JP2018067696A - Processing material for substrate pattern collapse suppression and processing method of substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing material for a substrate pattern collapse suppression excellent in collapse suppression of a substrate pattern and defect suppressing property, and a processing method of a substrate by using the same.SOLUTION: A processing material for a substrate pattern collapse suppression is used for a processing method of a substrate including a step where a substrate pattern collapse suppression film is formed by coating the processing material for a substrate pattern collapse suppression on a substrate pattern side surface of a substrate in which a substrate pattern is formed on one surface of the substrate. The processing material for a substrate pattern collapse suppression includes a first compound which is polymerized by a heat or light effect, and solvent. The first compound preferably has a crosslinking group. Preferably, the crosslinking group is a group containing a polymerizable carbon-carbon double bond, a group containing a polymerizable carbon-carbon triple bond, a substituted/unsubstituted cyclic ether group, or combination of them. Preferably, number of the crosslinking groups contained in the first compound is 2 or more.SELECTED DRAWING: None

Description

  The present invention relates to a substrate pattern collapse suppression processing material and a substrate processing method.

  In a manufacturing process such as a semiconductor device or a micro electro mechanical system (MEMS), a substrate (processed material) is processed with a liquid. For example, a substrate, a laminated film, a resist film, or the like is patterned by liquid processing or the like, and a fine structure is formed on the substrate. Further, impurities, residues, and the like remaining on the substrate are removed by cleaning with a liquid. Further, these steps are performed in combination. Then, after the liquid treatment, when the liquid is removed, the fine structure formed on the substrate may collapse due to the surface tension of the liquid.

  On the other hand, in semiconductor devices for networks and digital home appliances, miniaturization of substrate patterns has progressed as further miniaturization, higher integration, and higher speed have progressed. If the aspect ratio becomes higher as the substrate pattern becomes finer, there is a disadvantage that the substrate pattern is likely to collapse when the gas-liquid interface passes through the pattern when the wafer is dried after cleaning or rinsing. Since there is no effective countermeasure against this inconvenience, it is necessary to design a pattern so that the pattern does not collapse when the semiconductor device or micromachine is downsized, highly integrated, or increased in speed. The degree of freedom in pattern design is significantly hindered.

  Patent Document 1 discloses a technique for replacing the cleaning liquid from water to 2-propanol before the gas-liquid interface passes through the pattern as a technique for suppressing the collapse of the substrate pattern. However, it is said that there is a limit that the aspect ratio of the pattern that can be handled is 5 or less.

  Further, Patent Document 2 discloses that a wafer surface on which a concavo-convex pattern is formed by a film containing silicon is surface-modified by oxidation or the like, and a water-repellent protective film is formed on the surface using a water-soluble surfactant or silane coupling agent. A cleaning method is disclosed in which the capillary force is reduced by forming, thereby preventing the pattern from collapsing.

  Patent Documents 3 and 4 include a technique for preventing collapse of a substrate pattern by performing a hydrophobic treatment using a treatment liquid containing a silylating agent such as N, N-dimethylaminotrimethylsilane and a solvent. It is disclosed.

JP 2008-198958 A Japanese Patent No. 4403202 JP 2010-129932 A International Publication No. 10/47196 Pamphlet

  However, the conventional method has a problem that the collapse of the substrate pattern cannot be sufficiently suppressed in the field of fine structures such as semiconductor devices and microelectromechanical elements.

  The present invention has been made based on the circumstances as described above, and the purpose thereof is a substrate pattern collapse suppression treatment material excellent in substrate pattern collapse suppression and defect suppression, and processing of a substrate using the same. And to provide a method.

  The invention made in order to solve the above problems is to form a substrate pattern collapse inhibiting film by applying a substrate pattern collapse inhibiting treatment material on the substrate pattern side surface of the substrate having a substrate pattern formed on one surface. A substrate pattern collapse-suppressing treatment material used in a substrate processing method comprising the step of: a first compound (hereinafter, also referred to as “[A] compound”) that has a high molecular weight by the action of heat or light, and a solvent (Hereinafter also referred to as “[C] solvent”).

  Another invention made in order to solve the above-mentioned problem is that the substrate pattern collapses by applying the substrate pattern collapse-suppressing treatment material to the substrate pattern side surface of the substrate having the substrate pattern formed on one surface. The substrate processing method includes a step of forming a suppression film and a step of heating or irradiating the substrate pattern collapse suppression film.

  Here, the “substrate pattern” means a pattern other than the resist pattern formed on the substrate. “High molecular weight by the action of heat or light” is not only due to the high molecular weight by the direct action of heat or light, but also by the action of mediators such as acids and radicals generated by the action of heat or light. It is a concept including high molecular weight.

  The substrate pattern collapse suppressing treatment material and the substrate processing method of the present invention are excellent in substrate pattern collapse suppression. Further, for example, if a residue of the substrate pattern collapse suppression film is generated in the step of removing the substrate pattern collapse suppression film (removal step), it may cause a defect in the substrate pattern. This processing method is excellent in substrate pattern defect suppression during processing. Accordingly, these can be suitably used for manufacturing semiconductor devices that are expected to be further miniaturized in the future.

  Hereinafter, although embodiment of this invention is described, this invention is not limited to the following embodiment. That is, it is understood that modifications and improvements as appropriate to the following embodiments also belong to the scope of the present invention based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Should.

<Processing material for suppressing substrate pattern collapse>
The substrate pattern collapse suppression treatment material of the present invention forms a substrate pattern collapse suppression film on the substrate pattern side surface of the substrate having the substrate pattern formed on one surface by coating the substrate pattern collapse suppression treatment material. The [A] compound which is used for the processing method of a board | substrate provided with the process to make it high molecular weight by the effect | action of a heat | fever or light, and contains a [C] solvent.

  The substrate pattern collapse suppression treatment material may be used for embedding in the gap between the substrate patterns. Specifically, after a substrate having a substrate pattern formed on one surface is cleaned, the substrate pattern collapse suppressing treatment material is applied to the surface of the substrate on the substrate pattern side. As a result, a liquid such as a cleaning liquid or a rinsing liquid on the substrate is replaced with the substrate pattern collapse suppression treatment material, and a coating film (substrate pattern collapse suppression film) that fills the gaps in the substrate pattern is formed. According to this method, since the liquid can be removed without using an operation of drying the liquid, pattern collapse due to the gas-liquid interface passing through the side surface of the substrate pattern is suppressed. The substrate pattern collapse suppression film can be removed from the substrate by dry etching or the like as necessary.

  The said processing material for board pattern collapse suppression contains the [A] compound and a [C] solvent, and is excellent in the collapse suppression property and defect suppression property of a substrate pattern. The reason why the substrate pattern collapse-suppressing treatment material has the above-described configuration is not necessarily clear, but can be inferred as follows, for example. That is, since the substrate pattern collapse-suppressing treatment material contains a compound [A] that becomes a high molecular weight by the action of heat or light, the formed substrate pattern collapse-suppressing film is heated or irradiated with light [A]. The compound can have a high molecular weight, and as a result, heat resistance can be imparted to the substrate pattern collapse inhibiting film. Such a substrate pattern collapse suppression film suppresses the collapse of the substrate pattern because it can easily maintain the strength by suppressing thermal melting even if part or the whole becomes hot when removed from the substrate by dry etching or the like. However, it can be reliably removed by dry etching or the like. Thereby, it is thought that the said board | substrate pattern collapse suppression processing material is excellent in the collapse suppression property and defect suppression property of a substrate pattern.

[[A] Compound]
[A] The compound is not particularly limited as long as it is a component that can be polymerized by the action of heat or light, but a compound having a crosslinking group (hereinafter also referred to as “[a] crosslinking group-containing compound”) is preferable. Thus, by using the [a] crosslinking group-containing compound as the [A] compound, it is possible to easily and reliably increase the molecular weight by the action of heat or light. [A] A compound can be used individually by 1 type or in combination of 2 or more types. [A] The crosslinking group-containing compound may contain only one kind of crosslinking group or may contain two or more kinds of crosslinking groups.

  Here, the “crosslinking group” means that a covalent bond is formed between each other (by a group at another site having the same structure and itself) by a reaction under heating conditions, active energy ray irradiation conditions, acidic conditions, etc. A group that can be

  As the crosslinking group, a monovalent crosslinking group and a divalent crosslinking group are preferable.

Examples of the crosslinking group include a group containing a polymerizable carbon-carbon double bond, a group containing a polymerizable carbon-carbon triple bond, a substituted or unsubstituted cyclic ether group, an alkoxymethyl group, a formyl group, an acetyl group, and a methylol. Examples include a group (—CH ₂ OH), a dialkylaminomethyl group, a dimethylolaminomethyl group, and the like.

  Examples of the group containing a polymerizable carbon-carbon double bond include alkenyl groups such as vinyl groups and 2-propanyl groups, vinyloxy groups, (meth) acryloyl groups, and styryl groups.

  Examples of the group containing a polymerizable carbon-carbon triple bond include an ethynyl group, a propargyl group, a propargyloxy group, and a propargylamino group.

  Examples of the substituent in the substituted cyclic ether group include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an i-propyl group, and an n-propyl group, an n-butyl group, and a tert-butyl group. Is mentioned.

Examples of the substituted or unsubstituted cyclic ether group include substituted or unsubstituted oxiranyl groups such as an oxiranyl group, a glycidyl group, a 2-methylglycidyl group, a glycidyloxy group, and a 3,4-epoxycyclohexyl group;
Examples thereof include substituted or unsubstituted oxetanyl groups such as an oxetanyl group, an oxetanyloxy group, and a 3-ethyloxetane-3-yl group.

  Examples of the aryl group condensed with the cyclobutane ring include a phenyl group condensed with the cyclobutane ring and a naphthyl group condensed with the cyclobutane ring. In addition, a covalent bond is formed between aryl groups condensed with the cyclobutane ring under heating conditions.

  Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, and a t-butoxymethyl group.

  As the crosslinking group, a group containing a polymerizable carbon-carbon double bond, a polymerizable carbon-carbon triple bond-containing group, a substituted or unsubstituted cyclic ether group, and a combination thereof are preferable. An alkenyl group, a vinyloxy group, ( More preferred are a (meth) acryloyl group, a styryl group, an ethynyl group, a propargyl group, a propargyloxy group, a substituted or unsubstituted oxiranyl group, a substituted or unsubstituted oxetanyl group, and combinations thereof.

  [A] The number of the crosslinking groups contained in the crosslinking group-containing compound is preferably 2 or more. Thus, it is thought that the [a] crosslinkable group-containing compound has a plurality of the above-mentioned crosslinkable groups, thereby further improving the substrate pattern collapse suppression and defect suppression. The reason why the substrate pattern collapse-suppressing treatment material has the above-described configuration is not necessarily clear, but can be inferred as follows, for example. That is, it is considered that [a] the crosslinkable group-containing compound has a plurality of the above crosslinkable groups to promote high molecular weight. In addition, a cross-linking of [a] cross-linking group-containing compounds and cross-linking of [a] cross-linking group-containing compound and [B] specific group-containing compound described later form a three-dimensional network structure on the substrate pattern collapse-inhibiting film. It is considered that thermal melting at the time of removal by etching or the like is more effectively suppressed.

  [A] The cross-linking group-containing compound preferably further has a polar group other than the cross-linking group. Here, since a highly polar solution such as water is generally used for the substrate cleaning solution or the rinsing solution, when the cleaning solution or the rinsing solution held on the substrate is replaced with the substrate pattern collapse suppressing treatment material. In addition, [a] poor dispersion of the crosslinking group-containing compound can be suppressed. [A] The crosslinking group-containing compound may contain only one kind of the polar group or may contain two or more kinds of the polar groups.

  Examples of the polar group include hydroxy group, carboxy group, alkoxy group, cycloalkoxy group, aryloxy group, acyl group, amino group, amide group, cyano group, isocyanate group, sulfo group, sulfanyl group, and aldehyde group. Valent polar groups, divalent polar groups such as a carbonyl group, -O-, -S-, and -NR'-. R ′ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. In addition, the said polar group may be contained in the [a] bridge | crosslinking group containing compound in the state dissociated into the ionic group and the counter ion.

  Here, the “hydrocarbon group” includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The “hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The “chain hydrocarbon group” refers to a hydrocarbon group that does not include a cyclic structure but includes only a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group. The term “alicyclic hydrocarbon group” refers to a hydrocarbon group that includes only an alicyclic structure as a ring structure and does not include an aromatic ring structure, and includes a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic group. Includes both hydrocarbon groups. However, it is not necessary to be composed only of the alicyclic structure, and a part thereof may include a chain structure. “Aromatic hydrocarbon group” refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic structure.

  As the polar group, a hydroxy group, a carboxy group, a sulfanyl group, an amino group, and a combination thereof are preferable. These polar groups have a relatively high polarity and can be crosslinked by reacting with the crosslinking group by the action of heat or light. Therefore, the [a] crosslinkable group-containing compound further has the above-described polar group, whereby the hydrophilicity of the [a] crosslinkable group-containing compound can be effectively improved, and the [a] crosslinkable group-containing compound is produced by the action of heat or light. The high molecular weight of the compound can be promoted.

  [A] When the crosslinkable group-containing compound has a substituted or unsubstituted cyclic ether group as the crosslinkable group, it further has a hydroxy group, a carboxy group, a sulfanyl group, an amino group, or a combination thereof as the polar group. It is preferable. As described above, the [a] crosslinking group-containing compound having the above combination can promote the increase in the molecular weight of the [a] crosslinking group-containing compound by the action of heat or light.

  [A] Examples of the crosslinkable group-containing compound include a polymer having the above crosslinkable group (hereinafter, also referred to as “[a1] polymer”) and a compound other than a polymer having the crosslinkable group (hereinafter, referred to as “a”). Also referred to as “[a2] compound”). Hereinafter, the [a1] polymer and the [a2] compound will be described.

[[A1] polymer]
[A1] Examples of the polymer include a polymer having the structural unit (U1) containing the above-mentioned crosslinking group. The structural unit (U1) may contain the crosslinking group in the main chain or in the side chain. The number of the crosslinking groups contained in the structural unit (U1) is not particularly limited, but is preferably 1 or more and 10 or less, and more preferably 1 or more and 3 or less. The structural unit (U1) may further have the polar group. In this case, the number of the polar groups contained in the structural unit (U1) is not particularly limited, but is 1 or more and 10 or less. 1 or more and 3 or less are more preferable.

  [A1] The polymer preferably further has a structural unit (U2) containing the above polar group (excluding those corresponding to the structural unit (U1)). The structural unit (U2) may contain the polar group in the main chain or in the side chain. The number of polar groups contained in the structural unit (U2) is not particularly limited, but is preferably 1 or more and 10 or less, and more preferably 1 or more and 3 or less.

  [A1] When the polymer has the structural unit (U1) and does not have the structural unit (U2), the lower limit of the content ratio of the structural unit (U1) to the total structural units constituting the polymer [a1] 1 mol% is preferable, 20 mol% is more preferable, 50 mol% is further more preferable, and 80 mol% is especially preferable. By making the said content rate more than the said minimum, the high molecular weight of the [a1] polymer by the effect | action of a heat | fever or light can be accelerated | stimulated, As a result, the collapse inhibitory property and defect inhibitory property of a substrate pattern can be improved more.

  [A1] When the polymer has a structural unit (U1) and a structural unit (U2), the lower limit of the content ratio of the structural unit (U1) to all structural units constituting the [a1] polymer is 0.5 mol. %, More preferably 5 mol%, still more preferably 10 mol%, particularly preferably 15 mol%. On the other hand, the upper limit of the content is preferably 95 mol%, more preferably 70 mol%, further preferably 50 mol%, and particularly preferably 30 mol%. By making the said content rate into the said range, the high molecular weight of the [a1] polymer by the effect | action of a heat | fever or light can be accelerated | stimulated, As a result, the collapse suppression property and defect suppression property of a substrate pattern can be improved more.

  [A1] When the polymer has a structural unit (U2), the lower limit of the content ratio of the structural unit (U2) to all structural units constituting the [a1] polymer is preferably 5 mol%, and 30 mol%. More preferably, 50 mol% is further more preferable, and 70 mol% is especially preferable. On the other hand, the upper limit of the content is preferably 99.5 mol%, more preferably 95 mol%, still more preferably 90 mol%, and particularly preferably 85 mol%. By making the said content rate into the said range, the hydrophilicity of a [a1] polymer can be improved more and the high molecular weight of the [a1] polymer by the effect | action of a heat | fever or light can be accelerated | stimulated more.

  [A1] The polymer may have a structural unit containing neither a cross-linking group nor a polar group. [A1] The polymer may have a terminal group containing the cross-linking group and / or the polar group.

  [A1] As the polymer, a thermosetting resin, a photocurable resin, or the like can be used. Specifically, a resin having the above-described crosslinking group introduced (hereinafter, also referred to as “[ax] resin”), epoxy Examples thereof include resins, unsaturated polyesters, diallyl phthalate resins, polybutadiene liquid resins, and urethane liquid resins. The [ax] resin can be classified according to the type of the basic resin. For example, the (meth) acrylic resin introduced with the crosslinking group, the phenol resin introduced with the crosslinking group, the naphthol resin introduced with the crosslinking group, Fluorene resin introduced with a crosslinking group, styrene resin introduced with the crosslinking group, acenaphthylene resin introduced with the crosslinking group, indene resin introduced with the crosslinking group, arylene resin introduced with the crosslinking group, introduced with the crosslinking group Examples thereof include triazine resins, pyrene resins introduced with the above-mentioned crosslinking groups, calixarene resins introduced with the above-mentioned crosslinking groups, and the like.

((Meth) acrylic resin with the above-mentioned crosslinking group introduced)
Examples of the (meth) acrylic resin into which the crosslinking group is introduced include a polymer having a structural unit represented by the following formula (I). This structural unit corresponds to the structural unit (U1).

In the above Formula (I), ^{R 1} is a monovalent organic group having 1 to 20 carbon atoms comprising the above crosslinking group. X ¹ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

Examples of the monovalent organic group represented by R ¹ include a monovalent hydrocarbon group in which some or all of the hydrogen atoms are substituted with the above-described bridging group. As said hydrocarbon group, a C1-C20 alkyl group, a C3-C20 cycloalkyl group etc. are mentioned, for example, Among these, a C1-C20 alkyl group is preferable, C1-C1 An alkyl group of ˜5 is more preferred, and a methyl group is more preferred.

The number of crosslinking groups possessed by the monovalent organic group represented by R ¹ can be, for example, 1 or more and 10 or less, preferably 1 or more and 5 or less, and more preferably 1 or more and 2 or less. preferable.

The bridging group contained in R ¹ is preferably a substituted or unsubstituted cyclic ether group, more preferably a substituted or unsubstituted oxiranyl group and a substituted or unsubstituted oxetanyl group.

X ¹ is preferably a hydrogen atom or a methyl group from the viewpoint of polymerizability of the monomer giving the structural unit.

  The (meth) acrylic resin into which the crosslinking group is introduced preferably further has a structural unit represented by the following formula (II). This structural unit corresponds to the structural unit (U2).

In said formula (II), R < ² > is a C1-C20 monovalent organic group containing the said polar group. X ² is a hydrogen atom, a methyl group or a trifluoromethyl group.

Examples of the monovalent organic group represented by R ² include a monovalent hydrocarbon group in which part or all of the hydrogen atoms are substituted with the polar group. Examples of the monovalent hydrocarbon group include the same groups as those exemplified for R ¹ in the above formula (I). Among these, an alkyl group having 1 to 20 carbon atoms is preferable, and 1-5 alkyl groups are more preferable, and a methyl group and an ethyl group are more preferable.

