented by the formula (i). Means a hydrolysis condensate of a silane compound (hereinafter also referred to as "other silane compound"). The other silane compound is not particularly limited as long as it is hydrolyzed to generate a silanol group.
In said Formula (i), R <A> is a hydrogen atom, a fluorine atom, a C1-C5 alkyl group, a C2-C10 alkenyl group, a C6-C20 aryl group, or a cyano group. Some or all of the hydrogen atoms of the alkyl group may be substituted with an epoxyalkyloxy group, an acid anhydride group or a cyano group. Some or all of the hydrogen atoms of the said aryl group may be substituted by the hydroxy group. X is a halogen atom or -OR B. However, R B is a monovalent organic group. a is an integer of 0-3. However, R A, and when X is plural, each individual, a plurality of R A and X may be the same or different, respectively.
The alkyl group having 1 to 5 carbon atoms represented by the R A, for example, methyl, ethyl, n- propyl, n- butyl, n- pen alkyl group of a straight chain, such groups; And branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, t-butyl group and isoamyl group. Among these, a methyl group and an ethyl group are preferable and a methyl group is more preferable.
As the alkenyl group having 2 to 10 carbon atoms represented by the R A, for example, ethenyl group, 1-propene-1-yl group, 1-propene-2-yl group, 1-propene-3-yl group, 1- Buten-1-yl group, 1-buten-2-yl group, 1-buten-3-yl group, 1-buten-4-yl group, 2-buten-1-yl group, 2-buten-2-yl group, 1-pentene- 5-yl group, 2-penten-1-yl group, 2-penten-2-yl group, 1-hexene-6-yl group, 2-hexen-1-yl group, 2-hexen-2-yl group, etc. are mentioned.
Examples of the aryl group having 6 to 20 carbon atoms represented by the R A, for example, a phenyl group, a naphthyl group, methylphenyl group, ethyl phenyl group and the like. In addition, the aryl group may be substituted with a halogen atom. As an aryl group substituted by the halogen atom, a chlorophenyl group, a bromophenyl group, a fluorophenyl group etc. are mentioned, for example.
In addition, in this specification, said "epoxy" includes both oxiranyl and oxetanyl.
As an alkyl group substituted by the said epoxy alkyloxy group, For example, Oxiranyl alkyloxy groups, such as 2-glycidyl oxyethyl group, 3-glycidyl oxypropyl group, and 4-glycidyl oxybutyl group; Oxetanylalkyloxy groups, such as 3-ethyl-3- oxetanylpropyl group, 3-methyl-3- oxetanylpropyl group, 3-ethyl-2- oxetanylpropyl group, and 2-oxetanylethyl group Etc. can be mentioned. Among these, 3-glycidyloxypropyl group and 3-ethyl-3-oxetanylpropyl group are preferable.
As an alkyl group substituted by the said acid anhydride group, 2-anhydrous succinic-acid group substituted ethyl group, 3-anhydrous succinic-acid group substituted propyl group, 4-anhydrous succinic-acid group substituted butyl group, etc. are mentioned, for example. Among these, the 3-anhydride succinic acid group substituted propyl group is more preferable.
As an alkyl group substituted by the said cyano group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, etc. are mentioned, for example.
As an aryl group substituted by the said hydroxy group, 4-hydroxyphenyl group, 4-hydroxy-2-methylphenyl group, 4-hydroxy naphthyl group, etc. are mentioned, for example. Among these, 4-hydroxyphenyl group is preferable.
As a halogen atom represented by said X, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.
As the monovalent organic group in the above R B, an alkyl group, an alkylcarbonyl group is preferred. As said alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group is more preferable, a methyl group and an ethyl group are more preferable, and a methyl group especially desirable. Moreover, as said alkylcarbonyl group, a methylcarbonyl group and an ethylcarbonyl group are more preferable.
