JP7291727B2 - RESIN COMPOSITION USED FOR FORMING RESIST PATTERN AND METHOD FOR MANUFACTURING SEMICONDUCTOR PRODUCT - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition used for forming a resist pattern and a method for manufacturing a semiconductor product.

2. Description of the Related Art Conventionally, resist patterns have been used for various purposes in the manufacture of semiconductor products, display panels, and the like.
A typical example of utilization of a resist pattern is utilization as an etching mask (etching resist) when patterning is performed by etching. Etch resists are patterned coatings that are resistant to etching. Etching resists are mainly used in applications such as semiconductor circuit fabrication, printed circuit board fabrication, and solar cell fabrication. Such an etching resist is formed on a surface to be etched of an object to be etched such as a silicon substrate by a method such as photolithography or printing according to the size of the pattern.

For example, the composition for forming an etching resist includes a polymer having a monomer unit (a1) and a monomer unit (a2) as component A, a photoacid generator as component B, and a solvent as component C. and a positive photosensitive resin composition is known (see Patent Document 1). The monomer unit (a1) has a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group. A monomer unit (a2) has an epoxy group and/or an oxetanyl group. When the positive photosensitive resin composition described in Patent Document 1 is used, an etching resist patterned into a predetermined shape can be formed by photolithography.

In the manufacturing process of semiconductor products, display panels, etc., the above-mentioned resist patterns such as etching resists are often removed after playing a role such as a mask material. For removing the resist pattern, for example, an organic solvent or a basic remover is used. A basic stripping solution is often used because it is inexpensive and the waste solution after removal of the resist pattern can be easily treated.

JP 2012-181488 A

However, for resist patterns formed using conventionally known compositions, such as those described in Patent Document 1, it is often difficult to perform good stripping in a short time using a basic stripper. be.
For example, when etching is performed using an etchant containing an oxidant such as ozone, or when the surface of a silicon substrate is oxidized with an oxidant to form a silicon oxide film on the surface of the silicon substrate, the resist pattern is oxidized. come into contact with the agent.
In such a case, when the resist pattern after contact with the oxidizing agent is stripped with a basic stripping solution, stripping may be difficult in the first place, stripping may take a long time, or stripping residue may occur even if it can be stripped. Easy to wear.

The present invention has been made in view of the above problems, and is a resin used for forming a resist pattern that can form a resist pattern that can be easily and satisfactorily stripped with a basic stripping solution even after contact with an oxidizing agent. An object of the present invention is to provide a composition and a method for manufacturing a semiconductor product, which includes a step of forming a resist pattern using the resin composition.

The present inventors have found that the above problems can be solved by including a rosin ester resin as a binder resin in a resin composition used for forming a resist pattern, which contains a binder resin as a binder, and have completed the present invention. came to. More specifically, the present invention provides the following.

(1) A resin composition used for forming a resist pattern, containing a binder resin containing a rosin ester resin as a binder.

(2) The resin composition according to (1), containing one or more selected from the group consisting of fillers, surfactants, and antioxidants.

(3) The resin composition according to (2), which contains a filler, a surfactant, and an antioxidant.

(4) The resin composition according to (2) or (3), which contains an anionic surfactant as a surfactant, and the anionic surfactant contains a polyoxyethylene alkyl ether derivative.

(5) the polyoxyethylene alkyl ether derivative has one or more groups selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphate group, a sulfonic acid group, a carboxylic acid group, and a phosphate group; ).

(6) Any one of (2) to (5), including a surfactant of 0.1 parts by mass or more and 10 parts by mass or less with respect to a total of 100 parts by mass of components other than the solvent contained in the resin composition The resin composition according to 1.

(7) containing as an antioxidant one or more selected from the group consisting of hindered phenol antioxidants, aromatic amine antioxidants, and sulfur antioxidants, (2) to (6) The resin composition according to any one.

(8) Any of (2) to (7), containing an antioxidant of 0.1 parts by mass or more and 5 parts by mass or less with respect to the total 100 parts by mass of the mass of components other than the solvent contained in the resin composition 1. The resin composition according to claim 1.

(9) The resin composition according to any one of (1) to (8), comprising an aliphatic hydrocarbon group having 6 or more carbon atoms and an acid anhydride compound having a carboxylic acid anhydride group.

(10) The resin composition according to any one of (1) to (9), which is used for forming a resist pattern by printing.

(11) The resin composition according to any one of (1) to (10), wherein the resist pattern is used in contact with an oxidizing agent.

(12) an oxidant contacting step of contacting a semiconductor substrate provided with a resist pattern with an oxidant;
The resin composition according to (11), which is used for forming a resist pattern in a method for manufacturing a semiconductor product, which includes a stripping step of stripping the resist pattern after contact with the oxidizing agent from the semiconductor substrate with a basic stripping solution. thing.

(13) The semiconductor product is a back-contact solar cell,
a semiconductor substrate comprising, on at least one surface, a p-type semiconductor layer or an n-type semiconductor layer as a first semiconductor layer on the outermost surface, and an intrinsic semiconductor layer in contact with the first semiconductor layer;
a resist pattern is formed directly on the first semiconductor layer;
contacting a semiconductor substrate provided with a resist pattern with an etchant containing an oxidant to remove the first semiconductor layer and the intrinsic semiconductor layer at positions corresponding to the positions of the openings of the resist pattern;
After removing the first semiconductor layer and the intrinsic semiconductor layer, the resist pattern is stripped,
After removing the resist pattern, an intrinsic semiconductor layer is formed in the space from which the first semiconductor layer and the intrinsic semiconductor layer have been removed, and then a second semiconductor layer having a polarity opposite to that of the first semiconductor layer is formed. , (12).

(14) The semiconductor product is a back-contact solar cell,
a semiconductor substrate comprising, on at least one surface side, a p-type semiconductor layer or an n-type semiconductor layer as a first semiconductor layer, and an intrinsic semiconductor layer in contact with the first semiconductor layer;
a resist pattern is formed on the first semiconductor layer via a lift-off layer;
removing the lift-off layer at a position corresponding to the position of the opening of the resist pattern by contacting the semiconductor substrate provided with the resist pattern with an etchant containing an oxidant;
After the removal of the lift-off layer, the resist pattern is peeled off and the first semiconductor layer at the position corresponding to the position of the opening of the resist pattern is removed by etching,
forming a second semiconductor layer having a polarity opposite to that of the first semiconductor layer so as to cover the bottom and side surfaces of the space from which the first semiconductor layer has been removed and the lift-off layer;
The resin composition according to (12), wherein the second semiconductor layer in contact with the lift-off layer is removed along with the removal of the lift-off layer.

(15) A resist pattern forming step of forming a resist pattern on the surface of a semiconductor substrate using the resin composition according to any one of (1) to (9) by a printing method or a photolithography method; ,
an oxidant contact step of contacting a semiconductor substrate having a resist pattern with an oxidant;
A method for manufacturing a semiconductor product, comprising a stripping step of stripping the resist pattern after contact with the oxidizing agent with a basic stripping solution.

(16) A semiconductor product manufacturing method for manufacturing a back-contact solar cell as a semiconductor product,
a semiconductor substrate comprising, on at least one surface, a p-type semiconductor layer or an n-type semiconductor layer as a first semiconductor layer on the outermost surface, and an intrinsic semiconductor layer in contact with the first semiconductor layer;
a resist pattern is formed directly on the first semiconductor layer;
contacting a semiconductor substrate provided with a resist pattern with an etchant containing an oxidant to remove the first semiconductor layer and the intrinsic semiconductor layer at positions corresponding to the positions of the openings of the resist pattern;
After removing the first semiconductor layer and the intrinsic semiconductor layer, the resist pattern is stripped,
After removing the resist pattern, an intrinsic semiconductor layer is formed in the space from which the first semiconductor layer and the intrinsic semiconductor layer have been removed, and then a second semiconductor layer having a polarity opposite to that of the first semiconductor layer is formed. , (15).

(17) A method for manufacturing a semiconductor product for manufacturing a back-contact solar cell as a semiconductor product,
a semiconductor substrate comprising, on at least one surface side, a p-type semiconductor layer or an n-type semiconductor layer as a first semiconductor layer, and an intrinsic semiconductor layer in contact with the first semiconductor layer;
a resist pattern is formed on the first semiconductor layer via a lift-off layer;
removing the lift-off layer at a position corresponding to the position of the opening of the resist pattern by contacting the semiconductor substrate provided with the resist pattern with an etchant containing an oxidant;
After the removal of the lift-off layer, the resist pattern is peeled off and the first semiconductor layer at the position corresponding to the position of the opening of the resist pattern is removed by etching,
forming a second semiconductor layer having a polarity opposite to that of the first semiconductor layer so as to cover the bottom and side surfaces of the space from which the first semiconductor layer has been removed and the lift-off layer;
The method of manufacturing a semiconductor product according to (15), wherein the second semiconductor layer in contact with the lift-off layer is removed along with the removal of the lift-off layer.

