JP6363215B2 - Method for producing pattern forming body - Google Patents

Description

  The present invention relates to a method for producing a pattern forming body. More specifically, semiconductor integrated circuits, flat screens, microelectromechanical systems, sensor elements, optical recording media such as optical disks and high-density memory disks, optical components such as diffraction gratings and relief holograms, nanodevices, optical devices, flat panel displays Optical films and polarizing elements for manufacturing, thin film transistors for liquid crystal displays, organic transistors, color filters, overcoat layers, pillar materials, rib materials for liquid crystal alignment, microlens arrays, immunoassay chips, DNA separation chips, microreactors The present invention relates to a method for producing a pattern forming body used for producing nanobiodevices, optical waveguides, optical filters, photonic liquid crystals, imprint molds, permanent films and the like.

  The imprint method is a technique for transferring a fine pattern to a material by pressing a mold (generally called a mold or a stamper) on which a pattern is formed. In recent years, application in various fields is expected because it is possible to easily produce precise fine patterns by using the imprint method. In particular, a nanoimprint technique for forming a nano-order level fine pattern has attracted attention.

  As the imprint method, methods called a thermal imprint method and an optical imprint method have been proposed based on the transfer method. In the thermal imprint method, a mold is pressed on a thermoplastic resin heated to a temperature higher than the glass transition temperature, and then the thermoplastic resin is cooled to a temperature lower than the glass transition temperature, and then the mold is released. Is to be transferred to. This method can select various materials, but it also has problems that high pressure is required during pressing and that it is difficult to form a fine pattern due to thermal shrinkage.

  On the other hand, the optical imprint method is a method of transferring a fine pattern to a photocured product by peeling the mold after light curing the curable composition by light irradiation through a light transmissive mold or a light transmissive substrate. is there. In this method, imprinting on an uncured product does not require heating at high pressure and high temperature, and a fine pattern can be easily produced. Furthermore, since imprinting at room temperature is possible, it can be applied to the field of precision processing of ultrafine patterns such as the fabrication of semiconductor integrated circuits.

In recent years, an attempt to use a pattern obtained by the photoimprint method as a permanent film has been studied.
Non-Patent Document 1 proposes a process that uses an imprint method when forming a damascene structure in an insulating material of a semiconductor wiring portion. In such applications, the imprint composition requires heat resistance exceeding 250 ° C. in addition to good pattern transferability and the like, and a dual cure material that performs heat curing after ultraviolet curing is a candidate. Examples of the dual cure material include a composition comprising a bisallylnadiimide compound, a bismaleimide compound, a hydroxy (meth) acrylate compound, and a photopolymerization initiator disclosed in Patent Document 1. In this composition, a bismaleimide compound and a hydroxy (meth) acrylate compound are photocured, and a bisallylnadiimide compound is thermally cured to obtain a highly heat-resistant cured product having a heat-resistant temperature of 250 ° C. or higher. It becomes possible.

  Patent Document 2 proposes a method of using a multilayer film in an imprint lithography process. A polymerizable composition containing silicon is assumed as a laminated structure, and examples of candidate materials include spin-on glass that requires thermal curing after coating.

  As described above, when a pattern obtained by the photoimprint method is used as a permanent film, a heat treatment is further performed in recent years for surface treatment or curing.

JP 2010-229220 A Special table 2010-541193

Microelectron. Eng. (2003) 67, 221

However, the heat treatment is performed with respect to the pattern formed by the photo-imprinting method, as shown in FIG. 1, or bent pattern projection unit 1, and may fall, there is a pattern defects. In particular, pattern defects tend to occur as the pattern size is reduced.
Therefore, the objective of this invention is providing the manufacturing method of the pattern formation body by which the pattern defect was suppressed.

In the pattern formation by the photoimprint method, in principle, since the photocurable composition remains between the mold convex portion and the substrate, a film derived from the photocurable composition ( A residual film).
As a result of intensive studies, the present inventor has found that a pattern defect generated when a heat treatment is performed on a pattern formed by the photoimprint method is caused by the residual stress of the residual film. And before performing heat processing, it discovered that generation | occurrence | production of the pattern defect accompanying heat processing can be suppressed by removing or thinning the said remaining film, and came to complete this invention. The present invention provides the following.
<1> A photocurable composition is applied on a substrate or a mold having a pattern to form a pattern forming layer. After the pattern forming layer is sandwiched between the substrate and the mold, light is applied to the pattern forming layer. Irradiating to cure the pattern forming layer, releasing the mold from the surface of the cured pattern forming layer, and forming a pattern;
The process of manufacturing a pattern formation body including the process of heat-processing, after removing or thinning the film | membrane derived from the photocurable composition in the recessed part of a pattern.
<2> The method for producing a pattern forming body according to <1>, wherein the film derived from the photocurable composition is made 10 nm or less and then heat-treated.
<3> The method for producing a pattern forming body according to <1>, wherein the film derived from the photocurable composition is made 5 nm or less and then heat-treated.
<4> The method for producing a pattern forming body according to any one of <1> to <3>, wherein the film derived from the photocurable composition is removed or thinned by dry etching.
<5> The method for producing a pattern forming body according to any one of <1> to <4>, wherein the heat treatment is performed at a heat treatment temperature satisfying a relationship of the following formula (1):
Heat treatment temperature ≦ Tg + 10 ° C. (1)
Tg is the glass transition temperature of the photocurable composition used for forming the pattern forming layer.
<6> After the film derived from the photocurable composition is removed or thinned, and before the heat treatment, a composition containing a film forming component is applied to the surface of the pattern, <1> to <5 > The manufacturing method of the pattern formation body in any one of.
<7> The method for producing a pattern forming body according to any one of <1> to <6>, wherein the pattern forming body has a pattern having a width of 300 nm or less.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the manufacturing method of the pattern formation body by which the pattern defect was suppressed.

