JP2015065443A - Pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern forming method capable of suppressing peeling of a resist film.SOLUTION: A pattern forming method comprises the steps of: forming a first resin layer 31 composed mainly of an organic polymer on a substrate 20 (first resin layer forming step (1)); forming a second resin layer 32 composed mainly of an organic polymer on a surface of the first resin layer 31 (second resin layer forming step (2)); forming a recess 321 in the second resin layer 32 by pressure-welding and desorbing a stamper including a salient in the second resin layer 32 (recess forming step (PR3)); forming a filling part 33 composed mainly of an inorganic polymer in the recess 321 (filling part forming step (PR4)); and etching the first resin layer 31 and the second resin layer 32 using the filling part 33 as a mask (etching step (PR5)).

Description

  The present invention relates to a pattern forming method. More specifically, the present invention relates to a pattern forming method using an optical imprint lithography method using a translucent stamper.

In order to improve the integration degree and recording density of circuits such as semiconductor elements, a finer processing technique is required. As a fine processing technique, a photolithography technique using an exposure process can perform a fine processing of a large area at a time, but does not have a resolution below the wavelength of light. Accordingly, in recent years, photolithography technology using short wavelength light of 193 nm (ArF), 157 nm (F2), and 13.5 nm (EUV) has been developed. However, as the wavelength of light becomes shorter, the substances that can be transmitted at that wavelength are limited.
On the other hand, in methods such as electron beam lithography and focused ion beam lithography, the resolution does not depend on the wavelength of light and a fine structure can be created, but poor throughput is a problem.

On the other hand, as a technique for creating a fine structure with a wavelength equal to or less than the wavelength of light at a high throughput, a stamper on which a predetermined fine uneven pattern is created in advance by electron beam lithography or the like is pressed against a resist-coated substrate, There is known a nanoimprinting method in which a film is transferred onto a resist film on a substrate (see, for example, Non-Patent Documents 1 and 2 and Patent Documents 1 and 2).
The above-described nanoimprint method has various problems to be solved in order to realize this, and among them, there is a problem of “resist film peeling”. In the nanoimprint method, the resist-coated substrate is heated above the glass transition temperature to soften the resist, so that when the pressed stamper is peeled off from the resist film, the resist film is peeled off with a part of the resist film attached. This is referred to as “resist film peeling”. In order to solve this “resist film peeling”, improvement of a stamper has been studied. For example, Patent Document 3 below is known. Further, Patent Document 4 discloses a pattern forming method in which another material is embedded in a concave portion of a pattern after imprinting and the pattern is inverted.

US Pat. No. 5,772,905 US Pat. No. 5,956,216 JP 2008-162190 A JP 2008-135179 A

S. Wy. S. Y. Chou, "Nano Imprint Lithography technology" Applied Physics Letters, Vol. 76, 1995, p. 3114

Patent Document 3 is a stamper whose surface is fluorinated. However, this method has a problem that the effect of the surface treatment is lost as the number of times of use of the stamper is increased, and if the number of times of use of the stamper is large, "resist film peeling" may occur frequently. In this respect, the resist film (which is a shape-transferring layer referred to in the present invention) has not yet been prevented from peeling off.
On the other hand, Patent Document 4 discloses a method of etching a substrate to be processed by a RIE (reactive ion etching) method using a pattern after inversion as a mask. However, Patent Document 4 discloses a method of peeling a stamper. Although the pattern destruction due to the peeling of the resist film is reduced as compared with the conventional case, further excellent suppression of the peeling of the resist film is required.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a pattern forming method capable of suppressing “resist film peeling”.

That is, the present invention is as follows.
<1> a first resin layer forming step (1) for forming a first resin layer mainly composed of an organic polymer on a substrate;
A second resin layer forming step (2) for forming a second resin layer mainly composed of an organic polymer on the surface of the first resin layer;
A recess forming step (3) for forming a recess in the second resin layer by pressing and releasing a stamper having a protrusion on the second resin layer;
A filling part forming step (4) for forming a filling part mainly composed of an inorganic polymer in the concave part;
An etching step (5) for etching the first resin layer and the second resin layer using the filling portion as a mask.
<2> The pattern forming method according to <1>, wherein the inorganic polymer is polysiloxane.
<3> The pattern forming method according to <1> or <2>, wherein the first resin layer is made of a material having an etching rate slower than that of the second resin layer.

According to the pattern forming method of the present invention, a pattern can be formed while suppressing peeling of the resist film. Further, a residual film in which the resist film is left in the recess formed in the recess forming step is formed, so that an adhesive surface between the first resin layer and the second resin layer is increased, and the resist film is peeled off (first film). The delamination between the first resin film and the second resin film) can be more effectively suppressed. That is, normally, when a process such as etching is performed using a pattern as a mask, the remaining film in the concave portion which is avoided functions advantageously in this method. Even if the film thickness of the remaining film in the recesses varies, the etching process in step (5) and the pattern obtained by this method are not affected, and precise control of the remaining film in the recesses is unnecessary. It is.
When the inorganic polymer is polysiloxane, it is possible to obtain better selectivity in etching the first resin layer and the second resin layer and the filling portion. Furthermore, since the flatness of the coating film when applied by spin coating is good, when an unnecessary filling portion forming resin layer (a layer made of filling portion forming resin) is removed from the first resin layer. Damage to the filling portion forming resin to be left in the recess can be minimized. Moreover, since it can harden | cure at moderate baking temperature, the damage by the heat | fever to the 1st resin layer can be suppressed.
When the first resin layer is made of a material whose etching rate is slower than that of the second resin layer, a pattern with a higher aspect ratio can be produced by processing the substrate using the filling portion as a mask. In addition, since processing can be performed under more severe conditions, throughput can be increased.

It is explanatory drawing which illustrates typically a part of process of the pattern formation method of this invention. It is explanatory drawing which illustrates typically a part of process of the pattern formation method of this invention. It is explanatory drawing which illustrates typically a part of process of the pattern formation method of this invention. It is explanatory drawing which illustrates typically a part of process of the pattern formation method of this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. In the present specification, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate.

[1] Pattern Forming Method The pattern forming method of the present invention includes a first resin layer forming step (1), a second resin layer forming step (2), a recess forming step (3), and a filling portion forming step (4). And an etching step (5) (see FIGS. 1 and 2).

The “first resin layer forming step (1)” (PR (1) in FIG. 1) is a step of forming the first resin layer 31 mainly composed of an organic polymer on the substrate 20.
The first resin layer is a resin layer containing an organic polymer as a main component. The organic polymer as a main component means that the organic polymer (polymer having a carbon skeleton) is 95% by mass or more (100% by mass) when the entire first resin layer is 100% by mass. ) Means contained. That is, in other words, it means that the inorganic polymer described later is not contained, or even if it is contained, it is less than 5% by mass.
The first resin layer only needs to have an organic polymer as a main component, and the composition thereof is not particularly limited. For example, JP 2004-168748 A, JP 2005-128509 A, and JP 2007-240630 A. It is preferable to use a resin layer used as a resist underlayer film described in the publication. Furthermore, the 1st resin layer formed on the board | substrate using the following composition (1)-(3) for 1st resin layer formation is preferable.

〔式（１）において、Ｒは各々独立に水素原子、炭素数１〜６のアルキル基、−Ｒ^１ＯＨ、−Ｒ^２ＯＲ^３又は−Ｒ^４ＯＲ^５ＯＲ^６を示し、ｎは１又は２であり、Ｘは各々独立にハロゲン原子を示す。尚、Ｒ^１はメチレン基又は炭素数２〜６のアルキレン基、Ｒ^２はメチレン基又は炭素数２〜４のアルキレン基、Ｒ^３は炭素数１〜６のアルキル基、Ｒ^４はメチレン基又は炭素数２〜４のアルキレン基、Ｒ^５はメチレン基又は炭素数２〜６のアルキレン基、Ｒ^６は炭素数１〜６のアルキル基を示す。ｎは１又は２である。〕 The first resin layer forming composition (1) includes (1A) an alkali-soluble resin having a phenolic hydroxyl group, (1B) an acid generator represented by the following formula (1), (1C) a crosslinking agent, Containing.

In [Equation (1), R each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon ^atoms, -R 1 OH, ^-R 2 OR ³ or ^-R 4 ^OR 5 shows an OR ^6, n is 1 or 2 And each X independently represents a halogen atom. R ¹ is a methylene group or an alkylene group having 2 to 6 carbon atoms, R ² is a methylene group or an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group having 1 to 6 carbon atoms, and R ⁴ is a methylene group or alkylene group having 2 to 4 carbon atoms, ^{R 5} is a methylene group or an alkylene group having 2 to 6 carbon atoms, ^{R 6} represents an alkyl group having 1 to 6 carbon atoms. n is 1 or 2. ]

Examples of the alkali-soluble resin (1A) include novolak resin, polyhydroxystyrene {hydroxystyrene homopolymer, styrene derivatives such as hydroxystyrene, styrene, vinylbenzoic acid, and (meth) acrylic acid derivatives. A copolymer using at least hydroxystyrene}, a phenol-xylylene glycol condensation resin, and the like are preferable. Examples of the novolak resin include a phenol / formaldehyde condensation type, a cresol / formaldehyde condensation type, and a phenol-naphthol / formaldehyde condensation type.
2000 or more are preferable and, as for the polystyrene conversion weight average molecular weight of the said alkali-soluble resin (1A), 2000-20000 are more preferable. Moreover, 30-90 mass% is preferable with respect to 100 mass% of the whole composition (1) except a solvent, and, as for the content of alkali-soluble resin (1A), 40-80 mass% is more preferable.

The acid generator (1B) is a compound having an s-triazine skeleton, and includes 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (m -Methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- [2- {4,6-bis (trichloromethyl) -1,3,5-triazine- 2-yl} vinyl] phenoxy] ethanol, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- ( 2,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.
0.1-10 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin (1A), and, as for the compounding quantity of an acid generator (1B), 0.3-5 mass parts is more preferable, and 0.5-3 masses. Part is more preferred.

