KR20190039263A - Pattern forming method and semiconductor device manufacturing method - Google Patents

Abstract

A pattern forming method for improving the filling property of a curable composition for imprint on a substrate, and a method of manufacturing a semiconductor device using the pattern forming method. The pattern forming method includes the steps of forming a primer layer having a higher critical surface tension than the adhesive layer on the surface of the adhesion layer positioned on the substrate and a step of applying the curable composition for imprint to the surface of the primer layer .

Description

Pattern forming method and semiconductor device manufacturing method

The present invention relates to a pattern forming method and a semiconductor device manufacturing method.

The imprint method is a method of transferring a fine pattern onto a cured product by irradiating light through a light-transmissive mold or a light-transmissive substrate, photo-curing the curable composition for imprinting, and peeling the mold. Since this method enables imprinting at room temperature, it can be applied to the field of precision processing of ultrafine patterns such as fabrication of a semiconductor integrated circuit. Recently, new developments such as a nano-casting method combining the merits of both of them and a reverse imprint method of manufacturing a three-dimensional laminated structure have been reported.

Here, with the activation of the imprint method, the adhesion between the substrate and the curable composition for imprint was problematic. That is, in the imprint method, the curable composition for imprint is applied to the surface of the substrate, and light is irradiated in the state in which the mold is in contact with the surface of the substrate, thereby curing the curable composition for imprint and then peeling the mold. In the process, the cured product may be peeled from the substrate and adhere to the mold. This is considered to be due to the fact that the adhesion between the substrate and the cured product is lower than the adhesion between the mold and the cured product. In order to solve such a problem, it has been investigated to use an imprinting adhesion layer which improves adhesion between a substrate and a cured product (Patent Documents 1 to 3).

Patent Document 1: Japanese Published Patent Application No. 2009-503139 Patent Document 2: JP-A-2014-024322 Patent Document 3: JP-A-2014-192178

However, it has been found that when the curable composition for imprint is applied to the surface of the conventional adhesive layer, the filling property of the curable composition for imprint is inferior. Particularly, when the curable composition for imprint is applied by the ink jet (IJ) method, as shown in Fig. 2, when droplets of the curable composition for imprint 22 are dropped on the surface of the adhesive layer 21 at equal intervals, The droplet is diffused to the surface of the adhesion layer 21 to form a layered curable composition 22 for imprinting. However, if the wettability of the curable composition for imprint is low, the curable composition for imprint does not diffuse to the surface of the adhesive layer 21, and there is a case where a portion of the substrate not filled with the curable composition for imprint 22 remains . That is, improvement of the filling property of the curable composition for imprint on the substrate is required.

The object of the present invention is to provide a pattern forming method in which the filling property of a curable composition for imprint is improved on a substrate and a method of manufacturing a semiconductor device using the pattern forming method do.

Under the above-mentioned problems, the inventors of the present invention have conducted intensive studies, and as a result, discovered that the above problems can be solved by providing a primer layer having a high critical surface tension between the adhesive layer and the layer made of the curable composition for imprint.

Specifically, the above problem is solved by the following means <1>, preferably by <2> to <17>.

A method of manufacturing a semiconductor device, comprising the steps of: forming a primer layer having a critical surface tension higher than that of the adhesion layer on a surface of an adhesion layer positioned on a substrate; and applying a curable composition for imprint to a surface of the primer layer. Pattern formation method.

&Lt; 2 > The image forming method according to < 2 >, which comprises forming the primer layer using a composition for forming a primer layer containing a solvent, wherein the component constituting the adhesion layer is substantially not dissolved in a solvent contained in the composition for forming a primer layer &Lt; 1 &gt;.

<3> The pattern forming method according to <1> or <2>, wherein the component constituting the adhesion layer is not substantially thermally diffused to the primer layer.

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein at least one of the components constituting the primer layer has a functional group capable of forming at least one of hydrogen bonding and inter- Wherein the pattern forming method is a method of forming a pattern.

<5> A pattern forming method according to any one of <1> to <3>, wherein at least one of the components constituting the primer layer has a functional group capable of forming a hydrogen bond with a component constituting the adhesion layer .

&Lt; 6 > The liquid crystal display device according to < 6 >, wherein 95% by mass or more of the components constituting the primer layer is liquid at 25 [deg.] C and the contact angle of the component constituting the primer layer Is 5 DEG or less. &Lt; 5 > A pattern forming method according to any one of &lt; 1 &gt;

<7> The pattern forming method according to any one of <1> to <6>, wherein the viscosity of the curable composition for imprint at 23 ° C. is 8.0 mPa · s or less.

<8> The pattern forming method according to any one of <1> to <7>, wherein the surface tension of the curable composition for imprint at 25 ° C is 33 mN / m or more.

<9> The pattern forming method according to any one of <1> to <8>, wherein the primer layer satisfies at least one of A and B below.

A: a primer layer formed from a composition for forming a primer layer containing a component having a surface tension of at least 40 mN / m at 25 캜;

B: Critical surface tension of the primer layer at 25 캜 is 46 mN / m or more.

<10> The pattern forming method according to <9>, wherein the component having a surface tension of at least 40 mN / m at 25 ° C. is contained in a proportion of 20 mass% or more of the components constituting the primer layer.

<11> The composition according to any one of the above items, wherein the component having a surface tension of at least 40 mN / m at 25 ° C is a compound having a polyalkyleneglycol structure wherein the polyalkyleneglycol structure comprises a linear alkylene group and an oxygen atom And the pattern forming method according to < 9 >

<12> The pattern forming method according to any one of <9> to <11>, wherein at least one of the components having a surface tension of at least 40 mN / m at 25 ° C has no polymerizable group.

<13> The pattern forming method according to any one of <9> to <12>, wherein at least one of the components having a surface tension of at least 40 mN / m at 25 ° C is a liquid at 25 ° C.

<14> A pattern forming method according to any one of <9> to <13>, wherein 95% by mass or more of the components constituting the primer layer contained in the composition for forming a primer layer is a liquid at 25 ° C.

<15> The pattern forming method according to any one of <9> to <14>, wherein the component having a surface tension of at least 40 mN / m at 25 ° C has a weight average molecular weight of 200 or more and less than 1000.

<16> The pattern forming method according to any one of <1> to <15>, further comprising a step of providing the adhesion layer on a substrate.

<17> The pattern forming method according to any one of <1> to <16>, wherein the critical surface tension of the primer layer is higher than the critical surface tension of the adhesion layer by 5 mN / m or more.

<18> A method of manufacturing a semiconductor device, comprising the pattern forming method according to any one of <1> to <17>.

According to the present invention, it is possible to provide a pattern forming method in which the filling property of a curable composition for imprint is improved on a substrate, and a method of manufacturing a semiconductor device using the pattern forming method.

1 is a schematic view showing each step of a pattern forming method of the present invention.
Fig. 2 is a schematic diagram showing the wetting state of the curable composition for imprints when the curable composition for imprints is applied to the surface of a known adhesive layer by an ink-jet method.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, "~" is used to mean that the numerical values described before and after the numerical value are included as the lower limit value and the upper limit value.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate.

In this specification, the term "imprint " refers to pattern transfer of a size of preferably 1 nm to 10 mm, and more preferably, pattern transfer (nanoimprint) of a size of approximately 10 nm to 100 μm.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, the term "light" includes not only electromagnetic waves but also radiation of wavelengths in the ultraviolet, extrapolated, non-atomic, visible, and infrared regions. Radiation includes, for example, microwave, electron beam, extreme ultraviolet (EUV), and X-ray. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser can also be used. These lights may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light (composite light) having a plurality of different wavelengths.