It is a conceptual diagram which shows the generation | occurrence | production mechanism of a pattern defect.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “to” is used in the sense of including the numerical values described before and after it as lower and upper limits.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In the present specification, “imprint” preferably refers to pattern transfer having a size of 1 nm to 10 mm, and more preferably refers to pattern transfer having a size (nanoimprint) of approximately 10 nm to 100 μm.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “light” includes not only light in a wavelength region such as ultraviolet, near ultraviolet, far ultraviolet, visible, infrared, and electromagnetic waves, but also radiation. Examples of radiation include microwaves, electron beams, EUV, and X-rays. Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. The light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light having a plurality of different wavelengths (composite light).
The mass average molecular weight and the number average molecular weight in the present invention are those measured by gel permeation chromatography (GPC) unless otherwise specified. GPC was isolated by removing the solvent from the obtained polymer, and the obtained solid content was diluted to 0.1% by mass with tetrahydrofuran, and HLC-8020 GPC (manufactured by Tosoh Corporation) was used. It is possible to measure by using three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) connected in series as a column. The conditions can be performed using a RI detector with a sample concentration of 0.35% by mass, a flow rate of 0.35 mL / min, a sample injection amount of 10 μL, and a measurement temperature of 40 ° C.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
Solid content in this specification is solid content in 25 degreeC.
In this specification, the viscosity is 0.5 mPa · s or more and 5 mPa · s as a rotational speed at the time of measurement at 25 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd. Less than s is 100 rpm, 5 mPa · s or more and less than 10 mPa · s is 50 rpm, 10 mPa · s or more and less than 30 mPa · s is 20 rpm, and 30 mPa · s or more and less than 60 mPa · s is 10 rpm.

In the method for producing a pattern forming body of the present invention, a photocurable composition is applied on a substrate or a mold having a pattern to form a pattern forming layer, and the pattern forming layer is sandwiched between the substrate and the mold. Thereafter, the pattern forming layer is irradiated with light to cure the pattern forming layer, and the mold is released from the surface of the cured pattern forming layer to form a pattern (step 1), and the photocurability in the concave portion of the pattern And a step of performing heat treatment after removing or thinning the film derived from the composition (step 2).
According to the present invention, since the heat treatment is performed after the film (also referred to as the residual film) derived from the photocurable composition in the concave portion of the pattern is removed or thinned, the influence due to the residual stress of the residual film can be reduced. Generation of pattern defects accompanying processing can be suppressed. Hereinafter, each step will be described.

<Step 1>
In step 1, first, a photocurable composition is applied on a substrate or a mold having a pattern to form a pattern forming layer. The photocurable composition will be described later.
There is no limitation in particular as a base material, It can select by various uses. For example, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflection film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOC (Spin On Carbon), SOG (Spin On Glass), polyester Polymer substrate such as film, polycarbonate film, polyimide film, thin film transistor (TFT) array substrate, electrode plate of plasma display panel (PDP), conductive substrate such as ITO (indium tin oxide) or metal, insulating substrate, silicon, nitride Examples include semiconductor fabrication substrates such as silicon, polysilicon, silicon oxide, and amorphous silicon.
The shape of the substrate is not particularly limited, and may be a plate shape or a roll shape. Further, a light-transmitting or non-light-transmitting material can be selected according to the combination with the mold.
In order to improve the adhesiveness with the photocurable composition, the base material used in the present invention may be one in which a lower layer film is formed by applying the lower layer film forming composition to the surface of the base material. As the resin composition for forming the lower layer film, for example, a resin composition containing a polymerizable compound and a solvent is used. As the resin composition for forming the lower layer film, for example, those described in paragraph numbers 0017 to 0068 of JP 2014-24322A, paragraph numbers 0016 to 0044 of JP 2013-93552 A can be used, This content is incorporated herein. As a method for applying the resin composition for forming the lower layer film, a coating method is preferable. Examples of the coating method include the methods described above.

A pattern to be transferred is formed on the mold. The pattern on the mold can be formed according to the desired processing accuracy by, for example, photolithography or electron beam drawing. In this invention, since the pattern formation body which has a fine pattern can be manufactured efficiently, there exists a tendency for the effect of this invention to be exhibited notably as the pattern on a mold is finer. For example, the mold preferably has a pattern with a width of 300 nm or less, and more preferably has a pattern with a width of 100 nm or less. Moreover, 0.1-10 are preferable and, as for the aspect ratio of a pattern, 1-5 are more preferable.
The material of the mold is not particularly limited as long as it has predetermined strength and durability. Specific examples include light-transparent resins such as glass, quartz, acrylic resin, and polycarbonate resin, transparent metal vapor-deposited films, flexible films such as polydimethylsiloxane, photocured films, and metal films. Further, when a light transmissive substrate is used, a non-light transmissive mold can also be used. The material of the non-light transmissive mold is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, Fe, SiC, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, etc. Not constrained. Further, the shape of the mold is not particularly limited, and may be either a plate mold or a roll mold. The roll mold is applied particularly when continuous transfer productivity is required.
The mold used in the present invention may be a mold that has been subjected to a release treatment in order to improve the peelability between the photocurable composition and the mold surface. As such a mold, those treated with a silane coupling agent such as silicon-based or fluorine-based, for example, OPTOOL DSX manufactured by Daikin Industries, Ltd., Novec EGC-1720 manufactured by Sumitomo 3M Limited, etc. Commercially available release agents can also be suitably used.

As a method for applying the photocurable composition, a coating method is preferable. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, and an inkjet method.
The film thickness of the pattern forming layer varies depending on the intended use. For example, the film thickness after drying is preferably about 0.03 to 30 μm. Moreover, you may apply | coat a photocurable composition by multiple application | coating. In a method of placing droplets on a substrate by an inkjet method or the like, the amount of droplets is preferably about 1 pl to 20 pl, and the droplets are preferably arranged on the substrate or mold at intervals.

