WO2017150094A1

WO2017150094A1 - Method for producing planarization film, active light sensitive or radiation sensitive composition for forming planarization film, planarization film, and method for manufacturing electronic device

Info

Publication number: WO2017150094A1
Application number: PCT/JP2017/004367
Authority: WO
Inventors: 康智米久田; 康介越島
Original assignee: 富士フイルム株式会社
Priority date: 2016-03-02
Filing date: 2017-02-07
Publication date: 2017-09-08
Also published as: TW201800847A

Abstract

Provided are: a method for producing a planarization film, which is capable of forming a planarization film having excellent planarization properties; an active light sensitive or radiation sensitive composition for forming a planarization film; a planarization film; and a method for manufacturing an electronic device. This method for producing a planarization film comprises: a step A for forming a film on a stepped substrate with use of a composition that contains a resin (A) and a photoacid generator (B); a step B for exposing the film to light through a mask that is arranged in a position corresponding to a projected part of the stepped substrate; and a step C for obtaining a planarization film by removing the film provided on the projected part of the stepped substrate with use of a developer liquid. In this connection, the γ value of a test film that is obtained using the above-described composition is less than 1,000.

Description

Planarizing film manufacturing method, actinic ray-sensitive or radiation-sensitive planarizing film-forming composition, planarizing film, and electronic device manufacturing method

The present invention relates to a method for producing a planarizing film, an actinic ray-sensitive or radiation-sensitive composition for forming a planarizing film, a planarizing film, and a method for producing an electronic device.

In recent years, in the manufacture of semiconductor devices among electronic devices, further miniaturization of wiring has been demanded in order to improve the performance of elements due to high integration.
In order to obtain such fine wiring, fine processing by photolithography is performed. Specifically, fine processing by photolithography is performed by forming a film of a photoresist composition on a substrate such as a silicon wafer and actinic rays such as ultraviolet rays through a mask pattern on which a semiconductor device pattern is drawn. Is a processing method in which a silicon wafer is etched using the obtained resist pattern as a protective material.

As a kind of such a photoresist composition, Patent Document 1 discloses a composition for forming a resist underlayer film. Specifically, the resist underlayer film forming composition of Patent Document 1 includes a conductive compound having a specific structural unit, a crosslinking agent, a compound that promotes a crosslinking reaction, and an organic solvent (Claim 1).

JP 2014-10408 A

A stepped substrate having a hole shape and / or a trench shape may be used as a substrate used for manufacturing an electronic device as described above. In the manufacture of electronic devices, an actinic ray-sensitive or radiation-sensitive planarizing film-forming composition such as the above-described photoresist composition is embedded in the holes and trenches of the stepped substrate, and an exposure process and a development process are performed. As a result, a substantially flat planarizing film may be formed on the stepped substrate.
Here, the stepped substrate has a portion which is convex with respect to the hole and the trench, that is, a portion where the hole and the trench are not formed (hereinafter also referred to as “convex portion”). Therefore, when a flattening film is formed by applying a flattening film-forming composition to the entire surface of the stepped substrate, the flattening film located on the convex portion is raised more than the flattening film located on the holes and trenches. End up. That is, the surface of the obtained planarization film has an uneven shape corresponding to the unevenness of the stepped substrate, and the flatness of the planarization film may be insufficient.
Thus, when the flatness of the planarization film is not sufficient, when manufacturing an electronic device or the like using the stepped substrate on which the planarization film is formed, the processing accuracy of the electronic device may be adversely affected.

For such a problem, when exposing a film obtained by applying the planarization film-forming composition onto the substrate, a mask is placed at a position corresponding to the convex portion of the stepped substrate (the convex portion of the film). As a result of arranging and exposing, there was a case where the flatness was not sufficient, and an improvement was necessary.

Therefore, an object of the present invention is to provide a method for producing a planarization film that can form a planarization film having excellent flatness. Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive composition for forming a planarizing film, a planarizing film, and a method for producing an electronic device.

As a result of intensive studies on the above problems, the present inventors have controlled the characteristics of a film formed by an actinic ray-sensitive or radiation-sensitive planarizing film-forming composition (that is, a film before exposure). The inventors have found that the desired effect can be obtained.
That is, the present inventors have found that the above problem can be solved by the following configuration.

[1]
A method for producing a planarizing film for planarizing the surface of a stepped substrate having irregularities on the surface,
A step A of forming a film on the stepped substrate using the actinic ray-sensitive or radiation-sensitive planarizing film-forming composition containing the resin (A) and the photoacid generator (B);
A step B of exposing the film through a mask disposed at a position corresponding to the convex portion of the stepped substrate;
Using a developer, removing at least a portion of the film provided on the convex portion of the stepped substrate to obtain a planarization film; and
Have
A method for producing a planarization film, wherein a test film having a thickness T is formed on a silicon substrate using the composition for forming a planarization film, wherein the value of γ of the test film is less than 1000.
Here, γ is obtained by the following γ calculation method.
γ calculation method: silicon with respect to the test membrane of the formed thickness T on a substrate 99 places performs exposure while increasing every 0.8 mJ / cm ² exposure amount from 1 mJ / cm ² by using a KrF excimer laser Then, the exposed test film is baked at 130 ° C. for 60 seconds, and then a removal process is performed to remove a part of the test film after baking with an aqueous 2.38 mass% tetramethylammonium hydroxide solution. The film thickness at each exposure point of the test film after the removal treatment is calculated, and the point corresponding to the film thickness and the exposure amount at each exposure point on the orthogonal coordinates with the film thickness as the vertical axis and the exposure amount as the horizontal axis A line obtained by connecting the plotted points is created, and the vertical axis on the line connects the point of thickness T × 0.8 and the vertical axis of the point of thickness T × 0.4. of the absolute value of the slope γ (Å ^· cm 2 / mJ To.
[2]
The method for producing a flattening film according to the above [1], wherein the flattening film forming composition is a negative type.
[3]
Resin (A1) in which the resin (A) contains 0.5 to 30 mol% of repeating units having two or more crosslinkable sites that are crosslinked by the action of an acid, and a repeating unit having a phenolic hydroxyl group The method for producing a planarizing film according to the above [1] or [2], comprising at least one of a resin (A2) containing.
[4]
The method for producing a flattened film according to the above [3], wherein the resin (A1) has substantially no repeating unit having an acid-decomposable group.
[5]
The method for producing a flattened film according to the above [3] or [4], wherein the crosslinkable site crosslinked by the action of the acid contained in the resin (A1) is a hydroxy group.
[6]
The method for producing a planarizing film according to any one of [3] to [5] above, wherein the resin (A1) is a novolac resin.
[7]
The repeating unit according to any one of the above [3] to [6], wherein the repeating unit having two or more crosslinkable sites crosslinked by the action of the acid contained in the resin (A1) has a benzenediol structure. A method for producing a planarizing film.
[8]
The flat unit according to any one of [3] to [7], wherein the repeating unit having two or more crosslinkable sites crosslinked by the action of the acid contained in the resin (A1) has a resorcinol structure. A method for producing a chemical film.
[9]
The flat unit according to any one of [3] to [8], wherein the repeating unit having two or more crosslinkable sites crosslinked by the action of the acid contained in the resin (A1) has a hydroquinone structure. A method for producing a chemical film.
[10]
[1] to [1], wherein the planarizing film-forming composition does not contain a crosslinking agent or contains the crosslinking agent in an amount of 5% by mass or less based on the total solid content of the planarizing film-forming composition. 9]. The method for producing a planarizing film according to any one of [9].
[11]
The method for producing a planarizing film according to any one of [1] to [10] above, wherein the glass transition temperature of the resin (A) is 150 ° C. or lower.
[12]
The content of the resin (A) according to any one of the above [1] to [11], wherein the content of the resin (A) is 50 to 99% by mass with respect to the total solid content of the composition for flattening film formation. A method for producing a planarizing film.
[13]
The method for producing a flattened film according to any one of the above [1] to [12], wherein the composition for forming a flattened film further contains an acid diffusion controller.
[14]
The method for producing a flattening film according to any one of the above [1] to [13], wherein the flattening film forming composition further contains a surfactant.
[15]
An actinic ray-sensitive or radiation-sensitive planarizing film-forming composition used in the method for producing a planarizing film according to any one of [1] to [14], wherein the planarizing film A planarization film-forming composition, wherein when the test film having a thickness T is formed on a silicon substrate using the composition for formation, the value of γ of the test film is less than 1000.
[16]
A planarizing film obtained using the actinic ray-sensitive or radiation-sensitive planarizing film-forming composition as described in [15] above.
[17]
A method for manufacturing an electronic device, including the method for manufacturing a planarizing film according to any one of [1] to [14].

As described below, according to the present invention, it is possible to provide a method for producing a planarizing film capable of forming a planarized film having excellent flatness. Moreover, according to this invention, the actinic-ray-sensitive or radiation-sensitive composition for planarization film formation, a planarization film, and the manufacturing method of an electronic device can be provided.

Schematic which shows a part of process in the manufacturing method of the planarization film | membrane of this invention. Schematic which shows a part of process in the manufacturing method of the planarization film | membrane of this invention. Schematic which shows a part of process in the manufacturing method of the planarization film | membrane of this invention. Schematic which shows a part of process in the manufacturing method of the planarization film | membrane of this invention. Schematic for demonstrating the calculation method of (gamma). Schematic for demonstrating the calculation method of (gamma). Schematic for demonstrating the calculation method of (gamma). An example of the plot figure produced in order to calculate γ.

Hereinafter, embodiments of the present invention will be described.
In the notation of a group (atomic group) in the present invention, the notation that does not indicate substitution and non-substitution includes those having no substituent and those having 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).
“Actinic light” or “radiation” in the present invention means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB) and the like. In the present invention, “light” means actinic rays or radiation.
In addition, “exposure” in the present invention is not limited to exposure with an ultraviolet ray, an ultraviolet ray (EUV light) typified by an excimer laser, an X-ray, an electron beam, an ion unless otherwise specified. Drawing with particle beams such as beams is also included in exposure.
In the present invention, “to” is used to mean that the numerical values described before and after it are included as a lower limit and an upper limit.
In the present invention, (meth) acrylate represents acrylate and methacrylate, and (meth) acryl represents acryl and methacryl.
In the present invention, 1 Å (angstrom) corresponds to 0.1 nm.

[Manufacturing method of flattened film]
The planarizing film manufacturing method of the present invention is a planarizing film manufacturing method for planarizing the surface of a stepped substrate having irregularities on the surface, and includes at least the following steps A to C.
Step A: Step of forming a film on the stepped substrate using the actinic ray-sensitive or radiation-sensitive planarizing film forming composition containing the resin (A) and the photoacid generator (B) Step B Step of exposing the film through a mask arranged at a position corresponding to the convex portion of the stepped substrate Step C: Using a developer, the film provided on the convex portion of the stepped substrate Removing at least a portion to obtain a planarization film

Hereinafter, the method for producing a planarizing film of the present invention will be described in detail with reference to the drawings. 1 to 4 are schematic views showing an example of a method for producing a planarizing film of the present invention step by step.