The number of polar groups possessed by the monovalent organic group represented by R ² can be, for example, 1 or more and 10 or less, preferably 1 or more and 5 or less, and more preferably 1 or more and 2 or less. preferable.

As a polar group which the monovalent organic group represented by R ² has, a hydroxy group is preferable.

X ² is preferably a hydrogen atom or a methyl group from the viewpoint of polymerizability of the monomer giving the structural unit.

(Phenolic resin with the above-mentioned crosslinking group introduced)
The phenol resin into which the crosslinking group is introduced has a structural unit derived from a phenol compound, and the structural unit is a resin having the crosslinking group. The phenol resin into which the crosslinking group is introduced can be synthesized by, for example, forming the crosslinking group from the phenol structure of a resin obtained by reacting the phenol compound with an aldehyde compound using an acidic catalyst or an alkaline catalyst. it can.

  Examples of the phenol compound include phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol and the like.

Examples of aldehyde compounds include aldehydes such as formaldehyde;
Examples include aldehyde sources such as paraformaldehyde and trioxane.

(Naphthol resin introduced with the above-mentioned crosslinking group)
The naphthol resin into which the crosslinking group is introduced has a structural unit derived from a naphthol compound, and the structural unit is a resin having the crosslinking group. The naphthol resin into which the crosslinking group is introduced can be synthesized, for example, by forming the crosslinking group from a naphthol structure of a resin obtained by reacting the naphthol compound with an aldehyde compound using an acidic catalyst or an alkaline catalyst. it can. Examples of the naphthol compound include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like.

(Fluorene resin introduced with the above crosslinking group)
The fluorene resin into which the crosslinking group is introduced has a structural unit derived from a fluorene compound, and the structural unit is a resin having the crosslinking group. The fluorene resin into which the cross-linking group is introduced, for example, forms the cross-linking group from the hydroxyaryl structure of a resin obtained by reacting a fluorene compound having a hydroxyaryl structure with an aldehyde compound using an acidic catalyst or an alkaline catalyst. Can be synthesized.

  Examples of the fluorene compound include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (6-hydroxynaphthyl) fluorene, and the like.

(Styrene resin introduced with the above crosslinking group)
The styrene resin into which the cross-linking group is introduced has a structural unit derived from a compound having an aromatic ring and a polymerizable carbon-carbon double bond, and the structural unit is a resin having the cross-linking group. The styrene resin introduced with the cross-linking group forms the cross-linking group from the phenol structure of the resin having a structural unit derived from an aromatic ring having a phenolic hydroxy group and a compound having a polymerizable carbon-carbon double bond, for example. Can be synthesized.

(Acenaphthylene resin introduced with the above crosslinking group)
The acenaphthylene resin into which the crosslinking group is introduced has a structural unit derived from an acenaphthylene compound, and the structural unit is a resin having the crosslinking group. The acenaphthylene resin into which the crosslinking group is introduced can be synthesized, for example, by forming the crosslinking group from a phenol structure of a resin having a structural unit derived from an acenaphthylene compound having a hydroxyaryl structure.

(Indene resin with the above-mentioned crosslinking group introduced)
The indene resin into which the crosslinking group is introduced has a structural unit derived from an indene compound, and the structural unit is a resin having the crosslinking group. The indene resin into which the crosslinking group is introduced can be synthesized, for example, by forming the crosslinking group from a hydroxyaryl structure of a resin having a structural unit derived from an indene compound having a hydroxyaryl structure.

(Arylene resin having the above-mentioned crosslinking group introduced)
The arylene resin into which the crosslinking group is introduced is a resin having an arylene skeleton having the crosslinking group. The arylene resin into which the crosslinking group is introduced can be synthesized, for example, by forming the crosslinking group from the phenol structure of a resin having an arylene skeleton having a hydroxyaryl structure. Examples of the arylene skeleton include a phenylene skeleton, a naphthylene skeleton, and a biphenylene skeleton.

(Triazine resin introduced with the above crosslinking group)
The triazine resin into which the crosslinking group is introduced is a resin having a triazine skeleton having the crosslinking group. The triazine resin into which the crosslinking group is introduced can be synthesized, for example, by forming the crosslinking group from the phenol structure of a resin having a triazine skeleton having a hydroxyaryl structure.

(Pyrene resin introduced with the above crosslinking group)
The pyrene resin into which the crosslinking group is introduced is a resin having a pyrene skeleton having the crosslinking group. The pyrene resin into which the crosslinking group is introduced can be synthesized, for example, by forming the crosslinking group from a phenol structure of a resin having a pyrene skeleton having a hydroxyaryl structure. A resin having a pyrene skeleton having a hydroxyaryl structure can be obtained, for example, by reacting a pyrene compound having a phenolic hydroxyl group with an aldehyde compound using an acidic catalyst.

(Calixarene resin introduced with the above-mentioned crosslinking group)
The calixarene resin into which the crosslinking group is introduced is a cyclic oligomer in which a plurality of aromatic rings to which a phenolic hydroxyl group is bonded are bonded in a cyclic manner via a hydrocarbon group. The calixarene resin having the crosslinking group can be synthesized, for example, by forming the crosslinking group from the phenol structure of the calixarene resin.

(Epoxy resin)
Examples of the epoxy resin include bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, and bisphenol A novolak type. Epoxy resin, bisphenol F novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, urethane modified epoxy resin, rubber modified epoxy resin, etc. Is mentioned.

  [A1] The polymer is preferably [ax] resin.

  [A1] The lower limit of the weight average molecular weight (Mw) of the polymer is preferably 1,000, more preferably 1,300, still more preferably 2,000, and particularly preferably 4,000. On the other hand, the upper limit of the Mw is preferably 1,000,000, more preferably 200,000, still more preferably 50,000, and particularly preferably 10,000. By making said Mw into the said range, the applicability | paintability of the said substrate pattern collapse suppression processing material, embedding property, and the collapse suppression property and defect suppression property of a substrate pattern can be improved with sufficient balance. Here, “Mw” refers to a value measured by gel permeation chromatography using a standard polystyrene calibration curve.

[[A2] Compound]
Examples of the [a2] compound include a compound having a relatively low molecular weight (for example, a compound having a molecular weight of 50 or more and 1,000 or less), a compound having a relatively large molecular weight (for example, a compound having a molecular weight of more than 1,000 or less than 10,000), and the like. It is done. [A2] The number of the crosslinking groups contained in the compound is preferably 2 or more, 20 or less, more preferably 2 or more and 10 or less, and even more preferably 2 or more and 5 or less. By making the number of the said crosslinking group which a [a2] compound has into the said range, the high molecular weight by the effect | action of a heat | fever or light can be accelerated | stimulated, As a result, the collapse inhibitory property and defect inhibitory property of a substrate pattern can be improved more.

  When the [a2] compound further has the polar group, the number of the polar group possessed by the [a2] compound is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and 1 or more and 5 More than the number is more preferable. [A2] By making the number of the polar groups the compound has within the above range, hydrophilicity can be further improved, and as a result, coatability can be improved.

  Examples of the [a2] compound include a compound containing a polymerizable carbon-carbon double bond, a compound containing a polymerizable carbon-carbon triple bond, a polyfunctional oxirane compound, and a polyfunctional oxetane compound.

(Compound containing a polymerizable carbon-carbon double bond)
Examples of the compound containing a polymerizable carbon-carbon double bond include a polyfunctional (meth) acrylate compound, a compound having two or more alkenyloxy groups, a compound having two or more alkenyl groups, and the like.

  The polyfunctional (meth) acrylate is not particularly limited as long as it is a compound having two or more (meth) acryloyl groups. For example, the polyfunctional (meth) acrylate is obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid. Functional (meth) acrylates, polyfunctional (meth) acrylates modified with caprolactone, polyfunctional (meth) acrylates modified with alkylene oxide, polyfunctionals obtained by reacting (meth) acrylates having hydroxy groups with polyfunctional isocyanates Examples thereof include urethane (meth) acrylate, polyfunctional (meth) acrylate having a carboxy group obtained by reacting a hydroxy group-containing (meth) acrylate and an acid anhydride.

  Specific examples of the polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipenta. Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3- Butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (me ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate.

  Examples of the compound having two or more alkenyloxy groups include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, polyallyl (meth) acrylate, and the like. It is done.

  Examples of the compound having two or more alkenyl groups include hydrocarbon compounds such as divinylbenzene.

  As the compound containing a polymerizable carbon-carbon double bond, a polyfunctional (meth) acrylate compound is preferable, and pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate are more preferable.

(Polyfunctional oxirane compounds)
Examples of the polyfunctional oxirane compound include compounds represented by the following formulas.

(Polyfunctional oxetane compound)
Examples of the polyfunctional oxetane compound include xylylene bisoxetane, 1-butoxy-2,2-bis [(3-ethyloxetane-3-yl) methoxymethyl] butane, 3-ethyl-3 {[(3-ethyloxetane. -3-yl) methoxy] methyl} oxetane, 1,1,1-tris [(3-ethyloxetane-3-yl) methoxymethyl] propane, and the like.

  As the polyfunctional oxetane compound, xylylene bisoxetane, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, and a compound represented by the above formula are preferable.

  As the [a2] compound, a compound containing a polymerizable carbon-carbon double bond, a polyfunctional oxirane compound and a polyfunctional oxetane compound are preferable, and a polyfunctional (meth) acrylate compound, a polyfunctional oxirane compound and a polyfunctional oxetane compound are more preferable. preferable.

  The lower limit of the content of the [A] compound in the substrate pattern collapse suppression treatment material is preferably 0.1% by mass, more preferably 2% by mass, and even more preferably 5% by mass. On the other hand, the upper limit of the content is preferably 50% by mass, more preferably 40% by mass, and even more preferably 30% by mass. By making content of [A] compound into the said range, the applicability | paintability of the said substrate pattern collapse suppression processing material, embedding property, and the collapse suppression property and defect suppression property of a substrate pattern can be improved with sufficient balance.