The crosslinking agent (1C) acts as a crosslinking component (curing component) that reacts with the alkali-soluble resin (1A).
Examples of the cross-linking agent (1C) include compounds having at least two alkyl etherified amino groups in the molecule such as hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethylglycoluril, etc. ;
Phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-naphthol type epoxy resin, Oxirane ring-containing compounds such as phenol-dicyclopentadiene type epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins;
Dinuclear phenols such as 4,4′-biphenyldiol, 4,4′-methylenebisphenol, 4,4′-ethylidenebisphenol and bisphenol A, 4,4 ′, 4 ″ -methylidenetrisphenol and 4,4 Polynuclear phenols such as trinuclear phenols such as'-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol and polyphenols such as novolac;
2,3-tolylene diisocyanate, 2,4-tolylene diisocyanate, 3,4-tolylene diisocyanate, 3,5-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate And diisocyanates such as 1,4-cyclohexane diisocyanate;
These crosslinking agents may use only 1 type and may use 2 or more types together.

Furthermore, in these crosslinking agents, a crosslinking agent having an —OR _x group (where R _x is an n-butyl group or an iso-butyl group) is more preferable. The cross-linking agent containing an —OR _x group can control the sublimation property of the cross-linking agent (in particular, suppress the sublimation property of the cross-linking agent). In addition, a gas (under standard conditions) (1-butene, 2-butene, iso-butene) derived from the —OR _x group can be generated during pyrolysis, which is preferable because contamination at various places can be suppressed.

Specific examples of the crosslinking agent having an -OR _x group include -OR _x group-modified glycoluril compound, -OR _x group-modified polynuclear phenol, -OR _x group-modified amino resin, and the like. Among these, examples of the —OR _x group-modified glycoluril compound include the hexabutoxymethyl melamine and tetrabutoxymethyl glycoluril. As the —OR _x group-modified polynuclear phenol, the aforementioned polynuclear phenol is —OR _x. Examples of the —OR _x group-modified amino resin include co-condensates of urea, thiourea, ethylene urea, melamine benzoguanamine, and the like with formaldehyde, their n-butyl alcohol, and iso-butyl. Alcohol or methyl alcohol processed material etc. are mentioned.

1-100 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin (1A), and, as for the compounding quantity of a crosslinking agent (1C), 5-50 mass parts is more preferable. Furthermore, when the total of the alkyl etherified compound having an amino group and the oxirane ring-containing compound is 100% by mass, the content of the oxirane ring-containing compound is preferably 50% by mass or less, more preferably 5 to 40% by weight. preferable.
In addition, it can contain at least one of adhesion assistants (1D), surfactants (1E), solvents (1F), etc., which will be described later.

〔式（２）において、Ｒ^１は１価の有機基を示し、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子又は炭素数１〜６の置換可能なアルキル基を示す。〕

〔式（３）において、Ｒ^１は１価の有機基を示し、Ｒ^２は水素原子又は炭素数１〜６の置換可能なアルキル基を示し、ｎは０又は１である。〕 The first resin layer forming composition (2) comprises (2A) a polymer containing one of the structural unit represented by the following formula (2) and the structural unit represented by the following formula (3); 2B) An acid generator and (2C) a crosslinking agent.

In [formula (2), R ¹ represents a monovalent organic group, R ² and R ³ each independently represent a hydrogen atom or a substitutable alkyl group having 1 to 6 carbon atoms. ]

[In Formula (3), R ¹ represents a monovalent organic group, R ² represents a hydrogen atom or a C 1-6 substitutable alkyl group, and n is 0 or 1. ]

The monovalent organic group as R ^{1 in the} formula (2) includes a C 1-6 substitutable alkyl group, a hydroxyl group, a C 1-6 alkoxy group, a carbonyl group, and a C 1-6 carbon atom. An alkoxycarbonyl group, a methylol group, or an alkoxymethylol group having 1 to 6 carbon atoms.

Examples of the substitutable alkyl group having 1 to 6 carbon atoms as R ^{1 in the} formula (2) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a 1-methylpropyl group. , 2-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group and the like.
Furthermore, examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a polar group other than a hydrocarbon group. Only 1 type may be used for a substituent and it may use 2 or more types together. Moreover, when it has 2 or more types of substituents, each substituent may be the same and may differ. Among these, examples of the polar group include an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), hydroxy group, carboxyl group, oxo group (═O), alkyloxycarbonyl group, acetoxy group (—OCOCH ₃ ), etc. Is mentioned.

The alkoxy group having 1 to 6 carbon atoms as R ^{1 in the} formula (2) includes methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 1-methylpropoxy group, 2- Examples thereof include a methylpropoxy group, a t-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.
The alkoxycarbonyl group having 1 to 6 carbon atoms as R ^{1 in the} formula (2) includes a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, 1- Examples thereof include a methylpropoxycarbonyl group, a 2-methylpropoxycarbonyl group, a t-butoxycarbonyl group, an n-pentyloxycarbonyl group, and an n-hexyloxycarbonyl group.
The alkoxymethylol group having 1 to 6 carbon atoms as R ^{1 in the} formula (2) includes a methoxymethylol group, an ethoxymethylol group, an n-propoxymethylol group, an i-propoxymethylol group, an n-butoxymethylol group, 1- Examples thereof include a methylpropoxymethylol group, a 2-methylpropoxymethylol group, a t-butoxymethylol group, an n-pentyloxymethylol group, and an n-hexyloxymethylol group.

The substitutable alkyl group having 1 to 6 carbon atoms as R ² and R ³ in the formula (2) is the same as the substitutable alkyl group having 1 to 6 carbon atoms as R ^{1 in the} formula (2). Applicable. However, R ² and R ³ in the formula (2) may be the same or different, and R ² and R ³ in the formula (2) are the same as R ^{1 in the} formula (2). Or may be different.

  Examples of the monomer that gives the structural unit represented by the formula (2) include hydroxymethylacenaphthylene (3-, 4-, 5-), methoxymethylacenaphthylene (3-, 4-, 5-). -), Acetoxymethylacenaphthylene (3-, 4-, 5-) and the like are preferable. These monomers may use only 1 type and may use 2 or more types together.

In the said composition (2), when a polymer (2A) contains the structural unit represented by the said Formula (2), the 1st resin layer excellent in etching tolerance can be obtained.
As for the content rate of the structural unit represented by the said Formula (2) in a polymer (2A), 5-80 mol% is preferable with respect to a total of 100 mol% of all the structural units which comprise a polymer (2A), 30-80 mol% is more preferable, and 50-70 mol% is still more preferable.

The monovalent organic group as R ¹ in the formula (2) can be directly applied to the monovalent organic group as R ^{1 in the} formula (3). However, R ¹ of each of the formulas (2) and (3) may be the same or may be different.
The monovalent organic group as R ² in the formula (2) can be directly applied to the monovalent organic group as R ^{2 in the} formula (3). However, R ² in Formula (2) and Formula (3) may be the same or different.

In the said composition (2), when a polymer (2A) contains the structural unit represented by the said Formula (3), the 1st resin layer excellent in etching tolerance can be obtained.
As for the content rate of the structural unit represented by the said Formula (3) in a polymer (2A), 5-80 mol% is preferable with respect to a total of 100 mol% of all the structural units which comprise a polymer (2A), 30-80 mol% is more preferable, and 50-70 mol% is still more preferable.

〔式（４）において、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子又は炭素数１〜６の置換可能なアルキル基を示す。〕

〔式（５）において、Ｒ^１は水素原子又は炭素数１〜６の置換可能なアルキル基を示し、Ｒ^２は水素原子又はメチル基を示し、Ｘはメチレン基又はフェニレン基を示す。〕

〔式（６）において、Ｒ^１は１価の有機基を示し、ｎは０〜３の整数である。Ｒ^２は水素原子又は炭素数１〜６の置換可能なアルキル基を示す。〕 The polymer (2A) includes at least one of a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), and a structural unit represented by the following formula (6). One type can be contained.

[In Formula (4), R < ² > and R < ³ > shows a hydrogen atom or a C1-C6 substitutable alkyl group each independently. ]

In [formula (5), R ¹ represents a hydrogen atom or a substitutable alkyl group having 1 to 6 carbon atoms, R ² represents a hydrogen atom or a methyl group, X represents a methylene group or a phenylene group. ]

In [Equation (6), ^{R 1} represents a monovalent organic group, n is an integer of 0 to 3. R ² represents a hydrogen atom or a substitutable alkyl group having 1 to 6 carbon atoms. ]

The substitutable alkyl group having 1 to 6 carbon atoms as ^{R 2} and ^{R 3} in the formula (4), replaceable alkyl having 1 to 6 carbon atoms as ^{R 2} and ^{R 3} in the formula (2) The group can be applied as it is. However, the ^{R 2} and ^{R 3} of the the ^{R 2} and ^{R 3} in the formula (2) (4) may be another same or may be different. Among these, as R ² and R ^{3 in} the formula (4), a hydrogen atom or a methyl group is preferable.
Examples of the monomer that gives the structural unit represented by the formula (4) include acenaphthylene, 1-methylacenaphthylene, 1,2-dimethylacenaphthylene, and the like. These monomers may use only 1 type and may use 2 or more types together.
When the structural unit represented by the formula (4) in the polymer (2A) is included, the content ratio is 5 to 95 with respect to 100 mol% in total of all the structural units constituting the polymer (2A). Mol% is preferable, 10 to 90 mol% is more preferable, and 20 to 80 mol% is still more preferable.

The substitutable alkyl group having 1 to 6 carbon atoms as R ^{2 in the} formula (5) is the same as the substitutable alkyl group having 1 to 6 carbon atoms as R ² and R ^{3 in} the formula (2). Applicable. However, the formula (2) and R ² and R ³ with R ² of the formula (5) may be each other identical or different.
Examples of the monomer that gives the structural unit represented by the formula (5) include N-methylolacrylamide, N-methoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, dimethylaminopropylmethacrylamide. N-methoxymethylmethacrylamide, N-ethoxymethylmethacrylamide, N-butoxymethylmethacrylamide, N-isobutoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-methoxyphenylacrylamide, N-methylolphenylacrylamide, N- Examples include methoxyphenyl methacrylamide, N-methylolphenyl methacrylamide and the like. These monomers may use only 1 type and may use 2 or more types together.
When the structural unit represented by the formula (5) in the polymer (2A) is included, the content ratio is 5 to 80 with respect to 100 mol% in total of all the structural units constituting the polymer (2A). Mol% is preferable, 5 to 60 mol% is more preferable, and 5 to 60 mol% is still more preferable.