<Process A>
Step A uses an actinic ray-sensitive or radiation-sensitive planarizing film-forming composition containing a resin (A) and a photoacid generator (B) to form a film (hereinafter referred to as “resist film”) on a stepped substrate. Is also referred to as “.”. In the present invention, step A is also referred to as a resist film forming step. The resist film formed in step A is formed for the purpose of flattening the stepped substrate, and does not necessarily have to be used as an etching mask.

More specifically, a trench structure will be described as an example. First, a step substrate 10 is prepared as shown in FIG. The stepped substrate 10 is provided with a trench 12 having a predetermined opening width and depth (hereinafter also referred to as “concave portion 12”) and a convex portion 13 in which the trench 12 is not formed.
Next, as shown in FIG. 2, a planarization film forming composition is applied to the entire surface of the stepped substrate 10 to form a resist film 14. The resist film 14 has a convex upper film 14a formed by adhering the flat film forming composition on the convex part 13 and a concave part formed by flowing the flattening film forming composition into the trench 12. And a film 14b.

As a method for applying the planarization film forming composition on the stepped substrate 10, an appropriate known application method can be used. Examples of such a coating method include a spin coating method, a dip coating method, a roller blade method, and a spray method.

The composition for forming a protective film is preferably applied in an amount such that the coating film thickness (indicated as A in FIG. 2) on the convex upper film 14a is 500 to 5000 mm, and is 700 to 4000 mm. It is more preferable to apply in such an amount, and it is even more preferable to apply in an amount of 800 to 4000 mm.

In the present invention, the “step substrate” means a substrate provided with holes and / or trenches.
A method for manufacturing the stepped substrate 10 having the trench 12 is not particularly limited, and a known method can be used. For example, a method in which a photoresist process and an etching process are combined can be used. More specifically, a method of depositing an insulating film made of a mask nitride film / pad oxide film on a substrate and then etching it into a pattern can be used.

Examples of the stepped substrate 10 include a bottomed hole structure and a trench structure. As the bottomed hole structure, for example, the aspect ratio represented by height / diameter is 0.2 to 50, preferably 0.5 to 20, and more preferably 1 to 10. As the bottomed trench structure, for example, the aspect ratio represented by height / groove width is 0.2 to 50, preferably 0.5 to 20, and more preferably 1 to 10.
In addition, the measuring method of the opening width and depth of the hole structure and the trench structure can be measured by a publicly known method.
The stepped substrate 10 may have holes and trenches having the same opening size (groove width and diameter), depth and aspect ratio on the surface, and different opening sizes (groove width and diameter), depth, A plurality of types of holes and trenches having an aspect ratio may be provided.

The material constituting the stepped substrate 10 is not particularly limited, and silicon, silicon carbide, metal (for example, gold, silver, copper, nickel, and aluminum), metal nitride (for example, silicon nitride, titanium nitride, tantalum nitride, and the like) Tungsten nitride etc.), glass (eg quartz glass, borate glass and soda glass etc.), resin (eg polyethylene terephthalate and polyimide etc.) and metal oxides (eg silicon oxide, titanium oxide, zirconium oxide and oxide) Hafnium, etc.).

Details of the actinic ray-sensitive or radiation-sensitive planarizing film-forming composition used in this step (hereinafter also simply referred to as “composition” or “composition of the present invention”) will be described in detail later. To do.

In step A, the resist film 14 applied on the stepped substrate 10 may be baked (Pre Bake; PB).
The temperature during the baking process (PB) is preferably 70 ° C. to 200 ° C., and more preferably 80 ° C. to 180 ° C. Further, the time for performing the baking treatment (PB) is preferably 20 to 180 seconds, and more preferably 30 to 120 seconds.
The baking process (PB) can be performed using a known heating device.

<Process B>
Step B is a step of exposing the resist film through a mask arranged at a position corresponding to the convex portion of the stepped substrate. In the present invention, step B is also referred to as an exposure step.
Specifically, as shown in FIG. 3, the resist film 14 is irradiated with actinic rays or radiation through a mask 20 disposed at a position corresponding to the convex portion 13 of the stepped substrate 10. Part of the resist film 14A is exposed to form a resist film 14A after exposure.
The exposed resist film 14A includes a convex upper film 14a located in the unexposed area and a post-exposed concave film 14B located in the exposed area.
Although the example of FIG. 3 shows the state where the convex portion upper film 14a is not exposed, the present invention is not limited to this, and the convex portion upper film 14a may be slightly exposed by light diffracted at the time of exposure.

The exposure apparatus used in this step is not particularly limited, and a known apparatus may be used.
Although there is no restriction | limiting in the light source wavelength used for exposure apparatus, Infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, an electron beam, etc. can be mentioned, Preferably it is 250 nm or less, More preferably Is far ultraviolet light having a wavelength of 220 nm or less, particularly preferably 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (Extreme) Ultraviolet) (13 nm), electron beam, etc., preferably KrF excimer laser, ArF excimer laser, EUV or electron beam, more preferably KrF excimer laser, ArF excimer laser.

In this step, the mask 20 is disposed at a position corresponding to the convex portion 13 of the step substrate 10.
The “position corresponding to the convex portion 13 of the stepped substrate 10” specifically refers to a position where the convex portion 13 is not irradiated with light irradiated from the exposure apparatus when the resist film 14 is exposed. That is, the mask 20 is disposed so that the opening of the mask 20 is disposed above the recess 12 (above the recess upper film 14B).
As such a position, for example, when the surface of the stepped substrate 10 on which the resist film 14 is formed is viewed in plan, the position where the entire region within the contour of the convex portion 13 is covered, and the contour of the convex upper film 14a The position where the entire area is covered is mentioned.

<Process C>
Step C is a step of obtaining a planarizing film by removing at least a part of the film provided on the convex portion of the stepped substrate using a developer. In the present invention, step C is also referred to as a development step.
The example of FIG. 4 shows a state in which the convex film 14a located in the unexposed area is removed from the resist film 14A after exposure, and only the concave film 14B after exposure is left. That is, the exposed concave upper film 14B obtained through the development process is the planarizing film 14C.

The developer used in this step is not particularly limited, and for example, an alkali developer or a developer containing an organic solvent (hereinafter also referred to as “organic developer”) can be used. Among these, it is preferable to use an alkali developer.
Examples of the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine And secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammoni Tetraalkylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, and triethylbenzylammonium hydroxide, such as Alkaline aqueous solutions such as quaternary ammonium salts such as pyrrole and cyclic amines such as pyrrole and piperidine can be used. Furthermore, an appropriate amount of alcohol and / or surfactant can be added to the alkaline aqueous solution. The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass. The pH of the alkali developer is usually from 10.0 to 15.0. The alkali concentration and pH of the alkali developer can be appropriately adjusted and used. The alkali developer may be used after adding a surfactant or an organic solvent.
As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.

Further, after the development process or the rinsing process, it is possible to perform a process of removing the developer or the rinsing liquid adhering on the planarizing film with a supercritical fluid.

As the organic developer, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent, and a hydrocarbon solvent can be used. And the solvent described in paragraph <0507> of -218223, and isoamyl acetate, butyl butanoate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used relative to the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developer. .

In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

The vapor pressure of the organic developer at 20 ° C. is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less. By setting the vapor pressure of the organic developer to 5 kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.

An appropriate amount of a surfactant can be added to the organic developer as required. Two or more surfactants may be used in combination.
The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, Mention may be made of the surfactants described in US Pat. No. 5,360,692, US Pat. Preferably, it is a nonionic surfactant. The nonionic surfactant is not particularly limited, and it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.

The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

The organic developer may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the organic developer used in the present invention are the same as those in the basic compound that can be contained in the composition as an acid diffusion controller described later.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispensing). Law) and the like can be applied.

When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. There is no particular lower limit of the flow rate, and 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer within the above range, defects in the planarization film derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure in the above range, the pressure applied to the resist film by the developer is reduced, and the resist film and the planarizing film are inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
Moreover, you may implement the process of stopping image development, substituting with another solvent after the process developed using the developing solution containing an organic solvent.

In the method for producing a planarized film of the present invention, a step of developing using a developer containing an organic solvent (organic solvent developing step) and a step of developing using an aqueous alkaline solution (alkali developing step) are combined. May be used.

It is preferable to include the process of wash | cleaning using a rinse liquid after the process developed using the developing solution containing an organic solvent.
The rinsing solution used in the rinsing step after the step of developing using a developer containing an organic solvent is not particularly limited as long as the planarizing film is not dissolved, and a solution containing a general organic solvent may be used. it can. As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents should be used. Is preferred.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.

More preferably, after the step of developing using a developer containing an organic solvent, at least one selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and hydrocarbon solvents. The step of washing with a rinsing liquid containing an organic solvent is performed, more preferably the step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent, particularly preferably a monohydric alcohol. A cleaning step is performed using the rinsing liquid contained, and most preferably, a cleaning step is performed using a rinsing liquid containing a monohydric alcohol having 5 or more carbon atoms.

Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms are 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It can be.
As the rinsing liquid containing a hydrocarbon solvent, a hydrocarbon compound having 6 to 30 carbon atoms is preferable, a hydrocarbon compound having 7 to 30 carbon atoms is more preferable, and a hydrocarbon compound having 8 to 30 carbon atoms is more preferable. A hydrocarbon compound having 10 to 30 carbon atoms is particularly preferred.
When an ester solvent is used as the rinsing liquid, a glycol ether solvent may be used in addition to the ester solvent (one or more). Specific examples in this case include using an ester solvent (preferably butyl acetate) as a main component and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) as a subcomponent. Thereby, residue defects are suppressed.

A plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The vapor pressure of the rinsing liquid used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa or more at 20 ° C. More preferably, it is 3 kPa or less. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface is improved. It improves.

An appropriate amount of a surfactant can be added to the rinse solution.
In the rinsing step, washing is performed using a rinsing solution. The method of the cleaning treatment is not particularly limited. For example, the method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), and the like can be applied. Among these, it is preferable to perform a cleaning process by a spin coating method, and after the cleaning, rotate the substrate at a rotational speed of 2000 rpm to 4000 rpm to remove the rinse liquid from the substrate.

Further, it is also preferable to perform a baking process (Post Bake) after the rinsing process. The developer and rinse solution remaining on the surface and inside of the planarizing film are removed by baking. The post-baking is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

Further, after step B and before step C, the exposed resist film may be baked (post exposure bake; PEB).
The temperature in the baking treatment is not particularly limited, and is often 160 ° C. or less, and is preferably 150 ° C. or less because the effects of the present invention are more excellent. The lower limit is not particularly limited, and is often 50 ° C. or higher.
The baking time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds.
Baking can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
Baking promotes the reaction of the exposed area and improves the sensitivity and pattern profile.