As the silane compound represented by the formula (i), for example
As an aromatic ring containing trialkoxysilane, Phenyltrimethoxysilane, 4-methylphenyl trimethoxysilane, 4-ethylphenyl trimethoxysilane, 4-hydroxyphenyl trimethoxysilane, 3-methylphenyl trimethoxysilane, 3 -Ethylphenyltrimethoxysilane, 3-hydroxyphenyltrimethoxysilane, 2-methylphenyltrimethoxysilane, 2-ethylphenyltrimethoxysilane, 2-hydroxyphenyltrimethoxysilane, 2,4,6 -Trimethylphenyltrimethoxysilane and the like;
As alkyltrialkoxysilanes, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec -Butoxysilane, methyltri-t-butoxysilane, methyltriphenoxysilane, methyltriacetoxysilane, methyltrichlorosilane, methyltriisopropenoxysilane, methyltris (dimethylsiloxy) silane, methyltris (Methoxyethoxy) silane, methyltris (methylethylketoxime) silane, methyltris (trimethylsiloxy) silane, methylsilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane , Ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-t-butoxysilane, ethyltriphenoxysilane, ethylbistris (trimethylsiloxy Silane, ethyldichlorosilane, ethyltriacetoxysilane, ethyltrichlorosilane, n-propyl Methoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri- sec-butoxysilane, n-propyltri-t-butoxysilane, n-propyltriphenoxysilane, n-propyltriacetoxysilane, n-propyltrichlorosilane, iso-propyltrimethoxysilane, iso- Propyltriethoxysilane, iso-propyltri-n-propoxysilane, iso-propyltri-iso-propoxysilane, iso-propyltri-n-butoxysilane, iso-propyltri-sec-butoxysilane, iso-propyltri-t-butoxysilane, iso-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltree -iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-t-butoxysilane, n-butyltriphenoxysilane, n- Butyltrichlorosilane, 2-methylpropyltrimethock Silane, 2-methylpropyltriethoxysilane, 2-methylpropyltri-n-propoxysilane, 2-methylpropyltri-iso-propoxysilane, 2-methylpropyltri-n-butoxysilane, 2-methyl Propyltri-sec-butoxysilane, 2-methylpropyltri-t-butoxysilane, 2-methylpropyltriphenoxysilane, 1-methylpropyltrimethoxysilane, 1-methylpropyltriethoxysilane, 1- Methylpropyltri-n-propoxysilane, 1-methylpropyltri-iso-propoxysilane, 1-methylpropyltri-n-butoxysilane, 1-methylpropyltri-sec-butoxysilane, 1-methylpropyl Tri-t-butoxysilane, 1-methylpropyltriphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso Propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-t-butoxysilane, t-butyltriphenoxysilane, t-butyltrichloro Rosilane, t-butyldichlorosilane, etc .;
Examples of alkenyltrialkoxysilanes include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane and vinyltri-sec- Butoxysilane, vinyltri-t-butoxysilane, vinyltriphenoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltriisopropoxysilane, allyl tri- n-butoxysilane, allyltri-sec-butoxysilane, allyltri-t-butoxysilane, allyltriphenoxysilane, and the like;
As tetraalkoxysilanes, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra- t-butoxysilane and the like;
As tetraarylsilanes, Tetraphenoxysilane etc .;
Examples of the epoxy group-containing silanes include 3-oxetanylmethyloxypropyltrimethoxysilane, 3-oxetanylethyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and the like;
As the acid anhydride group-containing silane, 3- (trimethoxysilyl) propyl succinic anhydride, 2- (trimethoxysilyl) ethyl succinic anhydride, 3- (trimethoxysilyl) propyl maleic anhydride, 2- (trimeth Methoxysilyl) ethyl glutaric anhydride and the like;
As tetrahalosilanes etc., tetrachlorosilane etc. are mentioned.
As said other silane compound, benzyl trimethoxysilane, phenethyl trimethoxysilane, 4-phenoxyphenyl trimethoxysilane, 4-aminophenyl trimethoxysilane, 4-dimethylaminophenyl trimethoxysilane, 4-acetylaminophenyltrimethoxysilane, 3-methoxyphenyltrimethoxysilane, 3-phenoxyphenyltrimethoxysilane, 3-aminophenyltrimethoxysilane, 3-dimethylaminophenyltrimethoxysilane, 3 -Acetylaminophenyltrimethoxysilane, 2-methoxyphenyltrimethoxysilane, 2-phenoxyphenyltrimethoxysilane, 2-aminophenyltrimethoxysilane, 2-dimethylaminophenyltrimethoxysilane, 2- Acetylaminophenyltrimethoxysilane, 4-methylbenzyltrimethoxysilane, 4-ethylbenzyltrimethoxysilane, 4-methoxybenzyltrimethoxysilane, 4-phenoxybenzyltrimethoxysilane, 4-hydroxy Benzyltrimethoxysilane, 4-aminobenzyltrimethoxysilane, 4-dimethylaminobenzyltri Silane, and the like can be mentioned 4-acetylamino-benzyl trimethoxysilane.
The conditions for the hydrolysis condensation are not particularly limited as long as at least a part of the silane compound represented by the formula (i) is hydrolyzed to convert the hydrolyzable group (-OR B ) to a silanol group to cause a condensation reaction. As an example, it can carry out as follows.
As the water used for the hydrolysis condensation, it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably 0.1 to 3 moles, more preferably 0.3 to 2 moles and even more preferably 0.5 to 1.5 moles with respect to 1 mole of the total amount of the hydrolyzable groups of the silane compound represented by the formula (i). . By using such an amount of water, the reaction rate of hydrolysis and condensation can be optimized.
Although it does not specifically limit as a solvent which can be used for the said hydrolysis condensation, Ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid ester are preferable. Among these, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or 3-methoxypropionate methyl, 4-hydroxy-4-methyl- 2-pentanone (diacetone alcohol) is more preferable.
The hydrolysis condensation reaction is preferably an acid catalyst (e.g. hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, various Lewis acids). ), Nitrogen-containing compounds such as ammonia, primary amines, secondary amines, tertiary amines, pyridine, basic ion exchange resins, hydroxides such as sodium hydroxide; carbonates such as potassium carbonate; sodium acetate, etc. Carboxylates; various Lewis bases) or alkoxides (e.g., zirconium alkoxides, titanium alkoxides, aluminum alkoxides). For example, tri-i-propoxy aluminum can be used as aluminum alkoxide. As a usage-amount of a catalyst, it is 0.2 mol or less with respect to 1 mol of monomers of a hydrolyzable silane compound from a viewpoint of the acceleration of a hydrolysis condensation reaction, More preferably, it is 0.00001-0.1 mol.