[[B] specific group-containing compound]
The substrate pattern collapse suppression treatment material is a compound other than the [A] compound, and is a second compound having a molecular weight of 300 or more having a hydroxy group, a carboxy group, a sulfanyl group, an amino group, or a combination thereof (hereinafter, “[ B] "(also referred to as" specific group-containing compound "). [B] The above-mentioned group of the specific group-containing compound can react with the cross-linking group of the [a] cross-linking group-containing compound to form a covalent bond. Therefore, the treatment material for suppressing substrate pattern collapse contains the [B] specific group-containing compound, thereby promoting the high molecular weight of the [a] crosslinking group-containing compound by the action of heat or light. [B] Since the specific group-containing compound has a group having a relatively high polarity as described above, it can be easily dissolved or dispersed even when the polarity of the [C] solvent is relatively high. [B] Specific group-containing compounds can be used singly or in combination of two or more.

  [B] The specific group-containing compound may be a polymer or a compound other than a polymer. Examples thereof include a polymer having a hydroxy group, a polymer having a carboxy group, and a polymer having an amino group. Can be mentioned.

  [B] When the specific group-containing compound is a polymer, the polymer may have only a structural unit containing a hydroxy group, a carboxy group, a sulfanyl group, an amino group, or a combination thereof, and other structural units. May further be included. Moreover, the said polymer may have the terminal group containing the above-mentioned group.

(Polymer having a hydroxy group)
Examples of the polymer having a hydroxy group include polysaccharides, polyhydroxy acids and salts thereof, polyalkylene glycols, hydroxy group-containing vinyl polymers, phenol resins, and tannic acid.

  Examples of the polysaccharide include alginic acid, pectic acid, hydroxypropyl cellulose, carboxymethyl cellulose, agar, cardran, pullulan and the like.

  Examples of the polyhydroxy acids and salts thereof include polymalic acid and ammonium polymalate.

  Examples of the polyalkylene glycols include polyethylene glycol and polypropylene glycol.

  Examples of the hydroxy group-containing vinyl polymer include polyvinyl alcohol and hydroxy group-containing (meth) acrylic resin.

  Examples of the hydroxy group-containing (meth) acrylic resin include poly (2-hydroxyethyl (meth) acrylate), poly (2-hydroxypropyl (meth) acrylate), poly (2-hydroxybutyl (meth) acrylate), and the like. Is mentioned.

  As the phenol resin, for example, a novolac resin obtained by reacting a phenol compound with an aldehyde compound and / or divinyl compound using an acidic catalyst or the like, or using an alkaline catalyst with the phenol compound and the aldehyde compound is used. For example, a resol resin obtained by reaction.

  As the phenol compound, phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol and p-octylphenol are preferable. The said phenol compound can be used individually by 1 type or in combination of 2 or more types.

  Examples of the aldehyde compound include aldehydes such as formaldehyde, and aldehyde sources such as paraformaldehyde and trioxane. As said aldehyde compound, an aldehyde is preferable and formaldehyde is more preferable. The said aldehyde compound can be used individually by 1 type or in combination of 2 or more types.

  Examples of the divinyl compounds include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnoborn-2-ene, α-pinene, β-pinene, limonene, and 5-vinylnorbornadiene. Divinyl compounds can be used singly or in combination of two or more.

(Polymer having carboxy group)
Examples of the polymer having a carboxy group include polyamino acids and salts thereof, polyhydroxy acids and salts thereof, polyamic acids and salts thereof, carboxy group-containing vinyl polymers and salts thereof, and the like.

  Examples of the polyamino acids and salts thereof include polyaspartic acid, polyglutamic acid, polylysine and the like.

  Examples of the polyamic acids and salts thereof include polyamic acid and polyamic acid ammonium salt.

  Examples of the carboxy group-containing vinyl polymer and salts thereof include polyacrylic acid, polyacrylic acid ammonium salt, polymethacrylic acid, polymethacrylic acid ammonium salt, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrene carboxylic acid). Acid) and the like.

(Polymer having amino group)
Examples of the polymer having an amino group include an amino group-containing vinyl polymer, polyethyleneimine, and polyoxazoline.

  Examples of the amino group-containing vinyl polymer include polyvinylamine, polyallylamine, and polyvinylpyrrolidone.

  The polyethyleneimine is a water-soluble polymer having a branched structure obtained by polymerization of ethyleneimine, and includes a plurality of primary amines, secondary amines and / or tertiary amines.

  Examples of the polyoxazoline include polymethyl oxazoline, polyethyl oxazoline, polyhydroxypropyl oxazoline, and the like.

  Examples of the polymer having a sulfanyl group include a sulfanyl group-containing vinyl polymer.

  Examples of tannic acid include “tannic acid extract A”, “B tannic acid”, “N tannic acid”, “industrial tannic acid”, “purified tannic acid”, “Hi tannic acid”, “F tannic acid”, "Local tannic acid" (above, manufactured by Nippon Pharmaceutical Co., Ltd.), "Tannic acid: AL" (above, manufactured by Fuji Chemical Industry Co., Ltd.), "G tannic acid", "F tannic acid", "Hi tannic acid" (above, DSP Gokyo Food & Chemical Co.).

  [B] When the specific group-containing compound is a polymer, the molecular weight of the [B] specific group-containing compound means Mw, and the lower limit of Mw is preferably 1,000 and more preferably 1,500. On the other hand, the upper limit of the Mw is not particularly limited, but is preferably 1,000,000, more preferably 300,000, still more preferably 100,000, and particularly preferably 20,000. Thus, by making said Mw into the said range, applicability | paintability, embedding property, and the collapse inhibitory property and defect inhibitory property of a substrate pattern can be improved with good balance.

  [B] As the specific group-containing compound, a compound having a hydroxy group, a carboxy group, an amino group or a combination thereof is preferable, and a polymer having a hydroxy group, a polymer having a carboxy group, and a polymer having an amino group are preferred. More preferred are hydroxy group-containing (meth) acrylic resins, phenolic resins, polyacrylic acid, polyvinyl alcohol and polyethyleneimine.

  When the substrate pattern collapse suppression treatment material contains a [B] specific group-containing compound, the lower limit of the content of the [B] specific group-containing compound in the substrate pattern collapse suppression treatment material is [A] polymer. 10 mass parts is preferable with respect to 100 mass parts, 50 mass parts is more preferable, and 120 mass parts is further more preferable. On the other hand, the upper limit of the content is preferably 500 parts by mass, more preferably 300 parts by mass, and even more preferably 200 parts by mass. [B] By making content of a specific group containing compound into the said range, the applicability | paintability of the said substrate pattern collapse suppression processing material, embedding property, the collapse suppression property of a substrate pattern, and defect suppression property can be improved with sufficient balance.

[[C] solvent]
[C] The solvent used for the substrate pattern collapse suppression treatment material is not particularly limited, and for example, a polar solvent such as water or a polar organic solvent can be used. [C] The molecular weight of the solvent is preferably less than 300. [C] A solvent can be used individually by 1 type or in combination of 2 or more types.

  The polar organic solvent is not particularly limited, but from the viewpoint of embedding in a substrate pattern, alcohols, esters, alkyl ethers of polyhydric alcohols, hydroxy ketones, carboxylic acids, ethers, ketones, nitriles , Amides, amines and the like.

  Examples of the alcohols include monoalcohols such as methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, and isopropanol; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, triethylene glycol, and the like. Examples include polyhydric alcohols such as propylene glycol. Among these, methanol and isopropanol are preferable, and isopropanol is more preferable.

  Examples of the esters include hydroxycarboxylic acid esters such as n-butyl acetate, ethyl lactate, methyl glycolate, ethyl glycolate, methyl hydroxypropionate, ethyl hydroxypropionate, methyl hydroxybutyrate and ethyl hydroxybutyrate; propylene acetate Polyhydric alcohol carboxylates such as glycol; Polyhydric alcohol partial ether carboxylates such as propylene glycol monomethyl ether acetate; Polyhydric carboxylic acid diesters such as diethyl oxalate; Carbonates such as dimethyl carbonate and diethyl carbonate It is done.

  Examples of the alkyl ethers of the polyhydric alcohol include ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Monoalkyl ethers of polyhydric alcohols such as propylene glycol monobutyl ether; ethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, ethylene glycol dibutyl ether Ether, such as polyalkyl ethers of polyhydric alcohols such as propylene glycol dibutyl ether.

  Examples of the hydroxy ketones include α-hydroxy ketones such as hydroxy acetone, 1-hydroxy-2-butanone, 1-hydroxy-2-pentanone, 3-hydroxy-2-butanone, and 3-hydroxy-3-pentanone; Β-hydroxy ketones such as 4-hydroxy-2-butanone, 3-methyl-4-hydroxy-2-butanone, diacetone alcohol, 4-hydroxy-5,5-dimethyl-2-hexanone; 5-hydroxy-2 -Pentanone, 5-hydroxy-2-hexanone, etc. are mentioned.

  Examples of the carboxylic acids include formic acid and acetic acid.

  Examples of the ethers include tetrahydrofuran, 1,4-dioxane, dimethoxyethane, polyethylene oxide, and the like.

  Examples of the ketones include acetone and methyl ethyl ketone.

  Examples of the nitriles include acetonitrile.

  Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.

  Examples of the amines include triethylamine and pyridine.

  [C] The solvent is preferably a polar solvent, more preferably water, alcohols and esters, from the viewpoints of coatability and embedding on a substrate pattern, water, isopropanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether. And propylene glycol monomethyl ether acetate is more preferred.

  As said polar organic solvent, what can form 1 mass% or more of aqueous solution in 20 degreeC from a viewpoint of the applicability | paintability to a substrate pattern and an embedding property is preferable.