<Value of γ>
In the present invention, when a test film having a thickness T is formed on a silicon substrate using the planarizing film forming composition, the value of γ of the test film is less than 1000. That is, in the method for producing a planarization film of the present invention, a planarization film forming composition having a value of γ calculated by a γ calculation method described later of less than 1000 is used.
The value of γ of the test film is a parameter that can be calculated by a method to be described later, but mainly represents the sensitivity of the resist film to the exposure amount.
When the value of γ is large, the sensitivity of the resist film with respect to the exposure amount is high, and the thickness of the test film varies greatly even with a slight difference in the exposure amount. On the other hand, when the value of γ is small, the sensitivity to the exposure amount of the resist film is low, and even if the exposure amount varies, a difference in the thickness of the test film hardly occurs.
Here, in the planarization film manufacturing method described above, even if the convex upper film 14a, which is a masked part at the time of exposure of the resist film, is slightly exposed by diffracted light, the sensitivity of the resist film Is easily removed by development.
On the other hand, the recess upper film 14b, which is a portion not masked at the time of exposure of the resist film, has a low sensitivity to the exposure amount of the resist film, but is not masked, so that a sufficient exposure amount is given. Therefore, the concave upper film 14B after exposure is sufficiently cured and is not easily removed by development.
Thus, when the sensitivity to the exposure amount of the resist film is low, that is, the value of γ is small, the concave film 14b (the concave film 14B after exposure) is removed while removing the convex film 14a of the resist film. Since it can hold | maintain, it is estimated that the planarity of the planarization film | membrane 14C becomes the outstanding thing.

The value of γ needs to be less than 1000, but is preferably 900 or less, more preferably 800 or less, and even more preferably 500 or less from the viewpoint that the above-described effects are further improved. 100 or less is particularly preferable. The lower limit is not particularly limited, and is preferably 1 or more and more preferably 5 or more from the viewpoint of productivity.

Hereinafter, the calculation method of γ will be described with reference to the drawings.
First, as shown in FIG. 5, a test film (resist film) 120 having a thickness T is formed on a substrate 100. As a substrate to be used, a Si substrate (manufactured by Advanced Materials Technology) subjected to hexamethyldisilazane treatment is used.
The thickness T is usually 500 to 5000 mm, preferably 700 to 4500 mm, and more preferably 800 to 4000 mm.
The film (resist film) 120 having a thickness T is manufactured by applying the composition onto the substrate 100 by a spin coating method and baking (Pre Bake) at 140 ° C. for 60 seconds.
Then, a KrF excimer laser scanner (NA0.80), without passing through the exposure mask, the wafer having a resist film formed, while the amount of exposure from 1 mJ / cm ² increased every 0.8 mJ / cm ² 99-point exposure is performed. That is, exposure with different exposure amounts is performed for 99 different positions on the film surface. At that time, the exposure amount in each exposure position ^{is, 1mJ / cm 2 0.8mJ / cm} 2 every increase from. More specifically, as shown in FIG. 6, exposure is performed by changing the exposure amount at different portions of the film, as indicated by the white arrows. In FIG. 6, exposure is performed at three different positions on the film 120. In the rightmost exposure in FIG. 6, exposure is performed at an exposure amount AmJ / cm ² , and in the middle exposure, exposure is performed at an exposure amount (A + 0.8) mJ / cm ² , and the leftmost exposure is performed. Then, exposure is performed at an exposure amount (A + 1.6) mJ / cm ² . In this manner, exposure is performed while increasing the exposure amount by 0.8 mJ / cm ^{2 for} each exposure location.
Thereafter, the exposed resist film is baked at 130 ° C. for 60 seconds (Post Exposure Bake; PEB).
Thereafter, development processing is performed on the obtained film. As a development processing method, development is performed for 60 seconds with an aqueous tetramethylammonium hydroxide solution (2.38% by mass: “the concentration of tetramethylammonium hydroxide in the aqueous solution is 2.38% by mass”), and 30% with pure water. After rinsing for 2 seconds, spin drying is performed.
When the development process is performed, the film is removed at an unexposed portion, and the amount of removal of the film decreases as the exposure amount increases. The removal amount at that time varies depending on the exposure amount. For example, FIG. 7 is a view after the development processing is performed on the film shown in FIG. Becomes the thinnest. That is, a relationship of T1>T2> T3 is established. In FIG. 7, only the film thicknesses at three points are shown, but actually the film thicknesses at the 99 exposure points are measured.
Next, a plot diagram is created using the exposure amount and film thickness data at each exposure location. Specifically, the points corresponding to the film thickness and the exposure dose at each exposure location are plotted on orthogonal coordinates with the film thickness as the vertical axis and the exposure dose as the horizontal axis. That is, a graph is created with the film thickness at each exposure location on the vertical axis and the common logarithm of the exposure amount at each exposure location on the horizontal axis. The unit of the vertical axis is Å, and the unit of exposure amount is mJ / cm ² . FIG. 8 shows an example of a plot diagram. Each black circle in FIG. 8 corresponds to the result (film thickness and exposure amount) at each exposure location. In FIG. 8, for ease of explanation, the number of black circle plots is less than the actual 99 points.
Next, a line is created by connecting the plotted points in the obtained plot. On the obtained line, the vertical axis thickness value is 0.8 × T (80% thickness of T) point A, and the vertical axis thickness value is 0.4 × T (40 T). % B) is selected, and the absolute value of the slope of the straight line connecting the points A and B is calculated and set as γ.
For example, when the thickness T is 2000 mm, 0.8T corresponds to 1600 mm and 0.4T corresponds to 800 mm. Here, as shown in FIG. 8, when the value of the horizontal axis of the point where the thickness of the vertical axis is 1600 mm is X and the value of the horizontal axis of the point where the thickness of the vertical axis is 800 mm is Y, these two points Is calculated as (1600−800) / (XY), and its absolute value is γ.

The method for controlling γ described above is not particularly limited. For example, it can be performed by adjusting the type and amount of materials (for example, resin and photoacid generator) contained in the composition for forming a planarization film. . More specifically, the curability of the resin (A1) and the resin (A2) is maintained by using the resin (A1) and / or the resin (A2), which will be described later, and the photoacid generator (B) in combination. However, the value of γ can be reduced by reducing the crosslinking rate.
The value of γ can also be controlled by changing the temperature at PB, the development time during the development process, and the like.

[Composition for forming actinic ray-sensitive or radiation-sensitive planarizing film]
In the method for producing a planarizing film of the present invention, an actinic ray-sensitive or radiation-sensitive composition for forming a planarizing film is used. The actinic ray-sensitive or radiation-sensitive planarizing film-forming composition contains at least a resin (A) and a photoacid generator (B).
The planarization film-forming composition of the present invention is preferably a negative type. That is, when the flat film forming composition is exposed, the exposed portion is hardly dissolved by the developer.

Hereinafter, the components contained in the composition for forming an actinic ray-sensitive or radiation-sensitive planarizing film and components that may be contained will be described in detail.

<Resin (A)>
The resin (A) is not particularly limited as long as it can easily reduce the above-described γ value to less than 1000, and it becomes easier to adjust the above-described γ value to a value less than 1000, It is preferable that at least one of resin (A1) and resin (A2), which will be described later, is included from the viewpoint that a flattened film superior in flatness can be produced.
Resin (A) may be used individually by 1 type, and may use 2 or more types together.

The glass transition temperature (Tg) of the resin (A) is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, further preferably 80 ° C. or lower, and particularly preferably 50 ° C. or lower. preferable.
When the Tg of the resin (A) is 150 ° C. or less, the fluidity of the composition for forming a flattened film becomes good, and the flatness of the flattened film can be further improved.
In addition, since the fluidity | liquidity of the composition for planarization film formation becomes so favorable that Tg of resin (A) is low, the lower limit of Tg of resin (A) is not specifically limited, Resin (A) The lower limit of Tg is usually 5 ° C. or higher.
The glass transition temperature (Tg) was determined by weighing a vacuum-dried sample (about 2 mg) on an aluminum pan using a differential scanning calorimeter (DSC) Q2000 manufactured by TA Instruments, and measuring the aluminum pan using DSC. Obtained from the inflection point when the temperature is set at 10 ° C. to 200 ° C. at a rate of 2 ° C./min. When an inflection point of a DTA (differential thermal analysis) curve corresponding to the glass transition temperature is not observed by 200 ° C., Tg is determined to be 200 ° C. or higher.

The content of the resin (A) is preferably 50 to 99% by mass, more preferably 55 to 97% by mass, and more preferably 60 to 95% with respect to the total solid content of the flattening film forming composition. More preferably, it is mass%.
When the content of the resin (A) is 50% by mass or more, the curability of the flattened film becomes better.

(Resin (A1))
The resin (A1) is a resin containing 0.5 to 30 mol% of repeating units having two or more crosslinkable sites that are crosslinked by the action of an acid.
When the planarizing film-forming composition of the present invention is irradiated with actinic rays or radiation, the crosslinkable site of the resin (A1) is crosslinked by the action of the acid generated from the photoacid generator (B).
Here, since the crosslinking reaction of the crosslinkable site of the resin (A1) proceeds slowly, the planarization film-forming composition containing the resin (A1) has low sensitivity to actinic rays or radiation. Therefore, it is presumed that it becomes easier to adjust the value of γ by less than 1000.

Since the film formed on the convex part of the stepped substrate obtained by using the planarizing film forming composition is masked in the process B (exposure process), it is difficult to be exposed. Therefore, the cross-linking reaction of the cross-linkable site of the resin (A1) becomes slower, and the curability of the film formed on the convex portion of the step substrate is lowered. Thereby, the film formed on the convex portion of the stepped substrate is more easily removed in the step C (developing step).
On the other hand, the film (film embedded in the concave portion) formed on the concave portion of the stepped substrate obtained by using the planarization film forming composition is not masked in the step B (exposure step) and is sufficiently Since it is exposed, it cures well. For this reason, the film formed on the concave portion of the stepped substrate is difficult to be removed in the step C (developing step).
As a result, it is estimated that the flatness of the planarization film formed on the stepped substrate is further improved.

Hereinafter, a repeating unit having two or more crosslinkable sites that are crosslinked by the action of an acid is also simply referred to as “repeating unit (a1)”.

Examples of the crosslinkable site that is crosslinked by the action of an acid include a hydroxy group and an epoxy group. From the viewpoint of easy control of the reaction, a hydroxy group is preferable, and a phenolic hydroxyl group is more preferable.
The number of cross-linkable sites that are cross-linked by the action of an acid contained in the repeating unit is 2 or more, but preferably 2 to 4, and the curability of the composition for forming a flattened film is maintained. However, it is more preferable that the number is two from the viewpoint that the sensitivity can be lowered.
Two or more crosslinkable sites that are cross-linked by the action of an acid contained in the repeating unit may be the same or different from each other, but are preferably the same.

The resin (A1) is preferably a novolak resin from the viewpoint that it becomes easy to adjust the value of γ described above to less than 1000 and the flatness of the planarizing film is further improved.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst.
Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, hydroquinone, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.

Specific examples of the novolak resin include a condensation product of hydroquinone, resorcinol or a mixture thereof and formalin.
The novolak resin may be adjusted in molecular weight distribution using means such as fractionation. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, in the said novolak resin.

From the viewpoint that the repeating unit (a1) can easily adjust the value of γ described above to less than 1000, the flatness of the flattened film can be further improved, and swelling of the flattened film can also be suppressed. It preferably has a structure, and preferably has at least one of a resorcinol structure (see the following formula (a1-1)) and a hydroquinone structure (see the following formula (a1-2)).