As the monovalent organic group as R ^{1 in the} formula (6), the monovalent organic group as R ^{1 in the} formula (2) can be applied as it is. However, the formula (2) is R ¹ and the R ¹ in the formula (4) may be another same or may be different.
Moreover, as a C1-C6 substitutable alkyl group as R < ² > of said Formula (6), a C1-C6 substitutable alkyl group as R < ² > of said Formula (3) is applied as it is. it can. However, the formula (3) is R ² and the R ² in the formula (6) may be another same or may be different.
Examples of the monomer that gives the structural unit represented by the formula (6) include styrene, hydroxystyrene, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methoxystyrene. 2-hydroxymethylstyrene, 3-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro -3-methylstyrene, 4-t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene and the like. These monomers may use only 1 type and may use 2 or more types together.
When the structural unit represented by the formula (6) in the polymer (2A) is contained, the content ratio is 0.1% with respect to 100 mol% in total of all the structural units constituting the polymer (2A). -50 mol% is preferable, 1-30 mol% is more preferable, and 3-10 mol% is still more preferable.

  It is preferable that the polystyrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatography of a polymer (2A) is 500-10000, More preferably, it is 2000-5000.

  As the (2B) acid generator, onium salt compounds (including thiophenium salt compounds), halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, diazomethane compounds and the like can be used. As for this acid generator (2B), only 1 type may be used and 2 or more types may be used together.

  Examples of the onium salt compounds include 4,7-di-n-butoxynaphthyltetrahydrothiophenium salt compounds, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium salt compounds, 1- (6- thiophenium salt compounds such as n-butoxynaphthalen-2-yl) tetrahydrothiophenium salt compound and 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium salt compound; bis (4-t-butylphenyl) ) Iodonium salt compounds such as iodonium salt compounds and diphenyliodonium salt compounds; triphenylsulfonium salt compounds, 4-t-butylphenyldiphenylsulfonium salt compounds, 4-cyclohexylphenyldiphenylsulfonium salt compounds, 4-methanesulfonylphenyldiphenyls Sulfonium salt compounds such as Honiumu salt compounds; phosphonium salt compound; diazonium salt compound; pyridinium salt compounds; and the like.

Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples include (trichloromethyl) -s-triazine derivatives.
Examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like.
Examples of the sulfonated product include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds.
Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl- Examples include 1,1-dimethylethylsulfonyldiazomethane and bis (1,1-dimethylethylsulfonyl) diazomethane.

0.1-10 mass parts is preferable with respect to 100 mass parts of polymers (2A), as for the compounding quantity of an acid generator (2B), 0.3-5 mass parts is more preferable, 0.5-3 mass parts Is more preferable.
As the (2C) crosslinking agent, the (1C) crosslinking agent can be applied as it is. 1-100 mass parts is preferable with respect to 100 mass parts of polymers (2A), and, as for the compounding quantity of a crosslinking agent (2C), 5-50 mass parts is more preferable.
In addition, it is the same as the composition (1) that it can contain at least one of an adhesion assistant (1D), a surfactant (1E), a solvent (1F) and the like which will be described later.

〔式（７）において、Ｒ^１〜Ｒ^４は、各々独立に、水素原子、ヒドロキシル基、炭素数１〜２０の置換可能なアルキル基、炭素数１〜２０の置換可能なアルコキシ基、炭素数１〜２０のアルコキシカルボニル基、アセトキシ基、炭素数６〜１０のアリール基、イソシアネート基又はグリシジルエーテル基を表す。〕

〔式（８）において、Ｒ^５〜Ｒ^８は、各々独立に、水素原子、ヒドロキシル基、炭素数１〜２０の置換可能なアルキル基、炭素数１〜２０の置換可能なアルコキシ基、炭素数１〜２０のアルコキシカルボニル基、アセトキシ基、炭素数６〜１０のアリール基、イソシアネート基、グリシジルエーテル基、又は、下記式（９）で表される１価の有機基を表し、且つ、Ｒ^５〜Ｒ^８のうちの少なくとも１つは該式（９）で表される１価の有機基である。〕

〔式（９）において、Ｒ^９は炭素数１〜４のアルキレン基を表し、Ｒ^１０は炭素数４〜２０の環状構造を有する基を表す。〕

〔式（１０）において、Ｒ^１１は炭素数４〜２０脂環式炭化水素基を表す。〕 The first resin layer forming composition (3) is (3A) a structural unit represented by the following formula (7), a structural unit represented by the following formula (8), and a structure represented by the following formula (10). A polymer containing a unit, (3B) an acid generator, and (3C) a crosslinking agent are contained.

In [Equation ^(7), R 1 ~R ⁴ are each independently a hydrogen atom, a hydroxyl group, a substitutable alkyl group having 1 to 20 carbon atoms, a substitutable alkoxy group having 1 to 20 carbon atoms, carbon atoms A 1-20 alkoxycarbonyl group, an acetoxy group, a C6-C10 aryl group, an isocyanate group, or a glycidyl ether group is represented. ]

In [Equation ^(8), R 5 ~R 8 each independently represent a hydrogen atom, a hydroxyl group, a substitutable alkyl group having 1 to 20 carbon atoms, a substitutable alkoxy group having 1 to 20 carbon atoms, carbon atoms 1 to 20 alkoxycarbonyl group, acetoxy group, aryl group having 6 to 10 carbon atoms, isocyanate group, glycidyl ether group, or monovalent organic group represented by the following formula (9), and R ⁵ At least one of ˜R ⁸ is a monovalent organic group represented by the formula (9). ]

[In Formula (9), R ⁹ represents an alkylene group having 1 to 4 carbon atoms, and R ¹⁰ represents a group having a cyclic structure having 4 to 20 carbon atoms. ]

In [Equation ^{(10), R 11} represents a number from 4 to 20 alicyclic hydrocarbon group having a carbon. ]

Examples of the substitutable alkyl group having 1 to 20 carbon atoms as R ^{1 to} R ^{4 in the} formula (7) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, 1- Examples thereof include a methylpropyl group, a 2-methylpropyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group.
Furthermore, examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a polar group other than a hydrocarbon group. Only 1 type may be used for a substituent and it may use 2 or more types together. Moreover, when it has 2 or more types of substituents, each substituent may be the same and may differ. Among these, examples of the polar group include an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), hydroxy group, carboxyl group, oxo group (═O), alkyloxycarbonyl group, acetoxy group (—OCOCH ₃ ), etc. Is mentioned.
Examples of the substitutable alkoxy group having 1 to 20 carbon atoms as R ^{1 to} R ^{4 in the} formula (7) include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 1- Examples thereof include a methylpropoxy group, a 2-methylpropoxy group, a t-butoxy group, an n-pentyloxy group, and an n-hexyloxy group. Furthermore, as a substituent, the substituent in the said C1-C20 substitutable alkyl group can be applied as it is.
Examples of the alkoxycarbonyl group having 1 to 20 carbon atoms as R ^{1 to} R ^{4 in the} formula (7) include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, and an n-butoxycarbonyl group. 1-methylpropoxycarbonyl group, 2-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group and the like.
The aryl group having 6 to 10 carbon atoms as R ^{1 to} R ^{4 in the} formula (7) includes a phenyl group, a tolyl group (o-, m-, p-), a naphthyl group (1-, 2-), A phenanthryl group, an anthranyl group, etc. are mentioned.

Examples of the monomer that gives the structural unit represented by the formula (7) include phenol, cresol (o-, m-, p-), dimethylphenol (2,3-, 2,5-, 3,4- 3,5-, 2,4-, 2,6-), trimethylphenol (2,3,5-, 3,4,5-), butylphenol (2-t-, 3-t-, 4-t) -), Resorcinol, methylresorcinol (2-, 4-, 5-), catechol, 4-t-butylcatechol, methoxyphenol (2-, 3-), propylphenol (2-, 3-, 4-), Examples thereof include isopropylphenol (2-, 3-, 4-), 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, pyrogallol, thymol, and isothymol. These monomers may use only 1 type and may use 2 or more types together.
As for the content rate of the structural unit represented by the said Formula (7) in a polymer (3A), 1-30 mol% is preferable with respect to a total of 100 mol% of all the structural units which comprise a polymer (3A), 3-25 mol% is more preferable and 5-20 mol% is still more preferable.

^R 1 to R substitutable alkyl group having 1 to 20 carbon atoms as ^4, replaceable alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms in the formula (8), 6 carbon atoms Each group in the formula (7) can be directly applied to 10 to 10 aryl groups.
However, R ^{1 to} R ^{4 in the} formula (7) and R ^{5 to} R ^{8 in the} formula (8) may be the same as or different from each other.
As a C1-C4 alkylene group as R < ⁹ > of said Formula (9), a methylene group, ethylene group, a propylene group, an isopropylene group etc. are mentioned.

The group having a cyclic structure having 4 to 20 carbon atoms as R ^{10 in the} formula (9) is sufficient if it has a cyclic structure, a monovalent alicyclic hydrocarbon group, a monovalent aromatic group, a monovalent group. Groups having a heterocyclic structure of Examples of monovalent alicyclic hydrocarbon groups include alicyclic rings derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. And a monovalent group having. These alicyclic hydrocarbon groups may or may not have a substituent. Examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a t-butyl group. An alkyl group is mentioned. Examples of the monovalent aromatic group include a phenyl group, a tolyl group (o-, m-, p-), a naphthyl group (1-, 2-), a phenanthryl group, and an anthranyl group. Furthermore, examples of the group having a monovalent heterocyclic structure include monovalent groups derived from heterocyclic rings such as indole, pyrimidine, piperidine, morpholine, pyran, furan, piperazine, and pyridine.

Specific examples of R ^{10 in the} formula (9) include the following various groups. In the groups represented by the following formulas (11-1) to (11-29), the bonding positions of R ⁹ with respect to R ¹⁰ are only examples, and are not limited to these bonding positions. May be.