The reaction temperature and reaction time in the hydrolysis condensation are appropriately set. For example, the following conditions may be employed. The reaction temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 hour to 12 hours. By setting it as such reaction temperature and reaction time, a hydrolysis condensation reaction can be performed most efficiently. In this hydrolysis condensation, the reaction may be carried out in one step by adding a hydrolyzable silane compound, water and a catalyst into the reaction system at once, or by adding the hydrolyzable silane compound, water and a catalyst in several times, The hydrolysis condensation reaction can also be carried out in multiple stages. In addition, after the hydrolytic condensation reaction, a dehydrating agent may be added and then evaporated to remove water and the resulting alcohol from the reaction system.
As content of [A] polysiloxane in the said composition for resist underlayer film formation, 80 mass% or more is preferable with respect to the total solid in the composition for resist underlayer film formation, 90 mass% or more is more preferable, 95 mass % Or more is more preferable. In addition, the said composition for resist underlayer film formation may contain only 1 type of [A] polysiloxane, and may contain 2 or more types.
(A) The weight average molecular weight (Mw) of polystyrene conversion by gel permeation chromatography (GPC) of polysiloxane is 500-50,000 normally, 1,000-30,000 are preferable, 1,000-15,000 are more preferable, 1,000-5,000 are further desirable.
<[B] Solvent>
The solvent (B) is a solvent containing an organic solvent (B1). In addition, the solvent [B] may contain a compound (B2). In addition, the solvent [B] may contain other solvents other than the above-mentioned (B1) organic solvent and (B2) compound in the range which does not impair the effect of this invention. Each said component can also be used individually or in combination of 2 or more types. Hereinafter, each component will be described.
[(B1) Organic Solvent]
The organic solvent (B1) is a compound or carbonate compound represented by the formula (1), and an organic solvent having a standard boiling point of 150.0 ° C or higher. Since the composition for forming a resist underlayer film includes the specific organic solvent which is a high boiling point component, it is possible to reduce the film thickness change of the resist underlayer film according to the preservation of the composition, and together with the excellent storage stability, It has a high coating defect improvement property which can suppress unnecessary evaporation and can suppress solidification of the polymer component dissolved in a composition.
(B1) As for the standard boiling point of an organic solvent, 160 degreeC or more is preferable, 170 degreeC or more is more preferable, and 180 degreeC or more is more preferable. By making the standard boiling point of the (B1) organic solvent into the said range, the said composition can improve storage stability and application | coating defect improvement property.
The standard boiling point of the organic solvent (B1) is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, still more preferably 250 ° C. or lower, and particularly preferably 220 ° C. or lower. By making the standard boiling point of the said (B1) organic solvent into the said range, the residue of the organic solvent after formation of a resist underlayer film can be reduced.
In said Formula (1), R <1> and R <2> is a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 acyl group each independently. R 3 is a hydrogen atom or a methyl group. n is an integer of 1 to 4; When n is 2 or more, a plurality of R 3 may be the same or different.
As a C1-C4 alkyl group represented by said R <1> and R <2> , For example, linear alkyl groups, such as a methyl group, an ethyl group, n-propyl group, n-butyl group; And branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group and t-butyl group.
As a C1-C4 acyl group represented by said R <1> and R <2> , a formyl group, an acetyl group, a propionyl group, etc. are mentioned, for example.
As an organic solvent (B1) containing the compound represented by the said Formula (1), for example
Examples of the polyhydric alcohol compound include ethylene glycol (boiling point: 197 ° C), 1,2-propylene glycol (boiling point: 188 ° C), triethylene glycol (boiling point: 165 ° C), and the like;
As the polyhydric alcohol partial ether compound, ethylene glycol monopropyl ether (boiling point: 150 ° C), ethylene glycol monobutyl ether (boiling point: 171 ° C), ethylene glycol monophenyl ether (boiling point: 244 ° C), diethylene glycol monomethyl ether ( Boiling point: 194 ° C), diethylene glycol monoethyl ether (boiling point: 202 ° C), triethylene glycol monomethyl ether (boiling point: 249 ° C), diethylene glycol monoisopropyl ether (boiling point: 207 ° C), diethylene glycol mono Butyl ether (boiling point: 231 ° C), triethylene glycol monobutyl ether (boiling point: 271 ° C), ethylene glycol monoisobutyl ether (boiling point: 161 ° C), diethylene glycol monoisobutyl ether (boiling point: 220 ° C), di Propylene glycol monomethyl ether (boiling point: 187 ° C), tripropylene glycol monomethyl ether (boiling point: 242 ° C), dipropylene glycol monopropyl ether (boiling point: 212 ° C), propylene glycol monobutyl ether (boiling point: 170 ° C),Propylene glycol monobutyl ether (boiling point: 231 ℃), and the like;
As an ether compound, diethylene glycol dimethyl ether (boiling point: 162 degreeC), triethylene glycol dimethyl ether (boiling point: 216 degreeC), diethylene glycol methyl ethyl ether (boiling point: 176 degreeC), diethylene glycol diethyl ether (boiling point: 189 ° C), diethylene glycol dibutyl ether (boiling point: 255 ° C), dipropylene glycol dimethyl ether (boiling point: 171 ° C), diethylene glycol monoethyl ether acetate (boiling point: 217 ° C), ethylene glycol monobutyl ether acetate ( Boiling point: 188 ° C.) and the like.
As an organic solvent (B1) containing a carbonate compound, ethylene carbonate (boiling point: 244 degreeC), propylene carbonate (boiling point: 242 degreeC) etc. are mentioned, for example.