According to the present invention, a resin composition used for forming a resist pattern that can form a resist pattern that can be easily and satisfactorily stripped with a basic stripping solution even after contact with an oxidizing agent, and the resin composition is used. It is possible to provide a method for manufacturing a semiconductor product, which includes the step of forming a resist pattern with a

FIG. 2 is a diagram schematically showing a cross section of a semiconductor substrate to be processed, regarding an example of a method for manufacturing a back-contact solar cell without using a lift-off layer; FIG. 2 is a diagram schematically showing a cross section of a semiconductor substrate to be processed, regarding an example of a method of manufacturing a back-contact solar cell using a lift-off layer;

<<Resin composition>>
The resin composition will be described below. A resin composition is used for forming a resist pattern. The resin composition contains a binder resin containing a rosin ester resin as a binder.
The resin composition contains a filler, a surfactant, and the like in that it is easy to achieve a high level of both the durability of the resist pattern such as etching resistance and the strippability of the resist pattern after contact with an oxidizing agent using a basic stripping solution. and an antioxidant, more preferably one or more selected from the group consisting of a filler, a surfactant, and an antioxidant.
In the following, essential or optional components contained in the resin composition, applications, etc. will be described.

<Binder>
A binder is a component that imparts film forming properties for forming a resist pattern to the resin composition. Binders include binder resins and monomer compounds. The binder resin and the monomer compound are described below.

[Binder resin]
The resin composition contains a rosin ester resin as a binder resin. The binder resin may contain binder resins other than the rosin ester resin together with the rosin ester resin.

(rosin ester resin)
As described above, the resin composition contains a rosin ester resin as a binder resin. Therefore, a resist pattern that can be easily peeled off with a basic stripping solution even after contact with an oxidizing agent can be easily formed using the resin composition.

One of the reasons why it becomes difficult to remove the resist pattern with the basic remover after coming into contact with the oxidizing agent is the formation of an oxide film on the surface of the resist pattern that is poorly soluble in the basic remover. guessed.
In this respect, the present inventors have found that rosin ester resins conventionally used in various applications such as ink applications, adhesive applications, and paper sizing applications have excellent oxidation resistance stability.

As described above, when a resist pattern is formed using a resin composition containing a rosin ester resin with excellent oxidation resistance stability, the formation of an oxide film on the surface of the resist pattern after the resist pattern comes into contact with an oxidizing agent is easily suppressed. .
As a result, since the resin composition contains the rosin ester resin, even after contact with the oxidizing agent, it is easy to form a resist pattern that can be easily peeled off with a basic stripper.

The rosin ester resin is not particularly limited as long as it is conventionally recognized as a rosin ester resin by those skilled in the art. Conventionally known esterified products of various rosin acids and esterified products of various rosin acid derivatives can be used as the rosin ester resin.

Rosin ester resins are typically produced by reacting rosins with alcohols. However, the method for producing a rosin ester resin is not limited to the reaction between rosins and alcohols.

Preferable examples of rosins that give rosin ester resins include pimaric acid, abietic acid, dehydroabietic acid, isopimaric acid, maleopimaric acid, fumalopimaric acid, acrylopimaric acid, dihydroabietic acid, tetrahydroabietic acid, parastric acid, and neoabietic acid. resin acids such as acids; gum rosins containing these resin acids as main components; hydrogenated rosins; unmodified rosins such as wood rosins; disproportionated rosins; tall oil rosins; modified rosin such as

Organic acid-modified rosin obtained by modifying rosin acid or hydrogenated rosin with organic acid or organic acid anhydride is also preferable as rosin. Preferred organic acids include, for example, dibasic acids such as fumaric acid and maleic acid, and dibasic acid anhydrides such as maleic anhydride and phthalic anhydride.
Maleopimaric acid-modified rosins, phthalic anhydride-modified rosins, and phthalic anhydride-modified hydrogenated rosins are also preferred organic acid-modified rosins.

When reacting rosins with alcohols, rosins may be used singly or in combination of two or more.

Known alcohols can be used without particular limitation as the alcohols that give the rosin ester resin. Specific examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, phenethyl alcohol, benzyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, and decyl. alcohol, lauryl alcohol, stearyl alcohol, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, propylene glycol mono-tert-butyl ether, methyl carbitol, ethyl carbitol, butyl carbitol, hexyl carbitol and polyethylene glycol-monomethyl ether; monoalcohol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-pentanediol, 1,5-pentanediol, 1,6 -diols such as hexanediol, 3-methyl-1,5-pentanediol, 1,4-benzenedimethanol, dodecanediol and cyclohexanedimethanol; triols such as glycerin, trimethylolethane, and trimethylolpropane; pentaerythritol, and tetraols such as diglycerin; pentaols such as xylitol; hexaols such as dipentaerythritol and sorbitol; octaols such as tripentaerythritol.
Among these alcohols, monoalcohols such as n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, and lauryl alcohol; diols such as ethylene glycol, diethylene glycol, propylene glycol, and neopentyl glycol; glycerin, trimethylolethane; , trimethylolpropane, and cyclohexanedimethanol; and tetraols, such as pentaerythritol and diglycerin.

When reacting rosins with alcohols, the alcohols may be used singly or in combination of two or more.

The rosin ester resin is obtained by esterifying the above rosins and the above alcohols in any combination. The method of reacting rosins and alcohols is not particularly limited. Suitable methods include, for example, a method of reacting rosins and alcohols in the presence of a well-known esterification catalyst. As long as the desired rosin ester resin can be obtained, the rosin ester resin may be produced by a method other than the reaction of rosins and alcohols.

The content of the rosin ester resin in the resin composition is preferably 10 parts by mass or more and 98 parts by mass or less, and 15 parts by mass or more and 90 parts by mass with respect to the total 100 parts by mass of the components other than the solvent described later in the resin composition. It is more preferably 20 parts by mass or more and 80 parts by mass or less. When the rosin ester resin is used in an amount within this range, a good balance is achieved between durability against oxidizing agents, such as etchant resistance, and stripping performance with a basic stripping solution for resist patterns after contact with oxidizing agents. Easy to form a resist pattern.

(Other binder resins)
The resin composition may contain binder resins other than the rosin ester resin within a range that does not hinder the object of the present invention.
Other binder resins may be resins that have acidic groups such as carboxyl groups, phenolic hydroxyl groups, or sulfonic acid groups, and are soluble in basic stripping solutions, and basic stripping solutions that do not have acidic groups. It may be a resin that is insoluble with respect to. The other binder resin is preferably a resin that is soluble in the basic stripping solution, since the resist pattern to be formed can be easily stripped by the salt stripping solution.
Examples of resins soluble in basic stripping solutions include (meth)acrylic resins having structural units derived from acrylic acid or methacrylic acid, and polyhydroxystyrene resins having structural units derived from hydroxystyrenes. , and novolak resins derived from phenols and naphthols.
In the specification of the present application, "(meth)acrylic" means acrylic and methacrylic, "(meth)acrylate" means acrylate and methacrylate, and "(meth)acryloyl" means acryloyl. , and methacryloyl.
As the other binder resin, a (meth)acrylic resin having a structural unit derived from acrylic acid or methacrylic acid is more preferable because it is easy to adjust various properties of the resin by selecting a monomer.

Other binder resins include resins that have acidic groups such as carboxy groups, phenolic hydroxyl groups, or sulfonic acid groups, and that are soluble in basic stripping solutions. A resin protected by the obtained protecting group can also be preferably used.
Such resins are commonly used with photoacid generators. As the photoacid generator, known photoacid generators blended in various conventionally used photosensitive resin compositions can be used without particular limitation.
In a resin composition containing such a resin and a photoacid generator in combination, an acid is generated in the resin composition by exposure, and the protective group is eliminated by the generated acid, so that the binder resin is resistant to the basic stripping solution. Solubilize.
Such a resin composition is suitably used as a positive photosensitive resin composition from which exposed portions are removed with a basic stripping solution.