  The content ratio of the structural unit represented by the formula (8) in the polymer (3A) is preferably 30 to 90 mol% with respect to 100 mol% in total of all the structural units constituting the polymer (3A). 35-80 mol% is more preferable, and 40-75 mol% is still more preferable.

Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms as R ^{11 in the} formula (10) include norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. And divalent groups having an alicyclic ring derived from cycloalkanes and the like. These alicyclic hydrocarbon groups may or may not have a substituent. Examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a t-butyl group. An alkyl group is mentioned.

As the monomer that gives the structural unit represented by the formula (10), dicyclopentadiene, bicyclo (4,3,0) nona-3,7-diene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna- Examples include unsaturated alicyclic hydrocarbon compounds such as 2-ene, α-pinene, β-pinene and limonene. These monomers may use only 1 type and may use 2 or more types together.
In the case where isomers exist in these monomers, any isomer may be used, or only one isomer may be used, and a mixture of two or more isomers may be used. It may be used.

  The content ratio of the structural unit represented by the formula (10) in the polymer (3A) is preferably 9 to 60 mol% with respect to 100 mol% in total of all the structural units constituting the polymer (3A). 10-50 mol% is more preferable and 15-45 mol% is still more preferable.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the polymer (3A) is preferably 1500 to 200000, more preferably 2000 to 10000.
The method for preparing this polymer (3A) is not particularly limited. Usually, after preparing a copolymer containing the above formula (7) and the above formula (10), the above formula contained in the obtained copolymer is used. It can obtain by introduce | transducing group represented by said Formula (9) with respect to the structural unit of (7) using the compound represented by [HO-R < ⁹ > -R < ¹⁰ >].

  As the (3B) acid generator, the (2B) acid generator can be used as it is, and further, bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (camphorsulfonyl). Glyoxime derivatives such as -α-dimethylglyoxime can be used. These acid generators (3B) may use only 1 type, and may use 2 or more types together. 0.1-10 mass parts is preferable with respect to 100 mass parts of polymers (3A), as for the compounding quantity of an acid generator (3B), 0.3-5 mass parts is more preferable, 0.5-3 mass parts Is more preferable.

The (1C) crosslinking agent can be applied as it is to the (3C) crosslinking agent. 1-100 mass parts is preferable with respect to 100 mass parts of polymers (3A), and, as for the compounding quantity of a crosslinking agent (3C), 5-50 mass parts is more preferable.
In addition, it is the same as the composition (1) that it can contain at least one of an adhesion assistant (1D), a surfactant (1E), a solvent (1F) and the like which will be described later.

The adhesion aid (1D) is not particularly limited as long as it is a component that can improve the adhesion between the first resin layer and the substrate. Examples of the adhesion assistant (1D) include a functional silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate and the like. These adhesion assistants may be used alone or in combination of two or more.
When the adhesion assistant (1D) is used, the blending amount thereof is the alkali-soluble resin (1A) of the composition (1), the polymer (2A) of the composition (2), or the weight of the composition (3). 0.2-10 mass parts is preferable with respect to 100 mass parts of union (3A), and 0.5-8 mass parts is more preferable.

The surfactant (1E) is not particularly limited as long as it can adjust coating properties, striations, wettability, developability, and the like. As this surfactant (1E), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, polyethylene glycol Nonionic surfactants such as dilaurate and polyethylene glycol distearate, and the following trade names: KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 [above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.], F-top EF101, EF204, EF303, EF352 [above, manufactured by Tochem Products Co., Ltd.], Megafuck F171, F172, F173 [above, Dainippon Ink and Chemicals, Inc. Manufactured by Kogyo Co., Ltd.], FLORAD FC430, FC431, FC135, FC93 [above, manufactured by Sumitomo 3M], Asahi Guard AG710, Surflon S382, SC101, SC102, SC103, SC104, SC105, SC106 [ As described above, manufactured by Asahi Glass Co., Ltd.). These surfactants (1E) may be used alone or in combination of two or more.
When the surfactant (1E) is used, the blending amount thereof is the alkali-soluble resin (1A) of the composition (1), the polymer (2A) of the composition (2), or the weight of the composition (3). 15 mass parts or less are preferable with respect to 100 mass parts of union (3A), and 0.001-10 mass parts is more preferable.

The solvent (1F) is not particularly limited as long as it can dissolve the components constituting the first resin layer forming composition. Examples of the solvent (1F) include ethylene glycol monoalkyl ethers, ethylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol Monoalkyl ether acetates, lactic acid esters, aliphatic carboxylic acid esters, other esters (ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate) Methyl 3-methoxypropionate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutylpropionate, methyl acetoacetate, Methyl binates, etc.), aromatic hydrocarbons (toluene, xylene, etc.), ketones (methyl ethyl ketone, 2-heptanone, cyclohexanone, etc.), amides (N-methylformamide, N-methylacetamide, N-methylpyrrolidone, etc.) And lactones (γ-butyrolactone and the like). These solvent (1F) may use only 1 type, and may use 2 or more types together.
When the solvent (1F) is used, the blending amount thereof is the alkali-soluble resin (1A) of the composition (1), the polymer (2A) of the composition (2) or the polymer (2) of the composition (3) ( 3A) 100 to 3000 parts by mass are preferable with respect to 100 parts by mass, and 200 to 2000 parts by mass are more preferable.

  The material of the substrate is not particularly limited, and may be made of only one kind of material, or may be a laminate in which two or more layers of different materials are laminated. Examples of the material constituting the substrate include silicon, various metals (such as aluminum), various metal (such as aluminum) sputtered films, alumina, glass epoxy, paper phenol, and glass. Although the thickness of a board | substrate is not specifically limited, Usually, it is 1000-10000 nm. Further, the surface of the substrate may be subjected to surface modification or the like as necessary.

Although the thickness of the 1st resin layer formed on a board | substrate is not specifically limited, Usually, it is 1-1000 nm, it is preferable to set it as 5-500 nm, and it is still more preferable to set it as 10-100 nm.
Although the method of apply | coating the composition for 1st resin layer formation to a board | substrate is not specifically limited, For example, appropriate means, such as spin coating, cast coating, roll coating, are mentioned. Furthermore, you may volatilize the solvent in a coating film by prebaking (PB) as needed. The prebaking heating conditions are appropriately selected depending on the composition of the first resin layer forming composition, but the heating temperature is usually about 100 to 400 ° C, preferably 150 to 250 ° C. Furthermore, the heating time is usually 10 to 300 seconds, preferably 30 to 90 seconds.

The “second resin layer forming step (2)” [PR (2) in FIG. 1] is a step of forming the second resin layer 32 mainly composed of an organic polymer on the surface of the first resin layer 31. is there.
The second resin layer is a resin layer containing an organic polymer as a main component. The main component of the organic polymer means that the organic polymer is contained in an amount of 95% by mass or more (or 100% by mass) when the entire second resin layer is 100% by mass. . That is, in other words, it means that the inorganic polymer described later is not contained, or even if it is contained, it is less than 5% by mass.

  Furthermore, the second resin layer is a layer that can follow the surface shape of the stamped stamper and transfer the shape. Other properties are not limited, but a radiation-sensitive resin layer can be used. As this 2nd resin layer, the 2nd resin formed on the 1st resin layer using the composition for 2nd resin layer formation containing a polymerizable unsaturated compound and a radiation sensitive polymerization initiator A layer is preferred.

  The polymerizable unsaturated compound may be an unsaturated compound that can be polymerized by exposure in the presence of a radiation-sensitive polymerization initiator, and the type thereof is not particularly limited, but (meth) acrylic acid esters are preferable. These (meth) acrylic acid esters may be monofunctional, bifunctional, or trifunctional or higher, and these may be used alone or in combination of two or more.

  Examples of the monofunctional (meth) acrylic acid esters include 2-hydroxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, isobornyl (meth) acrylate, butyl (meth) acrylate, and 3-methoxybutyl (meth). An acrylate, (2- (meth) acryloyloxyethyl) (2-hydroxypropyl) phthalate, etc. are mentioned. These may use only 1 type and may use 2 or more types together.

  Examples of the bifunctional (meth) acrylic acid esters include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 , 9-nonanediol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, polyester both-end (meth) acryl-modified compound, polypropylene glycol both-end (meth) acryl-modified compound, polytetramethylene glycol both-end (meth) An acrylic modified compound etc. are mentioned. These may use only 1 type and may use 2 or more types together.

  Examples of the trifunctional or higher functional (meth) acrylic acid esters include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Examples include pentaerythritol hexa (meth) acrylate and tri (2- (meth) acryloyloxyethyl) phosphate. These may use only 1 type and may use 2 or more types together.

The kind of the radiation sensitive polymerization initiator is not particularly limited. Examples of the radiation-sensitive polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-hydroxy-cyclohexylphenyl. Ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 3-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde Fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin ethyl ether , Benzoin propyl ether, Michler's ketone, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl Propan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- ON, 2,4,6-trimethylbenzoylphenylphosphinate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- ON, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpen Tylphosphine oxide, methylbenzoylformate, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], etc. Can be mentioned. These may use only 1 type and may use 2 or more types together.
Although the compounding quantity of a radiation sensitive polymerization initiator is not specifically limited, 0.01-30 mass% is preferable with respect to the whole composition for 2nd resin film formation, 0.1-20 mass% is more preferable, 1 More preferred is ˜15% by mass.

The thickness of the second resin layer formed on the first resin layer is not particularly limited, but is usually 1 to 1000 nm, preferably 5 to 500 nm, and more preferably 10 to 100 nm.
Although the method of apply | coating the composition for 2nd resin layer formation on the 1st resin layer is not specifically limited, For example, appropriate means, such as spin coating, cast coating, roll coating, are mentioned. Furthermore, you may volatilize the solvent in a coating film by prebaking (PB) as needed. The heating conditions for this pre-baking are appropriately selected depending on the composition of the second resin layer forming composition, but the heating temperature is usually about 30 to 150 ° C, preferably 50 to 130 ° C. Furthermore, the heating time is usually 10 to 300 seconds, preferably 30 to 90 seconds.