The content of the repeating unit (a1) is preferably 0.5 to 30 mol% and preferably 1 to 20 mol% with respect to 100 mol% of all repeating units constituting the resin (A1). More preferably, it is 1 to 15 mol%, further preferably 1 to 10 mol%.
When the content of the repeating unit (a1) is 0.5 mol% or more, the flatness of the flattened film can be further improved. Moreover, since it can suppress that the sensitivity of the composition for planarization film formation falls too much because content of a repeating unit (a1) is 30 mol% or less, productivity of a planarization film becomes favorable.

The resin (A1) may have a repeating unit other than the repeating unit (a1). Examples of such a repeating unit include a repeating unit having a phenol structure, a repeating unit having an olefin structure, a repeating unit having an epoxy structure, a repeating unit having a methylol structure, and the like, from the viewpoint that the value of γ can be further reduced. A repeating unit having a phenol structure is preferred.
The content of repeating units other than the above repeating unit (a1) is preferably 70 to 99.5 mol%, based on 100 mol% of all repeating units constituting the resin (A1), and preferably 80 to 99 mol%. More preferably, it is 85 to 99 mol%, more preferably 90 to 99 mol%.

Resin (A1) has substantially a repeating unit having an acid-decomposable group from the viewpoint that when the exposure of the resist film is performed at a low exposure amount, the resist film in the exposed portion is too thin after development. Preferably not. Details of the acid-decomposable group will be described in the section of the resin (A2) described later.
Here, having substantially no repeating unit having an acid-decomposable group specifically means that the content of the repeating unit having an acid-decomposable group is 100% of all repeating units constituting the resin (A1). It means 0 to 5 mol% with respect to mol%, preferably 0 to 3 mol%, preferably 0 mol% (that is, having no repeating unit having an acid-decomposable group). ) Is more preferable.

The weight average molecular weight (Mw) of the resin (A1) is preferably 1000 to 30000, more preferably 1500 to 25000, and still more preferably 1500 to 20000.
Regarding the resin (A1), the weight average molecular weight (Mw), the number average molecular weight (Mn), and the dispersity (Mw / Mn) indicate polystyrene conversion values by GPC measurement.
For weight average molecular weight and number average molecular weight, HLC-8120 (manufactured by Tosoh Corporation) was used, and TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm) was used as an eluent. Calculated by using (tetrahydrofuran).
The dispersity (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and 1.1 to More preferably, it is 2.0. The smaller the molecular weight distribution, the better the resolution and resist shape, the smoother the side wall of the planarizing film, and the better the roughness.

Specific examples of resin (A1) are shown below. In the following formula, n, m, and p represent the number of repeating units.

(Resin (A2))
The resin (A2) is a resin containing a repeating unit having a phenolic hydroxyl group.
When the planarizing film-forming composition of the present invention is irradiated with an actinic ray or radiation sensitive, the phenolic hydroxyl group contained in the resin (A2) is crosslinked by the action of the acid generated from the photoacid generator (B).
Therefore, when the film (resist film) obtained using the planarization film-forming composition is irradiated with actinic rays or radiation, the resist film is cured by the action of the phenolic hydroxyl group contained in the resin (A2). By appropriately adjusting the content (mol%) of the repeating unit having a phenolic hydroxyl group and the content (mass%) of a crosslinking agent optionally used, the value of γ can be easily adjusted to less than 1000.

Since the film formed on the convex part of the stepped substrate obtained by using the planarizing film forming composition is masked in the process B (exposure process), it is difficult to be exposed. Therefore, the cross-linking reaction of the phenolic hydroxyl group contained in the film formed on the convex part does not proceed sufficiently, and the film formed on the convex part of the stepped substrate is further removed in the step C (development process). It becomes easy to be done.
On the other hand, the film (film embedded in the concave portion) formed on the concave portion of the stepped substrate obtained by using the planarization film forming composition is not masked in the step B (exposure step) and is sufficiently Since it is exposed, it cures well. For this reason, the film formed on the concave portion of the stepped substrate is difficult to be removed in the step C (developing step).
As a result, it is estimated that the flatness of the planarization film formed on the stepped substrate is further improved.

Resin (A2) should just contain the repeating unit which has a phenolic hydroxyl group, and it is preferable that it is resin which consists only of a repeating unit which has a phenolic hydroxyl group from the point that the flatness of a planarization film | membrane improves more. .
The repeating unit having a phenolic hydroxyl group is represented by the following general formula (IA) and the following general formula (IB) from the viewpoint that the flatness of the planarizing film is further improved. It is preferably at least one repeating unit selected from repeating units and repeating units represented by the following general formula (IC).
The repeating unit having a phenolic hydroxyl group may be used alone or in combination of two or more. From the viewpoint of further improving the flatness of the planarizing film, it may be used alone. preferable.

In the formula (IA), R ₁ represents a hydrogen atom or a methyl group. m represents 1 or 2.
In the formula (IC), R ₂ represents a hydrogen atom or a methyl group. n represents 1 or 2.

The content of the repeating unit having a phenolic hydroxyl group is preferably 5 mol% or more, more preferably 20 mol% or more, more preferably 50 mol, based on 100 mol% of all repeating units of the resin (A2). % Or more is more preferable, and 80 mol% or more is particularly preferable.
When the content of the repeating unit having a phenolic hydroxyl group is 5 mol% or more, the flatness of the flattened film can be further improved.

Hereinafter, a specific structure of the repeating unit represented by the formula (IA) is exemplified, but the present invention is not limited thereto.

It is particularly preferable that the repeating unit represented by the general formula (IA) has a structure represented by the formula (I) -a.

Hereinafter, a specific structure of the repeating unit represented by the formula (IC) is exemplified, but the present invention is not limited thereto.

The resin (A2) may further contain a repeating unit having an acid-decomposable group. The repeating unit having an acid-decomposable group may have an acid-decomposable group in at least one of the main chain and the side chain, and a repeating unit represented by the following general formula (II) is preferably used.

In formula (II), R ₁ represents a hydrogen atom or a methyl group. A represents a group that decomposes and leaves by the action of an acid.

An acid-decomposable group is a group that decomposes by the action of an acid to produce an alkali-soluble group.
Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) Imido group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group A group having
A preferred group as an acid-decomposable group (acid-decomposable group) is a group in which the hydrogen atom of these alkali-soluble groups is substituted with a group capable of leaving by the action of an acid.
Examples of the group leaving with an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), —C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, R ₃₆ to R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ to R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.
The acid-decomposable group is contained in the repeating unit represented by the general formula (II), but may be further contained in another repeating unit.

A in the repeating unit represented by the formula (II) represents a group that decomposes and leaves by the action of an acid, and is a hydrocarbon group (preferably having 20 or less carbon atoms, more preferably 4 to 12 carbon atoms). More preferred are a t-butyl group, a t-amyl group, and a hydrocarbon group having an alicyclic structure (for example, an alicyclic group itself, or a group in which an alicyclic group is substituted on an alkyl group), and t-butyl. Groups are more preferred.
The alicyclic structure may be monocyclic or polycyclic. Specific examples include monocyclo, bicyclo, tricyclo, and tetracyclo structures having 5 or more carbon atoms. The number of carbon atoms is preferably 6-30, and particularly preferably 7-25. These hydrocarbon groups having an alicyclic structure may further have a substituent. Further, examples of the substituent that may be included include an alkyl group having 1 to 4 carbon atoms, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a cyano group, and a nitro group.

The content of the repeating unit having an acid-decomposable group (preferably the repeating unit represented by formula (II)) is 50 mol% or less with respect to 100 mol% of all the repeating units of the resin (A2). Is preferable, and it is more preferable that it is 40 mol% or less.

Hereinafter, although the specific structure of the repeating unit represented by Formula (II) is illustrated, it is not this limitation.

It is particularly preferable that the repeating unit represented by the general formula (II) has a structure represented by the formula (II) -a.

In formula (II) -a, R ₁ represents a hydrogen atom or a methyl group.

Resin (A2) is not particularly limited, and may have a repeating unit other than the above. As the repeating unit other than the above, it is preferable to use a repeating unit represented by the following general formula (III) from the viewpoint of lowering the Tg of the resin (A2).

In general formula (III), R ₁ represents a hydrogen atom or a methyl group.
R ₂ represents a phenyl group or a cyclohexyl group, and is preferably a phenyl group. These phenyl group and cyclohexyl group may further have one or more substituents.
Examples of the substituent that the phenyl group and the cyclohexyl group may further include an alkyl group having 1 to 4 carbon atoms, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a cyano group, and a nitro group. Particularly preferred substituents are alkyl groups having 1 to 4 carbon atoms.
n represents an integer of 0 to 2, and is preferably 1.

When the resin (A2) has a repeating unit represented by the general formula (III), the content of the repeating unit represented by the general formula (III) is 100 mol% of all the repeating units of the resin (A2). On the other hand, it is preferably 50 mol% or less, more preferably 40 mol% or less, and further preferably 35 mol% or less.

Hereinafter, although the specific structure of the repeating unit represented by general formula (III) is illustrated, it is not this limitation.

The resin (A2) may further have a repeating unit other than the above. As the repeating unit other than the above, a repeating unit having a carboxylic acid group is preferably used from the viewpoint that the swelling of the planarizing film can be suppressed.
The repeating unit having a carboxylic acid group is at least one type of repeating unit selected from repeating units represented by the following formulas (IV-A) to (IV-C) from the viewpoint that the swelling of the planarization film can be further suppressed. Preferably it is a unit.
Further, among the repeating units represented by the formulas (IV-A) to (IV-C), the repeating unit represented by the formula (IV-A) is included from the viewpoint of further suppressing the swelling of the planarizing film. Is preferred.
The repeating unit having a carboxylic acid group may be used alone or in combination of two or more.

In the formula (IV-A), R _3A represents a hydrogen atom or a methyl group.
In formula (IV-B), R _3B-1 represents a hydrogen atom or a methyl group, and R _3B-2 represents an alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an adamantyl group, a diadamantyl group, or a group obtained by removing one hydrogen atom from a norbornane group.
In the formula (IV-C), R _3C represents a hydrogen atom or a methyl group, and Ar represents an aromatic hydrocarbon group. As the aromatic hydrocarbon group, a phenylene group or a naphthylene group is preferable.

When the resin (A2) has a repeating unit having a carboxylic acid group, the content of the repeating unit having a carboxylic acid group is 1 to 50 mol% with respect to 100 mol% of all the repeating units of the resin (A2). Preferably, it is 1 to 30 mol%, more preferably 5 to 30 mol%. When the content of the repeating unit having a carboxylic acid group is within the above range, swelling of the planarizing film can be further suppressed while maintaining the planarity of the planarizing film in a favorable range.

Hereinafter, specific structures of the repeating units represented by the general formulas (IV-A) to (IV-C) are exemplified, but the present invention is not limited thereto.