Next, in order to transfer the pattern to the pattern forming layer, a mold is pressed against the surface of the pattern forming layer. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred to the pattern forming layer.
Further, when pressing the mold against the surface of the pattern forming layer, helium may be introduced between the mold and the surface of the pattern forming layer. By using such a method, it is possible to promote the permeation of the gas mold and promote the disappearance of residual bubbles. Moreover, radical polymerization inhibition in exposure can be suppressed by reducing dissolved oxygen in the pattern forming layer. Further, a condensable gas may be introduced between the mold and the pattern forming layer instead of helium. By using such a method, it is possible to further promote the disappearance of residual bubbles by utilizing the fact that the introduced condensable gas condenses and decreases in volume. The condensable gas refers to a gas that condenses due to temperature or pressure, and for example, trichlorofluoromethane, 1,1,1,3,3-pentafluoropropane, or the like can be used. Regarding the condensable gas, for example, the description in paragraph 0023 of JP-A-2004-103817 and paragraph 0003 of JP-A-2013-247883 can be referred to, and the contents thereof are incorporated in the present specification.

  Next, the photocurable composition is cured by irradiating light with the mold pressed. The irradiation amount of light irradiation should just be sufficiently larger than the irradiation amount required for hardening of a photocurable composition. The irradiation amount necessary for curing is appropriately determined by examining the consumption of unsaturated bonds of the photocurable composition and the tackiness of the cured film.

The substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase the reactivity. As a pre-stage of light irradiation, if it is in a vacuum state, it is effective in preventing bubbles from being mixed, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the photocurable composition. May be. The preferred degree of vacuum during light irradiation is preferably in the range of 10 ⁻¹ Pa to normal pressure.

  The light used for curing the photocurable composition is not particularly limited, and examples thereof include high-energy ionizing radiation, light having a wavelength in the region of near ultraviolet, far ultraviolet, visible, infrared, or radiation. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, radiation such as γ rays, X rays, α rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used. Examples of the ultraviolet ray source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp. The radiation includes, for example, microwaves and extreme ultraviolet (EUV). In addition, a light-emitting diode (LED), semiconductor laser light, or laser light used in semiconductor microfabrication such as 248 nm KrF excimer laser light or 193 nm ArF excimer laser can also be suitably used in the present invention. These lights may be monochromatic lights, or may be lights having different wavelengths (mixed lights).

In the exposure, the exposure illuminance is desirably in the range of 1 to 50 mW / cm ² . By setting it to 1 mW / cm ² or more, the exposure time can be shortened, so that productivity is improved. By setting it to 50 mW / cm ² or less, deterioration of the properties of the permanent film due to side reactions can be suppressed. It tends to be preferable. The exposure amount is desirably in the range of 5 to 1000 mJ / cm ² . If it is this range, the sclerosis | hardenability of a photocurable composition is favorable. Further, during exposure, in order to prevent inhibition of radical polymerization by oxygen, an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.

  After hardening a pattern formation layer (layer which consists of a photocurable composition) by light irradiation, it may include the process of applying the heat | fever to the pattern hardened | cured as needed, and making it harden | cure further. For example, the heating temperature is preferably 150 to 280 ° C, and more preferably 200 to 250 ° C. The heating time is preferably, for example, 5 to 60 minutes, and more preferably 15 to 45 minutes.

  After curing the photocurable composition as described above, the pattern along the shape of the mold can be formed on the substrate by peeling the mold from the substrate. The pattern size varies depending on the application. For example, a pattern having a width of 300 nm or less is preferable, and a pattern having a width of 100 nm or less is more preferable. The lower limit can be, for example, 10 nm or more. Moreover, 0.1-10 are preferable and, as for the aspect ratio of a pattern, 1-5 are more preferable.

<Process 2>
Even if the pattern forming layer is sandwiched between the base material and the mold, since the photocurable composition remains between the mold convex portion and the base material, the photocuring is performed in the concave portion of the pattern formed on the base material. A film (residual film) derived from the sex composition exists. The remaining film is usually present at 15 nm or more.
In the manufacturing method of the pattern formation body of this invention, after the said remaining film is removed or thinned, it heat-processes. In the present invention, the removal of the remaining film may not be completely removed from the substrate. That is, a part of the remaining film may remain on the substrate. Further, the thinning of the remaining film means that the thickness of the remaining film is made thinner than that before the treatment.

The removal or thinning of the remaining film is not particularly limited, and can be performed by a method such as dry etching or wet etching. Dry etching (especially reactive ion etching) is particularly preferable because anisotropic etching is easy.
Examples of the dry etching method include an ion milling method, reactive ion etching, and sputter etching, and the ion milling method and reactive ion etching are particularly preferable.
Examples of the etching gas include O ₂ , Cl ₂ , CHF ₃ , CF ₄ , SF ₆ , C60, Ar, and the like.
Etching conditions are not particularly limited.
The removal or thinning of the remaining film is preferably performed so that the thickness of the remaining film is 10 nm or less, more preferably 5 nm or less. Generation | occurrence | production of the pattern defect at the time of the heating process mentioned later can be suppressed more effectively because the thickness of a remaining film shall be 10 nm or less. Furthermore, the heat treatment described below can be performed at a higher temperature.
Further, the thickness of the remaining film after the treatment can be processed to be 75% or less of the film thickness before the processing, can be processed to be 50% or less, and can be 30% or less. It can also be processed.
The thickness of the remaining film can be measured using, for example, an ellipsometer (DVA-LF, manufactured by Mizoji Optical Co., Ltd.).