The content of other binder resins in the resin composition is not particularly limited as long as the object of the present invention is not impaired. The content of the other binder resin is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 150 parts by mass or less, and 100 parts by mass or less with respect to 100 parts by mass of the rosin ester resin contained in the resin composition. is particularly preferred, and 0 parts by mass is most preferred.

[Monomer compound]
The resin composition may contain a monomer compound as a binder together with the binder resin.
A monomer compound is a compound that can be polymerized by a single polymerization reaction or an addition reaction, or by a reaction with a cross-linking agent. The monomer compound may be used together with a polymerization initiator such as a photopolymerization initiator or a curing agent depending on the type of the monomer compound, if necessary.

Preferred representative examples of the monomer compound include monomers having a radically polymerizable group such as (meth)acrylate monomers, epoxy group compounds, and oxetane compounds that are cured by exposure in the presence of a photopolymerization initiator. mentioned.
The monomer compound is not particularly limited as long as it is a compound conventionally blended in a resin composition used for forming a resist pattern.
Hereinafter, monomers having a radically polymerizable group and monomers other than the monomers having a radically polymerizable group, which are particularly suitable as the monomer compound, will be described.

(Monomer having a radically polymerizable group)
Suitable representatives of monomeric compounds include monomers having radically polymerizable groups, such as (meth)acrylate monomers, which are cured by exposure to light in the presence of a photoinitiator.
The radically polymerizable group in the monomer having a radically polymerizable group includes a (meth)acrylic group, a styrene group, an acrylonitrile group, a vinyl ester group, an N-vinylpyrrolidone group, a conjugated diene group, a vinylketone group, and a vinyl chloride group. mentioned.
Among these radically polymerizable groups, a (meth)acrylic group is preferred because of its good reactivity and easy availability of monomers.

When the resin composition contains a monomer having a radically polymerizable group, the resin composition can be cured by exposure to light. Therefore, such a resin composition can be used as a negative photosensitive resin composition.
When using such a resin composition, a resist pattern may be formed by forming a precursor pattern of a resist pattern by a printing method and then curing the precursor pattern by exposure. Moreover, you may form a resist pattern by the photolithography method, using a resin composition as a negative photosensitive resin composition. In this case, a negative photomask corresponding to the shape of the resist pattern is used.

Specific examples of monomers having a radically polymerizable group include (meth)acrylic monomers, styrene monomers, acrylonitrile, vinyl ester monomers, N-vinylpyrrolidone, conjugated diene monomers, vinyl ketone monomers, vinyl halides, halogen vinylidene-based monomers, polyfunctional monomers, and the like.

Specific examples of (meth)acrylic monomers include:
1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butane Di(meth)acrylates of alkanediols such as diol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, and ethylene glycol di(meth)acrylate;
EO-modified neopentyl glycol di(meth)acrylate, PO-modified neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol-polypropylene glycol di(meth)acrylate, polypropylene Glycol-polytetramethylene glycol di(meth)acrylate, glycerin di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A bis 2-(meth)acryloyloxyethyl ether, EO-modified bisphenol A di(meth)acrylate, PO-modified bisphenol A di(meth)acrylate, PO-EO-modified bisphenol A di(meth)acrylate, tetrabromobisphenol A bis2 -(meth)acryloyloxyethyl ether, 4,4-dimercaptodiphenyl sulfide di(meth)acrylate, EO-modified bisphenol F di(meth)acrylate, 2-(2-(meth)acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1,3-dioxane, 2-[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxan-2-yl]-2,2-dimethyl Bifunctional (meth)acrylate compounds such as ethyl and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate;
Trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, ethoxylation Trifunctional (meth)acrylate compounds such as isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and glycerin tri(meth)acrylate;
Dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(hydroxyethyl)isocyanurate polyhexanolide tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate Polyfunctional (meth)acrylate compounds such as acrylates and ditrimethylolpropane tetra(meth)acrylates can be mentioned.

Styrene-based monomers include styrene and α-methylstyrene.
Vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl butyrate.
Conjugated diene-based monomers include butadiene and isoprene.
Methyl vinyl ketone etc. are mentioned as a vinyl ketone-type monomer.
Vinyl halide and vinylidene halide monomers include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.

A monomer having a radically polymerizable group is usually used together with a photoinitiator. The type of photopolymerization initiator is not particularly limited, and is appropriately selected in consideration of the amount of exposure during exposure, the wavelength of the light source used for exposure, and the like.

(Other monomer compounds)
When the resin composition contains a monomer compound, as the monomer compound, monomer compounds other than the above-described monomer having a radically polymerizable group can be used.
As other monomer compounds, various monomer compounds conventionally blended in compositions for resist pattern formation can be used.
For example, epoxy compounds such as monofunctional to tetrafunctional epoxy compounds, various bisphenol-type epoxy resins such as bisphenol A-type epoxy resins and bisphenol F-type epoxy resins, various novolac-type epoxy resins, and resol-type epoxy resins; oxetane compounds; Tetraethoxysilane, and alkoxysilanes having a hydrolyzable group that generates a silanol group by hydrolysis such as tetramethoxysilane; Partial hydrolysis condensate of the above alkoxysilanes (siloxane compound); Hydrolysis and silsesquioxane compounds having a hydrolyzable group that generates a silanol group.

Other monomeric compounds are optionally used together with thermal acid generators, thermal base generators, photoacid generators, photobase generators, and known curing agents.
The amount of these acid generator, base generator and curing agent to be used is not particularly limited as long as the object of the present invention is not impaired. These acid generators, base generators and curing agents are used in amounts within the range normally used for other monomer compounds.

The amount of the monomer compound described above to be used is not particularly limited as long as the object of the present invention is not impaired. The amount of the monomer compound used is typically preferably 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 20 parts by mass or less relative to 100 parts by mass of the binder resin. .
It is also preferable that the resin composition does not contain a monomer compound because it is easy to set the amount of the rosin ester resin in the resin composition to be large.

<Filler>
The resin composition preferably contains a filler. As the filler, various fillers conventionally blended in compositions for resist pattern formation can be used.
Specific examples of fillers include inorganic fillers such as barium sulfate, barium titanate, silica (silicon oxide), talc, clay (hydrated magnesium silicate), magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. agents.
Pigments such as phthalocyanine blue, phthalocyanine green, iosine green, disazo yellow, victoria blue, crystal violet, titanium oxide, carbon black, and naphthalene black are also suitable fillers.

Fillers include barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, and aluminum hydroxide because they facilitate the formation of resist patterns with good opacity and resistance to ozone and hydrofluoric acid. , and mica powder are preferred. Among these, barium sulfate, barium titanate, silica, talc, and clay are more preferred.

The amount of filler added to the resin composition is not particularly limited as long as the object of the present invention is not impaired.
The amount of the filler to be added is preferably 1 part by mass or more and 70 parts by mass or less with respect to the total 100 parts by mass of the components other than the solvent, which will be described later, contained in the resin composition. In terms of easy formation of a resist pattern excellent in opacity and resistance to ozone and hydrofluoric acid, the amount of filler added is 5 parts by mass or more and 60 parts by mass or less is preferable, and 10 parts by mass or more and 50 parts by mass or less is more preferable.

<Surfactant>
The resin composition preferably contains a surfactant. Any of anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants can be used as surfactants.
The resin composition preferably contains an anionic surfactant as a surfactant because the resist pattern after contact with the oxidizing agent exhibits particularly good strippability with a basic stripping solution.
For example, a resist pattern formed using a resin composition containing an anionic surfactant may be stripped by bringing the resist pattern into contact with a flow of a basic stripping solution. It is easier to remove the resist pattern particularly favorably than when it is used.
When the resist pattern is stripped, it is not essential to bring the flow of the basic stripping liquid into contact with the resist pattern. When the flow of the basic stripping solution is brought into contact with the resist pattern, the stripping time can be easily shortened, and stripping residue is less likely to occur.

The ratio of the mass of the anionic surfactant to the total mass of the surfactant is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and most preferably 100% by mass. preferable.

When the resin composition contains an anionic surfactant, since the resist pattern after contact with the oxidizing agent is particularly easily stripped with a basic stripping solution, the resin composition contains, as the anionic surfactant, It preferably contains a polyoxyethylene alkyl ether derivative.