  [C] The lower limit of the dielectric constant of the solvent is preferably 6.0 from the viewpoint of embedding in the substrate pattern. Here, the dielectric constant of [C] solvent refers to a value measured using a liquid dielectric constant meter.

[[D1] acid generator and [D2] radical initiator]
The substrate pattern collapse suppression treatment material further contains [D1] an acid generator that generates acid by the action of heat or light, [D2] a radical initiator that generates radicals by the action of heat or light, or a combination thereof. It is preferable to do. Thus, the high molecular weight of the [A] compound can be accelerated | stimulated because the said processing material for substrate pattern collapse suppression contains a [D1] acid generator and / or a [D2] radical initiator. [D1] The acid generator and [D2] radical initiator can be used singly or in combination of two or more.

([D1] acid generator)
[D1] Examples of the acid generator include onium salts such as sulfonium salts, tetrahydrothiophenium salts, and iodonium salts, sulfone compounds such as N-sulfonyloxyimide compounds, organic halogen compounds, disulfones, and diazomethane sulfones. It is done.

Examples of the sulfonium salt include triphenylsulfonium salt compounds such as triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2- Bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (3-tetracyclo [4.4.0.12,5.17,10 ] Dodecanyl) -1,1-difluoroethanesulfonate, triphenylsulfonium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium salicylate, triphenylsulfonium Emissions Fur sulfonate, triphenylsulfonium salts such as triphenylsulfonium tricyclo [3.3.1.13,7] decanyl difluoromethane sulfonate;
4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2. 2.1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4.0.12,5.17,10] Dodecanyl) -1,1-difluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 4 -4-cyclohexylphenyl diphenylsulfonium salts such as cyclohexylphenyldiphenylsulfonium camphorsulfonate;
4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-t-butylphenyl Diphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4. 0.12, 5.17,10] dodecanyl) -1,1-difluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 4-t-butylphenyl Fe 4-t-butylphenyldiphenylsulfonium salts such as nylsulfonium camphorsulfonate;
Tri (4-t-butylphenyl) sulfonium trifluoromethanesulfonate, tri (4-t-butylphenyl) sulfonium nonafluoro-n-butanesulfonate, tri (4-t-butylphenyl) sulfonium perfluoro-n-octanesulfonate, Tri (4-t-butylphenyl) sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, tri (4-t-butylphenyl) sulfonium 2 -(3-tetracyclo [4.4.0.12,5.17,10] dodecanyl) -1,1-difluoroethanesulfonate, tri (4-t-butylphenyl) sulfonium N, N'-bis (nonafluoro-n -Butanesulfonyl) imidate, tri (-t-butylphenyl) sulfoniu Examples include tri (4-t-butylphenyl) sulfonium salts such as mucamphor sulfonate.

Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) Tetrahydrothiophenium 2- (3-tetracyclo [4.4.0.12,5.17,10] dodecanyl) -1,1-difluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydro 1- (4-n-butoxynaphthalene) such as thiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium camphorsulfonate -1-yl) tetrahydrothiophenium salt;
1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.12, 5.17,10] dodecanyl) -1,1-difluoroe Sulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium salt such as tetrahydrothiophenium camphorsulfonate.

Examples of the iodonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl. -1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium 2- (3-tetracyclo [4.4.0.12,5.17,10] dodecanyl) -1,1-difluoroethanesulfonate, diphenyliodonium N , N′-bis (nonafluoro-n-butanesulfonyl) imidate, diphenyliodonium salts such as diphenyliodonium camphorsulfonate;
Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2 -(3-tetracyclo [4.4.0.12,5.17,10] dodecanyl) -1,1-difluoroethanesulfonate, bis (4-t-butylphenyl) iodonium N, N'-bis (nonafluoro-n -Butanesulfonyl) imidate, bis (4-tert-butylphenyl) iodoni Examples thereof include bis (4-t-butylphenyl) iodonium salts such as umcamphor sulfonate.

Examples of the upper N-sulfonyloxyimide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) succinimide, N- (2- (3-tetracyclo [4.4.0.12] , 5.17,10] dodecanyl) -1,1-difluoroethanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide and the like;
N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (2- (3-tetracyclo [4.4.0.12,5.17,10] dodecanyl) -1,1-difluoroethanesulfonyloxy) bicyclo [2.2.1] hept- -Bicyclo [2.2.1] hept, such as -ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide Examples include -5-ene-2,3-dicarboximide compounds.

  [D1] The acid generator is preferably an iodonium salt, more preferably a diphenyliodonium salt, and even more preferably diphenyliodonium nonafluoro-n-butanesulfonate.

([D2] radical initiator)
[D2] Examples of radical initiators include organic peroxides, diazo compounds, alkylphenone compounds, carbazole oxime compounds, O-acyl oxime compounds, benzophenone compounds, thioxanthone compounds, biimidazole compounds, and triazines. Compounds, onium salt compounds, benzoin compounds, α-diketone compounds, polynuclear quinone compounds, imide sulfonate compounds, and the like.

Specific examples of the organic peroxide include dibenzoyl peroxide, diisobutyroyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, (3,5,5-trimethylhexanoyl) peroxide, dioctanoyl Diacyl peroxides such as peroxide, dilauroyl peroxide, distearoyl peroxide;
Hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide Hydroperoxides such as;
Di-t-butyl peroxide, dicumyl peroxide, dilauryl peroxide, peroxide, α, α′-bis (t-butylperoxy) diisopropylben, 2,5-dimethyl-2,5-bis (t -Dialkyl peroxides such as -butylperoxy) hexane, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne;
t-butyl peroxyacetate, t-butyl peroxypivalate, t-hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, 2,5-dimethyl-2 , 5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2 -Ethylhexanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, t-butylperoxy3,5,5-trimethylhexanoate , T-butyl peroxylaurate, 2,5-dimethyl-2,5-bis (m-toluoyl pero C) Hexane, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl -1-methylethyl peroxyneodecanoate, t-hexylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxybenzoate, t-hexylperoxybenzoate, bis (T-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy m-toluoyl benzoate, 3,3 ′, 4,4′-tetra Peroxyesters such as (t-butylperoxycarbonyl) benzophenone;
1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3 , 3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) butane Peroxyketals such as n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) pyropane;
t-hexyl peroxyisopropyl carbonate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxyallyl carbonate, di-n-propyl peroxycarbonate, diisopropyl peroxycarbonate, Bis (4-t-butylcyclohexyl) peroxycarbonate, di-2-ethoxyethyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, di-2-methoxybutyl peroxycarbonate, di (3-methyl-3- And peroxycarbonates such as (methoxybutyl) peroxycarbonate.

  Specific examples of the diazo radical polymerization initiator include azoisobutyronitrile, azobisisovaleronitrile, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2 , 4-dimethylvaleronitrile), 2,2-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbomoylazo) isobutyronitrile, 2,2 -Azobis [2-methyl-N- [1,1-bis (hydroxylmethyl) -2-hydroxylethyl] propionamide], 2,2-azobis (2-methyl-N- (2-hydroxylethyl) propionamide) 2,2-azobis [N- (2-propenyl) 2-methylpropionamide], 2,2-azobis (N-butyl-2-methyl) Propionamide), 2,2-azobis (N-cyclohexyl-2-methylpropionamide), 2,2-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2, 2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2-azobis [2- [1- (2-hydroxyethyl) 2-imidazolin-2-yl] Propane] dihydrochloride, 2,2-azobis (2- (2-imidazolin-2-yl) propane), 2,2-azobis (2 Methylpropionamidine) dihydrochloride, 2,2-azobis [N- (2-carboxyethyl) 2-methylpropionamidine], 2,2-azobis (2-methylpropionamidoxime), dimethyl 2,2'-azobis Examples include butyrate, 4,4′-azobis (4-cyanopentanoic acid), 2,2-azobis (2,4,4-trimethylpentane), and the like.

  Examples of the alkylphenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy- 2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like.

  [D2] The radical initiator is preferably an alkylphenone compound, more preferably 1-hydroxy-cyclohexyl-phenyl-ketone.

  When the substrate pattern collapse suppression treatment material contains a [D1] acid generator and / or [D2] radical initiator, the [D1] acid generator and [D2] radical initiation in the substrate pattern collapse suppression treatment material As a minimum of the total content of an agent, 0.01 mass part is preferred to 100 mass parts of [A] compound, 0.1 mass part is more preferred, and 0.2 mass part is still more preferred. On the other hand, as a minimum of the said total content, 10 mass parts is preferable with respect to 100 mass parts of [A] compounds, 5 mass parts is more preferable, and 2 mass parts is more preferable. By making the said total content into the said range, the high molecular weight increase of a [A] compound can be accelerated | stimulated more.

[Additive]
The substrate pattern collapse-suppressing treatment material may further contain an additive as an optional component as necessary, as long as the object of the present invention is not impaired. The said additive can be used individually by 1 type or in combination of 2 or more types.

  As the additive, a surfactant is preferable. When the processing material for suppressing the collapse of the substrate pattern further contains a surfactant, the coating property and the embedding property to the substrate pattern can be improved. Examples of the surfactant include nonionic surfactants, cationic surfactants, and anionic surfactants.

  Examples of the nonionic surfactant include ether type nonionic surfactants such as polyoxyethylene alkyl ether; ether ester type nonionic surfactants such as polyoxyethylene ether of glycerin ester; polyethylene glycol fatty acid ester, glycerin ester, sorbitan ester And ester type nonionic surfactants. Moreover, as a commercial item of the said nonionic surfactant, "Newcol 2320", "Newcol 714-F", "Newcol 723", "Newcol 2307", "Newcol 2303" (above, the Japan Emulsifier company make), " “Pionin D-1107-S”, “Pionin D-1007”, “Pionin D-1106-DIR”, “New Calgen TG310” (manufactured by Takemoto Yushi Co., Ltd.), “Dynaflow” (manufactured by JSR), etc. Is mentioned.