  In the “concave portion forming step (3)” (PR (3-1) to (3-3) in FIG. 1), the stamper 10 having the convex portion 11 is pressed and detached from the second resin layer 32, and the second step is performed. This is a step of forming a recess 321 in the resin layer 32.

  In this recess forming step, the second resin layer may or may not be penetrated by the pressure contact of the stamper, but among these, it is preferable not to penetrate the second resin layer. By leaving the second resin layer in the thickness direction without penetrating the second resin layer, the adhesion surface between the first resin layer and the second resin layer is increased, and the adhesion between them is increased, The resist peeling between the first resin film and the second resin film can be suppressed. In the case where the second resin layer is not penetrated, the thickness (remaining film thickness) of the bottom portion of the recess to be formed is not particularly limited, but is preferably 1 nm or more, more preferably 3 to 500 nm, and further preferably 5 to 150 nm.

  Moreover, the press contact and desorption conditions of the stamper with respect to the second resin layer are not particularly limited as long as the recess can be formed in the second resin layer, but the press contact pressure is preferably 0.1 MPa or more (100 MPa or less), 0.1 -50 MPa is more preferable. Furthermore, the pressure contact time is preferably 1 second or longer (600 seconds or shorter), more preferably 1 to 300 seconds. Moreover, the said press-contact and desorption should just be able to form a recessed part in a 2nd resin layer, may be performed only once, and may be performed twice or more.

The “stamper (10)” has a convex portion 11 for transfer on the surface thereof, and after pressing the stamper 10 against the second resin layer 32, the stamper 10 is detached so as to correspond to the convex portion 11 of the stamper 10. The recessed portion 321 thus formed can be formed (transferred) on the surface of the second resin layer 32.
This stamper 10 may or may not be transparent to radiation. When the stamper 10 has translucency and the second resin layer 32 contains a radiation sensitive polymerization initiator, the stamper 10 is exposed in a state of being pressed against the second resin layer 32 [in FIG. PR (3-2 ′) exposure step can be provided], whereby the protrusion 11 of the stamper 10 can be more easily transferred to the second resin layer 32. In this case, the transmittance for radiation is not particularly limited, but it is preferably 70% or more for the desired radiation (the radiation that the radiation-sensitive polymerization initiator can function), and is preferably 75 to 100%. Is more preferable, and 80 to 100% is still more preferable.

When the stamper is exposed while being pressed against the second resin layer, that is, when the exposure step [PR (3-2 ′) in FIG. 4] is provided, the second resin layer 32 may be completely cured by exposure. Further, after being incompletely cured, complete curing may be performed by heating in a later step.
The type of radiation used for exposure is not particularly limited, and radiation such as charged particle beams such as visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams {ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm), etc. Including} can be used.

  The stamper only needs to have mechanical characteristics as a stamper, and can further have transparency to radiation as described above. From such a viewpoint, a light-transmitting inorganic material is particularly preferable as the material constituting the stamper. As this translucent inorganic material, a quartz material {quartz (single crystal, polycrystal), various glasses (quartz glass, fluoride glass, calcium phosphate glass, borate glass, borosilicate glass, etc.) }, Silicon, spinel, corundum, sapphire and the like.

  A functional layer can be provided on the surface of the stamper (surface having a convex portion) as necessary. As the functional layer, a release layer, an ionization suppressing layer, an adhesion improving layer {a layer for improving adhesion between various layers (such as an interlayer between a stamper and a translucent electrode layer)}, a thermal diffusion layer, various optical functions Examples include a layer {reflection suppression, refractive index control layer, light transmission improving layer (made of silicon oxide), etc.}, an insulating layer, and the like. These various layers may use only 1 type and may use 2 or more types together. That is, for example, each layer may have only one layer or may have a multilayer structure of two or more layers. The thickness of each functional layer is not particularly limited, but the thickness of each layer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and particularly preferably 1 to 20 nm.

Of the functional layers, the release layer is a layer for facilitating separation of the stamper and the second resin film. When the release layer is provided, it is preferable that the release layer is disposed on a part or the entire surface of the convex portion of the stamper.
As the release layer, a silane compound having a halogenated organic group (such as a halogenated alkyl group) is preferably used. In such a case, a release layer composed of an organic monomolecular film self-assembled so that the halogenated organic group is located on the surface can be obtained. Examples of the silane compound include 3,3,3-trifluoropropyl group, tridecafluoro-1,1,2,2-tetrahydrooctyl group, heptadecafluoro-1,1,2,2-tetrahydrodecyl group, Examples include trichlorosilane and trialkoxysilane (such as trimethoxysilane and triethoxysilane) having various halogenated organic groups such as 3,3,4,4,5,5,6,6,6-nonafluorohexyl group. In addition, perfluorodecyltrichlorosilane, octadecyltrichlorosilane, dimethyldichlorosilane, and the like can be given. These may use only 1 type and may use 2 or more types together.

  Among the functional layers, the ionization suppression layer can be formed of a light-transmitting inorganic material such as a nitride, an oxide, an oxynitride, or a hydrogenated nitride. As nitrides, silicon nitride, aluminum nitride, indium nitride, gallium nitride, tin nitride, boron nitride, chromium nitride, silicon nitride carbide, etc .; as oxides, indium oxide, tin oxide, indium tin oxide, aluminum oxide, oxide Germanium, silicon oxide, zinc oxide, zirconium oxide, titanium oxide, yttrium oxide, erbium oxide, cerium oxide, tantalum oxide, hafnium oxide, etc .; oxynitrides include silicon oxynitride, tin oxynitride, boron oxynitride, oxynitride Aluminum, indium oxynitride, gallium oxynitride, chromium oxynitride, silicon oxynitride carbide, etc .; as hydronitrides, hydrogenated aluminum nitride, indium hydronitride, gallium hydronitride, silicon hydronitride, hydronitridation Tin, hydrogenated boron nitride, hydrogenated chromium nitride, hydronitrided Of silicon or the like; and the like. These may use only 1 type and may use 2 or more types together.

  The “filling portion forming step (4)” [PR (4-1) to (4-2) in FIG. 2] is a step of forming the filling portion 33 mainly composed of an inorganic polymer in the concave portion 321. .

This filling part is a part mainly composed of an inorganic polymer. The phrase “mainly composed of an inorganic polymer” means that the inorganic polymer is contained in an amount of 90% by mass or more (or 100% by mass) when the entire filling portion is 100% by mass. That is, in other words, it means that the organic polymer is not contained, or even if it is contained, it is less than 10% by mass.
This filling portion is a portion having an etching selectivity with respect to the first resin layer and the second resin layer mainly containing an organic polymer by containing an inorganic polymer as a main component. .
The inorganic polymer constituting the filling portion is a polymer whose skeleton is formed of an inorganic element. Examples of such inorganic elements include Si, Ti, Al, Zr and the like. Of these, Si is preferable, and the inorganic polymer is more preferably polysiloxane. In particular, a filling part formed by using a composition for forming a filling part containing a polysiloxane containing a structural unit represented by the following formula (12) and a structural unit represented by the following formula (13) and a solvent. Preferably there is.

〔式（１２）において、Ｒ^１は炭素数１〜４のアルキル基を示し、ｎは１〜４の整数である。〕

In [Equation (12), ^{R 1} represents an alkyl group having 1 to 4 carbon atoms, n represents an integer of 1 to 4. ]

The alkyl group having 1 to 4 carbon atoms of R ¹ in the formula (12) may be linear or branched. R ¹ in the formula (12) is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group or the like. Can be mentioned.

〔式（１４）において、Ｒ^１は炭素数１〜４のアルキル基を表し、Ｒ^２は炭素数１〜４のアルキル基を表し、ｎは１〜４の整数である。〕 Examples of the monomer that gives the structural unit represented by the formula (12) include silane compounds represented by the following formula (14).

In [Equation (14), ^{R 1} represents an alkyl group having 1 to 4 carbon atoms, ^{R 2} represents an alkyl group having 1 to 4 carbon atoms, n represents an integer of 1 to 4. ]

The description of R ¹ in the formula (12) can be applied as it is to R ¹ in the formula (14). The same applies to R ² in formula (14). However, R ¹ and R ² may be the same or different. Further, the three R ² in the formula (14) may be the same or different from each other.

  Examples of the silane compound represented by the formula (14) include 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, N-3- (methacryloxy-2-hydroxypropyl) -3-amino. Propyltriethoxysilane, 2- (trimethoxysilyl) ethyl methacrylate, 2- (triethoxysilyl) ethyl methacrylate, trimethoxysilylmethyl methacrylate, triethoxysilylmethyl methacrylate, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate, Examples include 3- [tris (dimethylvinylsiloxy)] propyl methacrylate, methacryloxypropyltris (methoxyethoxy) silane, and 3- (trichlorosilyl) propyl methacrylate. These monomers may use only 1 type and may use 2 or more types together.

Examples of the monomer that gives the structural unit represented by the formula (13) include a silane compound represented by the following formula (15).
Si (OR ¹ ) ₄ (15)
In [Equation (15), ^{R 1} represents a monovalent organic group. ]

Examples of the monovalent organic group for R ¹ in the formula (15) include an alkyl group and an aromatic group. The four R ^{1 s} in the formula (15) may be the same as or different from each other. These monovalent organic groups may be substituted or unsubstituted.
Examples of the monovalent alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Furthermore, examples of the substituted monovalent alkyl group include γ-aminopropyl group, γ-glycidoxypropyl group, and γ-trifluoropropyl group. Examples of the monovalent aromatic group include a phenyl group and a benzyl group.

  Examples of the silane compound represented by the formula (15) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra -Tert-butoxysilane, tetraphenoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraisocyanatosilane, tetrakis (butoxyethoxyethoxy) silane, tetrakis (dimethylsiloxy) silane, tetrakis (ethoxyethoxy) silane, tetrakis (2-ethylhexyl) Siloxy) silane, tetrakis (2-methacryloxyethoxy) silane, tetrakis (methoxyethoxyethoxy) silane, tetrakis (methoxyethoxy) silane, tetrakis (methoxypropo) Shi) silane, tetrakis (methyl ethyl ketone creaking Roh) silane, tetrakis (trichlorosilylethyl) silane, tetrakis (trimethylsiloxy) silane, tetrakis (vinyldimethylsiloxy) silane. These monomers may use only 1 type and may use 2 or more types together.