The weight average molecular weight (Mw) in the present invention refers to that measured by gel permeation chromatography (GPC) unless otherwise specified.

The pattern forming method of the present invention includes the steps of forming a primer layer having a critical surface tension higher than that of the adhesion layer on the surface of the adhesion layer positioned on the substrate and a step of applying a curable composition for imprint to the surface of the primer layer The process comprising the steps of: With such a constitution, the curable composition for imprint can be diffused to the surface of the primer layer in a short time or easily, and the filling property of the curable composition for imprint on the substrate can be improved.

Hereinafter, the method of the present invention will be described with reference to Fig. Needless to say, the configuration of the present invention is not limited to Fig.

&Lt; Step of forming adhesion layer on substrate >

The pattern forming method of the present invention preferably includes a step of forming an adhesion layer on a substrate. However, when the substrate on which the adhesion layer is formed in advance is used is used, this step is not necessarily required.

In the embodiment shown in FIG. 1, the adhesion layer 12 is formed on the substrate 11. Although the adhesive layer 12 is formed on the surface of the substrate 11 in FIG. 1, another layer may be formed between the substrate 11 and the adhesive layer 12. For example, the surface of the substrate 11 may be subjected to a surface treatment.

The material of the substrate is not particularly limited and reference may be made to the description of paragraph 0103 of Japanese Laid-Open Patent Publication No. 2010-109092 (corresponding US application, US2011 / 199592), the content of which is incorporated herein by reference. Other than the above, a sapphire substrate, a silicon carbide substrate, a gallium nitride substrate, an aluminum substrate, an amorphous aluminum oxide substrate, a polycrystalline aluminum oxide substrate, and a substrate made of GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGaInP , Or ZnO. Specific examples of materials for the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In the present invention, a silicon substrate is preferable.

In the present invention, the critical surface tension of the adhesive layer at 25 캜 is preferably 30 mN / m or more, more preferably 40 mN / m or more. The upper limit value is not specifically defined, but is preferably 70 mN / m or less and 60 mN / m or less, for example. The critical surface tension in this specification is measured according to the method described in the following embodiments.

The lower limit of the thickness of the adhesive layer is preferably 0.1 nm or more, more preferably 0.5 nm or more, and further preferably 1 nm or more. The upper limit of the thickness of the adhesion layer is preferably 20 nm or less, more preferably 15 nm or less, and further preferably 10 nm or less.

The adhesion layer is usually formed by applying a composition for forming an adhesion layer on a substrate. More specifically, a thin film is formed by applying a composition for forming an adhesion layer on a substrate, then volatilizing (drying) the solvent by heat or light irradiation, and / or curing the adhesion layer. As a method for applying the composition for forming the adhesion layer, there is no particular limitation, and reference may be made to the description of paragraph 0102 of Japanese Patent Laid-Open Publication No. 2010-109092 (corresponding US application, US2011 / 199592) Is used. In the present invention, a spin coat method or an ink jet method is preferable.

As the composition for forming the adhesion layer, a composition containing a component constituting the adhesion layer and a solvent is preferable.

As the component constituting the adhesive layer, a resin is preferable, a resin containing an ethylenic unsaturated group is more preferable, and an acrylic resin having an ethylenic unsaturated group in a side chain is more preferable. Specific examples of the resin constituting the adhesive layer include resins included in the composition for forming an adhesion layer described in Examples to be described later, resin (A) described in paragraphs 0017 to 0057 described in JP-A No. 2014-024322, (A2) are exemplified. The weight average molecular weight of the resin is preferably from 3,000 to 25,000. The component constituting the adhesion layer may contain additives other than the resin. However, the component constituting the adhesive layer in the present invention is preferably 70% by mass or more, and more preferably 80% by mass or more.

It is preferable that at least one of the components constituting the adhesion layer has a functional group capable of forming at least one of the components constituting the primer layer and the interaction between the hydrogen bond and the ion in order to secure the stability of the primer layer . Examples of the functional group include a hydroxyl group, an amino group, a carbonyl group, and a carboxyl group. Such a functional group is preferably contained in the resin.

With such a constitution, the adhesion layer and the primer layer are fixed by hydrogen bonding and / or ion interactions. This makes it possible to ensure coating uniformity of the primer layer and suppress surface roughness such as aggregation. Further, it is possible to more effectively inhibit the component constituting the adhesive layer from moving to a pattern which is a cured product of the imprinting curable composition or the imprinting curable composition provided as a primer layer or an upper layer thereof. As a result, a material capable of increasing the fixation force between the pattern and the mold is hardly present in the vicinity of the pattern, and the mold releasability of the pattern can be improved.

The component constituting the adhesive layer means a component contained in the adhesive layer. For example, a component obtained by removing the solvent from the composition for forming an adhesion layer, and the like. Similarly, the component constituting the primer layer means a component contained in the primer layer. For example, a component obtained by removing a solvent from a composition for forming a primer layer described later, and the like.

In the present invention, it is preferable that at least one (preferably all) of the components constituting the adhesive layer is substantially not dissolved in the solvent contained in the composition for forming a primer layer. With such a constitution, when forming the primer layer, the components constituting the adhesion layer are less likely to be incorporated into the primer layer, and the mold releasability of the pattern is not deteriorated. The term "substantially not soluble" means that the adhesive layer component eluted into the primer layer at the time of forming the primer layer is 10 mass% or less of the total primer layer-forming component. With such a constitution, the deterioration of the mold releasability can be effectively suppressed.

In the present invention, it is preferable that the component constituting the adhesion layer is a component which is not substantially thermally diffused into the primer layer. After the primer layer is formed on the surface of the adhesive layer, the adhesive layer may be heated together with the primer layer or the like. However, if the components constituting the adhesive layer are thermally diffused in the heating step, May be exacerbated. In the present invention, this is avoided by using a component which is not substantially thermally diffused into the primer layer as a component constituting the adhesion layer. The phrase "substantially not thermally diffused" means that the adhesion layer component eluted into the primer layer after forming the primer layer is 10% by mass or less of the total primer layer-forming component. With such a constitution, the deterioration of the mold releasability can be effectively suppressed.

As the heating in the present invention, it is also possible to use heating for drying the solvent contained in the composition for forming a primer layer when forming the primer layer, and for heating the curable composition for imprint to increase the reactivity of the curable composition for imprint Heating and the like are exemplified. The heating temperature is, for example, 50 to 200 占 폚, preferably 80 to 150 占 폚.

As the solvent which may be blended in the composition for forming the adhesion layer, there is exemplified the solvent described in paragraph 0059 of JP-A No. 2014-024322, the content of which is incorporated herein.

The composition for forming the adhesive layer used in the present invention preferably contains 0.001 to 2.0% by mass of the component constituting the adhesive layer and 98.0 to 99.999% by mass of the solvent. The component constituting the adhesive layer is preferably 0.05 to 0.5 By mass and 99.95 to 99.5% by mass of the solvent.

The components and the solvent constituting the adhesive layer may be contained in only one kind or two or more kinds respectively in the composition for forming the adhesive layer. When two or more of them are contained, the total amount is preferably in the above range.

Specific examples of the composition for forming the adhesion layer include (meth) acrylic resin (A) having an ethylenic unsaturated group (P) and a nonionic hydrophilic group (Q) described in JP-A No. 2014-024322 and having a weight average molecular weight of 1,000 or more, (B), and the acid value of the resin (A) is less than 1.0 mmol / g. The content of Japanese Patent Laid-Open Publication No. 2014-024322 is hereby incorporated by reference.

In addition, reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2014-024322 for the preparation of the composition for forming the adhesion layer and the formation method of the adhesion layer using the composition for forming the adhesion layer, and these contents are incorporated herein by reference .