After the remaining film is removed or thinned as described above, heat treatment is performed. By performing the heat treatment, a stronger pattern can be formed.
The heat treatment is preferably performed at a heat treatment temperature that satisfies the relationship of the following formula (1).
Heat treatment temperature ≦ Tg + 10 ° C. (1)
Tg is the glass transition temperature of the photocurable composition used for forming the pattern forming layer.
The lower limit of the heat treatment temperature is not particularly limited. It can select suitably according to the kind of photocurable composition and the kind of film formation composition mentioned later.
The heat treatment can be performed at a heat treatment temperature that satisfies the relationship of the following equation (1a), or can be performed at a heat treatment temperature that satisfies the relationship of the following equation (1b).
Tg−50 ° C. ≦ heat treatment temperature ≦ Tg + 10 ° C. (1a)
Tg−40 ° C. ≦ heat treatment temperature ≦ Tg + 10 ° C. (1b)
The glass transition temperature of the photocurable composition is such that the photocurable composition is cured by sandwiching the photocurable composition between release-treated glasses and irradiating it with a high-pressure mercury lamp at 1000 mJ / cm ^2. A strip sample having a width of 5 mm was cut out from the produced film and measured with a dynamic viscoelasticity measuring device DMS-6100 (manufactured by Seiko Instruments Inc.). The temperature increase rate was 5 ° C./min, the measurement frequency was 1 Hz, and the temperature at which the tanD value reached the maximum value was defined as the glass transition temperature. In addition, when there are two or more glass transition temperatures, the temperature having the larger peak area of tanD for calculating the glass transition temperature is adopted.
Further, in the present invention, even if the heat treatment is performed at a temperature (hereinafter also referred to as T ⁰ ) at which the pattern defect has occurred when the heat treatment is performed without removing or thinning the residual film, the pattern defect is generated. Can be suppressed. For this reason. The lower limit of the heat treatment temperature may be T ⁰ or more.
That is, the heat treatment can be performed at a heat treatment temperature that satisfies the relationship of the following formula (1c).
T ⁰ ≦ heat treatment temperature ≦ Tg + 10 ° C. (1c)
In addition, the pattern defect has arisen that the pattern formation after heat processing is confirmed with an atomic force microscope, and the pattern collapse can be confirmed in the range of 5 micrometers x 5 micrometers. Suppose that no pattern defect has occurred in a state in which pattern collapse cannot be confirmed.
Moreover, the minimum of heat processing temperature can also be 50 degreeC or more, for example, and can also be 60 degreeC or more.
That is, the heat treatment can be performed at a heat treatment temperature that satisfies the relationship of the following equation (1d), or can be performed at a heat treatment temperature that satisfies the relationship of the following equation (1e).
50 ° C. ≦ heat treatment temperature ≦ Tg + 10 ° C. (1d)
60 ° C. ≦ heat treatment temperature ≦ Tg + 10 ° C. (1e)
There is no particular limitation on the heat treatment time. It can select suitably according to the kind of photocurable composition and the kind of film formation composition mentioned later. For example, the lower limit is preferably 5 seconds or more, and the upper limit is preferably 2 hours or less.

In the present invention, a composition containing a film-forming component on the surface of the pattern (a film-forming composition) may be applied after removing or thinning the residual film and before heat treatment.
By applying the film-forming composition to the surface of the pattern, a film can be formed on the surface of the pattern during the subsequent heat treatment, and various functions can be imparted.
The film-forming component varies depending on the application and purpose. For example, a hydrophilic coating agent, a hydrophobic coating agent, a hard coating agent, an antistatic agent, a metal ink, an ultraviolet absorber, a heat ray cut agent, an anti-fingerprint coating agent, a refractive index adjusting agent, and the like can be given.
Examples of the hydrophilic coating agent include LAMBIC series manufactured by Osaka Organic Chemical Industry.
Examples of the hydrophobic coating agent include silane compounds and fluororesins. Examples of the silane compound include a silane coupling agent and siloxane. Examples of commercially available silane coupling agents include Daikin Industries, Ltd. OPTOOL series, Shin-Etsu Silicone Corporation KBM series, KBE series, and the like. Examples of siloxane include KPN-3504 (hydrolyzable group-containing siloxane) manufactured by Shin-Etsu Silicone Co., Ltd. Examples of the fluororesin include CYTOP series manufactured by Asahi Glass Co., Ltd.
Examples of the hard coating agent include Toyo Ink LCH series.
Examples of the antistatic agent include Toyo Ink's LAS series, YYS series, and TYP series.
Examples of the metal ink include gold ink, silver ink, and copper ink.
In the film forming composition, the content of the film forming component is preferably 0.001 to 20% by mass, and more preferably 0.01 to 10% by mass.
The solvent is not particularly limited as long as it can dissolve the film-forming component. Examples thereof include ethyl acetate, carbon tetrachloride, acetic acid, propylene glycol 1-monomethyl ether 2-acetate, benzene, cyclohexanone and the like.
70-99.999 mass% is preferable and, as for content of the solvent in the composition for film formation, 90-99.9 mass% is more preferable.

The method for producing a pattern formed body of the present invention can produce, for example, a pattern formed body having a pattern with a width of 300 nm or less (more preferably, a width of 100 nm or less). For this reason, what was formed using the conventional photolithographic technique can be formed with further high precision and low cost.
The pattern formed body obtained by the present invention can be used as a permanent film such as an overcoat layer or an insulating film used for a liquid crystal display (LCD) or the like, an etching resist for a semiconductor integrated circuit, a recording material, or a flat panel display. It is also possible to apply. It can also be used for resin molds, water repellent films, hydrophilic films and the like.

<Photocurable composition>
Next, the photocurable composition will be described. In the present invention, the photocurable composition used in the imprint method can be used as the photocurable composition. That is, the photocurable composition is preferably a photocurable composition for imprints.
The photocurable composition preferably contains a polymerizable compound and a photopolymerization initiator. As an example of the photocurable composition, for example, a composition in which the content of the polymerizable compound is 70% by mass or more and the content of the component having a weight average molecular weight of more than 2000 is 3% by mass or less is preferable. A composition in which the content of the polymerizable compound having a polymerizable unsaturated double bond is 70% by mass or more and the content of the polymerizable compound having a weight molecular weight of more than 2000 is 3% by mass or less. Hereinafter, each component will be described.