  The polysiloxane constituting the filling portion forming composition may contain other structural units in addition to the structural unit represented by the formula (12) and the structural unit represented by the formula (13). . As another structural unit, the structural unit represented by following formula (16) and the structural unit represented by following formula (17) are mentioned. These structural units may contain only 1 type and may contain 2 or more types.

〔式（１６）において、Ｒ^１は、水素原子、ヒドロキシル基、炭素数１〜５のアルキル基、又は−ＯＲ^２を表し、Ｒ^２は炭素数１〜５のアルキル基を表す。〕

In [Equation (16), ^{R 1} represents a hydrogen atom, a hydroxyl group, an alkyl group of 1 to 5 carbon atoms, or represents -OR ^{2, R 2} represents an alkyl group having 1 to 5 carbon atoms. ]

〔式（１７）において、Ｒ^１は、炭素数１〜４のアルキル基を表す。〕

In [Equation (17), ^{R 1} represents an alkyl group having 1 to 4 carbon atoms. ]

The alkyl group having 1 to 5 carbon atoms in R ¹ of the formula (16) may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a t-butyl group, and a pentyl group. . In the case where R ¹ is —OR ² , R ¹ in the same formula can be applied as it is as the alkyl group having 1 to 5 carbon atoms of R ² . However, R ¹ and R ² may be the same or different. Furthermore, the structural unit represented by the formula (16) may be contained in the polysiloxane only in one kind or in two or more kinds.

〔式（１８）において、Ｒ^１は、水素原子、ヒドロキシル基、炭素数１〜５のアルキル基、又は−ＯＲ^２を表し、Ｒ^２は炭素数１〜５のアルキル基を表し、Ｒ^３は１価の有機基を表す。〕 Examples of the monomer that gives the structural unit represented by the formula (16) include a silane compound represented by the following formula (18).

In [Equation (18), ^{R 1} represents a hydrogen atom, a hydroxyl group, an alkyl group of 1 to 5 carbon atoms, or represents -OR ^{2, R 2} represents an alkyl group having 1 to 5 carbon atoms, ^{R 3} is Represents a monovalent organic group. ]

Regarding R ¹ and R ² in the formula (18), the description of R ¹ and R ² in the formula (16) can be applied as it is. Furthermore, the explanation of R ¹ in the formula (15) can be applied as it is to R ³ in the formula (18).

  Examples of the silane compound represented by the formula (18) include 2-methylphenyltrimethoxysilane, 2-methylphenyltriethoxysilane, 2-methylphenyltri-n-propoxysilane, and 2-methylphenyltri-iso-propoxy. Silane, 2-methylphenyltri-n-butoxysilane, 2-methylphenyltri-sec-butoxysilane, 2-methylphenyltri-tert-butoxysilane, 2-methylphenyltrichlorosilane, 2-methylphenyltriacetoxysilane, 4-methylphenyltrimethoxysilane, 4-methylphenyltriethoxysilane, 4-methylphenyltri-n-propoxysilane, 4-methylphenyltri-iso-propoxysilane, 4-methylphenyltri-n-butoxysilane, 4 -Methylfe Rutri-sec-butoxysilane, 4-methylphenyltri-tert-butoxysilane, 4-methylphenyltrichlorosilane, 4-methylphenyltriacetoxysilane, 2-ethylphenyltrimethoxysilane, 2-ethylphenyltriethoxysilane, 2 -Ethylphenyltri-n-propoxysilane, 2-ethylphenyltri-iso-propoxysilane, 2-ethylphenyltri-n-butoxysilane, 2-ethylphenyltri-sec-butoxysilane, 2-ethylphenyltri-tert -Butoxysilane, 2-ethylphenyltrichlorosilane, 2-ethylphenyltriacetoxysilane, 4-ethylphenyltrimethoxysilane, 4-ethylphenyltriethoxysilane, 4-ethylphenyltri-n-propoxy 4-ethylphenyltri-iso-propoxysilane, 4-ethylphenyltri-n-butoxysilane, 4-ethylphenyltri-sec-butoxysilane, 4-ethylphenyltri-tert-butoxysilane, 4-ethylphenyl Trichlorosilane, 4-ethylphenyltriacetoxysilane, 4-propylphenyltrimethoxysilane, 4-propylphenyltriethoxysilane, 4-propylphenyltri-n-propoxysilane, 4-propylphenyltri-iso-propoxysilane, 4 -Propylphenyltri-n-butoxysilane, 4-propylphenyltri-sec-butoxysilane, 4-propylphenyltri-tert-butoxysilane, 4-propylphenyltrichlorosilane, 4-propylphenyltriace Toxisilane, 4-butylphenyltrimethoxysilane, 4-butylphenyltriethoxysilane, 4-butylphenyltri-n-propoxysilane, 4-butylphenyltri-iso-propoxysilane, 4-butylphenyltri-n-butoxysilane 4-butylphenyltri-sec-butoxysilane, 4-butylphenyltri-tert-butoxysilane, 4-butylphenyltrichlorosilane, 4-butylphenyltriacetoxysilane, 4-methoxyphenyltrimethoxysilane, 4-methoxyphenyl Triethoxysilane, 4-methoxyphenyltri-n-propoxysilane, 4-methoxyphenyltri-iso-propoxysilane, 4-methoxyphenyltri-n-butoxysilane, 4-methoxyphenyltri-sec-butyl Xysilane, 4-methoxyphenyltri-tert-butoxysilane, 4-methoxyphenyltrichlorosilane, 4-methoxyphenyltriacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso -Propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane and the like. These may use only 1 type and may use 2 or more types together.

  Among these silane compounds, 4-methoxyphenyltrimethoxysilane, 4-methoxyphenyltriethoxysilane, 4-methoxyphenyltri-n-propoxysilane, 4-methoxyphenyltri-iso-propoxysilane, 4-methoxyphenyl Tri-n-butoxysilane, 4-methoxyphenyltri-sec-butoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxy Silane and phenyltri-sec-butoxysilane are preferred. These may use only 1 type and may use 2 or more types together.

The alkyl group having 1 to 4 carbon atoms in R ¹ of the formula (17) may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a t-butyl group, and a pentyl group. . Moreover, the structural unit represented by Formula (17) may be contained in polysiloxane only by 1 type, and may be contained 2 or more types.

Examples of the monomer that gives the structural unit represented by the formula (17) include a silane compound represented by the following formula (19).
R ¹ Si (OR ² ) ₃ (19)
[In Formula (19), R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms, and R ² represents a monovalent organic group. ]

For R ¹ in the formula (19), the description of R ¹ in the formula (16) can be applied as it is. The explanation of R ³ in the formula (18) can be applied to R ² in the formula (19) as it is.

  Examples of the silane compound represented by the formula (19) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxy. Silane, methyltri-tert-butoxysilane, methyltriphenoxysilane, methyltriacetoxysilane, methyltrichlorosilane, methyltriisopropenoxysilane, methyltris (dimethylsiloxy) silane, methyltris (methoxyethoxy) silane, methyltris (methylethylketoxime) silane , Methyltris (trimethylsiloxy) silane, methylsilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethylto -Iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, ethylbis (trimethylsiloxy) silane, ethyldichlorosilane, ethyltriacetoxysilane, ethyltri Chlorosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri -Sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, n-propyltriacetoxysilane, n-propyltrichlorosilane, i-propyltrime Xysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri-sec-butoxysilane, i -Propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n- Butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, n-butyltrichlorosilane, 2-methylpropyltrimethoxysilane, 2-methylpropyl Trier Toxisilane, 2-methylpropyltri-n-propoxysilane, 2-methylpropyltri-iso-propoxysilane, 2-methylpropyltri-n-butoxysilane, 2-methylpropyltri-sec-butoxysilane, 2-methylpropyl Tri-tert-butoxysilane, 2-methylpropyltriphenoxysilane, 1-methylpropyltrimethoxysilane, 1-methylpropyltriethoxysilane, 1-methylpropyltri-n-propoxysilane, 1-methylpropyltri-iso- Propoxysilane, 1-methylpropyltri-n-butoxysilane, 1-methylpropyltri-sec-butoxysilane, 1-methylpropyltri-tert-butoxysilane, 1-methylpropyltriphenoxysilane, t-butyltrimethoxy Silane, t-butyltriethoxysilane, t-butyltri-t-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-tert -Butoxysilane, t-butyltriphenoxysilane, t-butyltrichlorosilane, t-butyldichlorosilane and the like. These may use only 1 type and may use 2 or more types together.

  Among these silane compounds, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n- Propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane and the like are preferable. These may use only 1 type and may use 2 or more types together.

In addition to the structural units represented by the formula (12), the formula (13), the formula (16), and the formula (17), the polysiloxane constituting the filling portion forming composition may be other A structural unit can be further included. Furthermore, as other structural units, each structural unit which uses the following each compound as a monomer is mentioned. These other structural units may be used alone or in combination of two or more.
Examples of the compound giving another structural unit include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diphenyldimethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, di-tert-butyldichlorosilane, and diethoxy. Divinylsilane, di (3-methacryloxypropyl) dimethoxysilane, dimethyldiethoxysilane, dimesityldimethoxysilane, dimesityldichlorodichlorosilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dimethyldiacetoxysilane, diethyldiethoxysilane, Dicyclopentyldimethoxysilane, di-n-butyldichlorosilane, di-t-butyldichlorosilane, di-cyclohexyldichlorosilane, acetoxypropyldichloro Silane, (3-acryloxypropyl) methyldichlorosilane, allylhexyldichlorosilane, allylmethyldichlorosilane, allylphenyldimethoxysilane, aminopropylmethyldiethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, dimethacryloxydimethoxysilane , T-butylmethyldichlorosilane, t-butylphenyldichlorosilane, 2- (carbomethoxy) ethylmethyldichlorosilane, 2-cyanoethylmethyldichlorosilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropylmethyldimethoxysilane, 3 -Cyanopropylphenyldichlorosilane, cyclohexylethyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldichlorosilane, Lucaptomethylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, isobutylmethyldimethoxysilane, phenylmethyldichlorosilane, ethylmethyldichlorosilane, 3-methacryloxypropylmethyldiethoxysilane, p-tolylmethyldichlorosilane, phenethylmethyl Examples include dichlorosilane, di (p-tolyl) dichlorosilane, di (3-glycidoxy) propyldimethoxysilane, di (3-glycidoxy) propyldiethoxysilane, (3-cyclohexenyl) propyldimethoxysilane, and the like.