The resin (A2) may further have a repeating unit other than the above. As the repeating unit other than the above, a repeating unit having a hydroxyl group is preferably used from the viewpoint of suppressing swelling of the planarizing film.
The repeating unit having a hydroxyl group is preferably at least one repeating unit selected from repeating units represented by the following formulas (VA) to (VB). The repeating unit having a hydroxyl group may be used alone or in combination of two or more.

In the formula (VA), R _4A-1 represents a hydrogen atom or a methyl group, and R _4A-2 represents a linear or branched alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 10, and more preferably 1 to 5.
In the formula (VB), R _4B-1 represents a hydrogen atom or a methyl group, and R _4B-2 represents an alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an adamantyl group, a diadamantyl group, or a group obtained by removing one hydrogen atom from a norbornane group.

When the resin (A2) has a repeating unit having a hydroxyl group, the content of the repeating unit having a hydroxyl group is 1 to 50 mol% with respect to 100 mol% of all the repeating units of the resin (A2). Preferably, it is 1 to 30 mol%, more preferably 5 to 30 mol%. When the content of the repeating unit having a hydroxyl group is within the above range, it is possible to further suppress swelling of the planarizing film while maintaining the planarity of the planarizing film in a favorable range.

Hereinafter, specific structures of the repeating units represented by the general formulas (VA) to (VB) are exemplified, but not limited thereto.

Resin (A2) may further have a repeating unit other than the above. As the repeating unit other than the above, a repeating unit based on styrene is preferably used from the viewpoint of lowering the Tg of the resin (A2). The repeating unit based on styrene is specifically a repeating unit represented by the following formula (VI).

When the resin (A2) has a repeating unit based on styrene, the content of the repeating unit based on styrene is 1 to 50 mol% with respect to 100 mol% of all repeating units of the resin (A2). Preferably, it is 1 to 30 mol%, more preferably 5 to 30 mol%. Since the content of the repeating unit based on styrene is within the above range, the resin (A2) can have a low Tg, and thus the flatness of the flattened film can be further improved.

The weight average molecular weight (Mw) of the resin (A2) is preferably 1500 to 25000, and more preferably 1500 to 20000.
The dispersity (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and still more preferably 1.0 to 2.0. .
The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the resin (A2) are polystyrene-converted values by GPC measurement, and can be measured by the same method as the resin (A1).

Specific examples of the resin (A2) will be shown below, but are not limited thereto.

The planarization film-forming composition of the present invention may contain two or more kinds of resins (A1). Similarly, two or more kinds of resins (A2) may be contained, and both the resin (A1) and the resin (A2) may be contained.

<Photoacid generator (B)>
The photoacid generator (B) contained in the composition of the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter, “compound (B)”, “acid generator”, “acid generator”). (B) "or" photo acid generator ") as long as it is not particularly limited.
The compound (B) is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation.

The compound (B) may be in the form of a low molecular compound or may be in a form incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
When the compound (B) is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
When the compound (B) is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above or may be incorporated in a resin different from the resin (A). . Specific examples of the case where the compound (B) is incorporated in a part of the polymer include paragraphs 0191 to 0209 in JP2013-54196A.

As the acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation used for micro resist, etc. The known compounds that generate an acid and mixtures thereof can be appropriately selected and used.
For example, examples of the acid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

As the acid generator, an acid generator having a pKa of the generated acid of −2 or more is preferable. Among these, pKa is preferably −1.5 or more, more preferably −1 or more, from the viewpoint that it is excellent in the flatness of the formed flattening film. Moreover, the upper limit of pKa is not particularly limited, and is preferably 1 or less.
pKa (acid strength) is one of the indexes for quantitatively expressing the strength of acid, and is synonymous with an acidity constant. Considering a dissociation reaction in which hydrogen ions are released from an acid, its equilibrium constant Ka is expressed by its negative common logarithm pKa. A smaller pKa indicates a stronger acid. In the present invention, the calculation is performed by calculation using the following software package 1.
Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

Preferred compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two _{members out} of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
Z ⁻ represents a non-nucleophilic anion.
Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

The “non-nucleophilic anion” is an anion having an extremely low ability to cause a nucleophilic reaction, and an anion capable of suppressing degradation with time due to an intramolecular nucleophilic reaction. Thereby, the temporal stability of the composition is improved.
Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.
Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms. An alkyl group is mentioned. The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent.
Examples of other non-nucleophilic anions include fluorinated phosphorus (for example, PF ₆ ⁻ ), fluorinated boron (for example, BF ₄ ⁻ ), fluorinated antimony and the like (for example, SbF ₆ ⁻ ). .

Examples of the non-nucleophilic anion of Z ⁻ include an aliphatic sulfonate anion in which at least α position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, an alkyl group Is preferably a bis (alkylsulfonyl) imide anion substituted with a fluorine atom, or a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms, a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, Pentafluorobenzenesulfonate anion, 3,5-bis (trifluoromethyl) benzenesulfonate anion.

The non-nucleophilic anion of Z ⁻ is preferably represented by the general formula (2). In this case, the volume of the generated acid is large and acid diffusion is suppressed.

In general formula (2),
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₇ and R ₈ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R ₇ and R ₈ , R ₇ and R ₈ are the same But it can be different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents an organic group containing a cyclic structure.
x represents an integer of 1 to 20, and y represents an integer of 0 to 10. z represents an integer of 0 to 10.

The anion of the general formula (2) will be described in more detail.

Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom as described above, and the alkyl group in the alkyl group substituted with a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, An alkyl group having 1 to 4 carbon atoms is more preferable. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ _{_{_{_{, CH 2 CH 2 CF 3,}}}} CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9 and _CH 2 CH ₂ C ₄ F ₉ is mentioned, among which fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

R ₇ and R ₈ represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom as described above. The alkyl group preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group substituted with at least one fluorine atom of R ₇ and R ₈ include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , and C ₆ F _13. , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ Examples thereof include C ₃ F ₇ , CH ₂ C ₄ F ₉ , and CH ₂ CH ₂ C ₄ F ₉ , among which CF ₃ is preferable.

L represents a divalent linking group, and represents —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, —N (Ri) — (wherein Ri represents a hydrogen atom or an alkyl group), an alkylene group (preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, particularly preferably a methylene group or an ethylene group, most preferably methylene group). Group), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), or a divalent linking group in which a plurality of these are combined. -, -CO-, -SO _2- , -CON (Ri)-, -SO ₂ N (Ri)-, -CON (Ri) -alkylene group-, -N (Ri) CO-alkylene group-, -COO -Alkylene group- or -OCO-a It is _preferably, -SO 2 - - Killen group, - COO -, - OCO -, - COO- alkylene group -, - more preferably - OCO- alkylene group. The alkylene group in -CON (Ri) -alkylene group-, -N (Ri) CO-alkylene group-, -COO-alkylene group-, and -OCO-alkylene group- is an alkylene group having 1 to 20 carbon atoms. And an alkylene group having 1 to 10 carbon atoms is more preferable. When there are a plurality of L, they may be the same or different.
The alkyl group for Ri is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group. , T-butyl group and the like.

The organic group containing the cyclic structure of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). For example, a tetrahydropyran ring, a lactone ring structure, and a sultone ring structure are also included.
The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, and a norbornyl group, a norbornene-yl group, or a tricyclodecanyl group (for example, A tricyclo [5.2.1.0 ^(2,6) ] decanyl group), a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferred, and an adamantyl group is particularly preferred. Moreover, nitrogen atom containing alicyclic groups, such as a piperidine group, a decahydroquinoline group, and a decahydroisoquinoline group, are also preferable. Among them, alicyclic groups having a bulky structure of 7 or more carbon atoms such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group, decahydroquinoline group and decahydroisoquinoline group are included. , PEB (post-exposure heating) is preferable from the viewpoint of suppressing diffusibility in the film. Of these, an adamantyl group and a decahydroisoquinoline group are particularly preferable.
Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Among these, a naphthalene ring having a low absorbance is preferable from the viewpoint of light absorbance at 193 nm.
Examples of the heterocyclic group include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, a furan ring, a thiophene ring, and a pyridine ring are preferable. Other preferred heterocyclic groups include the structures shown below (wherein X represents a methylene group or an oxygen atom, and R represents a monovalent organic group).

The organic group containing the cyclic structure may have a substituent, and the substituent may be an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), Examples thereof include aryl groups (preferably having 6 to 14 carbon atoms), hydroxy groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamido groups, and sulfonic acid ester groups.
Note that the carbon constituting the organic group containing a cyclic structure (carbon contributing to ring formation) may be a carbonyl carbon.

X is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. y is preferably 0 to 4, more preferably 0 or 1, and still more preferably 1. z is preferably 0 to 8, more preferably 0 to 4, and still more preferably 1.

In the anion in the general formula (2), as a combination of partial structures other than _{^{_{_{A, SO 3 - -CF 2 -CH}}}} 2 -OCO-, SO 3 - -CF 2 -CHF-CH 2 -OCO-, SO 3 ^{_{_{^{_{- -CF 2 -COO-, SO 3 -}}}}} -CF 2 -CF 2 -CH 2 -, _{^{_{_{and, SO 3 - -CF 2 -CH (}}}} CF 3) -OCO- are mentioned as preferred.

Further, in another aspect of the present invention, Z ^- is a non-nucleophilic anion, and may be a di-imide anion.
The disulfonylimidoanion is preferably a bis (alkylsulfonyl) imide anion.
The alkyl group in the bis (alkylsulfonyl) imide anion is preferably an alkyl group having 1 to 5 carbon atoms.
Two alkyl groups in the bis (alkylsulfonyl) imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms) and form a ring together with the imide group and the two sulfonyl groups. The ring structure that may be formed by the bis (alkylsulfonyl) imide anion is preferably a 5- to 7-membered ring, and more preferably a 6-membered ring.
These alkyl groups and alkylene groups formed by connecting two alkyl groups to each other can have a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryl Examples thereof include an oxysulfonyl group and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferable.

The non-nucleophilic anion of Z ⁻ has a fluorine content represented by (total mass of all fluorine atoms contained in the anion) / (total mass of all atoms contained in the anion) of 0.25 or less. Is preferably 0.20 or less, and more preferably 0.15 or less.

Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later. Can be mentioned.
In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (ZI) is a single bond or at least one of R ₂₀₁ to R ₂₀₃ of the other compound represented by the general formula (ZI). It may be a compound having a structure bonded through a linking group.

More preferred (ZI) components include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.

First, the compound (ZI-1) will be described.
The compound (ZI-1) is at least one of aryl group _R 201 _{~ R 203} of formula (ZI), arylsulfonium compounds, namely, compounds containing an arylsulfonium as a cation.
In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group optionally possessed by the arylsulfonium compound is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are an alkyl group (eg, having 1 to 15 carbon atoms), a cycloalkyl group (eg, having 3 to 15 carbon atoms), an aryl group (eg, having 6 to 6 carbon atoms). 14) may have at least one selected from the group consisting of an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group as a substituent.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group containing no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group or 2-oxocycloalkyl group. Or an alkoxycarbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group), and And a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group).
R ₂₀₁ to R ₂₀₃ may be further substituted with at least one selected from the group consisting of a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, and a nitro group.