<< polymerizable compound >>
The polymerizable compound is not particularly limited as long as it does not depart from the gist of the present invention. Examples of the polymerizable group that the polymerizable compound has include a group containing an ethylenically unsaturated bond, an epoxy group, and an oxetanyl group. Examples of the group containing an ethylenically unsaturated bond include a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, an allyl group, and a vinyl ether group. A (meth) acrylate group is preferred.
1-6 are preferable, as for the number of polymeric groups, 1-3 are more preferable, and 1 or 2 is still more preferable.
Examples of the polymerizable compound include compounds having 1 to 6 groups containing an ethylenically unsaturated bond; epoxy compounds, oxetane compounds; vinyl ether compounds; styrene derivatives; propenyl ethers, butenyl ethers, and the like. Specific examples of the polymerizable compound include those described in JP-A-2011-231308, paragraphs 0020 to 0098, the contents of which are incorporated herein. As the polymerizable compound, a (meth) acrylate compound is preferable.
As for content of a polymeric compound, 70-99.9 mass% is preferable in all the compositions except a solvent, More preferably, it is 80-99.9 mass%, More preferably, it is 85-99.9 mass%. is there. When using 2 or more types of polymeric compounds, it is preferable that the total amount is the said range About the compound (1-6 functional polymeric compound) which has 1-6 groups containing an ethylenically unsaturated bond explain.

  Specific examples of the compound having one group containing an ethylenically unsaturated bond include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, N-vinylpyrrolidinone, and 2-acryloyloxyethyl phthalate. 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl Carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , Acrylic acid dimer, benzyl (meth) acrylate, 1- or 2-naphthyl (meth) acrylate, butoxyethyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) cresol (meth) acrylate , Dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (Meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octyl (Meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as “ECH”) modified phenoxy acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meta) ) Acrylate, phenoxytetraethylene glycol (meth) acrylate, Polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tribromophenyl (meth) acrylate, EO-modified tri Examples include bromophenyl (meth) acrylate, tridodecyl (meth) acrylate, p-isopropenylphenol, N-vinylpyrrolidone, and N-vinylcaprolactam.

The compound having one group containing an ethylenically unsaturated bond is preferably a monofunctional (meth) acrylate compound from the viewpoint of photocurability. Among monofunctional (meth) acrylate compounds, a monofunctional (meth) acrylate having an aromatic structure and / or an alicyclic hydrocarbon structure is preferable from the viewpoint of dry etching resistance, and a monofunctional (meth) acrylate having an aromatic structure. Is more preferable.
The monofunctional (meth) acrylate having an aromatic structure and / or alicyclic hydrocarbon structure is benzyl (meth) acrylate, 2-phenoxyethyl acrylate, benzyl (meth) acrylate having a substituent on the aromatic ring (preferred substitution) As the group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group), 1- or 2-naphthyl (meth) acrylate, 1- or 2-naphthylmethyl (meth) acrylate, 1- Or 2-naphthylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate are preferred, 2-phenoxyethyl acrylate, Benzyl (meth) acrylate, good Benzyl having a substituent on the ring (meth) acrylate, monofunctional (meth) acrylate compound having a naphthalene structure is more preferable.

In the present invention, it is also preferable to use a compound having two or more groups containing an ethylenically unsaturated bond as the polymerizable compound.
Examples of compounds having two or more groups containing an ethylenically unsaturated bond include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, di (meth) acrylated isocyanurate, 1 , 3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, ECH-modified 1,6-hexanediol di (meth) acrylate Allyloxy polyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO modified Bisphenol F di (meth) acrylate, ECH-modified hexahydrophthalic acid diacrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO-modified neopentyl glycol diacrylate, propylene oxide "PO") modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, poly (ethylene glycol-tetra Methylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) acrylate, polyester (Di) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH-modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified tripropylene glycol di (meth) acrylate, Triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinylethyleneurea, divinylpropyleneurea, o-, m- , P-xylylene di (meth) acrylate, 1,3-adamantane diacrylate, norbornane dimethanol diacrylate.
Among these, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl hydroxypivalate Bifunctional (meth) such as glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, o-, m-, p-benzenedi (meth) acrylate, o-, m-, p-xylylene di (meth) acrylate Acrylate is preferably used in the present invention.
Moreover, the 2-6 functional (meth) acrylate compound which has an aromatic structure and / or an alicyclic hydrocarbon structure can also be used. For example, a polyfunctional (meth) acrylate compound containing an aromatic group (preferably a phenyl group or a naphthyl group) and having 2 to 4 (meth) acrylate groups may be mentioned. Specific examples include the following compounds.

Moreover, the photocurable composition may contain a polymerizable compound having a silicon atom and / or a fluorine atom. The polymerizable compound having a silicon atom and / or a fluorine atom preferably contains a fluorine atom, and more preferably has a fluorine-containing alkyl group having 1 to 9 carbon atoms.
The fluorine atom substitution rate of the fluorinated alkyl group having 1 to 9 carbon atoms is preferably 40 to 100%, more preferably 50 to 90%, and still more preferably 65 to 85%. The substitution rate of fluorine atoms means, for example, the ratio (%) in which hydrogen atoms are substituted with fluorine atoms in alkyl groups having 1 to 9 carbon atoms. Fluorine-containing alkyl group having 1 to 9 carbon atoms _preferably includes a -C _{n F 2n + 1} or _-C n _{F 2n H,} it is preferred to include a -C _{n F 2n + 1.} Here, n represents an integer of 1 to 9, and more preferably represents an integer of 4 to 8.
The polymerizability of the polymerizable compound having a silicon atom and / or a fluorine atom is preferably a (meth) acrylate group. The number of polymerizable groups is preferably 1 or 2, and more preferably 1.
100-600 are preferable and, as for the molecular weight of the polymeric compound which has a silicon atom and / or a fluorine atom, 300-500 are more preferable. As the polymerizable compound having a fluorine atom, for example, the description in paragraphs 0022 to 0023 of International Publication No. 2010/137724 can be considered, and the contents thereof are incorporated in the present specification. Examples of the polymerizable compound having a fluorine atom include 2- (perfluorohexyl) ethyl acrylate.
Moreover, in this invention, it is good also as an aspect which does not contain the polymeric compound which has a silicon atom and / or a fluorine atom substantially.