&Lt; Step of forming, on the surface of the adhesion layer, a primer layer having a higher critical surface tension than the adhesion layer &

In the present invention, on the surface of the adhesion layer 12, a primer layer 13 having a higher critical surface tension than the adhesion layer is formed. By forming such a primer layer, the filling property of the curable composition for imprint on the substrate can be improved.

The critical surface tension of the primer layer at 25 캜 is preferably higher than the critical surface tension of the adhesion layer, more preferably at least 2 mN / m, more preferably at least 3 mN / m, even more preferably at least 5 mN / m Is more preferable. The upper limit of the difference in critical surface tension between the primer layer and the adhesive layer is preferably 20 mN / m or less, more preferably 15 mN / m or less, and most preferably 10 mN / m or less. Within the above range, the effect of improving the uniformity and wettability of the film at the time of forming the primer layer can be improved more effectively.

The thickness of the primer layer is preferably 0.1 nm or more, more preferably 0.5 nm or more, and more preferably 1 nm or more. The upper limit of the thickness of the primer layer is preferably 20 nm or less, more preferably 15 nm or less, and even more preferably 10 nm or less.

In the present invention, the primer layer is usually formed using a composition for forming a primer layer. The composition for forming a primer layer preferably includes a solvent. Specifically, a composition for forming a primer layer is applied to the surface of the adhesion layer, and then the solvent is volatilized by heat or light irradiation to form a thin film. As a method of applying the composition for forming a primer layer, there is no particular limitation, and reference may be made to the description of paragraph 0102 of Japanese Patent Laid-Open Publication No. 2010-109092 (corresponding US application, US2011 / 199592) Is used. In the present invention, a spin coat method or an ink jet method is preferable.

When a composition for forming an adhesion layer containing a solvent is used at the time of forming the adhesion layer, the primer layer is formed by evaporating (drying) the solvent from the composition for forming the adhesion layer and / or curing the adhesion layer, It is preferable to apply the composition for layer formation. By such a constitution, components constituting the primer layer are dissolved in the solvent contained in the composition for forming the adhesion layer, and mixing of the adhesion layer and the primer layer can be effectively inhibited.

In addition, the preparation of the composition for forming the primer layer, the method of forming the primer layer formed of the composition for forming the primer layer, and the like can be performed in the same manner as the preparation of the composition for forming the adhesion layer and the formation of the adhesion layer.

In the present invention, in particular, the primer layer is formed using a composition for forming a primer layer containing a solvent, and the component constituting the adhesion layer is substantially dissolved in a solvent contained in the composition for forming a primer layer . By such a constitution, the deterioration of the mold releasability due to the incorporation of the adhesive layer component into the primer layer can be suppressed more effectively.

In the present invention, as described above, at least one (preferably all) of the components constituting the primer layer can form at least one of hydrogen bonding and ion interactions with the component constituting the adhesion layer It is preferable to have a functional group having a functional group. Examples of the functional group that the component constituting the primer layer may have include a hydroxyl group, an amino group, a carbonyl group, and a carboxyl group, and a hydroxyl group is preferable.

Also, 95% by mass or more (preferably 98% by mass or more, and more preferably 99% by mass or more) of the components constituting the primer layer is liquid at 25 占 폚, It is preferable that the contact angle at the surface of the adhesion layer at 25 占 폚 is 5 占 or less. The contact angle was measured according to the method described in the following Examples. With such a constitution, the primer layer can be more uniformly formed on the adhesive layer, and the filling property of the curable composition for imprinting can be made more uniform.

It is preferable that the component constituting the primer layer is compatible with the curable composition for imprinting. Here, commercial means that the components constituting the primer layer are sufficiently dissolved in the curable composition for imprint, so that there is no clear interface between the primer layer and the curable composition for imprint. As such, when the primer layer is used in the curable composition for imprint, a part of the curable composition for imprint is diffused into the primer layer when the imprint curable composition is filled, and the adhesion with the adhesive layer is formed, Can be effectively suppressed.

In the present invention, it is preferable that the primer layer satisfies at least one of A and B below.

A: a primer layer formed from a composition for forming a primer layer containing a component having a surface tension of at least 40 mN / m at 25 캜;

B: Critical surface tension of the primer layer at 25 캜 is 46 mN / m or more.

The primer layer formed of the composition for forming a primer layer is usually a liquid film, but may be a solid film within the scope of the present invention.

The component having a surface tension of 40 mN / m or more at 25 DEG C in the present invention preferably has a surface tension of 40 to 70 mN / m. By such a constitution, a primer layer having a high critical surface tension can be obtained. The surface tension was measured according to the method described in the following Examples.

In the present invention, the critical surface tension of the primer layer is preferably 46 mN / m or more. By such a constitution, the wettability of the curable composition for imprints applied to the surface of the primer layer is improved, and the filling property can be enhanced. The critical surface tension is measured according to the method described in the following Examples.

In the present invention, the critical surface tension of the primer layer formed of the composition for forming a primer layer is preferably 47 mN / m or more, and more preferably 48 mN / m or more. The upper limit of the critical surface tension of the primer layer is not particularly limited, but is preferably 70 mN / m or less, may be 65 mN / m or less, and may be 60 mN / m or less.

The composition for forming the primer layer preferably contains a component having a surface tension of at least 40 mN / m at 25 DEG C in a proportion of 20 mass% or more of the components constituting the primer layer, preferably 51 mass% or more More preferably 80% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, more preferably 99% by mass or more Is most preferable.

The composition for forming a primer layer may contain only one component having a surface tension of at least 40 mN / m at 25 占 폚, or may contain two or more components. When two or more of them are contained, the total amount is preferably in the above range.

In the present invention, as a component constituting the primer layer, a compound having a polyalkyleneglycol structure and the polyalkylene glycol structure is composed of linear alkylene groups and oxygen atoms (hereinafter referred to as "PEG" In some cases). The straight-chain alkylene group is preferably an alkylene group of 1 to 10 carbon atoms, more preferably an alkylene group of 1 to 5 carbon atoms, more preferably an alkylene group of 1 to 3 carbon atoms, and an alkylene group of 2 or 3 carbon atoms More preferably an alkylene group having 2 carbon atoms is particularly preferable. That is, in the present invention, the component constituting the primer layer preferably contains a compound having a polyethylene glycol structure.

PEG and the like preferably contain 3 to 50 alkylene glycol units. PEG or the like may be a component having a surface tension of 40 mN / m or more at 25 占 폚 or a component having a surface tension of less than 40 mN / m at 25 占 폚, but a component having a surface tension of 25 mN / .

When PEG or the like is a component having a surface tension of 40 mN / m or more at 25 캜, it preferably contains 3 to 20 alkylene glycol units, more preferably 5 to 17.

When the critical surface tension of the primer layer at 25 캜 is 46 mN / m or more, the composition for forming the primer layer is preferably a polyalkyleneglycol structure having a straight chain alkylene group and oxygen atom And the number of alkylene glycol units is preferably from 21 to 50, more preferably from 22 to 45.

PEG and the like may contain a structure other than a polyalkyleneglycol structure. However, PEG or the like is preferably composed of a polyalkyleneglycol structure by removing the terminal group. That is, PEG and the like are preferably represented by "a polyalkylene glycol structure-terminal group composed of an end-group-straight chain alkylene group and an oxygen atom". The terminal group here is preferably a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group. The number of carbon atoms of the alkyl group and the alkyl chain of the alkoxy group is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.

Specific examples of PEG and the like include compounds used in Examples described later.