  In the polysiloxane constituting the filling portion forming composition, the content ratio of the structural unit represented by the formula (12) is, when the total of all the structural units included in the polysiloxane is 100 mol%, It is preferable that it is 1-50 mol%, More preferably, it is 1-30 mol%, More preferably, it is 5-10 mol%. In this range, the filling portion has excellent adhesion, and also has excellent durability when used as a mask.

  In the polysiloxane constituting the filling portion forming composition, the content ratio of the structural unit represented by the formula (13) is, when the total of all the structural units included in the polysiloxane is 100 mol%, It is preferable that it is 50-99 mol%, More preferably, it is 50-80 mol%, More preferably, it is 50-60 mol%. In this range, the durability when used as a mask is excellent, and the storage stability of the filling portion forming composition is also excellent.

  The content ratio of the structural unit represented by the formula (16) in the polysiloxane constituting the filling portion forming composition is, when the total of all the structural units included in the polysiloxane is 100 mol%, It is preferable that it is 10 mol% or less, More preferably, it is 0-7 mol%, More preferably, it is 0-5 mol%.

  The content ratio of the structural unit represented by the formula (17) in the polysiloxane constituting the filling portion forming composition is preferably 50 mol% or less, more preferably 1 to 40 mol%, and further Preferably it is 1-30 mol%.

  In the polysiloxane constituting the filling portion forming composition, the content ratio of the other structural units is 10 mol% or less when the total of all the structural units contained in the polysiloxane is 100 mol%. It is preferably 1 to 8 mol%, more preferably 1 to 5 mol%.

The polystyrene-converted weight average molecular weight measured by GPC of the polysiloxane constituting the filling portion forming composition is preferably 500 to 100,000, more preferably 1000 to 50,000, and still more preferably 1000 to 10,000.
Moreover, it is preferable that the silanol abundance ratio in the polysiloxane which comprises the said composition for filling part formation is 1-2 times with respect to the Si-O-Si bond in an inorganic polymer, More preferably, 1- 1.7 times, more preferably 1 to 1.5 times. When the silanol abundance ratio is 1 to 2 times, the storage stability is particularly good. The silanol abundance ratio is measured by Si ²⁹ -NMR.
Furthermore, the polysiloxane which comprises the said various composition for filling part formation may be contained only 1 type in the composition for filling part formation, and may be contained 2 or more types.

Further, the solvent constituting the filling portion forming composition is not particularly limited as long as it can dissolve the polysiloxane and does not dissolve the second resin layer. Specifically, alcohols, ethers, esters, and the like, and those containing these are preferable, and alcohols are particularly preferable. Moreover, these solvents may use only 1 type and may use 2 or more types together.
Although the compounding quantity of a solvent is not specifically limited, 20-10000 mass parts is preferable with respect to 100 mass parts of polysiloxane, and 30-5000 mass parts is more preferable.

As said alcohol, C2-C10 alcohol is preferable. The alcohol having 2 to 10 carbon atoms may be linear or branched. As this alcohol, 1-butanol, 2-butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, 4-methyl-2-pentanol, heptanol, cycloheptanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether And propylene glycol monopropyl ether.
Examples of the ether include diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisopentyl ether and the like.
Examples of the ester include methyl lactate, ethyl lactate, and propylene glycol monomethyl ether acetate.
In addition to the polysiloxane and the solvent, the filler forming composition may contain other additives such as a surfactant and a crosslinking agent.

  The method for forming the filling portion is not particularly limited, but usually, the filling portion forming composition is applied onto the second resin layer having the recesses to form a film. The coating method in this case is not particularly limited, and examples thereof include appropriate means such as spin coating, cast coating, and roll coating. Furthermore, you may volatilize the solvent in a coating film by prebaking (PB) as needed. The prebaking heating conditions are appropriately selected depending on the composition of the filling portion forming composition, but the heating temperature is usually about 60 to 180 ° C, preferably 80 to 150 ° C. Further, the heating time is usually 10 to 300 seconds, preferably 30 to 180 seconds.

  Further, if necessary, a step of removing a part of the surface of the filling portion (a step of flattening) [PR (4-2) in FIG. 2] is performed in order to reveal the pattern of the second resin layer 32. Can be provided. The removal method is not particularly limited, but an etching method such as dry etch back or wet etch back, a CMP method, or the like can be used. Of these, dry etch back and CMP are preferable.

  The “etching step (5)” [PR (5-1) to (5-2) in FIG. 2] is a step of etching the first resin layer 31 and the second resin layer 32 using the filling portion 33 as a mask. is there.

In this etching step, etching may be performed in any way, but dry etching (a method of physically or chemically etching under reduced pressure) is preferable, and further, reactive ion etching (RIE). Is more preferable. The first resin layer and the second resin layer are mainly composed of an organic polymer, whereas the filling portion is composed mainly of an inorganic polymer, so that the etching rate in dry etching can be varied. The filling portion can function as a mask for the first resin layer and the second resin layer.
The source gas for dry etching is not particularly limited, but includes oxygen atoms such as O ₂ , CO, and CO ₂ , inert gases such as He, N ₂ , and Ar, and chlorine atoms such as Cl ₂ and BCl _2. A gas containing hydrogen, H ₂ , NH ₂ gas, or the like can be used. These gases may use only 1 type and may use 2 or more types together.

  Furthermore, in this etching process, the etching rate with respect to each of the first resin layer and the second resin layer is not particularly limited, and each etching rate may be the same or different. If they are different, either etching rate may be higher, but the etching rate of the first resin layer is slower than the etching rate of the second resin layer [PR (5-1) to (5 in FIG. -2)] is preferred. In this case, when processing the substrate to be processed, it is possible to form a pattern (mask) having better etching resistance (mask resistance).

Etch rate ratio, the can be a suitably the composition and use of the etching technique of each resin layer, in particular, the etch rate was S ₁ for the first resin layer, the etching rate for the second resin layer was S ₂ In this case, when the etching rate ratio is S ₁ / S ₂ , S ₁ / S ₂ is preferably 1 to 3, more preferably 1.5 to 3, and more preferably 2 to 3. It is particularly preferred.
The etching rate is a value measured by the following method. That is, the first resin film and the second resin film are formed with an arbitrary film thickness (film thickness before processing), and etching is performed based on a difference from a film thickness (film thickness after processing) after etching is performed under arbitrary conditions. Measure by calculating the speed.

In the pattern forming method of the present invention, the first resin layer forming step (1), the second resin layer forming step (2), the concave portion forming step (3), the filling portion forming step (4), and the etching step (5). In addition, other processes can be provided. As another step, a substrate processing step (6) for forming (transferring) a pattern on the substrate using the filling portion, the shape transfer layer and the resin layer after the etching step (5) as a mask [FIG. (PR (6)). Furthermore, a mask removing step (7) [PR (7) in FIG. 3] for removing the mask (filling portion, second resin layer and first resin layer) can be provided.
Each of these other processes may use only 1 type and may use 2 or more types together.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Here, “part” and “%” are based on mass unless otherwise specified.

[Preparation Example 1] Preparation of first resin layer forming composition 100 parts by mass of an alkali-soluble resin (1A) having the following phenolic hydroxyl group, 1.0 part by mass of a thermal acid generator (1B), and 25 crosslinker (1C) A composition for forming the first resin layer is prepared by dissolving, in 400 parts by mass of the solvent (1F), 2.5 parts by mass of the adhesion promoter (1D) and 0.2 parts by mass of the surfactant (1E). Prepared.
Alkali-soluble resin (1A) having a phenolic hydroxyl group; copolymer consisting of p-hydroxystyrene / styrene / vinylbenzoic acid = 18/80/2 (molar ratio), polystyrene-reduced weight average molecular weight (Mw) = 10,000 ,
Thermal acid generator (1B); 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine,
Cross-linking agent (1C): hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MW-390”),
Adhesion aid (1D); γ-glycidoxypropyltrimethoxysilane (manufactured by Chisso Corporation, trade name “S510”),
Surfactant (1E); Leveling agent / surfactant (manufactured by Neos, trade name “FTX-218”),
Solvent (1F); ethyl lactate / 2-heptanone = 80/65 (parts by mass)

[Preparation Example 2] Preparation of second resin film forming composition 100 parts by mass of butyl methacrylate, 50 parts by mass of 1,6-hexanediol dimethacrylate, 25 parts by mass of 2,4,6-trimethylbenzoyl-phenyl-phosphine oxide Were mixed and stirred uniformly to obtain a second resin film-forming composition.

[Preparation Example 3] Preparation of filling portion forming composition 0.54 g of maleic anhydride was dissolved by heating in 10.8 g of water to prepare an aqueous maleic acid solution. Next, 18.71 g of tetraethoxysilane and 53.5 g of propylene glycol monopropyl ether were placed in the flask. A cooling tube and a dropping funnel containing the previously prepared maleic acid aqueous solution were set in the flask, heated at 100 ° C. in an oil bath, and then slowly dropped with the maleic acid aqueous solution at 4 ° C. Reacted for hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool and then set in an evaporator, and ethanol generated during the reaction was removed to obtain a reaction product (polysiloxane having a weight average molecular weight of 2100).
The solid content in the obtained reaction product was 15.7% as a result of measurement by a firing method. Moreover, the weight average molecular weight of the obtained product (solid content) was 2100.
14.89 g of the reaction product obtained as described above was dissolved in 30.79 g of propylene glycol monoethyl ether, and this solution was further filtered through a filter having a pore size of 0.2 μm to obtain a filling part forming composition. It was.
The weight average molecular weight of the product (solid content) was measured by a size exclusion chromatography (SEC) method. As a measurement sample, a 2-methoxyethanol solution of LiBr—H ₃ PO ₄ having a concentration of 10 mmol / L was used as a solvent, and 0.1 g of the product was added to 100 cc of 10 mmol / L LiBr—H ₃ PO ₄ in 2-methoxyethanol. What was dissolved in was used. Standard sample: polystyrene (manufactured by WAKO), apparatus: high-speed GPC apparatus “HLC-8120GPC” (model name), manufactured by Tosoh Corporation, column: water-based / polar organic solvent-based GPC column “TSK-GEL SUPER” with a length of 15 cm AWM-H "(manufactured by Tosoh Corporation) is connected in series, and the measurement temperature is 40 ° C, the flow rate is 0.6 ml / min. , Detector: RI (built in the high-speed GPC device).