Of the components of the total polymerizable compound contained in the photocurable composition, the total of the polymerizable compounds having one polymerizable group (preferably, the polymerizable compound having one (meth) acrylate group) is the total polymerization. It is preferable that it is 0-60 mass% with respect to an ionic compound. The lower limit is more preferably 5% by mass or more, and further preferably 10% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 45% by mass or less. The total of the polymerizable compounds having two (meth) acrylate groups is preferably 40 to 100% by mass relative to the total polymerizable compounds. The lower limit is more preferably 50% by mass or more, and further preferably 55% by mass or more. The upper limit is more preferably 95% by mass or less, and still more preferably 90% by mass or less.
Of the components of the total polymerizable compound contained in the curable composition, the total of the polymerizable compounds having an alicyclic hydrocarbon group and / or an aromatic group is 30 to 100% by mass of the total polymerizable compound. It is preferably 50 to 100% by mass, more preferably 70 to 100% by mass.

<< photopolymerization initiator >>
Any photopolymerization initiator may be used as long as it is a compound that generates an active species that polymerizes the above-described polymerizable compound by light irradiation. As the photopolymerization initiator, a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable. In the present invention, a plurality of photopolymerization initiators may be used in combination.
As the radical photopolymerization initiator, for example, a commercially available initiator can be used. As these examples, for example, those described in paragraph No. 0091 of JP-A-2008-105414 can be preferably used. Among these, acetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds are preferred from the viewpoints of curing sensitivity and absorption characteristics. Examples of commercially available products include Irgacure OXE-01, Irgacure OXE-02, Irgacure 127, Irgacure 819, Irgacure 379, Irgacure 369, Irgacure 754, Irgacure 1800, Irgacure 651, Irgacure 907, Lucyrin TPO, Darocur BA 1173, etc. Manufactured).
The content of the photopolymerization initiator is preferably 0.01 to 15% by mass, more preferably 0.1 to 12% by mass, and still more preferably 0.2 to 7% in the entire composition excluding the solvent. % By mass. The photocurable composition may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Surfactant >>
The photocurable composition can contain a surfactant. As the surfactant, a nonionic surfactant is preferable.
The nonionic surfactant is a compound having at least one hydrophobic part and at least one nonionic hydrophilic part. The hydrophobic part and the hydrophilic part may be at the end of the molecule or inside, respectively. The hydrophobic part is composed of a hydrophobic group selected from a hydrocarbon group, a fluorine-containing group, and a Si-containing group, and the carbon number of the hydrophobic part is preferably 1 to 25, more preferably 2 to 15, and further preferably 4 to 10 Preferably, 5 to 8 is most preferable. Nonionic hydrophilic part includes alcoholic hydroxyl group, phenolic hydroxyl group, ether group (preferably polyoxyalkylene group, cyclic ether group), amide group, imide group, ureido group, urethane group, cyano group, sulfonamide group, lactone group It preferably has at least one group selected from the group consisting of a lactam group and a cyclocarbonate group. The nonionic surfactant may be any of hydrocarbon-based, fluorine-based, Si-based, or fluorine / Si-based nonionic surfactants, more preferably fluorine-based or Si-based, and further fluorine-based surfactants. preferable. Here, the “fluorine / Si-based surfactant” refers to one having both the requirements of both a fluorine-based surfactant and a Si-based surfactant.

  Commercially available fluorine-based nonionic surfactants include Sumitomo 3M Fluorard FC-4430 and FC-4431, Asahi Glass Co., Ltd. Surflon S-241, S-242 and S-243, Mitsubishi Materials Electronic Chemicals. EF-top EF-PN31M-03, EF-PN31M-04, EF-PN31M-05, EF-PN31M-06, MF-100, OMNOVA Polyfox PF-636, PF-6320, PF-656 PF-6520, Neos's Footgent 250, 251, 222F, 212M DFX-18, Daikin Industries, Ltd. Unidyne DS-401, DS-403, DS-406, DS-451, DSN-403N, DIC Megafac F-430, F-444, F-477, F-553, manufactured by F-556, F-557, F-559, F-562, F-565, F-567, F-569, R-40, DuPont Capstone FS-3100, Zonyl FSO-100.

When the photocurable composition of the present invention contains a surfactant, the content of the surfactant is preferably from 0.1 to 10% by mass, and from 0.2 to 5% by mass in the total composition excluding the solvent. Is more preferable, and 0.5-5 mass% is further more preferable. The photocurable composition may contain only one type of surfactant or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
Moreover, in this invention, it can also be set as the aspect which does not contain surfactant substantially. For example, it is preferable that the surfactant content is 0.01% by mass or less, more preferably 0.005% by mass or less, and even more preferably not contained.

<< Non-polymerizable compound >>
The photocurable composition includes a non-polymerizable compound having at least one hydroxyl group at the terminal or having a polyalkylene glycol structure in which the hydroxyl group is etherified and substantially not containing a fluorine atom and a silicon atom. You may go out. Here, the non-polymerizable compound refers to a compound having no polymerizable group. Further, “substantially not containing fluorine atoms and silicon atoms” means, for example, that the total content of fluorine atoms and silicon atoms is 1% or less, and that no fluorine atoms and silicon atoms are present. preferable. By not having fluorine atoms and silicon atoms, compatibility with polymerizable compounds is improved, especially in compositions that do not contain solvents, coating uniformity, pattern formation during imprinting, and line edges after dry etching The roughness is good.