  Examples of the cationic surfactant include aliphatic amine salts and aliphatic ammonium salts.

  Examples of the anionic surfactants include carboxylates such as fatty acid soaps and alkyl ether carboxylates; sulfonates such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, and α-olefin sulfonates; higher alcohol sulfates. Salts, sulfate esters such as alkyl ether sulfates; phosphate ester salts such as alkyl phosphates.

  As the surfactant, a nonionic surfactant is preferable from the viewpoint of the applicability of the substrate pattern collapse suppressing treatment material and the embedding property to the substrate.

  When the substrate pattern collapse inhibiting treatment material contains the surfactant, the lower limit of the surfactant content in the substrate pattern collapse inhibiting treatment material is preferably 0.0001% by mass, 0.001 % By mass is more preferable, 0.01% by mass is further preferable, and 0.05% by mass is particularly preferable. On the other hand, the upper limit of the content is preferably 1% by mass, more preferably 0.5% by mass, and still more preferably 0.2% by mass.

[Metal content]
It is preferable that the said processing material for board | substrate pattern collapse suppression contains a metal as much as possible from a viewpoint of reducing the contamination of a substrate pattern. Examples of the metal include sodium, potassium, magnesium, calcium, copper, aluminum, iron, manganese, tin, chromium, nickel, zinc, lead, titanium, zirconium, silver, and platinum. Although it does not specifically limit as a form of the said metal, For example, a metal cation, a metal complex, a metal metal, an ionic compound etc. are mentioned.

  The upper limit of the total metal content in the substrate pattern collapse suppression treatment material is preferably 30 mass ppb, more preferably 20 mass ppb, and even more preferably 10 mass ppb. The lower limit of the total content of the metals is not particularly limited and is preferably smaller, but is, for example, 1 mass ppb.

  The type and content of the metal in the substrate pattern collapse suppression treatment material can be measured by an ICP-MS method (Inductively Coupled Plasma-Mass Spectrum) or the like.

  The water contact angle (25 ° C., 50% RH) on the surface of the substrate pattern collapse suppression film formed by the substrate pattern collapse suppression treatment material is preferably less than 90 °, more preferably 70 ° or less. When the water contact angle is 90 ° or more, the embeddability in the substrate pattern may be lowered. Here, the substrate pattern collapse suppression film used for the measurement of the water contact angle is formed on a silicon substrate under the air at 120 ° C. for 1 minute.

<Manufacturing method of substrate pattern collapse suppression treatment material>
The substrate pattern collapse suppression treatment material is prepared by mixing the [A] compound, the [C] solvent, and optional components blended as necessary, and then filtering the obtained solution with a filter having a pore size of, for example, about 0.02 μm. Can be manufactured. The lower limit of the solid content concentration of the substrate pattern collapse suppression treatment material is preferably 0.1% by mass, more preferably 1% by mass, further preferably 3% by mass, and particularly preferably 10% by mass. As an upper limit of the said solid content concentration, 50 mass% is preferable, 40 mass% is more preferable, and 30 mass% is further more preferable. Here, the “solid content” in the substrate pattern collapse suppression treatment material refers to components other than the [C] solvent.

  Further, the obtained substrate pattern collapse suppression treatment material is further filtered with a nylon filter (for example, a filter using nylon 66 membrane as a filtration medium), an ion exchange filter, or a filter using an adsorption action by a zeta potential. Is preferred. Thus, by filtering with a nylon filter, an ion exchange filter, or a filter using an adsorption action by a zeta potential, it is possible to easily and surely reduce the metal content in the substrate pattern collapse suppression treatment material. The processing material for suppressing collapse of the substrate pattern having a relatively low metal content can be obtained at low cost. The substrate pattern collapse-inhibiting treatment material may be a known chemical purification method such as water washing or liquid extraction, or a combination of a chemical purification method and a physical purification method such as ultrafiltration or centrifugation. The metal content can also be reduced by purification by a method.

<Substrate processing method>
The substrate processing method includes a step of forming a substrate pattern collapse suppression film on the substrate pattern side surface of the substrate having a substrate pattern formed on one surface thereof by applying the substrate pattern collapse suppression processing material (substrate A pattern collapse suppressing film forming step) and a step of heating or irradiating the substrate pattern collapse suppressing film (heating or light irradiating step). In addition, although a heating or light irradiation process may be performed after a substrate pattern collapse suppression film formation process, you may perform simultaneously with a substrate pattern collapse suppression film formation process.

  The substrate to be processed by the substrate processing method is not particularly limited as long as a substrate pattern is formed on at least one surface, but a substrate containing silicon atoms or metal atoms is preferable, and metal, metal nitride, metal oxide More preferably, the substrate is mainly composed of silicon oxide, silicon or a mixture thereof. Here, the “main component” is a component having the largest content, for example, a component having a content of 50% by mass or more.

  As a material which comprises the said board | substrate pattern, the thing similar to what was illustrated as a material of the said board | substrate is mentioned, for example.

  The shape of the substrate pattern is not particularly limited, and examples thereof include a line and space pattern, a hole pattern, and a pillar pattern. The upper limit of the average interval of the line and space pattern is preferably 300 nm, more preferably 150 nm, further preferably 100 nm, and particularly preferably 50 nm. The average interval between the hole pattern and the pillar pattern is preferably 300 nm, more preferably 150 nm, and even more preferably 100 nm. By applying the substrate processing method to a substrate on which such a pattern with a minute interval is formed, the substrate pattern collapse suppression and defect suppression can be maximized.

  As a minimum of the average height of the above-mentioned substrate pattern, 100 nm is preferred, 200 nm is more preferred, and 300 nm is still more preferred. The upper limit of the average width of the substrate pattern (for example, the height direction center portion reference) is preferably 50 nm, more preferably 40 nm, and even more preferably 30 nm. The lower limit of the aspect ratio of the substrate pattern (average pattern height / average pattern width) is preferably 3, more preferably 5, and even more preferably 10. By applying the substrate processing method to a substrate on which such a fine and high aspect ratio pattern is formed, the substrate pattern collapse suppression and defect suppression can be maximized.

[Substrate pattern collapse suppression film forming process]
In this step, a substrate pattern collapse suppressing film is formed on the substrate pattern side surface of the substrate having the substrate pattern formed on one surface by coating the substrate pattern collapse suppressing treatment material. Thereby, even if liquids, such as a washing | cleaning liquid and a rinse liquid, are hold | maintained on the board | substrate, these liquids can be removed without drying. After this step, until the removal step described later, the substrate pattern is adjacent because at least part of the substrate pattern is buried in the substrate pattern collapse suppression film and each pattern is supported by the substrate pattern collapse suppression film. Pattern collapse such as contact between patterns is suppressed.

  A liquid such as a cleaning liquid or a rinsing liquid is usually held on the substrate. Therefore, in this step, the substrate pattern collapse-suppressing treatment material is applied while replacing the cleaning liquid or the rinsing liquid.

  The method for applying the substrate pattern collapse suppressing treatment material is not particularly limited, and for example, an appropriate method such as spin coating, cast coating, roll coating, or the like can be employed. After the coating, the substrate pattern collapse suppressing treatment material may be dried as necessary.

  Although it does not specifically limit as said drying method, For example, the method of heating in an atmospheric condition is mentioned. In this case, although it does not specifically limit as a minimum of heating temperature, 20 degreeC is preferable, 40 degreeC is more preferable, and 60 degreeC is further more preferable. On the other hand, as an upper limit of heating temperature, 100 degreeC is preferable and 80 degreeC is more preferable. As a minimum of heating time, 15 seconds are preferred, 30 seconds are more preferred, and 45 seconds are still more preferred. On the other hand, the upper limit of the heating time is preferably 1,200 seconds, more preferably 600 seconds, and even more preferably 300 seconds.

  In this step, the average thickness of the substrate pattern collapse suppression film to be formed may be made larger than the maximum height of the substrate pattern, and the substrate pattern may be completely buried with the substrate pattern collapse suppression film. Thus, it becomes easier to suppress the collapse of the substrate pattern by completely burying the substrate pattern with the substrate pattern collapse suppression film. In this case, the lower limit of the difference between the average thickness of the substrate pattern collapse suppression film and the maximum height of the substrate pattern (average thickness of the substrate pattern collapse suppression film−maximum height of the substrate pattern) is preferably 0.01 μm, 0 0.02 μm is more preferable, and 0.05 μm is even more preferable. The upper limit of the difference is preferably 5 μm, more preferably 3 μm, still more preferably 2 μm, and particularly preferably 0.5 μm.

  On the other hand, in this step, the average thickness of the substrate pattern collapse suppression film to be formed may be the same as or smaller than the maximum height of the substrate pattern, and a part of the substrate pattern may be exposed from the substrate pattern collapse suppression film. . Even in this case, since the vicinity of the bottom of the substrate pattern is buried in the substrate pattern collapse suppression film, the collapse of the substrate pattern is sufficiently suppressed.

[Heating or light irradiation process]
In this step, the substrate pattern collapse inhibiting film formed in the substrate pattern collapse inhibiting film forming step is irradiated with heating light, thereby increasing the molecular weight of the compound [A] contained in the substrate pattern collapse inhibiting film. This makes it difficult to thermally melt the substrate pattern collapse suppression film. In addition, when the [A] compound forms a three-dimensional crosslinked structure as the molecular weight increases, the three-dimensional crosslinked structure can make it more difficult to thermally melt the substrate pattern collapse inhibiting film.

  When heating at this process, as a minimum of heating temperature, 100 ° C is preferred, 120 ° C is more preferred, and 140 ° C is still more preferred. On the other hand, the upper limit of the heating temperature is preferably 400 ° C, more preferably 300 ° C, and even more preferably 250 ° C. As a minimum of heating time, 15 seconds are preferred and 30 seconds are more preferred. On the other hand, the upper limit of the heating time is preferably 10 minutes, more preferably 5 minutes, and even more preferably 2 minutes. By making heating temperature and heating time into the said range, [A] compound can be reliably made high molecular weight.