In the present invention, as described above, it is preferable that at least one of the components constituting the primer layer has a functional group capable of forming at least one of a component constituting the adhesion layer and a hydrogen bond and ion interactions, It is preferable that such a functional group has a surface tension of at least 40 mN / m at 25 캜. Particularly, when the component having a surface tension of at least 40 mN / m at 25 ° C is PEG or the like, one or both of the terminal groups may form at least one of hydrogen bonding and ion interactions with components constituting the adhesion layer (Preferably a hydroxyl group, an amino group, a carbonyl group, a carboxyl group or the like, more preferably a hydroxyl group).

In the present invention, the component having a surface tension of at least 40 mN / m at 25 캜 may be a compound other than PEG or the like. Examples thereof include polyhydric alcohols such as glycerol, ionic polymers such as polyvinyl alcohol, polyvinylacetamide and polystyrenesulfonic acid.

In the present invention, it is preferable that the composition for forming a primer layer contains a component other than PEG or the like having a surface tension of at least 40 mN / m at 25 DEG C and a PEG having a surface tension of less than 40 mN / m at 25 DEG C .

In the present invention, it is preferable that at least one (preferably all) of the components having a surface tension of not less than 40 mN / m at 25 DEG C does not have a polymerizable group. With such a configuration, mold releasability can be further improved.

In the present invention, it is preferable that at least one of the components having a surface tension of at least 40 mN / m at 25 占 폚 is a liquid at 25 占 폚. It is more preferable that 95% by mass or more (preferably 98% by mass or more, and more preferably 99% by mass or more) of the components constituting the primer layer is liquid at 25 占 폚. By using a liquid, the surface roughness of the primer layer can be more effectively reduced.

In the present invention, the weight average molecular weight of at least one (preferably all) of the components having a surface tension of at least 40 mN / m at 25 캜 is preferably 200 or more and less than 1,000, and more preferably 300 or more and less than 800. By such a constitution, the compatibility of the component constituting the primer layer and the curable composition for imprint is improved.

In addition to the above, components constituting the primer layer may include a polymerizable compound.

The polymerizable compound may be a monofunctional polymerizable compound or a multifunctional polymerizable compound, preferably a multifunctional polymerizable compound, more preferably a 2 to 4 functional polymerizable compound, a bifunctional or trifunctional polymerizable compound Is more preferable. Specific examples of the polymerizable compound include polymerizable compounds which may be contained in a curable composition for imprint described later.

The upper limit of the content of the polymerizable compound in the components constituting the primer layer is preferably 50 mass% or less, and more preferably 20 mass% or less. The lower limit value of the content of the polymerizable compound is preferably 10% by mass or more when blended.

The composition for forming a primer layer may contain only one kind of polymerizable compound or two or more kinds of the polymerizable compound. When two or more of them are contained, the total amount is preferably in the above range.

In the present invention, the composition for forming a primer layer preferably includes a solvent. By including a solvent, application is possible. The solvent is preferably a solvent having at least one of an ester group, a carbonyl group, a hydroxyl group and an ether group. Specific examples of the solvent include propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclohexanone, 2-heptanone,? -Butyrolactone, butyl acetate, propylene glycol mono Methyl ether, and ethyl lactate. Of these, PGMEA,? -Butyrolactone and cyclohexanone are more preferable, and PGMEA is particularly preferable.

The solvent contained in the composition for forming the adhesion layer and the solvent contained in the composition for forming the primer layer are preferably different solvents.

In the present invention, the composition for forming a primer layer preferably contains 0.001 to 2.0% by mass of a constituent of the primer layer and 98.0 to 99.999% by mass of a solvent, more preferably 0.05 to 0.5% by mass of a constituent of the primer layer And more preferably 99.95 to 99.5 mass% of the solvent. The component constituting the primer layer preferably contains a component having a surface tension of at least 40 mN / m at 25 DEG C and contains a component having a surface tension of at least 40 mN / m at 25 DEG C in a proportion of 99 mass% Is more preferable.

The component and the solvent constituting the primer layer may be contained in only one kind or two or more kinds respectively in the composition for forming a primer layer. When two or more of them are contained, the total amount is preferably in the above range.

&Lt; Step of applying the curable composition for imprint to the surface of the primer layer >

The present invention includes a step of applying a curable composition for imprint (14) to the surface of a primer layer (13) as shown in Fig. As a method of applying the curable composition for imprint, there is no particular limitation, and reference may be made to paragraph 0102 of Japanese Patent Laid-Open Publication No. 2010-109092 (corresponding US application, US2011 / 199592), which is incorporated herein by reference do. The application is preferably carried out by an inkjet method. The curable composition for imprint may be applied by multiple application. In the method of disposing droplets on the surface of the primer layer by the ink-jet method or the like, the amount of droplets is preferably about 1 to 20 pL, and it is preferable to arrange the droplets on the surface of the primer layer with a droplet gap therebetween. The interval of the droplet is preferably 10 to 1000 mu m. In the case of the inkjet method, the liquid droplet interval is set as the arrangement interval of the inkjet nozzles.

The volume ratio of the layered impregnation curable composition 14 to the primer layer 13 when applied to the substrate is preferably 1: 1 to 500, more preferably 1: 10 to 300 , More preferably from 1: 50 to 200.

&Lt; Pattern formation >

In the pattern forming method of the present invention, the step of curing the curable composition for imprints by irradiating light in a state where the curable composition for imprint, the primer layer and the adhesive layer are placed between the substrate and the mold having the pattern, It is preferable to further include a step. By performing such a process, for example, as shown in Fig. 1, a pattern 15 is obtained.

Specifically, in order to transfer a desired pattern to the layered imprinting curable composition, the mold is pressed (pressed) onto the surface of the layered imprinting curable composition. As a result, a fine pattern previously formed on the pressing surface of the mold can be transferred to the curable composition for imprinting in the form of a layer.

The mold may be a light-transmissive mold or a light-transmissive mold. When a light-transmissive mold is used, it is preferable to irradiate light from the mold side. On the other hand, in the case of using a light-transmissive mold, it is preferable to use a light-transmissive substrate as the substrate and irradiate light from the substrate side. In the present invention, it is more preferable to use a light-transmissive mold to irradiate light from the mold side.

The mold usable in the present invention is a mold having a pattern to be transferred. The pattern on the mold can be patterned according to the desired processing precision, for example, by photolithography, electron beam lithography, etc. In the present invention, the mold pattern forming method is not particularly limited. The pattern formed by the pattern forming method of the present invention may also be used as a mold.

The material constituting the light transmissive mold used in the present invention is not particularly limited, but may be glass, quartz, light-permeable resin such as polymethyl methacrylate (PMMA), polycarbonate resin, transparent metal vapor deposition film, A photocurable film, a metal film, and the like.

In the present invention, the non-light-transmitting mold material used when a light-transmitting substrate is used is not particularly limited, but any material having a predetermined strength may be used. Specifically, a ceramic substrate, a vapor deposition film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, a substrate such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, or amorphous silicon is exemplified It is not constrained.

In the pattern forming method of the present invention, when the imprint lithography is performed using the curable composition for imprinting, it is preferable that the mold pressure is 10 atm or less. When the mold pressure is 10 atm or less, the mold or the substrate is hardly deformed, and the pattern accuracy tends to be improved. In addition, it is also preferable that the device is reduced because the pressure is low. The mold pressure is preferably selected from a range capable of securing the uniformity of the mold transfer within a range in which the residual film of the curable composition for imprinting of the convex portions of the mold is reduced.

In the pattern forming method of the present invention, the irradiation amount of the light irradiation in the step of irradiating the light to the imprinting curable composition may be sufficiently larger than the minimum irradiation amount necessary for curing. The amount of irradiation necessary for curing is appropriately determined by examining the amount of unsaturated bonds in the curable composition for imprint.