It is preferable that the dielectric constant of (B1) organic solvent is 13 or more and 200 or less. By making the dielectric constant of (B1) the organic solvent into the said range, the said composition can improve the solubility of [A] polysiloxane, and as a result, coating defect improvement property can be improved. In addition, a "dielectric constant" means the ratio of the dielectric constant of an organic solvent and the dielectric constant of a vacuum. As a dielectric constant of a compound, the value described in the literature ["Chemical Handbook basic edition revised 5th edition") etc. can be referred. The dielectric constant of the compound which is not described in the said chemical manual is the value measured at 20 degreeC by the method of JISC2138.
As an organic solvent (B1) which has a dielectric constant of the said range, For example, Carbonate compounds, such as ethylene carbonate (a dielectric constant: 90) and propylene carbonate (a dielectric constant: 63); Ethylene glycol (relative dielectric constant: 41) etc. are mentioned.
(B1) It is preferable that the static surface tension of an organic solvent is 20 mN / m or more and 50 mN / m or less. As static surface tension of this (B1) organic solvent, 20 mN / m or more and 40 mN / m or less are more preferable, and 20 mN / m or more and 30 mN / m or less are more preferable. By making the static surface tension of (B1) an organic solvent into the said range, the said composition can improve the solubility of [A] polysiloxane, and as a result, can improve coating defect improvement.
As an organic solvent (B1) which has the static surface tension of the said range, for example
Diethylene glycol monomethyl ether (static surface tension: 29.8 mN / m),
Triethylene glycol monomethyl ether (static surface tension: 31.9 mN / m),
Diethylene glycol monoisopropyl ether (static surface tension: 29.9 mN / m),
Ethylene glycol monobutyl ether (static surface tension: 24.0 mN / m),
Diethylene glycol monobutyl ether (static surface tension: 26.2 mN / m),
Triethylene glycol monobutyl ether (static surface tension: 27.7 mN / m),
Ethylene glycol monoisobutyl ether (static surface tension: 22.5 mN / m),
Diethylene glycol monoisobutyl ether (static surface tension: 24.6 mN / m),
Dipropylene glycol monomethyl ether (static surface tension: 25.1 mN / m),
Tripropylene glycol monomethyl ether (static surface tension: 25.7 mN / m),
Dipropylene glycol monopropyl ether (static surface tension: 27.9 mN / m),
Propylene glycol monobutyl ether (static surface tension: 26.8 mN / m),
Dipropylene glycol monobutyl ether (static surface tension: 23.7 mN / m),
Diethylene glycol dimethyl ether (static surface tension: 25.3 mN / m),
Triethylene glycol dimethyl ether (static surface tension: 27.5 mN / m),
Diethylene glycol methyl ethyl ether (static surface tension: 24.0 mN / m),
Diethylene glycol diethyl ether (static surface tension: 23.3 mN / m),
Diethylene glycol dibutyl ether (static surface tension: 23.6 mN / m),
Dipropylene glycol dimethyl ether (static surface tension: 21.1 mN / m),
Diethylene glycol monoethyl ether acetate (static surface tension: 26.2 mN / m) etc. are mentioned.
The content of the (B1) organic solvent in the solvent [B] is preferably 1% by mass or more and 50% by mass or less, more preferably 1.5% by mass or more and 30% by mass or less, still more preferably 2% by mass or more and 20% by mass or less. . By making the content rate of the (B1) organic solvent in the solvent (B) into the said range, the said composition can improve storage stability and application | coating defect improvement property effectively.
[(B2) Compound]
(B2) A compound is an alkylene glycol monoalkyl ether acetate compound whose standard boiling point is less than 150.0 degreeC. As the compound (B2), a propylene glycol monoalkyl ether acetate compound is preferable. By making (B2) a compound into the said specific compound, the said composition can further improve the solubility of [A] polysiloxane with respect to the [B] solvent, As a result, storage stability and coating defect improvement property can be improved further.
As said (B2) compound, For example, ethylene glycol monomethyl ether acetate (boiling point: 145 degreeC) etc. as an ethylene glycol monoalkyl ether compound; A propylene glycol monomethyl ether acetate (boiling point: 146 degreeC) etc. are mentioned as a propylene glycol monoalkyl ether acetate compound. Among these, a propylene glycol monoalkyl ether acetate compound is preferable and propylene glycol monomethyl ether acetate is more preferable.
As content rate of the compound (B2) in the solvent (B), 10 mass% or more and 99 mass% or less are preferable, and 50 mass% or more and 99 mass% or less are more preferable. By making the content rate of the said (B2) compound into the said range, the solubility of the [A] polysiloxane with respect to the [B] solvent can be improved effectively.
[Other solvents]
The solvent (B) is an organic solvent other than the (B1) organic solvent and the (B2) compound (for example, an organic solvent other than the (B1) organic solvent and the (B2) compound) in a range that does not impair the effects of the present invention. (B3) organic solvent, (B4) water, etc.) may be included.
As said (B3) organic solvent, it is for example
Ethylene glycol monomethyl ether (boiling point: 125 ° C), ethylene glycol monoethyl ether (boiling point: 135 ° C), ethylene glycol monoisopropyl ether (boiling point: 142 ° C), and ethylene glycol dimethyl ether (boiling point) as an ethylene glycol alkyl ether compound 82 ° C.), ethylene glycol diethyl ether (boiling point: 121 ° C.), and the like; Examples of the propylene glycol alkyl ether compound include propylene glycol-1-methyl ether (boiling point: 120 ° C), propylene glycol-1-ethyl ether (boiling point: 133 ° C), propylene glycol-1-propyl ether (boiling point: 149.8 ° C), and the like. Can be. Among these, a propylene glycol alkyl ether compound is preferable, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether and propylene glycol-1-propyl ether are more preferable, and propylene glycol-1-ethyl ether is still more preferable. .