Next, the compound (ZI-3) will be described.
The compound (ZI-3) is a compound represented by the following general formula (ZI-3), which is a compound having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _1c to R _5c are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to form a ring structure. In addition, this ring structure may contain at least one selected from the group consisting of an oxygen atom, a sulfur atom, a ketone group, an ester bond and an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, more preferably 5- or 6-membered rings.

Examples of the group formed by combining any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group, and examples of the alkylene group include a methylene group and an ethylene group. .
Z _c ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

The alkyl group as R _1c to R _{5c may} be either linear or branched, and examples thereof include an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms. Can do.
Examples of the cycloalkyl group as R _1c to R _5c include cycloalkyl groups having 3 to 10 carbon atoms.
The alkoxy group as R _1c to R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms, And a cyclic alkoxy group having 3 to 10 carbon atoms.
The aryl group as R _1c to R _5c is preferably an aryl group having 5 to 15 carbon atoms.
Specific examples of the alkoxy group in the alkoxycarbonyl group as R _1c ~ _{R 5c} are the same as specific examples of the alkoxy group as the _{_R} 1c _~ _R _5c.
Specific examples of the alkyl group in the alkylcarbonyloxy group and alkylthio group as R _1c ~ _{R 5c} are the same as specific examples of the alkyl group of the _{_R} 1c _~ _R _5c.
Specific examples of the cycloalkyl group in the cycloalkyl carbonyl group as R _1c ~ _{R 5c} are the same as specific examples of the cycloalkyl group of the _{_R} 1c _~ _R _5c.
Specific examples of the aryl group in the aryloxy group and arylthio group as R _1c ~ _{R 5c} are the same as specific examples of the aryl group of the _{_R} 1c _~ _R _5c.

Examples of the cation in the compound (ZI-2) or (ZI-3) in the present invention include cations described in paragraphs 0036 and after of US Patent Application Publication No. 2012/0076996.

Next, the compound (ZI-4) will be described.
The compound (ZI-4) is represented by the following general formula (ZI-4).

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
R ₁₄ is independently a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group, when a plurality of R ₁₄ are present. Represents. These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ 's are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom and a nitrogen atom. In one embodiment, it is preferred that two R ₁₅ are alkylene groups and are bonded to each other to form a ring structure.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ^{− in} formula (ZI).

In the general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -Butyl group, t-butyl group and the like are preferable.
Examples of the cation of the compound represented by the general formula (ZI-4) in the present invention include paragraphs 0121, 0123 and 0124 of JP2010-256842A, and paragraphs 0127 and 0129 of JP2011-76056A. And cations described in 0130 and the like.

Next, general formulas (ZII) and (ZIII) will be described.
In the general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
The aryl group for R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group in R ₂₀₄ to R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group), and And cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 to 15 carbon atoms). ), An aryl group (eg, having 6 to 15 carbon atoms), an alkoxy group (eg, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

Among the acid generators, particularly preferable examples include compounds exemplified in US2012 / 0207978A1 <0143>.
The acid generator can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.
An acid generator can be used individually by 1 type or in combination of 2 or more types.

The content of the acid generator in the composition (when there are a plurality of types) is preferably 0.1 to 30% by mass, more preferably 0.5 to 25%, based on the total solid content of the composition. % By mass, more preferably 0.5 to 20% by mass, particularly preferably 0.5 to 15% by mass.
In addition, when the acid generator is represented by the above general formula (ZI-3) or (ZI-4) (when there are a plurality of types), the content is the total solid content of the composition. As a reference, 0.1 to 35% by mass is preferable, 0.5 to 30% by mass is more preferable, and 0.5 to 25% by mass is particularly preferable.
Although the specific example of an acid generator is shown below, this invention is not limited to this.

<Acid diffusion control agent>
It is preferable that the planarization film forming composition further contains an acid diffusion controller.
The acid diffusion controller acts as a quencher that traps the acid generated from the acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid. Examples of the acid diffusion controller include a basic compound, a low-molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, a basic compound whose basicity decreases or disappears upon irradiation with actinic rays or radiation, or An onium salt that is a weak acid relative to the acid generator can be used.
The content of the acid diffusion controller is not particularly limited, and is preferably 0.01% by mass or more based on the total solid content in the composition in terms of more excellent effects of the present invention, and 0.2% by mass. % Or more is more preferable. The upper limit is not particularly limited, and is often 2.0% by mass or less.
In addition, only 1 type may be used for an acid diffusion control agent and it may use 2 or more types together.

Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

Regarding the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
Specific examples of preferred compounds include those exemplified in US2012 / 0219913A1 <0379>.
Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably 6 to 12 carbon atoms may be bonded to the nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. In addition to the alkyl group, the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, provided that at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable.
The following compounds are also preferable as the basic compound.

As basic compounds, in addition to the compounds described above, JP2011-22560A [0180] to [0225], JP2012-137735A [0218] to [0219], WO2011 / 158687A1 [0416] to The compounds described in [0438] can also be used.
These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

It is preferable that the ratio of the acid generator (the total when there are a plurality of types) and the basic compound used in the composition is acid generator / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the decrease in resolution. The acid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.

A low molecular weight compound having a nitrogen atom and a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (D-1)”) is an amine having a group on the nitrogen atom that is released by the action of an acid. A derivative is preferred.
As the group capable of leaving by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, and a hemiaminal ether group are preferable, and a carbamate group and a hemiaminal ether group are particularly preferable. .
The molecular weight of the compound (D-1) is preferably 100 to 1,000, more preferably 100 to 700, and particularly preferably 100 to 500.
Compound (D-1) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
R _b each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group. (Preferably having 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). R _b may be connected to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R _b are substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, and an oxo group, an alkoxy group, and a halogen atom. May be. The same applies to the alkoxyalkyl group represented by _Rb .

R _b is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
Examples of the ring formed by connecting two R _b to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
Specific examples of the group represented by the general formula (d-1) include, but are not limited to, the structures disclosed in US2012 / 0135348A1 <0466>.

The compound (D-1) particularly preferably has a structure represented by the following general formula (6).

In General Formula (6), R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two R _a may be the same or different, and two R _a may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
R _b has the same meaning as R _b in formula (d-1), and preferred examples are also the same.
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as R _a are the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as R _b may be substituted. It may be substituted with a group similar to the group described above.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of R _a (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above group) , R _b includes the same groups as the specific examples described above.
Specific examples of the particularly preferable compound (D-1) in the present invention include compounds disclosed in US2012 / 0135348A1 <0475>, but are not limited thereto.

The compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
In the present invention, the compound (D-1) can be used singly or in combination of two or more.

A basic compound whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (PA)”) has a proton acceptor functional group and is irradiated with actinic rays or radiation. Is a compound whose proton acceptor properties are degraded, disappeared, or changed from proton acceptor properties to acidic properties.

The “proton acceptor functional group” is a functional group having electrons or a group capable of electrostatically interacting with protons, such as a functional group having a macrocyclic structure such as a cyclic polyether, or π It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to conjugation. The “nitrogen atom having an unshared electron pair that does not contribute to π conjugation” is, for example, a nitrogen atom having a partial structure represented by the following formula.

Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.

The compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity. Here, “decrease, disappearance of proton acceptor property, or change from proton acceptor property to acid” is a change in proton acceptor property resulting from addition of a proton to a proton acceptor functional group, Specifically, when a proton adduct is produced from a compound (PA) having a proton acceptor functional group and a proton, it means that the equilibrium constant in the chemical equilibrium is reduced.
Proton acceptor property can be confirmed by measuring pH.

In the present invention, the acid dissociation constant pKa of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation preferably satisfies pKa <−1, more preferably −13 <pKa <−1. More preferably, −13 <pKa <−3.

In the present invention, the “acid dissociation constant pKa” represents the acid dissociation constant pKa in an aqueous solution. For example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.) The lower the value, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the following software package 1, Hammett The values based on the substituent constants and the database of known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

The compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition upon irradiation with actinic rays or radiation. Since the compound represented by the general formula (PA-1) has an acidic group together with the proton acceptor functional group, the proton acceptor property is reduced or disappeared compared to the compound (PA), or the proton acceptor property is reduced. It is a compound that has changed to acidic.

In general formula (PA-1),
Q represents —SO ₃ H, —CO ₂ H, or —W ₁ NHW ₂ R _f . Here, R _f represents an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and W ₁ and W ₂ each independently represents —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or —N (R _x ) R _y —. Here, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x may be bonded to R _y to form a ring, or R _x may be bonded to R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.

The general formula (PA-1) will be described in more detail.
The divalent linking group in A is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. More preferred is an alkylene group having at least one fluorine atom, and the preferred carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.

The monovalent organic group in R _x is preferably an organic group having 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent.
The alkyl group in R _x may have a substituent, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. It may be.
The cycloalkyl group in R _x may have a substituent, and is preferably a monocyclic cycloalkyl group or a polycyclic cycloalkyl group having 3 to 20 carbon atoms, and an oxygen atom, a sulfur atom, It may have a nitrogen atom.
The aryl group for R _x may have a substituent, and preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
The aralkyl group in R _x may have a substituent, and preferably has 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.
The alkenyl group in R _x may have a substituent, may be linear, or may be branched. The alkenyl group preferably has 3 to 20 carbon atoms. Examples of such alkenyl groups include vinyl groups, allyl groups, and styryl groups.

Examples of the substituent when R _x further has a substituent include a halogen atom, a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Examples include carbamoyl group, cyano group, carboxylic acid group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, nitro group, hydrazino group, and heterocyclic group. .

Preferred _examples of the divalent organic group for R _y include an alkylene group.
Examples of the ring structure that R _x and R _y may be bonded to each other include a 5- to 10-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring.

The proton acceptor functional group for R is as described above, and examples thereof include azacrown ether, primary to tertiary amines, and groups having a heterocyclic aromatic structure containing a nitrogen atom such as pyridine and imidazole.
The organic group having such a structure is preferably an organic group having 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.

The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkyl group in the alkenyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkenyl group in the proton acceptor functional group or ammonium group in R is the above R _{The same} as the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group mentioned as _x .

When B is —N (R _x ) R _y —, R and R _x are preferably bonded to each other to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.
Examples of the monocyclic structure include a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring containing a nitrogen atom. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures.

As _{R f} in _-W 1 NHW ₂ R _f represented by Q, preferred is an alkyl group which may have a fluorine atom of 1 to 6 carbon atoms, more preferably perfluoroalkyl of 1 to 6 carbon atoms It is a group. Further, as W ₁ and W ₂ , at least one is preferably —SO ₂ —, and more preferably, both W ₁ and W ₂ are —SO ₂ —.
Q is particularly preferably —SO ₃ H or —CO ₂ H from the viewpoint of the hydrophilicity of the acid group.
Among the compounds represented by the general formula (PA-1), a compound in which the Q site is a sulfonic acid can be synthesized by using a general sulfonamidation reaction. For example, a method in which one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine compound to form a sulfonamide bond, and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is used. It can be obtained by a method of ring-opening by reacting with an amine compound.

The compound (PA) is preferably an ionic compound. The proton acceptor functional group may be contained in either the anion portion or the cation portion, and is preferably contained in the anion portion.
Preferred examples of the compound (PA) include compounds represented by the following general formulas (4) to (6).