In the imprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually carried out at room temperature, but light irradiation may be performed while heating to increase the reactivity. As a preliminary stage of light irradiation, light irradiation in a vacuum state can be carried out because it is effective in preventing air bubble mixing, suppressing a decrease in reactivity due to oxygen incorporation, and improving adhesion between the mold and the curable composition for imprint. In the pattern forming method of the present invention, the preferred degree of vacuum at the time of light irradiation ranges from 10 &lt; ^-1 &gt; Pa to atmospheric pressure.

At the time of exposure, it is preferable that the exposure light intensity is in the range of 1 mW / cm ² to 500 mW / cm ² .

The pattern forming method of the present invention may include a step of curing the layered curable composition for imprint (pattern formation layer) by light irradiation, and then, if necessary, curing the layer by applying heat to the cured pattern . The temperature for heating and curing the imprinting curable composition after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C. The time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.

Next, the curable composition for imprint used in the present invention will be described.

The curable composition for imprint used in the present invention is not specifically defined, and a known curable composition for imprint can be used.

In the present invention, it is preferable that the viscosity of the curable composition for imprint is low and the surface tension is designed to be high in order to enable rapid charging by using the capillary force.

Specifically, the viscosity of the curable composition for imprints at 23 ° C is preferably 20.0 mPa · s or less, more preferably 15.0 mPa · s or less, even more preferably 10.0 mPa · s or less, and more preferably 8.0 mPa · s Or less. The lower limit of the viscosity is not particularly limited, but may be 5.0 mPa · s or more, for example.

The surface tension of the curable composition for imprints at 25 캜 is preferably 30 mN / m or more, more preferably 33 mN / m or more. By using the curable composition for imprints having a high surface tension, the capillary force is increased, and rapid charging of the curable composition for imprint to the mold pattern becomes possible. The upper limit of the surface tension is not particularly limited, but is preferably 40 mN / m or less from the viewpoint of imparting ink-jet aptitude.

In the present invention, by using the primer layer, it is possible to improve the wettability of the curable composition for imprint with high surface tension, which has a high capillary force and a good filling property with respect to the mold pattern but has poor wettability with the adhesive layer. Is high.

The surface tension of the curable composition for imprints at 25 캜 is measured according to the method described in the following Examples.

The type and the like of the curable composition for imprint used in the present invention are not specifically defined, but preferably include a polymerizable compound and a photopolymerization initiator. It may also contain a sensitizer, a release agent, an antioxidant, a polymerization inhibitor, a solvent, and the like.

The polymerizable compound contained in the curable composition for imprints used in the present invention may be a monofunctional polymerizable compound, a polyfunctional polymerizable compound or a mixture of both. It is preferable that at least a part of the polymerizable compounds contained in the curable composition for imprint is a liquid at 25 占 폚. By including the polymerizable compound which is liquid at 25 占 폚 in this way, the viscosity of the curable composition for imprinting can be lowered even if the curable composition for imprint does not substantially contain a solvent, so that it can be applied by the inkjet method. Here, the term substantially containing no solvent means, for example, that the content of the solvent in the curable composition for imprint is 5% by mass or less, more preferably 3% by mass or less, and particularly 1% by mass or less.

The curable composition for imprints used in the present invention is preferably a polymer (preferably a polymer having a weight average molecular weight of more than 1,000, more preferably a weight average molecular weight of more than 2,000, more preferably a weight average molecular weight of 10,000 or more Polymer) may be substantially not contained. The term substantially containing no polymer means, for example, that the content of the polymer is 0.01 mass% or less of the curable composition for imprint, preferably 0.005 mass% or less, and more preferably, no content.

The kind of the monofunctional polymerizable compound used in the curable composition for imprinting is not specifically defined unless it is within the scope of the present invention.

The monofunctional polymerizable compound used in the curable composition for imprint preferably has a linear or branched hydrocarbon hydrocarbon chain having 4 or more carbon atoms. In the present invention, the monofunctional polymerizable compound may be contained singly or two or more monofunctional polymerizable compounds may be contained.

The molecular weight of the monofunctional polymerizable compound used in the curable composition for imprint is preferably 100 or more, more preferably 200 or more, and still more preferably 220 or more. The upper limit of the molecular weight is preferably 1,000 or less, more preferably 800 or less, still more preferably 300 or less, and particularly preferably 270 or less. When the lower limit of the molecular weight is 200 or more, the volatility tends to be suppressed. When the upper limit of the molecular weight is 300 or less, the viscosity tends to be reduced.

The monofunctional polymerizable compound used in the imprinting curable composition preferably has a boiling point of 85 캜 or higher, more preferably 110 캜 or higher, and more preferably 130 캜 or higher at 667 Pa. By setting the boiling point at 667 Pa to 85 占 폚 or higher, volatility can be suppressed. The upper limit of the boiling point is not particularly limited, but the boiling point at 667 Pa can be set at 200 캜 or lower, for example.

The kind of the polymerizable group of the monofunctional polymerizable compound used in the curable composition for imprint is not specifically defined, but examples thereof include an ethylenically unsaturated bond-containing group, an epoxy group and the like, and an ethylenically unsaturated bond-containing group is preferable. Examples of the ethylenically unsaturated bond-containing group include (meth) acryl group, vinyl group and the like, more preferably a (meth) acryl group, and more preferably an acryl group. The (meth) acryl group is preferably a (meth) acryloyloxy group.

The kind of the atoms constituting the monofunctional polymerizable compound used in the curable composition for imprint is not particularly limited but is preferably composed of only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom and a halogen atom, And it is more preferable that it consists of only atoms selected from atoms and hydrogen atoms.

The monofunctional polymerizable compound used in the curable composition for imprint preferably has a linear or branched hydrocarbon hydrocarbon chain having 4 or more carbon atoms. In the present invention, the hydrocarbon chain represents an alkyl chain, an alkene chain, or an alkene chain, preferably an alkyl chain or an alkene chain, and more preferably an alkyl chain.

In the present invention, the alkyl chain represents an alkyl group and an alkylene group. Likewise, the alkenic chain represents an alkenylene group and an alkenylene group, and an alkenylene chain represents an alkenylene group and an alkenylene group. Among them, a straight-chain or branched alkyl group or an alkenyl group is more preferable, and a straight-chain or branched alkyl group is more preferable, and a straight-chain alkylene group is more preferable.

The straight-chain or branched hydrocarbon radical (preferably an alkyl group) preferably has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 or more carbon atoms, more preferably 10 or more carbon atoms, desirable. The upper limit of the number of carbon atoms is not particularly limited, but may be, for example, 25 or less.

The straight-chain or branched hydrocarbon hydrocarbon chain may contain an ether group (-O-), but it is preferable that the hydrocarbon group does not include an ether group from the viewpoint of improvement in releasability.

By using such a monofunctional polymerizable compound having a hydrocarbon radical, the modulus of elasticity of the cured film is reduced with a relatively small addition amount, and the releasability is improved. In addition, when a monofunctional polymerizable compound having a straight chain or branched alkyl group is used, the interfacial energy of the mold and the cured film can be reduced, and further the releasability can be improved.

Preferable hydrocarbon groups of the monofunctional polymerizable compound used in the curable composition for imprint include (1) to (3).

(1) a straight chain alkyl group having 8 or more carbon atoms

(2) a branched alkyl group having a carbon number of 10 or more

(3) an alicyclic ring or an aromatic ring substituted with a linear or branched alkyl group having 5 or more carbon atoms

(1) a straight chain alkyl group having 8 or more carbon atoms

The straight-chain alkyl group having 8 or more carbon atoms is more preferably a carbon number of 10 or more, still more preferably 11 or more carbon atoms, and particularly preferably 12 or more carbon atoms. The number of carbon atoms is preferably 20 or less, more preferably 18 carbon atoms or less, more preferably 16 carbon atoms or less, and particularly preferably 14 carbon atoms or less.