Since it is particularly easy to obtain the effect of adding a polyoxyethylene alkyl ether derivative as an anionic surfactant, the polyoxyethylene alkyl ether derivative has a sulfonic acid group, a carboxyl group, a phosphate group, a sulfonic acid group, a carboxylic acid group, and phosphate groups.
The counter cations constituting the sulfonate group, carboxylate group, and phosphate group may be metal cations such as sodium ions and potassium ions, and inorganic cations such as non-metallic inorganic cations such as ammonium ions. It may be an organic cation such as an organic quaternary ammonium cation.
As the counter cation, a metal cation is preferable, and an alkali metal cation such as a sodium ion and a potassium ion is more preferable, because the polyoxyethylene alkyl ether derivative is easily available.
The number of the above groups possessed by the polyoxyethylene alkyl ether derivative is not particularly limited as long as the polyoxyethylene alkyl ether derivative functions well as an anionic surfactant. The number of the above groups possessed by the polyoxyethylene alkyl ether derivative is typically preferably 1 or more and 3 or less, more preferably 1 or 2, and particularly preferably 1.

Suitable examples of polyoxyethylene alkyl ether derivatives used as surfactants include:
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene behenyl ether;
Polyoxyethylene polyoxypropylene alkyl ethers such as polyoxyethylene polyoxypropylene cetyl ether and polyoxyethylene polyoxypropylene decyltetradecyl ether;
Polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether;
Sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monooleate, and sorbitan trioleate;
Sulfate-type anionic surfactants of polyoxyethylene alkyl ethers such as sodium polyoxyethylene alkyl ether sulfate, which are alkyl ethers having an alkyl group having 12 to 18 carbon atoms;
Phosphate-type anionic surfactants such as polyoxyethylene alkyl ether phosphate;
Polyoxyethylene alkyl, which is an alkyl ether having an alkyl group having 12 to 15 carbon atoms, such as sodium polyoxyethylene lauryl ether phosphate, sodium polyoxyethylene oleyl ether phosphate, and sodium polyoxyethylene stearyl ether phosphate Alkyl ethers having alkyl groups of 12 to 15 carbon atoms, such as sodium ether phosphate, potassium polyoxyethylene lauryl ether phosphate, potassium polyoxyethylene oleyl ether phosphate, and potassium polyoxyethylene stearyl ether phosphate and polyoxyethylene alkyl ether phosphates such as polyoxyethylene alkyl ether potassium phosphate.

Among the surfactants described above, anionic surfactants having a polyoxyalkylene skeleton are preferred, and anionic surfactants that are polyoxyethylene alkyl ether derivatives are more preferred. Potassium oxyethylene lauryl ether phosphate is particularly preferred.

The amount of surfactant added to the resin composition is not particularly limited as long as the object of the present invention is not impaired. The amount of the surfactant added in the resin composition is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 8 parts by mass with respect to the total 100 parts by mass of the components other than the solvent described later. Part or less is more preferable, and 1 part by weight or more and 5 weight or less is particularly preferable. By using the surfactant in an amount within this range, a good balance can be achieved between the durability against oxidizing agents such as etchant resistance and the stripping performance of the resist pattern with a basic stripping solution after contact with the oxidizing agent. It is easy to form a certain resist pattern.

<Antioxidant>
The resin composition is easy to form a resist pattern that has an excellent balance between durability against an oxidizing agent such as etchant resistance and stripping performance with a basic stripping solution for the resist pattern after contact with the oxidizing agent. It preferably contains an inhibitor. The type of antioxidant is not particularly limited as long as it is an antioxidant conventionally blended in a composition for forming a resist pattern.

Antioxidants include hindered phenol-based antioxidants, aromatic amine-based antioxidants, and sulfur-based antioxidants, since the stripping performance of the resist pattern with a basic stripping solution after contact with the oxidizing agent is particularly excellent. It is preferably one or more selected from the group consisting of. As these antioxidants, known antioxidants can be used without particular limitation as long as the objects of the present invention are not impaired.
In this specification, an antioxidant that corresponds to both an aromatic amine antioxidant and a hindered phenol antioxidant is described as a hindered phenol antioxidant. An antioxidant that corresponds to both a sulfur-based antioxidant and a hindered phenol-based antioxidant is described as a hindered phenol-based antioxidant.

Specific examples of suitable hindered phenolic antioxidants include α-tocopherol, butylhydroxytoluene (2,6-di-tert-butyl-p-cresol), sinapyl alcohol, vitamin E, n-octadecyl-3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis(4- methyl-6-tert-butylphenol), 2,2′-methylenebis(4-ethyl-6-tert-butylphenol), 4,4′-methylenebis(2,6-di-tert-butylphenol), 2,2′- methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2′-ethylidene-bis(4,6-di-tert -butylphenol), 2,2′-butylidene-bis(4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-N- Bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] , bis[2-tert-butyl-4-methyl-6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert -butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4′-thiobis(6 -tert-butyl-m-cresol), 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-thiobis(4-methyl-6-tert-butylphenol), bis(3, 5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4'-dithiobis(2,6-di-tert-butylphenol), 4,4'-trithiobis(2,6-di-tert-butylphenol) , 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3 ,5-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N' -bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate , 1,3,5-tris{2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]oxy}ethyl isocyanurate, pentaerythritol tetra[3-(3,5-di -tert-butyl-4-hydroxyphenyl)propionate], bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid]ethylenebis(oxyethylene), 3,5-di-tert -butyl-4-hydroxybenzoic acid _-C7 - _C9 alkyl ester, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid- _C7 - _C9 alkyl ester, 3,3' ,3′,5,5′,5′-hexa-tert-butyl-a,a′,a′-(methylene-2,4,6-tolyl)tri-p-cresol, hexamethylenebis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4-{[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino}-2,6- Di-tert-butylphenol, 4,4′-thiobis-(3-methyl-6-tert-butylphenol) (SEENOX BCS, Sipro Kasei), and 1,1,3-tris-(2-methyl-4-hydroxy- 5-tert-butylphenyl)butane (SX336B, Cipro Kasei) and the like.

As a hindered phenolic antioxidant, penta Erythritol tetra [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] ethylene bis ( oxyethylene), 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate-n-octadecyl, 3,5-di-tert-butyl-4-hydroxybenzoate-C ₇ to C ₉ Alkyl ester, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid- _C7 - _C9 alkyl ester, 3,3',3',5,5',5'-hexa- tert-butyl-a,a',a'-(methylene-2,4,6-tolyl)tri-p-cresol, and hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxy phenyl)propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and bis[3-(3-tert-butyl-4-hydroxy-5 -methylphenyl)propionic acid]ethylenebis(oxyethylene) is particularly preferred.

Specific examples of suitable aminic antioxidants include 4,4′-bis(α,α-dimethylbenzyl)diphenylamine, 4,4′-dioctyldiphenylamine, phenyl-α-naphthylamine, phenothiazine, N-phenyl-N '-Isopropyl-p-phenylenediamine (Noclac 810-NA (Ouchi Shinko Kagaku Kogyo)) and N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (Noclac 6C (Ouchi Shinko chemical industry)) and the like.

As amine-based antioxidants, 4 and 4' are preferred in terms of easy formation of resist patterns with excellent oxidation resistance to oxidizing agents such as ozone and strippability with a basic stripping solution after contact with oxidizing agents. -Bis(α,α-dimethylbenzyl)diphenylamine, 4,4′-dioctyldiphenylamine, N-phenyl-N′-isopropyl-p-phenylenediamine (Nocrac 810-NA (Ouchi Shinko Kagaku Kogyo)), and N- Phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (Noclac 6C (Ouchi Shinko Kagaku Kogyo)) is more preferred, and N-phenyl-N'-isopropyl-p-phenylenediamine (Noclac 810- NA (Ouchi Shinko Chemical Industry)), and N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (Nocrac 6C (Ouchi Shinko Chemical Industry)) are more preferred, and N-phenyl- Particularly preferred is N'-(1,3-dimethylbutyl)-p-phenylenediamine (Nocrac 6C (Ouchi Shinko Kagaku Kogyo)).

Specific examples of suitable sulfur-based antioxidants include 2,4-bis(octylthiomethyl)-6-methylphenol, 2,4-bis(dodecylthiomethyl)-6-methylphenol, 4,6-bis (Octylmethyl)-o-cresol, pentaerythritol tetrakis-(3-laurylthiopropionate) (trade name: SEENOX 412S (Shipro Kasei)), and distearyl 3,3'-thiodipropionate (trade name: SEENOX DS (Shipro Kasei)).