Example 1 Example Using First Resin Layer (1) First Resin Layer Forming Step A first resin layer forming composition prepared above is spin-coated on a 6-inch silicon wafer (substrate). Then, heating was performed at 180 ° C. for 1 minute and at 300 ° C. for 1 minute using a hot plate to form a 300 nm-thick first resin layer.

(2) Second resin layer forming step 10 μL of the second resin layer forming composition prepared previously is dropped onto the first resin layer obtained up to the above (1), and the second resin layer is formed by spin coating. Formed.

(3) Concave formation step The second resin layer obtained up to the above (2) has a concavo-convex pattern of 70 nm line (convex width) / 140 nm space (aspect ratio: 1) (that is, convex part of 70 nm line) A quartz stamper is pressed at a pressure of 0.4 MPa for 120 seconds, irradiated with light of illuminance of 2.5 mW / cm with a high-pressure mercury lamp for 30 seconds, and then the stamper is detached to remove the second resin layer. A recess was formed on the surface.
When the cross section of the obtained concave portion was observed with a scanning electron microscope (manufactured by Hitachi Keiki Service Co., Ltd., model “S9380”), the concave portions having a substantially square cross section with a width of 70 nm and a depth of 70 nm were arranged at intervals of 140 nm. The concavo-convex pattern arranged in (1) was formed. The remaining film thickness (distance from the bottom surface of the recess to the bottom surface of the second resin layer) was 100 nm.

(4) Filling part forming step The previously prepared filling part forming composition is spin-coated on the second resin layer provided with the concave portions obtained up to the above (3), and 1 at 150 ° C. using a hot plate. Heated for minutes. Then, the excess part (part which protruded from the recessed part) formed with the composition for filling part formation was removed by etching back on fluorine conditions, and the filling part was formed in the recessed part of a 2nd resin layer.
When the cross section of the obtained filling portion was observed with a scanning electron microscope (manufactured by Hitachi Keiki Service Co., Ltd., model “S9380”), a substantially square cross-sectional shape having a width of 70 nm and a height of 70 nm was obtained without any defects in the concave portion. The filled portion had been filled at intervals of 140 nm.

(5) Etching Step The second resin layer and the first resin layer were etched by reactive ion etching (RIE) under oxygen conditions using the filling portion obtained up to (4) as a mask to form a pattern. When a cross section of the obtained pattern was observed with a scanning electron microscope (manufactured by Hitachi Keiki Service Co., Ltd., model “S9380”), a concave / convex pattern in which concave portions having a width of 70 nm × depth of 70 nm were arranged at intervals of 140 nm was obtained. I was able to get it.

[Comparative Example 1] Example using no first resin layer In Example 1, the first resin layer forming step (1) was not performed, and the second resin layer was formed directly on the substrate (that is, directly in contact with the substrate). Except for forming the second resin layer, a recess forming step (the remaining film thickness was also 100 nm) and a filling portion forming step were performed in the same manner as in Example 1. Then
A pattern was formed by etching the second resin layer by reactive ion etching (RIE) under an oxygen condition using the filling portion obtained so far as a mask. When the cross section of the obtained pattern was observed with a scanning electron microscope (manufactured by Hitachi Instruments Service Co., Ltd., model “S9380”), collapse of the pattern was observed.

  In addition, in this invention, it can restrict to what is shown to said specific Example, It can be set as the Example variously changed within the range of this invention according to the objective and the use.

10; Stamper, 11; Recess,
20; substrate,
31; first resin layer;
32; second resin layer, 321; recess,
33; Filling part, 33 ′; Filling part forming resin composition,
PR (1); first resin layer forming step,
PR (2); second resin layer forming step,
PR (3), PR (3-1), PR (3-2), PR (3-3); recess forming step,
PR (3-2 ′); exposure step,
PR (4-1), PR (4-2); filling portion forming step,
PR (5), PR (5-1), PR (5-2); etching process,
PR (6); substrate processing step,
PR (7); mask removing step.

That is, the present invention is as follows.
<1> a first resin layer forming step (1) for forming a first resin layer mainly composed of an organic polymer on a substrate;
A second resin layer forming step (2) for forming a second resin layer mainly composed of an organic polymer on the surface of the first resin layer;
A recess forming step (3) for forming a recess in the second resin layer by pressing and releasing a stamper having a protrusion on the second resin layer;
Forming a filling portion that forms a filling portion containing an inorganic polymer as a main component in the recess by applying the filling portion forming composition onto the second resin layer in which the recess is formed to form a film. Step (4);
An etching step (5) for etching the first resin layer and the second resin layer using the filling portion as a mask , and
The filling portion forming composition contains an inorganic polymer and a solvent,
The first resin layer is made of a material having an etching rate slower than that of the second resin layer,
In the recess forming step (3), the second resin layer is left in the thickness direction when the stamper is pressed .
<2> The pattern forming method according to <1>, wherein the inorganic polymer is polysiloxane.

According to the pattern forming method of the present invention, a pattern can be formed while suppressing peeling of the resist film. Further, a residual film in which the resist film is left in the recess formed in the recess forming step is formed, so that an adhesive surface between the first resin layer and the second resin layer is increased, and the resist film is peeled off (first film). The delamination between the first resin film and the second resin film) can be more effectively suppressed. That is, normally, when a process such as etching is performed using a pattern as a mask, the remaining film in the concave portion which is avoided functions advantageously in this method. Even if the film thickness of the remaining film in the recesses varies, the etching process in step (5) and the pattern obtained by this method are not affected, and precise control of the remaining film in the recesses is unnecessary. It is.
When the inorganic polymer is polysiloxane, it is possible to obtain better selectivity in etching the first resin layer and the second resin layer and the filling portion. Furthermore, since the flatness of the coating film when applied by spin coating is good, when an unnecessary filling portion forming resin layer (a layer made of filling portion forming resin) is removed from the first resin layer. Damage to the filling portion forming resin to be left in the recess can be minimized. Moreover, since it can harden | cure at moderate baking temperature, the damage by the heat | fever to the 1st resin layer can be suppressed.
Since the first resin layer is made of slow material etching rate than the second resin layer can be manufactured with high aspect ratio patterns by the case of processing the substrate filling portion as a mask. In addition, since processing can be performed under more severe conditions, throughput can be increased.

In the concave portion forming step, the pressing of the stamper, has such passed through the second resin layer. By leaving the second resin layer in the thickness direction without penetrating the second resin layer, the adhesion surface between the first resin layer and the second resin layer is increased, and the adhesion between them is increased, The resist peeling between the first resin film and the second resin film can be suppressed. Although the thickness (residual film thickness) of the bottom part of the recessed part formed without penetrating this 2nd resin layer is not specifically limited, 1 nm or more is preferable, 3-500 nm is more preferable, 5-150 nm is still more preferable.

This filling part is a part mainly composed of an inorganic polymer. The phrase “mainly composed of an inorganic polymer” means that the inorganic polymer is contained in an amount of 90% by mass or more (or 100% by mass) when the entire filling portion is 100% by mass. That is, in other words, it means that the organic polymer is not contained, or even if it is contained, it is less than 10% by mass.
This filling portion is a portion having an etching selectivity with respect to the first resin layer and the second resin layer mainly containing an organic polymer by containing an inorganic polymer as a main component. .
The inorganic polymer constituting the filling portion is a polymer whose skeleton is formed of an inorganic element. Examples of such inorganic elements include Si, Ti, Al, Zr and the like. Of these, Si is preferable, and the inorganic polymer is more preferably polysiloxane.
In addition, the filling part in this invention is formed using the composition for filling part formation containing an inorganic polymer and a solvent.
In particular, a filling part formed by using a composition for forming a filling part containing a polysiloxane containing a structural unit represented by the following formula (12) and a structural unit represented by the following formula (13) and a solvent. Preferably there is.

Filling unit, a filling unit forming composition is formed by forming a film by coating a second resin layer on which a recess is formed. The coating method in this case is not particularly limited, and examples thereof include appropriate means such as spin coating, cast coating, and roll coating. Furthermore, you may volatilize the solvent in a coating film by prebaking (PB) as needed. The prebaking heating conditions are appropriately selected depending on the composition of the filling portion forming composition, but the heating temperature is usually about 60 to 180 ° C, preferably 80 to 150 ° C. Further, the heating time is usually 10 to 300 seconds, preferably 30 to 180 seconds.

Furthermore, in this etching process, the etching rate for each of the first resin layer and the second resin layer has become different, the etching rate of the first resin layer is lower than the etching rate of the second resin layer [PR in Figure 2 (Refer to (5-1) to (5-2) ]. In this case, when processing the substrate to be processed, it is possible to form a pattern (mask) having better etching resistance (mask resistance).

Claims (3)

A first resin layer forming step (1) for forming a first resin layer mainly composed of an organic polymer on a substrate;
A second resin layer forming step (2) for forming a second resin layer mainly composed of an organic polymer on the surface of the first resin layer;
A recess forming step (3) for forming a recess in the second resin layer by pressing and releasing a stamper having a protrusion on the second resin layer;
A filling part forming step (4) for forming a filling part mainly composed of an inorganic polymer in the concave part;
An etching step (5) for etching the first resin layer and the second resin layer using the filling portion as a mask.   The pattern forming method according to claim 1, wherein the inorganic polymer is polysiloxane.   The pattern forming method according to claim 1, wherein the first resin layer is made of a material having an etching rate slower than that of the second resin layer.

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