(2) a branched alkyl group having a carbon number of 10 or more

The branched alkyl group having 10 or more carbon atoms is preferably 10 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, more preferably 10 to 14 carbon atoms, and particularly preferably 10 to 12 carbon atoms.

(3) an alicyclic ring or an aromatic ring substituted with a linear or branched alkyl group having 5 or more carbon atoms

The straight-chain or branched alkyl group having 5 or more carbon atoms is more preferably a straight-chain alkylene group. The number of carbon atoms in the alkyl group is preferably at least 6, more preferably at least 7, and even more preferably at least 8. The number of carbon atoms in the alkyl group is preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less.

The ring structure of the alicyclic or aromatic ring may be monocyclic or bicyclic, but is preferably monocyclic. In the case of axial ring, the number of rings is preferably two or three. The ring structure is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring. The ring structure is an alicyclic or aromatic ring, but it is preferably an aromatic ring. Specific examples of the ring structure include, but are not limited to, cyclohexane ring, norbornene ring, isobornene ring, tricyclodecane ring, tetracyclododecane ring, adamantane ring, benzene ring, naphthalene ring, anthracene ring, Among them, a cyclohexane ring, a tricyclodecane ring, an adamantane ring and a benzene ring are more preferable, and a benzene ring is more preferable.

The monofunctional polymerizable compound used in the curable composition for imprints is preferably a compound in which a linear or branched hydrocarbon hydrocarbon group having 4 or more carbon atoms and a polymerizable group are bonded directly or via a linking group. And a compound in which any one of the groups is directly bonded to the polymerizable group is more preferable. As the linking group, -O-, -C (= O) -, -CH ₂ -, or a combination thereof is exemplified. As the monofunctional polymerizable compound used in the present invention, (1) a linear alkyl (meth) acrylate in which a linear alkyl group having at least 8 carbon atoms and a (meth) acryloyloxy group are directly bonded is particularly preferable.

Examples of the monofunctional polymerizable compound used in the curable composition for imprint include the following first and second groups. However, it is needless to say that the present invention is not limited to these. The first group is more preferable than the second group.

Group 1

[Chemical Formula 1]

Group 2

(2)

The amount of the monofunctional polymerizable compound used in the curable composition for imprint to the entire polymerizable compound in the imprinting curable composition is more than 5 mass% and less than 30 mass%. The lower limit value is preferably 6 mass% or more, more preferably 8 mass% or more, further preferably 10 mass% or more, and particularly preferably 15 mass% or more. The upper limit value is more preferably 29 mass% or less, still more preferably 27 mass% or less, and particularly preferably 25 mass% or less. When the amount of the monofunctional polymerizable compound is 6 mass% or more with respect to the total polymerizable compound, the releasability can be improved, and defects and mold breakage can be suppressed at the time of releasing the mold. In addition, by setting the content to 29 mass% or less, the Tg of the cured film of the curable composition for imprint can be increased, and the etching processability, particularly the pattern bending during etching, can be suppressed.

In the present invention, a monofunctional polymerizable compound other than the monofunctional polymerizable compound may be used as long as it does not deviate from the object of the present invention, or a monofunctional polymerizable compound in the polymerizable compound described in Japanese Patent Laid-open Publication No. 2014-170949 And these contents are included in this specification.

In the present invention, it is preferable that 90% by mass or more of the entire monofunctional polymerizable compound contained in the curable composition for imprint is a monofunctional polymerizable compound having the groups (1) to (3), and 95% More preferable.

The multifunctional polymerizable compound used in the curable composition for imprint is not particularly limited, but it preferably contains at least one of an alicyclic structure and an aromatic ring structure and has a viscosity at 25 캜 of 150 mPa s or less. Such a compound may be referred to as a cyclic structure-containing polyfunctional polymerizable compound in the following description. In the present invention, by using the cyclic structure-containing polyfunctional polymerizable compound, it is possible to more effectively suppress the etching property, particularly, the disconnection of the pattern after etching. This is presumably because the etching selectivity ratio with respect to the object to be processed (for example, Si, Al, Cr, or an oxide thereof) at the time of etching is further improved.

The curable composition for imprints may contain only one kind of cyclic structure-containing polyfunctional polymerizable compound, or may contain two or more kinds.

The molecular weight of the cyclic structure-containing polyfunctional polymerizable compound used in the curable composition for imprints is preferably 1,000 or less, more preferably 800 or less, further preferably 500 or less, still more preferably 350 or less, desirable. When the upper limit of the molecular weight is 1,000 or less, the viscosity tends to be reduced.

The lower limit of the molecular weight is not particularly limited, but may be 200 or more, for example.

The number of polymerizable groups in the cyclic structure-containing polyfunctional polymerizable compound used in the imprinting curable composition is preferably 2 or more, preferably 2 to 7, more preferably 2 to 4, still more preferably 2 or 3, and 2 Is particularly preferable.

The kind of the polymerizable group of the cyclic structure-containing polyfunctional polymerizable compound used in the curable composition for imprint is not specifically defined, but examples thereof include an ethylenically unsaturated bond-containing group, an epoxy group and the like, and an ethylenically unsaturated bond-containing group is preferable. Examples of the ethylenically unsaturated bond-containing group include (meth) acryl group, vinyl group and the like, more preferably a (meth) acryl group, and more preferably an acryl group. The (meth) acryl group is preferably a (meth) acryloyloxy group. May contain two or more polymerizable groups in one molecule or two or more polymerizable groups of the same kind.

The type of the atoms constituting the cyclic structure-containing polyfunctional polymerizable compound used in the curable composition for imprint is not particularly limited, but is preferably composed of only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom and a halogen atom, And is more preferably composed of atoms selected from atoms, oxygen atoms and hydrogen atoms.

The ring structure contained in the cyclic structure-containing polyfunctional polymerizable compound used in the curable composition for imprint may be monocyclic or bicyclic, but is preferably monocyclic. In the case of axial ring, the number of rings is preferably two or three. The ring structure is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring. The ring structure may be an alicyclic or aromatic ring, but it is preferably an aromatic ring. Specific examples of the ring structure include, but are not limited to, cyclohexane ring, norbornene ring, isobornene ring, tricyclodecane ring, tetracyclododecane ring, adamantane ring, benzene ring, naphthalene ring, anthracene ring, Among them, a cyclohexane ring, a tricyclodecane ring, an adamantane ring and a benzene ring are more preferable, and a benzene ring is more preferable.

The number of ring structures in the cyclic structure-containing polyfunctional polymerizable compound used in the curable composition for imprints may be one or two or more, preferably one or two, and more preferably one. In the case of condensed rings, condensed rings are regarded as one.

The cyclic structure-containing multifunctional polymerizable compound used in the curable composition for imprints may be a (polymerizable group) - (a single bond or a divalent linking group) - (a divalent group having a ring structure) - (a single bond or a divalent linking group) Polymerizable group). Here, as the linking group, an alkylene group is more preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable.

The cyclic structure-containing polyfunctional polymerizable compound used in the curable composition for imprint is preferably represented by the following general formula (1).

(3)

In the general formula (1), Q represents a divalent group having an alicyclic structure or an aromatic ring structure.

The preferable range of the alicyclic or aromatic ring (ring structure) in Q is the same as the above, and the preferable range is also the same.

Examples of the multifunctional polymerizable compound used in the curable composition for imprint include the following first and second groups. However, it is needless to say that the present invention is not limited to these. The first group is more preferable.