In the general formulas (4) to (6), A, X, n, B, R, R _f , W ₁ and W ₂ have the same meanings as those in the general formula (PA-1).
C ⁺ represents a counter cation.
The counter cation is preferably an onium cation. More specifically, in the acid generator, a sulfonium cation described as S ⁺ (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ) in general formula (ZI), I ⁺ (R ₂₀₄ ) in general formula (ZII) ( A preferred example is the iodonium cation described as R ₂₀₅ ).
Specific examples of the compound (PA) include compounds exemplified in US2011 / 0269072A1 <0280>.

In the present invention, a compound (PA) other than the compound that generates the compound represented by the general formula (PA-1) can be appropriately selected. For example, an ionic compound that has a proton acceptor moiety in the cation moiety may be used. More specifically, a compound represented by the following general formula (7) is exemplified.

In the formula, A represents a sulfur atom or an iodine atom.
m represents 1 or 2, and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3, and when A is an iodine atom, m + n = 2.
R represents an aryl group.
R _N represents an aryl group substituted with a proton acceptor functional group. X ⁻ represents a counter anion.
Specific examples of X ⁻ include the same as the above-mentioned anion of the acid generator.
Specific examples of the aryl group of R and R _N is a phenyl group are preferably exemplified.

Specific examples of the proton acceptor functional group R _N are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).
Specific examples of the ionic compound having a proton acceptor site in the cation moiety include compounds exemplified in US2011 / 0269072A1 <0291>.
Such a compound can be synthesized with reference to methods described in, for example, JP-A-2007-230913 and JP-A-2009-122623.

Compound (PA) may be used alone or in combination of two or more.

In the composition of the present invention, an onium salt that becomes a weak acid relative to the acid generator can be used as an acid diffusion control agent.
When an acid generator and an onium salt that generates an acid that is a relatively weak acid (preferably a weak acid having a pKa of more than −1) with respect to the acid generated from the acid generator are used in combination, actinic rays or radiation When the acid generated from the acid generator collides with an onium salt having an unreacted weak acid anion by irradiation, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

The onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

In the formula, R ⁵¹ represents a hydrocarbon group which may have a substituent, and Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S). R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. Each of the M ⁺ is independently a sulfonium cation or an iodonium cation.

Preferable examples of the sulfonium cation or iodonium cation represented by M ⁺ include the sulfonium cation exemplified for the acid generator (ZI) and the iodonium cation exemplified for (ZII).

Preferable examples of the anion moiety of the compound represented by the general formula (d1-1) include the structures exemplified in paragraph [0198] of JP2012-242799A.
Preferable examples of the anion moiety of the compound represented by the general formula (d1-2) include the structures exemplified in paragraph [0201] of JP2012-242799A.
Preferable examples of the anion moiety of the compound represented by the general formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.

An onium salt that is a weak acid relative to an acid generator is a compound having a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety being linked by a covalent bond (hereinafter referred to as “compound”). (Also referred to as (D-2) ”).
The compound (D-2) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

In general formulas (C-1) to (C-3),
R ₁ , R ₂ and R ₃ represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond linking the cation moiety and the anion moiety.
-X ^- it ^{^is,} -COO ^_-, -SO 3 _- represents an anion portion selected from _{^{_{-R 4 -, -SO 2 -,}}} -N. R ₄ is a group having a carbonyl group: —C (═O) —, a sulfonyl group: —S (═O) ₂ —, and a sulfinyl group: —S (═O) — at the site of connection with the adjacent N atom. Represents a valent substituent.
R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In (C-3), two of R ₁ to R ₃ may be combined to form a double bond with the N atom.

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.

L ₁ as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L ₁ is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.
Preferable examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ] Can be mentioned.
Preferable examples of the compound represented by the general formula (C-2) include compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.
Preferable examples of the compound represented by the general formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP 2012-252124 A.

<Surfactant>
The planarization film-forming composition preferably further contains a surfactant from the viewpoints of film-forming properties, planarization film adhesion, development defect reduction, and the like.

Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink and Chemicals), Florad FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), etc. Hexane polymer KP341 (manufactured by Shin-Etsu Chemical Co.) and acrylic or methacrylic acid-based (co) polymer Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.). The compounding amount of these surfactants is usually 2 parts by mass or less, preferably 1 part by mass or less per 100 parts by mass of the solid content in the composition of the present invention.
These surfactants may be added alone or in some combination.

The surfactant is any one of fluorine-based and / or silicon-based surfactants (fluorine-based surfactants and silicon-based surfactants, surfactants containing both fluorine atoms and silicon atoms), or It is preferable to contain 2 or more types.
As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540 No. 7, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A 2002-277862, US Pat. No. 5,405,720. No. 5,360,692, No. 5,529,881, No. 5,296,330, No. 5,543,098, No. 5,576,143, No. 5,294,511, No. 5,824,451. The following commercially available surfactants can also be used as they are.
Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block linked body) or a poly (block linked body of oxyethylene and oxypropylene) group, may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

For example, as a commercially available surfactant, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by Dainippon Ink & Chemicals, Inc.) can be mentioned. Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy) (Ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group Coalesce, etc. Can.

The amount of the surfactant used is preferably 0.0001 to 6% by mass, and more preferably 0.001 to 4% by mass, based on the total solid content of the flattening film forming composition.

<Solvent>
The planarization film-forming composition preferably contains a solvent from the viewpoint of applicability.
Solvents that can be used in preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 4 carbon atoms). 10), an organic solvent such as a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate and the like.
Specific examples of these solvents include those described in US Patent Application Publication No. 2008/0187860 <0441> to <0455>, and isoamyl acetate, butyl butanoate, and methyl 2-hydroxyisobutyrate. .

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be appropriately selected. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate or the like is preferable, and propylene glycol monomethyl ether (PGME). , Also known as 1-methoxy-2-propanol), ethyl lactate is more preferred. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2 -Heptanone is most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
The solvent preferably includes propylene glycol monomethyl ether acetate.

The content in the case of containing a solvent is not particularly limited, and the solid content concentration of the composition for forming a flattened film is preferably 0.1 to 30% by mass, and preferably 1 to 20% by mass. Further preferred. The application | coating property with respect to a level | step difference board | substrate improves by making solid content concentration of the composition for planarization film formation into the said range.

<Other ingredients>
When the flattening film-forming composition of the present invention contains the resin (A1), the flattening film-forming composition does not contain a cross-linking agent (that is, crosslinking with respect to the total solid content of the flattening film-forming composition). It is preferable that the content of the agent is 0% by mass) or 5% by mass or less based on the total solid content of the composition for flattening film formation. That is, the content of the crosslinking agent in the planarizing film-forming composition of the present invention is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and 0 to 1% by mass. More preferably, it is particularly preferable that it is not contained at all (0% by mass).
Thus, when the composition for planarization film formation of this invention contains resin (A1), content of a crosslinking agent is 0-5 mass%, and the composition for planarization film formation is used. Since the curing speed of the resulting resist film can be reduced, the removability of the resist film provided on the convex portion of the stepped substrate is improved, and the flatness of the planarizing film is further improved.
Specific examples of the crosslinking agent include the crosslinking agents described in paragraphs 0450, 0479 and 0485 of JP-A-2015-68860.
On the other hand, when the composition for planarization film formation of this invention contains resin (A2), the composition for planarization film formation uses 5 crosslinking agents with respect to the total solid of the composition for planarization film formation. Preferably, the content is 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and particularly preferably 0.5 to 3% by mass. . As a result, the curing rate of the resist film obtained by using the planarizing film-forming composition can be reduced, so that the resist film provided on the convex portion of the stepped substrate has good removability, and the flatness of the planarizing film is improved. More improved.

It is preferable that the composition of the present invention and other various materials used (for example, a developing solution, a rinsing solution, etc.) do not contain impurities such as metals (solid metal and metal ions). Examples of the metal impurity component include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, and Li. The total content of impurities contained in these materials is preferably 1 ppm or less, more preferably 10 ppb or less, further preferably 100 ppt or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less.
Examples of a method for removing impurities such as metals from the various materials include filtration using a filter. The filter pore diameter is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. The filter may be a composite material obtained by combining these materials and ion exchange media. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
In addition, as a method for reducing impurities such as metals contained in the above various materials, a method of selecting a raw material having a low metal content as a raw material constituting various materials, and performing filter filtration on the raw materials constituting various materials. Examples thereof include a method and a method in which distillation is performed under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark). The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
In addition to filter filtration, impurities may be removed by an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent metal impurities from being mixed in the manufacturing process. Whether or not the metal impurities have been sufficiently removed from the manufacturing apparatus can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing apparatus. The content of the metal component contained in the cleaning liquid after use is more preferably 100 ppt (parts per trigger) or less, further preferably 10 ppt or less, and particularly preferably 1 ppt or less.

<Method for Preparing Composition for Forming Flattened Film>
The preparation method (manufacturing method) of the composition for planarization film formation of this invention is not restrict | limited in particular, A well-known method is employable. For example, the planarization of the present invention can be achieved by adding a predetermined amount of the resin (A) and the photoacid generator (B) (and the above-described components as necessary) to the solvent, and appropriately stirring the mixture. A film-forming composition can be obtained. Moreover, you may process filtration etc. at a desired timing as needed.

[Planarization film]
The planarization film of the present invention is obtained using the above-described composition for planarization film formation. The planarizing film of the present invention is provided on a stepped substrate and is used for planarizing unevenness on the surface of the stepped substrate.
Here, “the stepped substrate provided with the flattening film is flat” means that when the cross section of the stepped substrate is observed using a scanning electron microscope, the surface of the flattening film is based on the upper surface of the stepped substrate. It means that the unevenness is in the range of 0 to 300 mm. Referring to FIG. 1 as an example, the surface of the stepped substrate 10 on which the resist film 14 is provided (upper surface of the convex portion 13) is defined as a reference surface (0 point), and the distance (convex portion) of the planarization film from the reference surface. If the distance is within the range of 0 to 300 mm, the planarizing film can be said to be flat.

[Electronic device manufacturing method]
The present invention also relates to an electronic device manufacturing method including the flat film manufacturing method described above. For example, after a resist underlayer film (SOG: Spin on Glass) and / or a photoresist layer is provided on the planarization film of the present invention, a pattern can be formed by photolithography. As the resist underlayer film forming composition and the photoresist composition, known materials can be appropriately used.
An electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (home appliance, OA (Office Appliance) -related device, media-related device, optical device, communication device, etc.). It is.

Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to this.

<Preparation of composition for flattening film formation>
The components shown in Table 1 below were dissolved in a solvent in the proportions shown in the same table (mass% in the total mass of the composition) to prepare resist solutions for each, and this was prepared as a UPE having a pore size of 1.0 μm (ultra High molecular weight polyethylene) filter. Thereby, a composition for forming a planarization film (resist composition) having a solid content concentration of 9.5% by mass was prepared.
All resist compositions shown in Table 1 are negative.