The polyalkylene structure of the non-polymerizable compound is preferably a polyalkylene glycol structure containing an alkylene group having 1 to 6 carbon atoms, more preferably a polyethylene glycol structure, a polypropylene glycol structure, a polybutylene glycol structure, or a mixed structure thereof. Further, a polyethylene glycol structure, a polypropylene glycol structure, or a mixed structure thereof is more preferable, and a polypropylene glycol structure is particularly preferable.
Further, it may be substantially composed only of a polyalkylene glycol structure except for a terminal substituent. The term “substantially” as used herein means that the constituents other than the polyalkylene glycol structure are 5% by mass or less, preferably 1% by mass or less. In particular, as the non-polymerizable compound, it is particularly preferable to include a compound consisting essentially only of a polypropylene glycol structure.
The polyalkylene glycol structure preferably has 3 to 100 alkylene glycol structural units, more preferably 4 to 50, still more preferably 5 to 30, more preferably 6 It is particularly preferable to have ~ 20.

The non-polymerizable compound preferably has at least one hydroxyl group at the terminal or is etherified. If the terminal has at least one hydroxyl group or the hydroxyl group is etherified, the remaining terminal may be a hydroxyl group or a hydrogen atom of the terminal hydroxyl group substituted. The group in which the hydrogen atom of the terminal hydroxyl group may be substituted is preferably an alkyl group (that is, polyalkylene glycol alkyl ether) or an acyl group (that is, polyalkylene glycol ester). More preferred is a polyalkylene glycol in which all terminals are hydroxyl groups. A compound having a plurality of (preferably 2 or 3) polyalkylene glycol chains through a linking group can also be preferably used, but a linear structure in which the polyalkylene glycol chains are not branched is preferred. . In particular, a diol type polyalkylene glycol is preferred.
Preferred examples of the non-polymerizable compound include polyethylene glycol, polypropylene glycol, mono- or dimethyl ether thereof, mono- or dibutyl ether, mono- or dioctyl ether, mono- or dicetyl ether, monostearate ester, monooleate ester, poly These are oxyethylene glyceryl ether, polyoxypropylene glyceryl ether, and trimethyl ethers thereof.

As a weight average molecular weight of a nonpolymerizable compound, 150-6000 are preferable, 200-3000 are more preferable, 250-2000 are more preferable, 300-1200 are further more preferable.
In the present invention, when the photocurable composition contains a non-polymerizable compound, the content of the non-polymerizable compound is preferably from 0.1 to 20% by mass in the entire composition excluding the solvent, from 0.2 to 15 mass% is more preferable, and 0.5-10 mass% is still more preferable. Moreover, in this invention, it can also be set as the aspect which does not contain a nonpolymerizable compound substantially. “Substantially not containing a non-polymerizable compound” means, for example, that the content of the non-polymerizable compound is preferably 0.01% by mass or less, more preferably 0.005% by mass or less, and even more not containing it. preferable.

<< Solvent >>
A solvent can be contained in the photocurable composition as necessary. A preferable solvent is a solvent having a boiling point of 80 to 200 ° C. at normal pressure. Any solvent can be used as long as it can dissolve each component, and examples thereof include the same solvents as those described in the lower layer film-forming resin composition. Among these, a solvent containing propylene glycol monomethyl ether acetate is most preferable from the viewpoint of coating uniformity.
The content of the solvent in the photocurable composition is optimally adjusted depending on the viscosity of the photocurable composition, the coating property, and the target film thickness. From the viewpoint of improving the coating property, In a range of 99% by mass or less. When apply | coating a photocurable composition to a base material by the inkjet method, it is preferable that a solvent does not contain substantially (for example, 3 mass% or less). On the other hand, when a pattern having a film thickness of 500 nm or less is formed by a method such as spin coating, it may be contained in a range of 20 to 99% by mass, preferably 40 to 99% by mass, particularly 70 to 98% by mass. preferable.

<< Other ingredients >>
In addition to the above-described components, the curable composition may include a polymerization inhibitor, a photosensitizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiaging agent, a plasticizer, an adhesion promoter, if necessary. Thermal polymerization initiator, photobase generator, colorant, inorganic particles, elastomer particles, basic compound, photoacid generator, photoacid growth agent, chain transfer agent, antistatic agent, flow regulator, antifoaming agent, dispersion An agent, a release agent and the like may be included. Specific examples of such components include those described in JP-A-2008-105414, paragraph numbers 0092 to 0093 and paragraph numbers 0099 to 0137, the contents of which are incorporated herein. Further, the corresponding descriptions of WO 2011/126101 pamphlet, WO 2013/051735 pamphlet, JP 2012-041521 A and JP 2013-093552 A can be referred to, and the contents thereof are incorporated in the present specification.

The photocurable composition can be prepared by mixing the above-described components. Mixing of each component is normally performed in the range of 0 degreeC-100 degreeC. Moreover, after mixing each component, it is preferable to filter with a filter, for example. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can also be refiltered.
Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon-6 and nylon-6,6, polyolefin resin such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably about 0.003 to 5.0 μm, for example. By setting it within this range, it becomes possible to reliably remove fine foreign matters such as impurities and aggregates contained in the composition while suppressing filtration clogging.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent hole diameters are the same or smaller than the first filtering hole diameter. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co. .

The photocurable composition preferably has a viscosity of 100 mPa · s or less at 25 ° C., more preferably 70 mPa · s or less, still more preferably 50 mPa · s or less, and 30 mPa · s or less. Is particularly preferred. The lower limit is, for example, preferably 1 mPa · s or more, preferably 2 mPa · s or more, and preferably 3 mPa · s or more.
Moreover, when applying a photocurable composition by the inkjet method, it is preferable that the viscosity of a photocurable composition is 25 mPa * s or less in 25 degreeC, It is more preferable that it is 12 mPa * s or less, 11 mPa -It is more preferable that it is s or less, and it is especially preferable that it is 10 mPa-s or less. By setting it as such a range, inkjet discharge precision and pattern formation property can be improved.
In addition, in permanent films (resist for structural members) used for liquid crystal displays (LCDs) and resists used for substrate processing of electronic materials, metals or organic substances in the resist are used so as not to hinder the operation of products. It is desirable to avoid contamination of ionic impurities as much as possible. For this reason, when using a pattern formation body for the above-mentioned use, as a density | concentration of the ionic impurity of the metal or organic substance in a photocurable composition, it is 1 ppm or less, Preferably it is 100 ppb or less, More preferably, it is 10 ppb or less. It is preferable.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

<Preparation of photocurable composition>
The raw materials shown in the following table were mixed and filtered through a 0.1 μm PTFE (polytetrafluoroethylene) filter to prepare a photocurable composition.