Group 1

[Chemical Formula 4]

Group 2

[Chemical Formula 5]

The cyclic structure-containing polyfunctional polymerizable compound is preferably contained in an amount of 30 mass% or more, more preferably 45 mass% or more, further preferably 50 mass% or more, based on the total polymerizable compound in the imprinting curable composition, More preferably 55 mass% or more, and may be 60 mass% or more and 70 mass% or more. The upper limit value is preferably less than 95 mass%, more preferably 90 mass% or less, and may be 85 mass% or less. By setting the lower limit value at 30% by mass or more, the etching selectivity with respect to the object to be processed (for example, Si, Al, Cr, or an oxide thereof) at the time of the etching process is improved and the disconnection of the pattern after the etching process is suppressed can do.

The curable composition for imprints may contain a multifunctional polymerizable compound other than the cyclic structure-containing multifunctional polymerizable compound. These other multifunctional polymerizable compounds may be contained in one kind alone or in two or more kinds.

Examples of other multifunctional polymerizable compounds used in the curable composition for imprints include multifunctional polymerizable compounds having no cyclic structure among the polymerizable compounds described in JP-A-2014-170949, the contents of which are incorporated herein by reference do. More specifically, for example, the following compounds are exemplified.

[Chemical Formula 6]

The blending amount of the other multifunctional polymerizable compound is preferably 5 to 30% by mass based on the total polymerizable compound in the curable composition for imprinting. It is also possible to adopt a constitution in which other polyfunctional polymerizable compounds are not substantially mixed. Means that the amount of the polymerizable compound in the curable composition for imprint is, for example, 3 mass% or less, and more preferably 1 mass% or less.

As the photopolymerization initiator, sensitizer, releasing agent, antioxidant, polymerization inhibitor, solvent and the like, which may be blended in the curable composition for imprint, in addition to the components described in the following examples, JP-A-2013-036027, JP- 2014-090133, JP-A-2013-189537, and JP-A-2016-037872. For the blending amount and the like, the description of the above publication can be referred to.

Specific examples of the curable composition for imprints that can be used in the present invention include compositions described in the following examples, Japanese Laid-Open Patent Publication Nos. 2013-036027, 2014-090133, 2013-189537, The compositions described in the specification of the patent application 2016-037872 are exemplified, the contents of which are incorporated herein by reference. Also, with reference to the preparation of the curable composition for imprints and the method of forming the film (pattern formation layer), reference may be made to the disclosure of the above publications, and these contents are incorporated herein by reference.

<Pattern>

As described above, the pattern formed by the pattern forming method of the present invention can be used as a permanent film used for a liquid crystal display (LCD) or the like, or as an etching resist for manufacturing semiconductor devices. That is, the present invention also discloses a method of manufacturing a semiconductor device including the pattern forming method of the present invention.

In addition, a grid pattern is formed on a glass substrate of a liquid crystal display device using a pattern formed by the pattern forming method of the present invention. A polarizing plate having a large reflection and absorption and a large screen size (for example, 55 inches, Can be manufactured at low cost. For example, the polarizing plates described in JP-A-2015-132825 and WO2011 / 132649 can be produced. One inch is 25.4 mm.

The permanent membrane is then transported and stored by bottling it into a container such as a gallon bottle or a quart bottle. In this case, the container may be replaced with inert nitrogen, argon, or the like for the purpose of preventing deterioration . At the time of transportation and storage, the temperature may be room temperature. However, in order to prevent deterioration of the permanent film, the temperature may be controlled in the range of -20 ° C to 0 ° C. Of course, it is preferable to shield the light to a level at which the reaction does not proceed.

Specifically, the pattern formed by the pattern forming method of the present invention may be a recording medium such as a magnetic disk, a light receiving element such as a solid-state image pickup element, a light emitting element such as an LED or an organic EL, an optical device such as a liquid crystal display An optical component such as a diffraction grating, a relief hologram, an optical waveguide, an optical filter and a microlens array, a member for a flat panel display such as a thin film transistor, an organic transistor, a color filter, an antireflection film, a polarizing plate, , Guided patterns for directed self-assembly (DSA) using self-organization of nanobio devices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals and block copolymers Can be suitably used for the production of

The pattern formed by the pattern forming method of the present invention is also useful as an etching resist (mask for lithography). In the case of using the pattern as an etching resist, first, a silicon substrate (silicon wafer or the like) on which a thin film such as SiO ₂ is formed, or the like is used as the substrate, To form a fine pattern of nano or micron order. The present invention is particularly advantageous in that a fine pattern of nano order can be formed, and further, a pattern of 50 nm or less in size, particularly 30 nm or less can be formed. The lower limit of the size of the pattern to be formed in the pattern forming method of the present invention is not specifically defined, but may be, for example, 1 nm or more.

Thereafter, a desired pattern can be formed on the substrate by etching with hydrogen fluoride in the case of wet etching or etching gas such as CF _{4 in} the case of dry etching. The pattern has good etching resistance particularly for dry etching. That is, the pattern formed by the pattern forming method of the present invention is preferably used as a mask for lithography.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts used, the ratios, the treatment contents, the treatment procedures and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

The ratio of each component in Tables 2 to 4 is a mass ratio.

&Lt; Preparation of composition for forming adhesion layer >

As shown in the following Table 2, the resin and the solvent were blended and filtered with a polytetrafluoroethylene filter (PTFE filter) of 0.1 m to prepare Composition A-1 to A-5 for Adhesive Layer Formation.

&Lt; Preparation of composition for forming primer layer >

Various compounds were compounded and filtered with a 0.1 占 퐉 PTFE filter as shown in Table 3 below to prepare compositions B-1 to B-12 for forming primer layers. Among the components contained in the composition for forming a primer layer, the component in which the surface tension is measured and the solvent (propylene glycol monomethyl ether acetate) are liquid at 25 占 폚.

&Lt; Preparation of curable composition for imprint &

As shown in the following Table 4, various compounds were mixed, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (produced by Tokyo Kasei Kogyo Co., Ltd.) (0.02% by mass) based on the total amount of the polymerizable compound. This was filtered with a 0.1 占 퐉 PTFE filter to prepare curable compositions C-1 to C-10 for imprints.

&Lt; Formation of adhesion layer and primer layer >

On the silicon wafer, the composition for forming the adhesion layer shown in Table 5 or Table 6 was spin-coated and heated using a hot plate at 220 占 폚 for 1 minute, and the solvent was dried to form a 5 nm thick adhesion layer. Subsequently, a composition for forming a primer layer shown in Table 5 or Table 6 was spin-coated on the surface of the adhesion layer and heated for 1 minute using a hot plate at 100 占 폚, and the solvent was dried to form a primer layer. The film thicknesses of the adhesion layer and the primer layer were measured by an ellipsometer and an atomic force microscope.

&Lt; Measurement of weight average molecular weight >

The weight average molecular weight was measured under the following conditions.

Column type: Three column-connected columns of TSKgel Super Multipore HZ-H (manufactured by TOSOH CORPORATION, 4.6 mm ID x 15 cm)

Developing solvent: tetrahydrofuran

Column temperature: 40 DEG C

Sample concentration: 0.35 mass%

Flow rate: 0.35 mL / min

Sample injection amount: 10 μL

Device name: Tosoh HLC-8020GPC

Detector: RI (Refractive Index) detector

Calibration base resin: polystyrene

&Lt; Measurement of Critical Surface Tension >

The critical surface tension was measured for each of the adhesion layer and the primer layer formed above.