Among the above preferred antioxidants, 2,4-bis(octylthiomethyl)-6-methylphenol, 2,4-bis(octylthiomethyl)-6-methylphenol, and 2,4-bis(octylthiomethyl)-6- -bis(dodecylthiomethyl)-6-methylphenol, 4,6-bis(octylmethyl)-o-cresol, 4-[[4,6-bis(octylthio)-1,3,5-triazine-2- yl]amino]-2,6-di-tert-butylphenol and dioctadecyl 3,3′-thiodipropionate are more preferred, 2,4-bis(octylthiomethyl)-6-methylphenol, 2,4 -bis(dodecylthiomethyl)-6-methylphenol, 4,6-bis(octylmethyl)-o-cresol, 4-[[4,6-bis(octylthio)-1,3,5-triazine-2- yl]amino]-2,6-di-tert-butylphenol is more preferred, 2,4-bis(octylthiomethyl)-6-methylphenol, and 2,4-bis(dodecylthiomethyl)-6-methylphenol is particularly preferred.

As the antioxidant, one type may be used alone, or two or more types may be used in combination.

The amount of the antioxidant added to the resin composition is not particularly limited as long as the object of the present invention is not impaired. The amount of the antioxidant added to the resin composition is preferably 0.1 parts by mass or more and 5 parts by mass or less, and 0.5 parts by mass or more and 4 parts by mass with respect to the total 100 parts by mass of the components other than the solvent described later. The following are more preferable, and 0.8 parts by mass or more and 3 parts by mass or less are particularly preferable. By using an amount of the antioxidant within this range, a good balance can be achieved between durability against oxidizing agents, such as etchant resistance, and stripping performance of the resist pattern with a basic stripping solution after contact with the oxidizing agent. It is easy to form a certain resist pattern.

<Acid anhydride compound>
The resin composition contains an acid anhydride compound having an aliphatic hydrocarbon group having 6 or more carbon atoms and a carboxylic acid anhydride group for the purpose of finely adjusting the stripping property of the resist pattern with a basic stripping solution. You can stay.

The number of acid anhydride groups in the acid anhydride compound is not particularly limited. The number of acid anhydride groups in the acid anhydride compound may be two or more, but usually one.
The number of aliphatic hydrocarbon groups in the acid anhydride compound is not particularly limited. The number of aliphatic hydrocarbon groups in the acid anhydride compound is typically preferably 1 or more and 4 or less, preferably 1 or 2.

The valence of the aliphatic hydrocarbon group in the acid anhydride compound is not particularly limited, and it may be monovalent or polyvalent (bivalent or higher).
The structure of the aliphatic hydrocarbon group is not particularly limited, and may be chain, cyclic, or a combination of chain and cyclic. When the aliphatic hydrocarbon group is chain, it may be linear or branched.
The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Although the number of unsaturated bonds in the unsaturated aliphatic hydrocarbon group is not particularly limited, it is typically one.
The upper limit of the number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited as long as the objects of the present invention are not impaired. The upper limit of the number of carbon atoms in the aliphatic hydrocarbon group may be, for example, 30 or less, 20 or less, or 15 or less.
The lower limit of the number of carbon atoms in the aliphatic hydrocarbon group is 6 or more, may be 8 or more, or may be 10 or more.

Acid anhydride compounds are non-aromatic compounds containing heteroatoms such as aromatic hydrocarbon groups, aromatic heterocyclic groups, N, O, S, P, and Si, in addition to acid anhydride groups and aliphatic hydrocarbon groups. may have a family group.
Examples of non-aromatic groups include carboxy groups, sulfonic acid groups, phosphate groups, amino groups, carbamoyl groups (—CO—NH ₂ ), cyano groups, nitro groups, —O—, —S—, —NH— , -CO-, -CO-O-, -CO-NH-, -O-CO-O-, -NH-CO-NH-, -O-CO-NH-, -SS-, -SO- , -SO ₂ -, -SO ₂ -O-, -SO ₂ -NH-, and -N=N-. Non-aromatic groups are not limited to these groups.

For example, when an acid anhydride group (--CO--O--CO--) is bonded to an aliphatic hydrocarbon group to form a ring such as a 5- or 6-membered ring, the aliphatic hydrocarbon group and the acid anhydride The number of carbon atoms in the aliphatic hydrocarbon group is the number of carbon atoms obtained by subtracting the number of non-carbonyl carbon atoms in the ring (2) from the number of carbon atoms in the entire structure or partial structure consisting of the compound group.
As a specific example, in hexahydrophthalic anhydride, 6, which is the number obtained by subtracting 2 from the number of carbon atoms of 8 in the entire structure of hexahydrophthalic anhydride, is the number of carbon atoms in the aliphatic hydrocarbon group. In butylsuccinic anhydride, 6, which is the number obtained by subtracting 2 from the number of carbon atoms of 8 in the entire structure of butylsuccinic anhydride, is the number of carbon atoms in the aliphatic hydrocarbon group.

In the acid anhydride compound, the acid anhydride group does not have to form a ring. Examples of acid anhydride compounds having an acid anhydride group that does not form a ring include pentanoic anhydride and octanoic anhydride.

In the anhydride compound, the anhydride group may be attached to the aromatic group. The aromatic group that binds to the acid anhydride group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. In this case, the acid anhydride compound is directly attached to the aromatic group, or linked to the aromatic group such as -O-, -S-, -CO-, -CO-O-, and -CO-NH-. It has an aliphatic hydrocarbon group with 6 or more carbon atoms bonded through a group. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon ring condensed with an aromatic hydrocarbon group.
Specific examples of acid anhydride compounds having an acid anhydride group bonded to an aromatic group include n-hexylphthalic anhydride and n-hexyloxyphthalic anhydride.

Specific examples of the acid anhydride compounds described above include 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, bicyclo[2,2,1]heptane- 2,3-dicarboxylic anhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, tetrapropenylsuccinic anhydride, 2-octenylsuccinic anhydride 1,1-cyclohexanediacetic anhydride, icosahydro-3,4,9,10-perylenetetracarboxylic anhydride, 1,1′-bicyclohexane-3,3′,4,4′-tetracarboxylic acid dianhydride, decahydronaphthalene-1,2-dicarboxylic anhydride, 2-dodecenylsuccinic anhydride and the like.

Among the above acid anhydride compounds, it is easy to mix uniformly with the resin composition and easy to form a resist pattern with excellent stripping properties with a basic stripping solution after contact with an oxidizing agent. , 4-methylhexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, tetrapropenylsuccinic anhydride, and 2-octenylsuccinic anhydride are preferred, 4-methylhexahydrophthalic anhydride, 1,2 ,3,6-tetrahydrophthalic anhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and 2-octenylsuccinic anhydride are more preferred.

The amount of the acid anhydride compound added to the resin composition is not particularly limited as long as the object of the present invention is not impaired. The amount of the acid anhydride compound added to the resin composition is preferably 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the total mass of components other than the solvent described later.
The amount of the acid anhydride compound added to the resin composition will be described later, because the viscosity of the resin composition can be easily maintained within an appropriate range, and a resist pattern having excellent strippability with a basic stripping solution can be easily formed. It is more preferably 0.2 parts by mass or more and 10 parts by mass or less, and even more preferably 0.3 parts by mass or more and 5 parts by mass or less with respect to the total 100 parts by mass of the components other than the solvent.

<Thixotropy-imparting agent>
As will be described later, printing is one preferred method for forming resist patterns on substrates. In order to form a resist pattern on a substrate by printing, the resin composition may need to be thixotropic. Thixotropy is the property of decreasing viscosity (pseudoplasticity) when subjected to shear stress. In order to impart thixotropic properties to the resin composition, it is preferable to add a thixotropic agent to the resin composition.

The thixotropy-imparting agent is not particularly limited as long as the object of the present invention is not impaired, and both organic thixotropy-imparting agents and inorganic thixotropy-imparting agents can be suitably used.
Representative examples of organic thixotropic agents include polyethylene waxes, amide waxes, hydrogenated castor oil waxes, and polyamide waxes.
Representative examples of the inorganic thixotropy-imparting agents include clay-type thixotropy-imparting agents that are clay components modified with stearic acid Al salts, Ca salts, or Zn salts; salts such as lecithin salts or alkylsulfonates; Clay, bentonite, fumed silica, and the like.

As a thixotropy-imparting agent, it is easy to obtain the desired effect by adding a small amount to the resin composition, and has good miscibility with the resin composition and good dispersion stability in the resin composition. are preferably polyethylene waxes, hydrogenated castor oil wax systems, polyamide wax systems, fumed silica, and bentonite.