In the case of light irradiation in this step, examples of the light to be irradiated include visible light, ultraviolet light, far ultraviolet light, and X-rays, and among these, ultraviolet light is preferable. The lower limit of the integrated irradiation amount (exposure amount) in this step is preferably 100 J / m ^{2 and} more preferably 200 J / m ² . On the other hand, the upper limit of the total irradiation amount is preferably ^{2,000J / m 2, 1,000J / m} 2 is more preferable. By setting the integrated irradiation amount within the above range, the compound [A] can be reliably increased in molecular weight. Note that “integrated dose” refers to an integrated value measured by an illuminometer.

  In this step, both heating and light irradiation may be performed.

[Removal process]
The substrate processing method usually further includes a step (removal step) of removing the substrate pattern collapse suppression film after the heating or light irradiation step. For example, heat treatment, plasma treatment, dry etching (ashing), ultraviolet irradiation, electron beam irradiation, or the like can be used to remove the substrate pattern collapse suppression film. According to these methods, since the substrate pattern collapse suppression film can be changed directly from the solid phase to the gas phase, pattern collapse due to the gas-liquid interface passing through the side surface of the substrate pattern can be suppressed.

Dry etching can be performed using a known dry etching apparatus. The etching gas used in the dry etching can be appropriately selected depending on the elemental composition of the substrate pattern collapse suppression film to be etched. For example, CHF ₃ , CF ₄ , C ₂ F ₆ , C ₃ F ₈ , SF ₆ Fluorine gas such as Cl ₂ , chlorine gas such as Cl ₂ and BCl ₃ , oxygen gas such as O ₂ , O ₃ and H ₂ O, H ₂ , NH ₃ , CO, CO ₂ , CH ₄ and C ₂ H ₂ Reducing gases such as C ₂ H ₄ , C ₂ H ₆ , C ₃ H ₄ , C ₃ H ₆ , C ₃ H ₈ , HF, HI, HBr, HCl, NO, NH ₃ , BCl ₃ , He, N _2. An inert gas such as Ar can be used. In addition, these gases can also be mixed and used.

  Although it does not specifically limit as a minimum of the substrate temperature in dry etching, -120 degreeC is preferable, -50 degreeC is more preferable, 20 degreeC is further more preferable, 80 degreeC is especially preferable, 180 degreeC is further especially preferable. On the other hand, the upper limit of the substrate temperature is preferably 800 ° C., more preferably 400 ° C., further preferably 350 ° C., and particularly preferably 300 ° C.

  The substrate processing method can be suitably used for the above-described processing step of the substrate cleaning method including a step of cleaning the substrate (cleaning step) and a step of processing the substrate after cleaning (processing step). This cleaning method can be suitably used for cleaning a substrate after wet etching or dry etching.

  In the cleaning step, at least one of cleaning the substrate using a cleaning liquid and rinsing the substrate using a rinsing liquid is performed. Examples of the cleaning liquid include sulfate ion-containing stripping liquid, chlorine ion-containing cleaning liquid, fluorine ion-containing cleaning liquid, nitrogen compound-containing alkaline cleaning liquid, and phosphoric acid-containing cleaning liquid. In cleaning the substrate, cleaning with two or more cleaning liquids may be continuously performed. The cleaning solution preferably contains hydrogen peroxide. As the sulfuric acid ion-containing cleaning liquid, sulfuric acid / hydrogen peroxide (SPM) in which hydrogen peroxide and sulfuric acid are mixed is preferable, whereby organic substances such as resist can be suitably removed. As the chlorine ion-containing cleaning solution, a mixed aqueous solution of hydrogen peroxide and hydrochloric acid (SC-2) is preferable, and thus the metal can be suitably removed. Examples of the fluorine ion-containing cleaning liquid include a mixed aqueous solution of hydrofluoric acid and ammonium fluoride. As the nitrogen compound-containing alkaline cleaning liquid, a mixed aqueous solution (SC-1) of hydrogen peroxide and ammonia is preferable, whereby particles can be suitably removed. Examples of the rinsing liquid include ultrapure water.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[Mw and Mn]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of each polymer in the examples were measured using a Tosoh GPC column (one "G2000HXL", one "G3000HXL", and "G4000HHR"). Gel permeation chromatograph (Tosoh's “Easical PS-1”) as a standard under the analysis conditions of 1.00 mL / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C. HLC-8220 ").

<Synthesis of [A] Compound>
[Synthesis Example 1] (Synthesis of Compound (A-2))
In a nitrogen atmosphere, in a 100 mL three-necked flask, 11.8 g (80 mol%) of 2-hydroxyethyl methacrylate and 3.2 g (20 mol%) of glycidyl methacrylate, introduction of water-soluble functional groups at the polymer ends and molecular weight 0.87 g of 1-thioglycerol as a compound for adjustment is dissolved in 35 g of commercially available isopropanol (IPA), and 0.06 g of dimethyl-2,2′-azobisisobutyrate as a polymerization initiator is further added. The mixture was added and heated to 80 ° C. to initiate polymerization. After stirring for 7 hours, the heating was stopped and the mixture was cooled to obtain an isopropanol solution of the compound (A-2) represented by the following formula (A-2) described later. Mw of the obtained compound (A-2) was 2,800, and Mw / Mn was 1.9.

[Synthesis Example 2] (Synthesis of Compound (A-3))
Under a nitrogen atmosphere, in a 100 mL three-necked flask, 11.1 g (80 mol%) of 2-hydroxyethyl methacrylate and 3.9 g (20 mol%) of 3-ethyl-3-oxetanylmethyl methacrylate were added to the end of the polymer. 0.81 g of 1-thioglycerol as a compound for introducing a water-soluble functional group and adjusting the molecular weight is dissolved in 35 g of commercially available isopropanol (IPA), and dimethyl-2,2′-azobis is used as a polymerization initiator. An additional 0.06 g of isobutyrate was added and heated to 80 ° C. to initiate polymerization. After stirring for 7 hours, the heating was stopped and the mixture was cooled to obtain an isopropanol solution of the compound (A-3) represented by the formula (A-3) described later. Mw of the obtained compound (A-3) was 8,500, and Mw / Mn was 4.7.

[Synthesis Example 3] (Synthesis of Compound (A-7))
A reactor equipped with a condenser, a thermometer and a stirrer was charged with 100 parts by mass of 2,7-dihydroxynaphthalene, 100 parts by mass of propylene glycol monomethyl ether acetate and 50 parts by mass of paraformaldehyde, and 2 parts by mass of oxalic acid was further added. Then, the temperature was raised to 120 ° C. while dehydrating, and the reaction was carried out for 5 hours to obtain Intermediate X. The weight average molecular weight (Mw) of the obtained intermediate X was 2,000.

  Next, 10 parts by mass of the intermediate X, 10 parts by mass of propargyl bromide, 10 parts by mass of triethylamine, and 40 parts by mass of tetrahydrofuran were charged into a separable flask equipped with a thermometer, and reacted at 50 ° C. for 12 hours while stirring. . After completion of the reaction, the reaction solution was cooled to 30 ° C. or lower by water cooling. After cooling, this reaction solution was poured into a large amount of n-heptane. Thereafter, the precipitated solid was separated by a decantation method, and the separated solid was washed with a large amount of n-heptane. Subsequently, this solid was dissolved in methyl isobutyl ketone, and the remaining triethylamine was removed by washing sequentially with 1% by mass of oxalic acid and pure water. Then, after concentrating the obtained organic layer, the obtained concentrate was dried at 50 degreeC for 17 hours, and the compound (A-7) represented by a following formula (A-7) was obtained. In addition, the introduction rate of the propargyl group in the compound (A-7) was 90%.

<[B] Synthesis of specific group-containing compound>
[Synthesis Example 4] (Synthesis of Compound (B-1))
In a nitrogen atmosphere, commercially available 15 g of 2-hydroxyethyl methacrylate and 0.87 g of 1-thioglycerol as a compound for introducing a water-soluble functional group at the polymer end and adjusting the molecular weight in a 100 mL three-necked flask Was dissolved in 35 g of isopropanol (IPA), 0.06 g of dimethyl-2,2′-azobisisobutyrate as a polymerization initiator was added, and the polymerization was started by heating to 80 ° C. After stirring for 7 hours, the heating was stopped and the mixture was cooled to obtain an isopropanol solution of the compound (B-1) represented by the following formula (B-1). Mw of the obtained compound (B-1) was 3,100, and Mw / Mn was 1.9.

[Synthesis Example 5] (Synthesis of Compound (B-6))
A 1,000 mL three-necked flask equipped with a thermometer, a condenser and a magnetic stirrer was charged with 500 g of phenol, 106 g of 86% paraformaldehyde and 13 g of 37% formaldehyde under a nitrogen atmosphere, and 1.46 g of zinc acetate was added for 4 hours. A reflux reaction was performed. Next, after leaving the reaction solution to separate into an organic phase and an aqueous layer, the upper aqueous layer was removed. Thereafter, the remaining lower organic layer is depressurized at 150 ° C. to 2 mmHg to remove moisture and unreacted monomers, whereby a compound (B-6) which is a phenol resin having a structural unit represented by the following formula (B-6) ) Mw of the obtained compound (B-6) was 1,500.

<Preparation of processing material for suppressing substrate pattern collapse>
Each component used for preparation of the processing material for substrate pattern collapse suppression is shown below.

[[A] Compound]
The name and structural formula of each [A] compound are shown below.
A-1: Pentaerythritol tetraacrylate A-2: Methacrylic resin obtained in Synthesis Example 1 (A-2)
A-3: Methacrylic resin obtained in Synthesis Example 2 (A-3)
A-4: An oxirane compound represented by the following formula (A-4) A-5: 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane A-6: xylylenebis Oxetane A-7: Compound (A-7) obtained in Synthesis Example 3

  In said formula, n is an integer of 1-3.