2 [mu] L of a solvent having different surface tension was dropped on the surface of the adhesion layer or the primer layer, and the contact angle [theta] at the point of 500 ms was measured. (A contact angle?) Is plotted on an xy plane (x: surface tension of solvent, cos: calculated from y: contact angle?), And a linear function approximating the measurement result is calculated according to a least squares method , And the extrapolated value of the linear function at cos? = 1 is defined as the critical surface tension (unit: mN / m) of the adhesion layer or the primer layer.

As the solvent, water (surface tension: 72.9 mN / m), glycerin (63.2), fumamide (58.5), ethylene glycol (50.2), y-butyrolactone (44.1), oleic acid (32.2), cyclohexanone 34.1) and methyl acetate (25.0) were used.

The contact angle was measured at 25 占 폚 using DMs-401 manufactured by Kyowa Chemical Co., The value after 500 msec after the droplet landing was measured as n = 3, and the average value was defined as a contact angle.

&Lt; Measurement of surface tension &

The surface tension of each composition or compound was measured by using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Gaimen Kagaku Co., Ltd. and using a glass plate at 25 ± 0.2 ° C. The unit is expressed in mN / m.

<Viscosity>

The viscosity of the curable composition for imprint was measured at 23 ± 0.2 ° C using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd.

The rotation speed at the time of measurement was as shown in Table 1 according to the viscosity.

[Table 1]

&Lt; Evaluation of surface roughness of primer layer >

The primer layer obtained above was scanned with a square of 10 mu m using an atomic force microscope (AFM, manufactured by Burkill AG, Dimension Icon), and the arithmetic mean surface roughness (Ra) was measured, Respectively. The results are shown in Tables 5 and 6 below.

A: Ra < 0.4 nm

B: 0.4 nm? Ra <1.0 nm

C: 1.0 nm? Ra

<Evaluation of peeling failure>

The curable composition for imprints whose temperature was adjusted to 25 캜 was ejected onto the surface of the primer layer obtained above with a droplet amount of 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fuji Film Dymatics Co., So that droplets were arranged in a square arrangement with intervals of about 100 mu m, and the curable composition for imprints was formed into a layer shape. Next, a quartz mold (rectangular line / space pattern (1/1), line width 60 nm, groove depth 100 nm, line edge roughness 3.5 nm) was pressure-contacted to the layered imprinting curable composition, . Further, the mold was exposed from the mold side under the condition of 300 mJ / cm ² using a high-pressure mercury lamp, and then the mold was peeled off to transfer the pattern to the curable composition for imprinting.

The pattern transferred to the curable composition for imprint was observed with an optical microscope (STM6-LM, made by Olympus), and the peeling failure of the pattern was evaluated according to the following criteria.

A: No peeling failure was observed in the entire pattern.

B: Peeling failure was observed in an area of less than 10% of the pattern.

C: Peeling failure was observed in an area of 10% or more of the pattern.

&Lt; Evaluation of chargeability &

On the surface of the primer layer obtained above, the curable composition for imprints shown in Table 4 whose temperature was adjusted to 25 占 폚 was ejected in a droplet amount of 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fuji Film DYMATIX , And droplets were applied on the surface of the primer layer so that the liquid droplets were arranged in a square arrangement with intervals of about 100 탆, and the curable composition for imprinting was formed into a layer shape. Next, a quartz substrate was pressed against the pattern-forming layer to planarize the curable composition for imprinting. Further, after exposure from the mold side using a high-pressure mercury lamp at 300 mJ / cm ² , the quartz substrate was peeled off to obtain a flat film.

The surface of the flat film was observed with an optical microscope (STM6-LM made by Olympus), and the filling property was evaluated based on the following criteria.

A: In the imprint area, a region of uncharged (a region where no cured product of the imprinting curable composition was present) was not generated.

B: Uncharged at an inkjet droplet boundary was confirmed in a region of the imprint area.

C: Unfilled at the inkjet droplet boundary was confirmed over the entire surface of the imprint area.

D: A region where the ink-jet droplets were not connected to each other and the flat film could not be formed was confirmed.

[Table 2]

[Table 3]

[Table 4]

In Table 4, n1 is 12, and n + m + 1 is 7 to 13. [

[Table 5]

[Table 6]

As is apparent from Tables 5 and 6, when the primer layer had a higher critical surface tension than the adhesion layer, the filling property of the curable composition for imprints was excellent. On the other hand, when the primer layer had a lower critical surface tension than the adhesion layer, the filling property of the curable composition for imprint was poor.

11 substrate
12 Adhesive layer
13 primer layer
14 Curable composition for imprint
15 patterns
21 Adhesive layer
22 Curable composition for imprint

Claims (18)

A step of forming a primer layer having a higher critical surface tension on the surface of the adhesion layer positioned on the substrate than the adhesion layer;
And applying the curable composition for imprint to the surface of the primer layer. The method according to claim 1,
And forming the primer layer by using a composition for forming a primer layer containing a solvent,
Further, the component constituting the adhesion layer is substantially not dissolved in the solvent contained in the composition for forming a primer layer. The method according to claim 1 or 2,
Wherein a component constituting the adhesion layer is substantially not thermally diffused to the primer layer. The method according to any one of claims 1 to 3,
Wherein at least one of the components constituting the primer layer has a functional group capable of forming at least one of a component constituting the adhesion layer and a hydrogen bond and an interaction between ions. The method according to any one of claims 1 to 3,
Wherein at least one of the components constituting the primer layer has a functional group capable of forming a hydrogen bond with a component constituting the adhesion layer. The method according to any one of claims 1 to 5,
Wherein 95% by mass or more of the components constituting the primer layer is liquid at 25 占 폚 and the contact angle of the component constituting the primer layer on the surface of the adhesion layer at 25 占 폚 after 10 seconds of dropping is 5 占Or less. The method according to any one of claims 1 to 6,
Wherein the viscosity of the curable composition for imprint at 23 占 폚 is 8.0 mPa 占 퐏 or less. The method according to any one of claims 1 to 7,
Wherein the surface tension of the curable composition for imprint at 25 캜 is 33 mN / m or more. The method according to any one of claims 1 to 8,
Wherein the primer layer satisfies at least one of A and B below;
A: a primer layer formed from a composition for forming a primer layer containing a component having a surface tension of at least 40 mN / m at 25 캜;
B: Critical surface tension of the primer layer at 25 캜 is 46 mN / m or more. The method of claim 9,
Wherein the component having a surface tension at 25 占 폚 of 40 mN / m or more is contained in a proportion of 20 mass% or more of the components constituting the primer layer. The method according to claim 9 or 10,
Wherein the component having a surface tension of at least 40 mN / m at 25 DEG C is a compound having a polyalkyleneglycol structure and the polyalkylene glycol structure is composed of a linear alkylene group and an oxygen atom, / RTI &gt; The method according to any one of claims 9 to 11,
Wherein at least one of the components having a surface tension of at least 40 mN / m at 25 占 폚 does not have a polymerizable group. The method according to any one of claims 9 to 12,
Wherein at least one of the components having a surface tension of at least 40 mN / m at 25 占 폚 is a liquid at 25 占 폚. The method according to any one of claims 9 to 13,
Wherein at least 95 mass% of the components constituting the primer layer contained in the composition for forming a primer layer is a liquid at 25 占 폚. The method according to any one of claims 9 to 14,
Wherein a weight average molecular weight of the component having a surface tension of at least 40 mN / m at 25 DEG C is 200 or more and less than 1,000. The method according to any one of claims 1 to 15,
Further comprising a step of providing the adhesion layer on the substrate. The method according to any one of claims 1 to 16,
Wherein the critical surface tension of the primer layer is higher than the critical surface tension of the adhesion layer by 5 mN / m or more. A method of manufacturing a semiconductor device, comprising the pattern forming method according to any one of claims 1 to 17.

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