As content rate of the other solvent in the solvent (B), 70 mass% or less is preferable, and 50 mass% or less is more preferable.
<[C] acid diffusion control agent>
The acid diffusion control agent (C) is a component that suppresses diffusion of an acid generated in the resist film during exposure. By further containing the acid diffusion control agent [C], the composition for forming the resist underlayer film of the present invention can effectively suppress the diffusion of acid in the resist film generated via the resist underlayer film while maintaining the above effects. The shape of the resist pattern formed by a multilayer resist process can be improved. In addition, [C] acid diffusion control agent may be used independently and may use 2 or more types together.
The acid diffusion control agent (C) is preferably a nitrogen-containing compound. Since the acid diffusion control agent (C) is a nitrogen-containing compound, the composition can more effectively suppress the diffusion, and as a result, the shape of the resist pattern formed by the multilayer resist process can be further improved.
As said nitrogen containing compound, an amine compound, an amide group containing compound, a urea compound, a nitrogen containing heterocyclic compound, etc. are mentioned, for example.
As said amine compound, For example, Mono (cyclo) alkylamines; Di (cyclo) alkyl amines; Tri (cyclo) alkyl amines; Substituted alkyl anilines or derivatives thereof; Ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4, 4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane , 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis (1- ( 4-aminophenyl) -1-methylethyl) benzene, 1,3-bis (1- (4-aminophenyl) -1-methylethyl) benzene, bis (2-dimethylaminoethyl) ether, bis (2-di Ethylaminoethyl) ether, 1- (2-hydroxyethyl) -2-imidazolidinone, 2-quinoxalinol, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine , N, N, N ', N ", N" -pentamethyldiethylenetriamine, etc. are mentioned.
Examples of the amide group-containing compound include Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-butoxycarbonyl-2-carboxy-4-hydroxypyrrolidine and Nt-butoxycarbonyl Nt-butoxycarbonyl group containing amino compounds, such as 2-carboxypyrrolidine; N-t-amyloxycarbonyl group containing amino compounds, such as N-t-amyloxycarbonyl-4-hydroxy piperidine; N- (9-anthranylmethyloxycarbonyl) group containing amino compounds, such as N- (9-anthranylmethyloxycarbonyl) piperidine; Formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone And N-acetyl-1-adamantylamine.
Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tri-n. -Butylthiourea etc. are mentioned.
As said nitrogen-containing heterocyclic compound, For example, imidazole; Pyridines; Piperazines; Pyrazine, pyrazole, pyridazine, quinoxaline, purine, pyrrolidine, piperidine, piperidineethanol, 3- (N-piperidino) -1,2-propanediol, morpholine, 4-methylmor Pauline, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabi Cyclo [2.2.2] octane and the like.
Among these, amide group-containing compounds are preferable, Nt-butoxycarbonyl group-containing amino compounds and Nt-amyloxycarbonyl group-containing amino compounds are more preferable, and Nt-butoxycarbonyl-4-hydroxypiperidine and Nt-part Especially preferred are oxycarbonyl-2-carboxy-4-hydroxypyrrolidine, Nt-butoxycarbonyl-2-carboxy-pyrrolidine, Nt-amyloxycarbonyl-4-hydroxypiperidine.
As content of the [C] acid diffusion control agent, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] polysiloxane, and 1 mass part-5 mass parts are more preferable. By making the said content into the said range, the shape of a resist pattern can be improved.
<Other optional ingredients>
The composition for forming a resist underlayer film may contain other optional components such as colloidal silica, colloidal alumina, an organic polymer, and a surfactant. Other arbitrary components can also be used individually or in combination of 2 types or more, respectively. In addition, content of other arbitrary components can be suitably selected according to the objective.
As said organic polymer, For example, polymers, such as an acrylate compound, a methacrylate compound, an aromatic vinyl compound; Vinylamide polymers, dendrimers, polyimides, polyamic acids, polyarylenes, polyamides, polyquinoxalines, polyoxadiazoles, fluoropolymers, and the like.
As said surfactant, nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, silicone type surfactant, polyalkylene oxide type surfactant, fluorine-containing surfactant etc. are mentioned, for example. .
<The manufacturing method of the composition for resist underlayer film forming>
The composition for resist underlayer film formation of this invention can be manufactured by mixing [A] polysiloxane, [B] solvent, a [C] acid diffusion control agent, other arbitrary components, etc. in predetermined ratio as needed.
≪ Pattern formation method >
The pattern forming method of the present invention comprises:
(1) forming a resist underlayer film on the substrate to be processed using the composition for forming a resist underlayer film;
(2) forming a resist film on the resist underlayer film using a resist composition;
(3) exposing the resist film by irradiation of exposure light through a photomask;
(4) a step of developing the exposed resist film to form a resist pattern, and
(5) A step of sequentially dry etching the resist underlayer film and the substrate to be processed using the resist pattern as a mask
Respectively.
Since the said composition for resist underlayer film formation has the said characteristic, according to the pattern formation method of this invention, a favorable resist pattern can be formed.