The amount of the thixotropic agent used in the resin composition is not particularly limited as long as the object of the present invention is not impaired. The amount of the thixotropy-imparting agent used in the resin composition is 100 parts by mass of the resin composition from the viewpoint of good miscibility with the resin composition and good dispersion stability in the resin composition. , preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

<Solvent>
The resin composition may contain a solvent for the purpose of adjusting coatability or printability when forming a resist pattern, or for the purpose of adjusting the drying property of the formed resist pattern.
The type of solvent is not particularly limited as long as it is a solvent conventionally blended in a resin composition for forming a resist pattern.

Specific examples of solvents include alcohols such as methanol, ethanol, n-butyl alcohol, methoxybutanol (3-methoxy-1-butanol), tert-butanol, cyclohexanol, and methylcyclohexanol;
Polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, and glycerin;
Glycol ethers such as methyl cellosolve, cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether;
Glycol acetates such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate;
Glycol diethers such as methyl triglyme and ethyl monoglyme;
Esters such as ethyl acetate, methyl acetate, isobutyl acetate, and ethyl lactate;
carbonate esters such as propylene carbonate;
Ethers other than glycol ethers, glycol acetates, and glycol diethers, such as diisopropyl ether, methyl tertiary butyl ether, and tetrahydrofuran;
Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, and diacetone alcohol;
Aliphatic hydrocarbons such as n-hexane;
aromatic hydrocarbons such as toluene and xylene;
chlorinated aromatic hydrocarbons such as chlorobenzene and ortho-dichlorobenzene;
Examples include chlorinated aliphatic hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethylene, and trichlorethylene. These solvents may be used alone, or two or more of them may be combined and used as a mixed solvent.

The reason will be described later, but the resin composition can be suitably used for forming a resist pattern by a printing method.
When a resist pattern is formed by a printing method, the solvent can be methyl cellosolve, cellosolve, or Glycol ethers such as butyl cellosolve, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; glycol acetates such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate are preferred.
Diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate are more preferable as the solvent because of their low toxicity.

A resin composition is obtained by uniformly mixing the components described above in a desired ratio.

<Application>
As described above, the above resin composition is preferably used for forming a resist pattern by printing. Generally, the size of a resist pattern formed by a printing method is larger than the size of a resist pattern formed by a photolithography method. As the size of the resist pattern increases, it tends to be more difficult to remove the resist pattern using a remover. However, when a resist pattern is formed using the above resin composition, even after contact with an oxidizing agent, the resist pattern can be removed satisfactorily with a basic remover, and the pattern size formed by the printing method is Even a large resist pattern can be removed satisfactorily with a basic remover.

As described above, by using the above resin composition, it is possible to form a resist pattern that can be easily stripped with a basic stripping solution even after contact with an oxidizing agent.
Therefore, the above resin composition is suitably used to form a resist pattern that is used in contact with an oxidizing agent. However, the application of the resin composition is not limited to the formation of resist patterns used in contact with an oxidizing agent.

A resist pattern is usually formed on a substrate. Substrate materials used for forming resist patterns include substrates made of stainless steel, copper, and other metals; composite substrates such as metal foil laminated substrates in which metal foils such as copper foil are laminated; silicon A substrate (silicon wafer) and the like are included. The above composite substrate is used for printed circuit boards and the like. Silicon wafers are used to manufacture semiconductor products such as solar cells and various semiconductor devices.

For the purpose of increasing the adhesion of the resist pattern to the substrate surface, the surface of the substrate is sometimes subjected to surface cleaning and/or surface treatment in order to adjust the contact angle of the substrate surface.
Surface cleaning includes cleaning of contaminants with organic solvents, alkaline cleaning solutions, ozone, etc., cleaning by etching using acidic substances such as chromic acid, sulfuric acid, and hydrochloric acid, and cleaning by physical methods such as polishing and shot blasting. , electrochemical cleaning by oxide film treatment, and cleaning using ions, plasma, etc., can be employed.
The method for cleaning the substrate surface is not limited to these methods. As the cleaning method, any well-known cleaning method can be appropriately adopted as long as it is a method capable of removing contaminants.

Surface treatments include treatment of the substrate surface with an adhesion enhancer.
Suitable examples of the adhesion improver include coupling agents such as silane coupling agents, aluminate coupling agents, and titanate coupling agents, and chelate compounds. Among these, silane coupling agents and chelate compounds are exemplified because of their easy availability and high effect of improving adhesion.

Preferred specific examples of silane coupling agents include β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltriethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3 -(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)- 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N -phenyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3 -chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane.

Preferred specific examples of chelate compounds include N-hydroxyethyl-ethylenediaminotriacetic acid, nitrilotriacetic acid, hydroxyethylidene-1,1-diphosphate, aminotrimethylene phosphate, ethylenediamino-tetramethylene phosphate, diethylene tria Minopentamethylene phosphate, diethylenetriaminopentamethylene phosphate, hexamethylenediaminotetraethylene phosphate and the like can be mentioned.

The surface treatment using the above-mentioned adhesion improver may be performed by applying the adhesion improver to the substrate surface, and by including the adhesion improver in the resin composition, it is performed simultaneously with the formation of the resist pattern. good too.
It is preferable to apply the adhesion improver directly to the substrate surface because it is easy to suppress redeposition of the surface of the substrate and it is easy to obtain the effect of improving the adhesion of the resist pattern.
When the adhesion promoter is applied directly to the substrate surface, even compounds that can impair the stability or other properties of the resin composition can be used.
Prior to applying the adhesion promoter to the substrate surface, the substrate surface is preferably cleaned as described above.

If necessary, a resist pattern is formed on a substrate that has been subjected to surface cleaning and/or surface treatment as described above, using the above resin composition, by a known method such as photolithography or printing. is formed.
The method of forming the resist pattern is appropriately selected depending on the pattern size and the like. The printing method is preferable because the apparatus for forming the resist pattern is relatively inexpensive and the operation for forming the resist pattern is easy.

When forming a resist pattern by a printing method, a resist pattern is formed by applying a resin composition onto a substrate according to a desired pattern shape and then drying, thermally curing, or photocuring the applied pattern. be.
Drying or thermal curing can be carried out by air drying at room temperature or by heating in an oven or on a hot plate. The heating temperature is not particularly limited as long as thermal decomposition or undesired thermal denaturation does not occur in the resist pattern. The heating temperature is typically preferably 50° C. or higher and lower than 500° C., more preferably 80° C. or higher and 400° C. or lower, and still more preferably 100° C. or higher and 300° C. or lower.
The heating time is not particularly limited as long as the drying and heat curing proceed to the desired extent and the resist pattern is not thermally decomposed or undesiredly thermally denatured. The heating time is, for example, preferably 10 seconds to 24 hours, more preferably 30 seconds to 12 hours, and particularly preferably 1 minute to 1 hour.

A typical example of the purpose of using the resist pattern is an etching mask. When the resist pattern is used as an etching mask, etching is performed using an etchant that does not chemically decompose the resist pattern and is capable of etching the substrate surface.
A preferred example of the etching method will be described later in detail in the application of the resin composition to the production of back-contact solar cells, which is a particularly preferred use.

A more preferred use of the resin composition is
an oxidant contact step of contacting a semiconductor substrate having a resist pattern with an oxidant;
Formation of a resist pattern in a method for manufacturing a semiconductor product, including a stripping step of stripping the resist pattern after being brought into contact with an oxidizing agent from the semiconductor substrate with a basic stripping solution.
This is because, in the manufacture of semiconductor products, an oxidizing agent is often used for the purpose of etching or for the purpose of forming an oxide film such as a silicon oxide film.

The semiconductor product is not particularly limited as long as it is manufactured by processing a semiconductor substrate, and includes various solar cells and transistor elements such as TFT and MOSFET. MOSFETs are also applied to solid-state imaging devices such as CMOS devices.

The oxidizing agent is not particularly limited as long as it is a chemical generally known as an oxidizing agent. The oxidant may be used as a gas or as a liquid.
Examples of oxidizing agents include nitric acid, sulfuric acid, ozone, and hydrogen peroxide. Plasmas derived from oxygen-containing gases (eg, oxygen plasmas) are also included as oxidants.
Chemicals containing an oxidizing agent that are widely used in the manufacture of semiconductor products include an etchant containing ozone and hydrofluoric acid (hydrofluoric acid). Such etchants are used for etching silicon substrates, especially as particularly suitable etchants for silicon substrates. The etchant containing ozone and hydrofluoric acid (hydrofluoric acid) is usually an aqueous solution, but may contain an organic solvent as long as the etching performance is not impaired.

A particularly preferred application of the resin composition is formation of a resist pattern in a method for manufacturing a back-contact solar cell as a semiconductor product.