  Compound (A-6) is a mixture of a compound in which n is 1 in the above formula (A-6), a compound in which n is 2 and a compound in which n is 3.

([B] specific group-containing compound)
B-1: Methacrylic resin (B-1) obtained in Synthesis Example 4
B-2: Polyacrylic acid (Mw 5,000) (manufactured by Wako Pure Chemical Industries, Ltd.)
B-3: Polyvinyl alcohol (degree of polymerization 500) (manufactured by Wako Pure Chemical Industries, Ltd.)
B-4: Polyethyleneimine (Mw 10,000) (manufactured by Wako Pure Chemical Industries, Ltd.)
B-5: Compound (tannic acid) represented by the following formula (B-5)
B-6: Phenol resin (B-6) obtained in Synthesis Example 5

([C] solvent)
C-1: Water C-2: Isopropanol (IPA)
C-3: Propylene glycol monomethyl ether acetate

([D1] acid generator)
D-1: Diphenyliodonium nonafluoro-n-butanesulfonate represented by the following formula (D-1)

([D2] radical initiator)
D-2: 1-hydroxy-cyclohexyl-phenyl-ketone represented by the following formula (D-2)

([E] surfactant)
E-1: Nonionic surfactant ("Dynaflow" from JSR)

[Example 1]
[A] 25 mass parts of (A-1) as a compound and 1 mass part of (D-2) as a [D2] compound were dissolved in 100 mass parts of (C-3) as a [C] solvent. The substrate pattern collapse suppression treatment material of Example 1 was prepared.

[Example 2]
Except that the isopropanol solution of the compound (A-2) obtained in Synthesis Example 1 was diluted with isopropanol so as to have the composition shown in Table 1, the same operation as in Example 1 was performed, and the substrate pattern collapse of Example 2 was suppressed. A treatment material was prepared. In Table 1, “-” indicates that the corresponding component was not used.

[Examples 3-14 and Comparative Examples 1-3]
[A] compound or its isopropanol solution, [B] specific group-containing compound, [C] solvent, [D1] acid generator, [D2] radical initiator, and / or so as to have the composition shown in Table 1 below. [E] Surfactant was mix | blended and the processing material for board | substrate pattern collapse suppression of Examples 3-14 and Comparative Example 3 was adjusted by operating similarly to Example 1 or 2 other than that point. Moreover, the solvent (C-1) and (C-2) were used as the substrate pattern collapse suppression treatment materials of Comparative Examples 1 and 2, respectively.

<Processing of substrate>
[Formation of coating film]
On the substrate pattern side surface of the substrate having a substrate pattern formed on one surface, each substrate pattern collapse suppression treatment material prepared in Examples 1-14 and Comparative Examples 1-3 was applied to a simple spin coater (Mikasa's By coating with “1H-DX2”), a substrate on which a treatment film for suppressing pattern collapse prevention was formed was obtained. The coating conditions were the conditions of 500 rpm in the atmosphere. As the substrate, a silicon wafer on which a dense pillar pattern was formed was used. This pillar pattern has an average pillar height of 380 nm, an average width of the top surface (top) of the pillar of 35 nm, an average cross-sectional width of 20 nm in the center of the pillar height direction, and an average pitch between the pillars of 100 nm (pillar width). Direction center part reference).

[heating]
The silicon wafer after the coating was baked on a hot plate at 180 ° C. for 60 seconds to increase the molecular weight of the compound [A] contained in the pattern collapse prevention treatment film.

<Evaluation>
About each processing material for board | substrate pattern collapse suppression of Examples 1-14 and Comparative Examples 1-3, the applicability | paintability, embedding property, and the collapse | damage suppression property and defect suppression property of a substrate pattern were evaluated with the following method. The evaluation results are shown in Table 1.

[Applicability]
About each silicon wafer substrate in which the said pattern collapse prevention suppression film | membrane was formed, the presence or absence of the streak-like defect (striation) which goes to the circumferential direction from the center was observed visually. The applicability is “A” (very good) when there are no streak defects, “B” (good) when there is a partial defect, and when there is a defect on the entire surface. Was evaluated as "C" (bad). In Comparative Examples 1 and 2, since the pattern collapse prevention inhibiting film was not formed, the applicability was not evaluated.

[Embeddability]
A cross section of each silicon wafer substrate on which the substrate pattern collapse prevention inhibiting film was formed was cut out, and the embedding property of each pattern collapse inhibiting film was evaluated using FE-SEM (Hitachi High-Technologies “S4800”). The embedding property is “A” (very good) when the pattern collapse suppression film is embedded to the bottom of the pattern and the pattern top is not exposed. The pattern collapse suppression film is embedded to the bottom of the pattern, but voids are observed. The case where the pattern collapse suppression film was not embedded up to the bottom of the pattern and the top was exposed was evaluated as “C” (defective). In Comparative Examples 1 and 2, since the pattern collapse prevention suppressing film was not formed, the embedding property was not evaluated.

[Inhibition of substrate pattern collapse]
Using an ashing device ("Luminous NA-1300" manufactured by ULVAC) to each silicon wafer substrate on which the pattern collapse suppression film is formed, N ₂ / H ₂ (= 97/3 (volume%)) mixed gas Then, dry etching (ashing) treatment was performed to remove the pattern collapse suppression film. The substrate temperature during dry etching was 250 ° C. The number of pillars remaining without collapsing in each substrate after removal was determined on the observation screen of the FE-SEM. The substrate pattern collapse inhibition property is “A” (very good) when the ratio of pillars remaining without collapse is more than 90%, and the ratio of pillars remaining without collapse is more than 70%. % Or less was evaluated as “B” (good), and the percentage of pillars remaining without collapse was evaluated as “C” (defective).

[Defect suppression of substrate pattern]
The substrate from which the substrate pattern collapse inhibiting film was removed was observed with the FE-SEM, and the presence or absence of a residue attached to the pillar upper surface (top) in the field of view (2,500 nm × 2,500 nm) was measured. The defect suppression property of the substrate pattern was evaluated as “A” (good) when the residue did not remain, and “B” (defective) when the residue remained at one or more places.

  As can be seen from the results in Table 1, the substrate pattern collapse suppression treatment materials of the examples are excellent in coating properties, embedding properties, and substrate pattern collapse suppression properties and defect suppression properties.

  The substrate pattern collapse suppressing treatment material and the substrate processing method of the present invention are excellent in substrate pattern collapse suppression. Further, for example, if a residue of the substrate pattern collapse suppression treatment material is generated in the step of removing the substrate pattern collapse suppression film (removal step), it may cause a defect in the substrate pattern, but the substrate pattern collapse suppression treatment material of the present invention And the processing method of a board | substrate is excellent in the defect inhibitory property of the substrate pattern at the time of a process. Accordingly, these can be suitably used for manufacturing semiconductor devices that are expected to be further miniaturized in the future.

Claims (15)

A substrate used in a substrate processing method comprising a step of forming a substrate pattern collapse suppression film on a substrate pattern side surface of a substrate having a substrate pattern formed on one surface by applying a substrate pattern collapse suppression treatment material. A processing material for suppressing pattern collapse,
A first compound that becomes high molecular weight by the action of heat or light;
A substrate pattern collapse-suppressing treatment material comprising a solvent.   The processing material for substrate pattern collapse suppression according to claim 1, wherein the first compound has a crosslinking group.   The substrate pattern according to claim 2, wherein the cross-linking group is a group containing a polymerizable carbon-carbon double bond, a group containing a polymerizable carbon-carbon triple bond, a substituted or unsubstituted cyclic ether group, or a combination thereof. Treatment material for preventing collapse.   The bridging group is an alkenyl group, vinyloxy group, (meth) acryloyl group, styryl group, ethynyl group, propargyl group, propargyloxy group, substituted or unsubstituted oxiranyl group, substituted or unsubstituted oxetanyl group, or a combination thereof. The processing material for suppressing substrate pattern collapse according to claim 3.   The number of the said crosslinking group which the said 1st compound has is 2 or more, The processing material for board | substrate pattern collapse suppression of Claim 2, 3 or 4.   The substrate pattern collapse-suppressing treatment material according to any one of claims 2 to 5, wherein the first compound has a polar group other than the crosslinking group.   The substrate pattern collapse-suppressing treatment material according to claim 6, wherein the polar group is a hydroxy group, a carboxy group, a sulfanyl group, an amino group, or a combination thereof.   The compound according to any one of claims 2 to 7, further comprising a second compound having a molecular weight of 300 or more, which is a compound other than the first compound and has a hydroxy group, a carboxy group, a sulfanyl group, an amino group, or a combination thereof. The processing material for board | substrate pattern collapse suppression as described in claim | item.   The processing material for suppressing substrate pattern collapse according to any one of claims 1 to 8, further comprising an acid generator, a radical initiator, or a combination thereof.   The substrate solvent for preventing collapse of a substrate pattern according to any one of claims 1 to 9, wherein the solvent is a polar solvent.   The substrate pattern collapse-suppressing treatment material according to any one of claims 1 to 10, wherein a content ratio of the first compound is 0.1 mass% or more and 50 mass% or less.   The processing material for substrate pattern collapse suppression according to any one of claims 1 to 11, further comprising a surfactant.   The processing material for suppressing collapse of a substrate pattern according to any one of claims 1 to 12, which is used for embedding in a gap of a substrate pattern. The substrate pattern collapse suppression by applying the substrate pattern collapse suppression treatment material according to any one of claims 1 to 13 on the substrate pattern side surface of the substrate on which the substrate pattern is formed on one surface. Forming a film;
And a step of heating or irradiating the substrate pattern collapse inhibiting film.   The substrate processing method according to claim 14, wherein the substrate contains a silicon atom or a metal atom.