[Step (1)]
In this step, a resist underlayer film is formed on the substrate to be processed using the resist underlayer film forming composition. Examples of the substrate to be processed include silicon wafers, wafers coated with aluminum, and the like.
As a formation method of the said resist underlayer film, the coating film of the said composition for forming a resist underlayer film is formed by apply | coating to the surface of a to-be-processed board | substrate, another underlayer film mentioned later, etc., and this coating film is heat-processed or of ultraviolet-ray It can form by irradiating and heat-processing and hardening. As a method of apply | coating the said composition for resist underlayer film forming, a spin coating method, a roll coating method, an immersion method, etc. are mentioned, for example. Moreover, heating temperature is 50 degreeC-450 degreeC normally, and 150 degreeC-300 degreeC is preferable. The heating time is usually 5 seconds to 600 seconds.
Moreover, the said to-be-processed board | substrate may be previously formed using the composition for forming a resist underlayer film of this invention, and the other underlayer film (henceforth "other underlayer film") different from a resist underlayer film may be formed. As another underlayer film, the organic antireflection film etc. which are disclosed by Unexamined-Japanese-Patent No. 6-12452, Unexamined-Japanese-Patent No. 59-93448, etc. are mentioned, for example.
The film thickness of the resist underlayer film is usually 10 nm to 1,000 nm, preferably 10 nm to 500 nm.
[Step (2)]
In this step, a resist film is formed on the resist underlayer film using a resist composition. Specifically, after applying a resist composition so that the resist film obtained may become a predetermined | prescribed film thickness, the solvent in a coating film will be volatilized by prebaking, and a resist film is formed.
Examples of the resist composition include a positive or negative chemically amplified resist composition containing an acid generator, a positive resist composition containing an alkali-soluble resin and a quinonediazide-based photosensitive agent, an alkali-soluble resin and a crosslinking agent. The negative resist composition etc. which are mentioned are mentioned.
The total solid content concentration of the said resist composition is 1 mass%-50 mass% normally. In addition, the said resist composition is generally used for the formation of a resist film by filtering with a filter of about 0.2 micrometer in pore size, for example. In this step, a commercially available resist composition may be used as it is.
The method of applying the resist composition is not particularly limited, and for example, a spin coating method and the like can be given. In addition, although the temperature of prebaking is adjusted suitably according to the kind of resist composition used, etc., it is 30 degreeC-200 degreeC normally, and 50 degreeC-150 degreeC is preferable.
[Step (3)]
In this step, the resist film is exposed by irradiation of exposure light through a photomask. As said exposure light, it selects suitably from visible light, an ultraviolet-ray, far ultraviolet rays, X-rays, etc. according to the kind of photo-acid generator used for a resist composition. Among these, far ultraviolet rays are preferable, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F 2 excimer laser light (wavelength 157 nm), Kr 2 excimer laser light (wavelength 147 nm), ArKr excimer Laser light (wavelength 134 nm) and extreme ultraviolet rays (wavelength 13 nm, etc.) are more preferable, and ArKr excimer laser light (wavelength 134 nm) is especially preferable.
After the exposure, postbaking may be performed to improve the resolution, pattern profile, developability, and the like. Although the temperature of this postbaking is suitably adjusted according to the kind etc. of the resist composition used, it is 50 degreeC-200 degreeC normally, and 70 degreeC-150 degreeC is preferable.
[Step (4)]
In this step, the exposed resist film is developed to form a resist pattern. The developer used in this step is appropriately selected depending on the type of resist composition used. Examples of the developer include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, Diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] -7- undecene, And alkaline aqueous solutions such as 5-diazabicyclo [4.3.0] -5-nonene and the like. An appropriate amount of water-soluble organic solvents, such as alcohols, such as methanol and ethanol, surfactant, etc. can also be added to these alkaline aqueous solutions, for example.
After development in the developing solution, a predetermined resist pattern is formed by washing and drying.
[Step (5)]
In this step, the resist underlayer film and the substrate to be processed are sequentially dry-etched using the resist pattern as a mask. Dry etching can be performed using a known dry etching apparatus. Further, as the source gas at the time of dry etching it is also different depending on the element composition of the etched, but O 2, CO, CO 2 gas containing oxygen atoms such as, He, N 2, an inert gas such as Ar, Cl 2, chlorine-based gas such as BCl 4, CHF 3, can be used a fluorine-based gas, H 2, NH 3 gas or the like of such as CF 4. These gases may be mixed and used.
Moreover, after these processes, you may have the process of removing the resist underlayer film which remains on a to-be-processed substrate. In addition, the resist pattern may be formed without undergoing a development process such as a nanoimprint method.
[Example]
Hereinafter, although the Example of this invention demonstrates more concretely, this invention is not restrict | limited to these Examples. In addition, the measurement of the solid content concentration of polysiloxane and the polystyrene conversion weight average molecular weight (Mw) was performed by the following method.
<Solid content concentration of polysiloxane>
0.5 g of a solution containing polysiloxane was calcined at 250 ° C. for 30 minutes, and the mass of the obtained solid content was measured to obtain a solid content concentration (mass%) of polysiloxane.
<Polystyrene equivalent weight average molecular weight (Mw)>
Monodisperse polystyrene under analytical conditions of a toso prepared GPC column (G2000HXL: 2, G3000HXL: 1, G4000HXL: 1), flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C Polystyrene conversion weight average molecular weight (Mw) was measured by the gel permeation chromatography (GPC) which makes it a standard.