A preferable example of the method for manufacturing a back-contact solar cell is the following method in which no resist pattern is formed on the lift-off layer.
in particular,
A method for manufacturing a back-contact solar cell as a semiconductor product, comprising:
a semiconductor substrate comprising, on at least one surface, a p-type semiconductor layer or an n-type semiconductor layer as a first semiconductor layer on the outermost surface, and an intrinsic semiconductor layer in contact with the first semiconductor layer;
a resist pattern is formed directly on the first semiconductor layer;
contacting a semiconductor substrate provided with a resist pattern with an etchant containing an oxidant to remove the first semiconductor layer and the intrinsic semiconductor layer at positions corresponding to the positions of the openings of the resist pattern;
After removing the first semiconductor layer and the intrinsic semiconductor layer, the resist pattern is stripped,
After removing the resist pattern, an intrinsic semiconductor layer is formed in the space from which the first semiconductor layer and the intrinsic semiconductor layer have been removed, and then a second semiconductor layer having a polarity opposite to that of the first semiconductor layer is formed. The method.

Another preferred method for manufacturing a back-contact solar cell is the following method of forming a resist pattern on the lift-off layer.
in particular,
A semiconductor product manufacturing method for manufacturing a back-contact solar cell as a semiconductor product,
a semiconductor substrate comprising, on at least one surface side, a p-type semiconductor layer or an n-type semiconductor layer as a first semiconductor layer, and an intrinsic semiconductor layer in contact with the first semiconductor layer;
a resist pattern is formed on the first semiconductor layer via a lift-off layer;
removing the lift-off layer at a position corresponding to the position of the opening of the resist pattern by contacting the semiconductor substrate provided with the resist pattern with an etchant containing an oxidant;
After the removal of the lift-off layer, the resist pattern is peeled off and the first semiconductor layer at the position corresponding to the position of the opening of the resist pattern is removed by etching,
forming a second semiconductor layer having a polarity opposite to that of the first semiconductor layer so as to cover the bottom and side surfaces of the space from which the first semiconductor layer has been removed and the lift-off layer;
This is a method for removing the second semiconductor layer that has been in contact with the lift-off layer along with the removal of the lift-off layer.

A back-contact solar cell has p-type and n-type semiconductor layers formed on the back surface of a silicon substrate (crystalline silicon substrate) opposite to the light-receiving surface, and electrodes formed thereon. This is a back electrode type solar cell.
Conventionally, the most commonly manufactured and sold solar cells are crystalline silicon solar cells. A crystalline silicon solar cell is usually provided with a metal electrode from the viewpoint of current extraction efficiency. However, when a metal electrode is provided on the light-receiving surface of a crystalline silicon solar cell, it is difficult to obtain a power generation efficiency corresponding to the area of the light-receiving surface because the opaque metal electrode partially blocks the light received by the light-receiving surface.

Back-contact solar cells do not require a metal electrode on the light-receiving surface, and thus can solve the above-mentioned problem of power generation efficiency in crystalline silicon solar cells.

In a back-contact solar cell, as described above, the p-type and n-type semiconductor layers are patterned on the back surface so that they are formed at predetermined positions. When patterning such a semiconductor layer, a resist pattern as an etching mask and an etchant containing an oxidant, especially an etchant containing ozone and hydrofluoric acid are used.
Therefore, it is strongly desired that the resist pattern used for patterning the semiconductor layer on the back surface of the back-contact solar cell can be easily and satisfactorily stripped with a basic stripping solution even after contact with an oxidizing agent.
For the reasons described above, the above resin composition is particularly preferably used as a material for forming a resist pattern as an etching mask in the production of a back-contact type solar cell.

Hereinafter, referring to FIG. 1 (FIGS. 1(a) to 1(e)) as a preferred example of a method for manufacturing a back-contact solar cell, using the above resin composition and not forming a lift-off layer, A method for manufacturing a back-contact solar cell will be described.
As a method for manufacturing a back-contact solar cell, for example, the method described in Japanese Unexamined Patent Application Publication No. 2018-50005 can be referred to.

The semiconductor substrate has, on at least one surface, a p-type semiconductor layer or an n-type semiconductor layer as the first semiconductor layer 12 on the outermost surface. The semiconductor substrate comprises an intrinsic semiconductor layer in contact with the first semiconductor layer 12 .
FIG. 1(a) schematically shows a cross section perpendicular to the surface direction of a suitable semiconductor substrate that satisfies the above requirements.
The semiconductor substrate shown in FIG. 1A has a crystalline silicon substrate 10 at the center in the thickness direction. The semiconductor substrate includes intrinsic semiconductor layers 11 on both sides of a crystalline silicon substrate 10 in contact with the crystalline silicon substrate 10 .
The semiconductor substrate shown in FIG. 1A includes a first semiconductor layer 12 in contact with one intrinsic semiconductor layer 11 and an insulating layer 14 in contact with the other intrinsic semiconductor layer 11 .
In addition, in the semiconductor substrate shown in FIG. 1A, the surface on the insulating layer 14 side becomes the front surface, which is the light receiving surface, when the back-contact solar cell is manufactured. On the other hand, the surface on the side of the first semiconductor or the like 12 is the back surface on which the electrodes are formed when the back contact solar cell is manufactured.

A resist pattern 16 is formed as shown in FIG. 1(b) on the first semiconductor layer 12 in the semiconductor substrate shown in FIG. 1(a). A method for forming the resist pattern 16 is not particularly limited. As a method for forming the resist pattern 16, a printing method and a photolithography method are preferable, and a printing method is more preferable. The printing method is not particularly limited, and various printing methods such as screen printing, flexographic printing, offset printing, and inkjet printing can be applied. Among these printing methods, screen printing is preferable because the printing equipment is inexpensive and the resist pattern 16 having a desired shape can be formed accurately and efficiently.

When the resin composition is a photosensitive resin composition, the resist pattern 16 may be formed by photolithography. In the photolithography method, after the resin composition is coated on the first semiconductor layer 12, the coating film is exposed to actinic rays such as ultraviolet rays through a negative or positive photomask corresponding to the desired pattern shape. After exposure, a resist pattern 16 is formed by dissolving and removing unnecessary portions with a developer.

Regarding the size of the resist pattern 16, the thickness is preferably 0.5 μm or more and 100 μm or less, more preferably 1 μm or more and 70 μm or less. The pattern line width is preferably 10 μm or more and 3 mm or less, more preferably 50 μm or more and 1 mm or less. The interval between patterns (the width of the non-resist portion) is preferably 20 μm or more and 5 mm or less, more preferably 50 μm or more and 2 mm or less.

Next, etching is performed by bringing the semiconductor substrate including the resist pattern 16 into contact with an etchant containing an oxidant. As a result, as shown in FIG. 1C, the first semiconductor layer 12 and the intrinsic semiconductor 11 at positions corresponding to the positions of the openings of the resist pattern 16 are removed.

The etchant containing an oxidizing agent is as described above, and an etchant containing ozone and hydrofluoric acid (hydrofluoric acid) is particularly preferably used.
The concentration of ozone in such an etching solution is preferably 0.1 ppm or more and 100 ppm or less, more preferably 1 ppm or more and 70 ppm or less. The concentration of hydrofluoric acid is preferably 0.5% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 8% by mass or less.

The etching method is not particularly limited as long as it can remove the first semiconductor layer 12 and the intrinsic semiconductor 11 .
Examples of the etching method include a method of immersing the semiconductor substrate having the resist pattern 16 in an etchant, a liquid deposition method of pouring the etchant onto the surface to be etched, and a spray method of spraying the etchant onto the surface to be etched.
Etching time is not particularly limited, and etching is performed until the first semiconductor layer 12 and the intrinsic semiconductor 11 are removed.

After etching is performed as described above to remove the first semiconductor layer 12 and the intrinsic semiconductor layer 11, the resist pattern 16 is removed as shown in FIG. 1(d).
Stripping of the resist pattern 16 is performed with a basic stripping solution.

Examples of basic stripping solutions include basic alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, and sodium metasilicate; ammonia, ethylamine, n-propylamine, diethylamine, di-n - propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and Aqueous solutions of basic amines such as 1,5-diazabicyclo[4,3,0]-5-nonane can be used.
The concentration of the above basic component in the basic stripping solution is not particularly limited as long as the resist pattern can be stripped satisfactorily. The concentration of the basic component can be determined in consideration of the strength of basicity of the basic component. The concentration of the basic component in the basic stripping solution is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 5% by mass or less.
Various additives such as water-soluble organic solvents, surfactants, and buffer components such as borax may be added to the basic stripping solution as long as the objects of the present invention are not impaired.