[Supplement under rule 26 04.04.2017]

The structure of the resin in Table 1, the molar ratio of each repeating unit, Mw (weight average molecular weight), Pd (molecular weight distribution), and Tg (glass transition temperature) are shown in Table 2 below.
Each numerical value in the “Composition” column represents the molar ratio of the repeating units in each resin. For example, in P-1, the left repeating unit: the right repeating unit = 90: 10.

[Supplement under rule 26 04.04.2017]

[Supplement under rule 26 04.04.2017]

In Table 1, the structure of the acid generator is as follows.

In Table 1, the structure of the acid diffusion controller is as follows.

In Table 1, the structures of the additives A-1 and A-2 are as follows. Additive A-3 is “Megafac R41” (trade name) manufactured by DIC.

In Table 1, the structure of the crosslinking agent is as follows.

In Table 1, the solvents are as follows.
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)
SL-3: Cyclohexanone SL-6: Ethyl 3-ethoxypropionate (EEP)

<Evaluation test>
(Γ (contrast) evaluation method)
The resist composition prepared above is applied on a Si substrate (manufactured by Advanced Materials Technology) subjected to hexamethyldisilazane treatment, and the applied resist composition is baked at 140 ° C. for 60 seconds (Pre Bake; PB). Then, a film (resist film) having a thickness T described in Table 3 was formed.
Then, a KrF excimer laser scanner (NA0.80), without passing through the exposure mask, the wafer having a resist film formed, while the amount of exposure from 1 mJ / cm ² increased every 0.8 mJ / cm ² 99-point exposure was performed.
After that, the exposed resist film was baked at 130 ° C. for 60 seconds (Post Exposure Bake; PEB). Subsequently, development was performed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 60 seconds, rinsed with pure water for 30 seconds, and then spin-dried. In this way, test films for Examples and Comparative Examples for measuring γ were obtained.
About each test film | membrane, the film thickness of an exposure part of 99 points | pieces is measured, and the film thickness in each exposure location is set to the orthogonal coordinate which used the film thickness (Å) as the vertical axis and the exposure amount (mJ / cm ² ) as the horizontal axis. And the point corresponding to the exposure amount was plotted, and the plot figure was produced (refer FIG. 8).
In the obtained plot, a line obtained by connecting the plotted points is created, and the vertical axis on the line connects the point of thickness T × 0.8 and the vertical axis of the point of thickness T × 0.4. Was calculated as γ (の · cm ² / mJ). Table 3 summarizes the values of γ of the test films of Examples and Comparative Examples.

(Flatness)
The resist composition was applied to the entire surface of a SiO ₂ wafer substrate (stepped substrate) having wiring grooves (trench: L / S = 25 nm / 25 nm, Height = 100 nm) by spin coating. The applied resist composition was baked (Pre Bake; PB) on a hot plate under the conditions shown in Table 3 to form a resist film.
Next, using a KrF excimer laser scanner (NA 0.80) through a mask arranged at a position corresponding to the convex portion of the stepped substrate (portion where the wiring groove is not formed), the exposure amount is 40 mJ / cm ² . The resist film was exposed under the conditions.
Thereafter, the exposed resist film was baked (Post Exposure Bake; PEB) under the conditions shown in Table 3. Subsequently, development was performed with the developer shown in Table 3 for the development time shown in Table 3, rinsed with pure water for 30 seconds, and then spin-dried. In the example using nBA (n-butanol) as the developer, rinsing was not performed.
Subsequently, each of the planarized films of Examples and Comparative Examples was obtained by subjecting the resist film after spin drying to post-bake treatment (Post Bake) under the conditions shown in Table 3.
Using a scanning electron microscope (S-4800, manufactured by Hitachi High-Tech Co., Ltd.), the cross-sectional shapes of the flattened films of Examples and Comparative Examples were observed, and whether the flatness was good or bad was judged according to the following evaluation criteria. Specifically, referring to FIG. 1 as an example, the surface of the stepped substrate 10 on which the resist film 14 is provided (the upper surface of the convex portion 13) is used as a reference surface (0 point), and the unevenness of the planarization film from the reference surface. (The maximum value of the length in the direction perpendicular to the upper surface of the convex portion 13).
AA: The distance of the unevenness of the planarization film from the reference surface is 0 mm or more and 100 mm or less A: The distance of the unevenness of the planarization film from the reference surface is more than 100 mm and 300 mm or less B: The distance of the unevenness of the planarization film from the reference surface is More than 300 mm and less than 500 mm C: The distance of the unevenness of the planarization film from the reference surface is more than 500 mm

In the column of developer in Table 3, “TMAH” means tetramethylammonium hydroxide and “nBA” means n-butanol.

[Supplement under rule 26 04.04.2017]

From the comparison between the case where the value of γ is less than 1000 (Example) and the case where the value of γ is 1000 or more (Comparative Example) as shown in the evaluation results in Table 3, the value of γ is less than 1000. In some cases (Examples), a flattened film having excellent flatness could be produced on the stepped substrate. From this, it was shown that the value of γ is related to the flatness of the flattened film.

(Swelling)
The following swelling evaluation tests were carried out using the flattened films of Examples and Comparative Examples obtained in the same manner as the “flatness” described above.
Using the optical interference type film thickness measuring device VM-1020, each flattened film of the example and the comparative example was immersed in a swelling evaluation liquid (PGMEA / PGME = 70/30) kept at 50 ° C. for 5 minutes. The swelling was observed, and the swelling property of the flattened film was evaluated according to the following evaluation criteria.
Specifically, referring to FIG. 4, the upper surface of the flattened resist film 14C provided on the stepped substrate 10 is defined as a reference surface (point 0), and the distance (flatness) from the reference surface to the upper surface after swelling. The maximum length in the direction perpendicular to the upper surface of the resist film 14C after the formation was measured (shown as “ΔFT” (Å) in Table 4 to be described later).
AA: The distance between the upper surface of the resist film after being immersed in the swelling evaluation liquid and the reference surface is 20 mm or less A: The distance between the upper surface of the resist film after being immersed in the swelling evaluation liquid and the reference surface is more than 20 mm and 50 mm or less. B: The distance between the upper surface of the resist film after being immersed in the swelling evaluation solution and the reference surface exceeds 50 mm.

The results of the swelling evaluation test are shown in Table 4.

[Supplement under rule 26 04.04.2017]

By comparing Example 7 (Resin P-2), Example 15 (Resin P-8) and Example 16 (Resin P-9), a repeating unit having a phenolic hydroxyl group and a repeating unit having a carboxylic acid group It was shown that the swelling of the flattened film tends to be suppressed by using a resin having a succinic acid (resin P-8 of Example 15 and resin P-9 of Example 16).

10 Stepped substrate 12 Trench (concave)
13 Convex part 14 Resist film 14a Convex part upper film 14b Concave part upper film 14A Resist film 14B after exposure Exposed part upper film 14C After exposure Flattening film 20 Mask 100 Substrate 120 Resist film

Claims

A method for producing a planarizing film for planarizing the surface of a stepped substrate having irregularities on the surface,
Step A of forming a film on the stepped substrate using the actinic ray-sensitive or radiation-sensitive planarizing film-forming composition containing the resin (A) and the photoacid generator (B);
A step B of exposing the film through a mask disposed at a position corresponding to the convex portion of the stepped substrate;
Using a developer, removing at least a portion of the film provided on the convex portion of the stepped substrate to obtain a planarization film; and
Have
A method for producing a planarization film, wherein a test film having a thickness T is formed on a silicon substrate using the composition for planarization film formation, wherein the value of γ of the test film is less than 1000;
Here, γ is obtained by the following γ calculation method;
γ calculation method: silicon relative to said test film formed thickness T on a substrate 99 places performs exposure while increasing every 0.8 mJ / cm 2 exposure amount from 1 mJ / cm 2 by using a KrF excimer laser Then, the exposed test film is baked at 130 ° C. for 60 seconds, and then a removal process is performed to remove a part of the test film after baking with an aqueous 2.38 mass% tetramethylammonium hydroxide solution. The film thickness at each exposure point of the test film after the removal treatment is calculated, and the point corresponding to the film thickness and the exposure amount at each exposure point on the orthogonal coordinates with the film thickness as the vertical axis and the exposure amount as the horizontal axis A line obtained by connecting the plotted points is created, and the vertical axis on the line connects the point of thickness T × 0.8 and the vertical axis of the point of thickness T × 0.4. The absolute value of the slope of γ is γ, and the unit of γ is Å ・m is 2 / mJ.
The method for producing a flattening film according to claim 1, wherein the composition for forming a flattening film is a negative type.
Resin (A1) in which the resin (A) contains 0.5 to 30 mol% of repeating units having two or more crosslinkable sites that are cross-linked by the action of an acid, and a repeating unit having a phenolic hydroxyl group The manufacturing method of the planarization film | membrane of Claim 1 or 2 containing at least one of resin (A2) containing this.
The method for producing a planarizing film according to claim 3, wherein the resin (A1) has substantially no repeating unit having an acid-decomposable group.
The method for producing a flattened film according to claim 3 or 4, wherein the crosslinkable site crosslinked by the action of the acid contained in the resin (A1) is a hydroxy group.
The method for producing a planarizing film according to any one of claims 3 to 5, wherein the resin (A1) is a novolac resin.
The planarizing film according to any one of claims 3 to 6, wherein the repeating unit having two or more crosslinkable sites that are crosslinked by the action of the acid contained in the resin (A1) has a benzenediol structure. Manufacturing method.
The planarizing film according to any one of claims 3 to 7, wherein the repeating unit having two or more crosslinkable sites crosslinked by the action of the acid contained in the resin (A1) has a resorcinol structure. Production method.
The planarizing film according to any one of claims 3 to 8, wherein the repeating unit having two or more crosslinkable sites crosslinked by the action of the acid contained in the resin (A1) has a hydroquinone structure. Production method.
10. The planarizing film forming composition does not contain a crosslinking agent, or the crosslinking agent is contained in an amount of 5% by mass or less based on the total solid content of the planarizing film forming composition. 2. A method for producing a planarizing film according to claim 1.
The method for producing a planarizing film according to any one of claims 1 to 10, wherein the resin (A) has a glass transition temperature of 150 ° C or lower.
The planarizing film according to any one of claims 1 to 11, wherein a content of the resin (A) is 50 to 99 mass% with respect to a total solid content of the planarizing film forming composition. Manufacturing method.
The method for producing a planarizing film according to any one of claims 1 to 12, wherein the composition for forming a planarizing film further contains an acid diffusion controller.
The method for producing a planarizing film according to any one of claims 1 to 13, wherein the composition for forming a planarizing film further contains a surfactant.
An actinic ray-sensitive or radiation-sensitive planarizing film-forming composition used in the method for producing a planarizing film according to any one of claims 1 to 14, wherein the planarizing film-forming composition is used. When a test film having a thickness T is formed on a silicon substrate using an object, a composition for forming a flattened film, wherein the value of γ of the test film is less than 1000.
A planarizing film obtained using the actinic ray-sensitive or radiation-sensitive planarizing film-forming composition according to claim 15.
An electronic device manufacturing method comprising the planarizing film manufacturing method according to any one of claims 1 to 14.