<Synthesis of [A] polysiloxane>
[A] polysiloxane was synthesized using the following silane compound.
M-1: tetramethoxysilane
M-2: Phenyltrimethoxysilane
M-3: 4-methylphenyltrimethoxysilane
M-4: Methyltrimethoxysilane
Synthesis Example 1 Synthesis of Polysiloxane (A-1)
0.55 g of oxalic acid was dissolved in 7.66 g of water to prepare an aqueous oxalic acid solution. Thereafter, (M-1) 12.95 g (60 mol%), (M-2) 5.80 g (30 mol%), (M-3) 3.01 g (10 mol%) and propylene glycol-1-ethyl ether 70.03 In the flask containing g, a cooling tube and a dropping funnel in which the oxalic acid aqueous solution was added were set. Subsequently, after heating the said flask to 60 degreeC in the oil bath, the said oxalic acid aqueous solution was dripped slowly and it was made to react at 60 degreeC for 2 hours. After the completion of the reaction, the flask containing the reaction solution was allowed to cool, set in an evaporator, and residual water and methanol produced by the reaction were removed to obtain 49.2 g of a solution containing polysiloxane (A-1) as a solid content. Solid content concentration of the said solution was 15 mass%, and Mw of polysiloxane (A-1) was 1,500.
Synthesis Example 2 (Synthesis of Polysiloxane (A-2))
The solution containing polysiloxane (A-2) was synthesize | combined by the method similar to the synthesis example 1 except having used each monomer which provides [A] polysiloxane by the usage-amount shown in Table 1. Table 1 shows solid content concentration and Mw of the solution containing obtained polysiloxane (A-2).
Synthesis Example 3 (Synthesis of Polysiloxane (A-3))
1.28 g of oxalic acid was dissolved in 12.85 g of water to prepare an aqueous oxalic acid solution. Thereafter, a cooling tube and the aqueous solution of oxalic acid were placed in a flask containing 25.05 g (90 mol%) of (M-1), 3.63 g (10 mol%) of (M-2) and 57.19 g of propylene glycol-1-ethyl ether. The dropping funnel was placed. Subsequently, after heating the said flask to 60 degreeC in the oil bath, the said oxalic acid aqueous solution was dripped slowly and it was made to react at 60 degreeC for 4 hours. After the completion of the reaction, the flask containing the reaction solution was allowed to cool, set in an evaporator, and residual water and generated methanol were removed to obtain 97.3 g of a solution containing polysiloxane (A-3) as a solid content. Solid content concentration of polysiloxane (A-3) in the said solution was 18 mass%, and Mw of polysiloxane (A-3) was 2,000.
<Preparation of the composition for forming a resist underlayer film>
It shows below about each component other than [A] polysiloxane.
[B] Solvent
(B1) organic solvent
B1-1: ethylene glycol monobutyl ether
(Standard boiling point: 171 DEG C, static surface tension: 24.0 mN / m)
B1-2: diethylene glycol diethyl ether
(Standard boiling point: 189 ° C., static surface tension: 23.3 mN / m)
B1-3: diethylene glycol monomethyl ether
(Standard boiling point: 194 DEG C, static surface tension: 29.8 mN / m)
B1-4: diethylene glycol monoethyl ether acetate
(Standard boiling point: 217 DEG C, static surface tension: 26.2 mN / m)
(B2) compound
B2: propylene glycol monomethyl ether acetate (standard boiling point: 146 degreeC)
(Other solvents)
B3: propylene glycol-1-ethyl ether (standard boiling point: 133 ° C)
B4: water
[C] acid diffusion control agents
Compounds represented by the following formulas (C-1) to (C-4)
Example 1
[A] 1.94 parts by mass of (A-1) as polysiloxane, (B1) 4.88 parts by mass of (B1-1) as organic solvent, 68.32 parts by mass of (B2) as compound (B2), 24.40 parts by mass of (B3) as other solvent And (B4) 0.4 parts by mass and 0.06 parts by mass of (C-1) as the [C] acid diffusion control agent were mixed to prepare a composition for forming a resist underlayer film.
[Examples 2 to 12 and Comparative Examples 1 to 4]
Except having performed the kind and compounding quantity of each component to mix | blend as Table 2, it carried out similarly to Example 1, and produced the composition for each resist underlayer film formation. In addition, "-" in Table 2 shows that the corresponding component is not mix | blended.
<Evaluation>
The composition for resist underlayer film formation prepared above was evaluated according to the following method. The evaluation results are shown in Table 3.
Initial coating defect suppression
The composition for forming a resist underlayer film immediately after the manufacture was applied onto the silicon wafer to be a substrate by spin coating using a coating / developing device (CLEAN TRACK ACT12, manufactured by Tokyo Electron), and then the resulting coating film was 220 After drying at 占 폚 for 60 seconds, the mixture was cooled to 23 占 폚 to form a resist underlayer film with a thickness of 30 nm. In addition, the film thickness was measured using the optical film thickness meter (UV-1280SE, KLA Tencor). Then, the coating defect was measured using the surface defect observation apparatus (brand name "KLA2800", KLA Tencore Corporation), and this measurement result was made into coating defect improvement property (immediately after manufacture). At this time, when there were 100 coating defects, application defect improvement property (immediately after manufacture) was evaluated as good "(circle)", and when it exceeded 100 pieces, it evaluated as defective "x".