The symbols in the table are as follows.
(Polymerizable compound)
A-1: Neopentyl glycol diacrylate (Light acrylate NP-A manufactured by Kyoeisha Chemical Co., Ltd.)
A-2: benzyl acrylate (Biscoat # 160 manufactured by Osaka Organic Chemical Co., Ltd.)
(Photopolymerization initiator)
B-1: Irgacure 819 (manufactured by BASF)
B-2: Irgacure 127 (manufactured by BASF)
(Other ingredients)
C-1: Polypropylene glycol (Mw = 400, manufactured by Wako Pure Chemical Industries, Ltd.)
C-2: Capstone FS-3100 (manufactured by Dupont)

<Preparation of evaluation sample>
As the mold, a quartz mold having a Line / Space pattern with a line width of 30 nm and a depth of 60 nm was used.
The said photocurable composition was apply | coated on the silicon wafer using the inkjet apparatus (DMP-2831 by FUJIFILM Dimatix). The droplet size was 6 pL, and it was applied in a square lattice with 280 um intervals.
A quartz mold was pressed against the coating area, left at atmospheric pressure for 30 seconds, and then photocured from the quartz mold surface with a high-pressure mercury lamp. The irradiation amount was 100 mJ / cm ² .
After the exposure, the quartz mold was removed to obtain an evaluation sample.

<Measurement of remaining film>
It was 30 nm (initial residual film) when the film thickness of the area | region (pattern recessed part) in which the pattern of the said sample was not formed was measured using the ellipsometer (DVA-LF, the product made from a groove bottom optical industry).

<Residual film processing>
The sample was subjected to reactive ion etching using an etching apparatus.
The etching gas was O ₂ gas, and the sample was cooled to 20 ° C. during the etching.
The etching rate of the sample was about 1 nm / s.
The residual film thickness after etching was confirmed with an ellipsometer (DVA-LF, manufactured by Mizoji Optical Co., Ltd.). In Comparative Examples 1 to 4, no remaining film treatment was performed.

<Verification of heat-resistant temperature of sample>
Various samples were placed on a hot plate set at a predetermined temperature and heated. The heating temperature was 40 to 180 ° C. and the heating time was 1 min.
The pattern forming property of the sample after heating in the above process was confirmed with an atomic force microscope.
If the pattern collapse in the range of 5 μm x 5 μm confirmed by the atomic force microscope can be confirmed, it is determined that the pattern defect has occurred. The temperature at which pattern defects due to heating did not occur was defined as the heat resistant temperature.

<Measurement of glass transition point>
A photo-curable composition is cured by irradiating a high-pressure mercury lamp with 1000 mJ / cm ² to produce a film having a thickness of 150 μm, a strip-like sample having a width of 5 mm is cut out from the produced film, and a dynamic viscoelasticity measuring apparatus Measurement was performed with DMS-6100 (manufactured by Seiko Instruments Inc.). The temperature increase rate was 5 ° C./min, the measurement frequency was 1 Hz, and the temperature at which the tanD value reached the maximum value was defined as the glass transition temperature. When there were two or more glass transition temperatures, the temperature with the larger peak area of tanD for calculating the glass transition temperature was adopted.

As shown in Tables 2 to 5, the heat-resistant temperature could be increased by removing or thinning the remaining film before the heat treatment. For this reason, it turns out that an Example can suppress generation | occurrence | production of the pattern defect accompanying a heating compared with a comparative example.
In Example 1-1, after the remaining film was removed, a film-forming composition (0.5% by mass of trifluoropropyltrimethoxysilane dissolved in ethanol) was spin-coated and applied at 140 ° C. for 5 hours. When heat treatment was performed for a minute, an uneven pattern with no pattern defects and a film formed on the surface could be formed.

1 convex pattern

Claims (7)

A photocurable composition is applied on a base material or a mold having a pattern to form a pattern forming layer. After the pattern forming layer is sandwiched between the base material and the mold, light is applied to the pattern forming layer. Curing the pattern forming layer, releasing the mold from the surface of the cured pattern forming layer, and forming a pattern;
And a step of performing heat treatment after removing or thinning the film derived from the photocurable composition in the concave portion of the pattern.   The manufacturing method of the pattern formation body of Claim 1 which performs the said heat processing, after making the film | membrane derived from the said photocurable composition into 10 nm or less.   The manufacturing method of the pattern formation body of Claim 1 which performs the said heat processing, after making the film | membrane derived from the said photocurable composition into 5 nm or less.   The manufacturing method of the pattern formation body of any one of Claims 1-3 which removes or thins the film | membrane derived from the said photocurable composition by dry etching. The manufacturing method of the pattern formation body of any one of Claims 1-4 which performs the said heat processing at the heat processing temperature which satisfy | fills the relationship of the following Formula (1);
Heat treatment temperature ≦ Tg + 10 ° C. (1)
Tg is the glass transition temperature of the photocurable composition used for forming the pattern forming layer.   The composition containing a film forming component is applied to the surface of the pattern after removing or thinning the film derived from the photocurable composition and before performing the heat treatment. The manufacturing method of the pattern formation body of any one.   The manufacturing method of the pattern formation body of any one of Claims 1-6 in which the said pattern formation body has a pattern of width 300nm or less.

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