[Evaluation of Preservation Stability (1)]
(Inhibition of film thickness change over time)
Each resist underlayer film was formed on the surface of the silicon wafer by using a spin coater to apply the composition for forming a resist underlayer film at a rotational speed of 2,000 rpm for 20 seconds, and then dried at 250 ° C. for 60 seconds on a hot plate. . For each formed resist underlayer film, the film thickness was measured at the position of 50 points using the above optical film thickness meter, and the average film thickness thereof was determined to obtain an initial film thickness T0. In addition, using the composition for forming a resist underlayer film after heating at 80 ° C. for 5 hours, each resist underlayer film was formed in the same manner as described above, the film thickness was measured, and the average film thickness thereof was obtained. ). Further, the difference (T-T0) between the initial film thickness T0 and the film thickness T after storage is obtained, and the ratio [(T-T0) / T0] of the magnitude of the difference with respect to the initial film thickness T0 is calculated as the film thickness change rate. "(Circle)" and the case where the value exceeds 8% and the case where it is 10% or less were evaluated as "x" when the value was 8% or less as "(circle)".
[Evaluation of Preservation Stability (2)]
(Coating defect suppression over time)
Each of the prepared resist underlayer film-forming compositions was stored at 40 ° C. for one week, and then, using each composition after storage, a resist underlayer film was formed and applied in the same manner as described in the above "Coating defect improvement property (right after manufacture)". After measuring a defect, this measurement result was made into coating defect improvement property (after storage). At this time, when there were 100 coating defects, application defect improvement property (after storage) was evaluated as good "(circle)", and when it exceeded 100 pieces, it evaluated as defective "x".
As can be seen from the results in Table 3, in the examples, coating defect improvement and storage stability (time-dependent film thickness change suppression and time-dependent application defect suppression) were all good. On the other hand, in the comparative example, it was seen that it was poor in application | coating defect improvement property (right after manufacture, after storage).
This invention can provide the composition for resist underlayer film formation which has the outstanding storage stability and the high coating defect improvement property which can suppress generation | occurrence | production of coating defect, and the pattern formation method using this composition. Therefore, the said composition for resist underlayer film formation and the pattern formation method can be used suitably for the manufacturing process of the semiconductor device which refine | miniaturizes a pattern.
Claims (11)
[B] solvent
As a composition for forming a resist underlayer film containing
[B] the solvent
(B1) An organic solvent having a compound represented by the following formula (1) or a carbonate compound and having a standard boiling point of 150.0 ° C or higher.
A composition for forming a resist underlayer film comprising a.
≪ Formula 1 >
(In formula 1, R <1> and R <2> is respectively independently a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 acyl group, R <3> is a hydrogen atom or a methyl group, n is an integer of 1-4, , when n is 2 or more, a plurality of R 3 may be the same or different.)
(I)
(In Formula i, R A is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a cyano group, and part or all of the hydrogen atoms of the alkyl group. May be substituted with an epoxyalkyloxy group, an acid anhydride group or a cyano group, some or all of the hydrogen atoms of the aryl group may be substituted with a hydroxy group, and X is a halogen atom or -OR B , provided that R is B is a monovalent organic group, a is an integer of 0 to 3, provided that when R A and X are each plural, a plurality of R A and X may be the same or different.)
(2) forming a resist film on the resist underlayer film using a resist composition;
(3) exposing the resist film by irradiation of exposure light through a photomask;
(4) a step of developing the exposed resist film to form a resist pattern, and
(5) A step of sequentially dry etching the resist underlayer film and the substrate to be processed using the resist pattern as a mask
≪ / RTI >
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| JP2004310019A (en) | 2003-03-24 | 2004-11-04 | Shin Etsu Chem Co Ltd | Antireflection film material, substrate having antireflection film and method for forming pattern |
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| KR20070103085A (en) * | 2005-03-01 | 2007-10-22 | 제이에스알 가부시끼가이샤 | Composition for underlayer film of resist and process for producing the same |
| US20100075248A1 (en) * | 2008-09-22 | 2010-03-25 | Honeywell International Inc. | Bottom antireflective coatings exhibiting enhanced wet strip rates, bottom antireflective coating compositions for forming bottom antireflective coatings, and methods for fabricating the same |
| JP2012036385A (en) * | 2010-07-14 | 2012-02-23 | Jsr Corp | Polysiloxane composition and method for forming pattern |
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| JP2004310019A (en) | 2003-03-24 | 2004-11-04 | Shin Etsu Chem Co Ltd | Antireflection film material, substrate having antireflection film and method for forming pattern |
| JP2005018054A (en) | 2003-06-03 | 2005-01-20 | Shin Etsu Chem Co Ltd | Antireflection film material, antireflection film using the same and pattern forming method |
| KR20050049353A (en) * | 2003-11-20 | 2005-05-25 | 도오꾜오까고오교 가부시끼가이샤 | Undercoating layer material for lithography and wiring forming method using the same |
| KR20070103085A (en) * | 2005-03-01 | 2007-10-22 | 제이에스알 가부시끼가이샤 | Composition for underlayer film of resist and process for producing the same |
| US20100075248A1 (en) * | 2008-09-22 | 2010-03-25 | Honeywell International Inc. | Bottom antireflective coatings exhibiting enhanced wet strip rates, bottom antireflective coating compositions for forming bottom antireflective coatings, and methods for fabricating the same |
| JP2012036385A (en) * | 2010-07-14 | 2012-02-23 | Jsr Corp | Polysiloxane composition and method for forming pattern |
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