The stripping of the resist pattern 16 with the basic stripping solution can be performed by the same etching method as described above, except that the etchant is changed to the basic stripping solution.

After the resist pattern 16 is removed, as shown in FIG. and the second semiconductor layer 13 having the opposite polarity are formed in this order.
Such an operation is performed, for example, by a well-known method that combines the formation and stripping of a resist pattern and the CVD method.
Thus, a semiconductor substrate in which the first semiconductor layer 12 and the second semiconductor layer 13 are patterned in a desired state is obtained.
A back-contact solar cell can be manufactured by subjecting the semiconductor substrate in the state shown in FIG.

Hereinafter, as another preferred example of a method for manufacturing a back-contact solar cell, referring to FIG. A method for manufacturing a back-contact solar cell to be formed will be described.
As a method for manufacturing a back-contact solar cell, for example, the method described in Japanese Unexamined Patent Application Publication No. 2018-50005 can be referred to.

The semiconductor substrate has a p-type semiconductor layer or an n-type semiconductor layer as the first semiconductor layer 12 on at least one surface side. The semiconductor substrate comprises an intrinsic semiconductor layer in contact with the first semiconductor layer 12 .
FIG. 2(a) schematically shows a cross section perpendicular to the surface direction of a suitable semiconductor substrate that satisfies the above requirements.
The semiconductor substrate shown in FIG. 2A is similar to the semiconductor substrate shown in FIG.
In addition, in the semiconductor substrate shown in FIG. 2A, the surface on the insulating layer 14 side becomes the front surface, which is the light receiving surface, when the back-contact solar cell is manufactured. On the other hand, the surface on the lift-off layer 15 side is the back surface on which electrodes are formed when the back-contact solar cell is manufactured.

The above-described lift-off layer 15 has a resistance to being peeled off by the basic stripping solution used for stripping the resist pattern 16, and the first semiconductor layer 12 and the second semiconductor layer 13 are not excessively etched. It is a layer that can be removed with a stripping solution.
Examples of the material of the lift-off layer 15 include silicon oxide. Hydrofluoric acid or the like can be used as a stripping solution for stripping the lift-off layer 15 while leaving the first semiconductor layer 12 and the second semiconductor layer 13 .

A resist pattern 16 is formed as shown in FIG. 2(b) on the lift-off layer 15 in the semiconductor substrate shown in FIG. 2(a). The method of forming the resist pattern is the same as the method described for the method of manufacturing the back-contact solar cell shown in FIG.

Next, etching is performed by bringing the semiconductor substrate including the resist pattern 16 into contact with an etchant containing an oxidant. As a result, as shown in FIG. 2C, the lift-off layer 15 at positions corresponding to the positions of the openings of the resist pattern 16 is removed.
The etching method is the same as the method described for the method of manufacturing the back-contact solar cell shown in FIG.
By adjusting the etching time, it is possible to remove only the lift-off layer 15 .

The etchant containing an oxidizing agent is as described above, and an etchant containing ozone and hydrofluoric acid (hydrofluoric acid) is particularly preferably used.
The concentration of ozone in the etchant used for removing the lift-off layer 15 is preferably 0.1 ppm or more and 100 ppm or less, more preferably 1 ppm or more and 70 ppm or less. The concentration of hydrofluoric acid is preferably 0.5% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 8% by mass or less.

After removing the lift-off layer 15 by etching as described above, the resist pattern 16 is peeled off and the first position corresponding to the position of the opening of the resist pattern 16 (the position corresponding to the opening of the lift-off layer 15) is removed. Removal of the semiconductor layer 12 is performed.
The order in which the resist pattern 16 is stripped and the first semiconductor layer 12 is partially removed at a predetermined position is not particularly limited.

First, after removing the resist pattern 16, a method for partially removing the first semiconductor layer 12 at a predetermined position will be described.
In this method, first, the resist pattern 16 is removed as shown in FIG. 2(d1).
Stripping of the resist pattern 16 is performed with a basic stripping solution.
The method of stripping the resist pattern 16 with a basic stripping solution is the same as the method described for the method of manufacturing the back-contact solar cell shown in FIG.

After the resist pattern 16 is removed, the first semiconductor layer 12 at the position corresponding to the position of the opening of the resist pattern 16 (the position also corresponding to the opening of the lift-off layer 15) shown in FIG. is removed by etching. FIG. 2(e) shows the state after the first semiconductor layer 12 has been removed by etching.
Although the etching method for removing the first semiconductor layer 12 is not particularly limited, plasma etching is preferred because it is less likely to damage the lift-off layer 15 .

Next, a method for removing the resist pattern 16 after partial removal at a predetermined position of the first semiconductor layer 12 will be described.
In this method, first, as shown in FIG. 2(d2), the first semiconductor layer 12 at the position corresponding to the position of the opening of the resist pattern 16 (the position also corresponding to the opening of the lift-off layer 15) is etched. removed by In this case, an etchant containing ozone and hydrofluoric acid (hydrofluoric acid) is used as an etchant for etching the first semiconductor layer 12 . Here, the removal of the lift-off layer 15 and the removal of the first semiconductor layer 12 may be performed continuously using an etchant containing ozone and hydrofluoric acid (hydrofluoric acid).

Then, the resist pattern 16 shown in FIG. 2(d2) is removed.
Stripping of the resist pattern 16 is performed with a basic stripping solution.
The method of stripping the resist pattern 16 with a basic stripping solution is the same as the method described for the method of manufacturing the back-contact solar cell shown in FIG. FIG. 2E shows the state after the resist pattern 16 has been removed.

Then, following the removal of the first semiconductor layer 12, as shown in FIG. A second semiconductor layer 13 having a polarity opposite to that of the first semiconductor layer 12 is formed. Although the method of forming the second semiconductor layer 13 is not particularly limited, it is performed by, for example, the CVD method.

After the formation of the second semiconductor layer 13 , the second semiconductor layer 13 located in contact with the lift-off layer 15 is removed along with the removal of the lift-off layer 15 .
By removing the lift-off layer 15, only the second semiconductor layer 13 located in contact with the lift-off layer 15 is selectively removed, and as shown in FIG. The second semiconductor layer 13 is filled only in the space from which 12 has been removed by etching.
Thus, a semiconductor substrate in which the first semiconductor layer 12 and the second semiconductor layer 13 are patterned in a desired state is obtained.
A back-contact solar cell can be manufactured by subjecting the semiconductor substrate in the state shown in FIG.

The method using the lift-off layer 15 shown in FIG. 2 is complicated for the patterning of the semiconductor layer required in the step of FIG. It is advantageous in that no operation is required.

The present invention will be described in more detail below with reference to examples. The invention is in no way limited to these examples.

Performance evaluation of the resin composition or the resist pattern formed using the resin composition was performed according to the following method for the resin compositions of Examples and Comparative Examples, which will be described later.

<Performance evaluation>
(viscosity)
According to the method described in JISZ8803, the viscosity of the resin composition was measured using a Brookfield viscometer. Since the resin composition has a relatively high viscosity, the viscosity was measured using a HB type viscometer (manufactured by Eiko Seiki). The viscosity measured in the range of 25±1° C. at 5 rpm using a cone-plate rotor is the viscosity defined herein.

(Printability)
Using a screen printing plate with L (line width)/S (space width) = 400 µm/600 µm, emulsion thickness = 20 µm, under the conditions of squeegee pressure = 0.20 MPa and speed = 100 mm/min, an amorphous silicon layer was formed as a lift-off layer. A resist pattern having a predetermined pattern was printed by a screen printer on the lift-off layer of the silicon wafer on which was formed. The printability was evaluated based on the following evaluation criteria from the faintness, spread of the pattern, and thickness of the pattern during printing.
◯: No blurring. The pattern spread width is 50 μm or less, and the thickness is ±3 μm or less with respect to the set value. Screen printing is possible, and there is no problem with printing.
△: No blurring. The pattern spread is 50 μm, the width is 70 μm or less, and the thickness is ±5 μm or less with respect to the set value, which is somewhat problematic for screen printing.
x: There is faintness. The pattern spreading width exceeds 70 μm. The thickness is ±5 μm or more with respect to the set value, and the screen printing is defective.

(Ozone resistance, hydrofluoric acid resistance)
A resist pattern was formed by screen printing and drying at 120° C. for 30 minutes on a cell in which a p-layer (holes) was formed on a textured silicon wafer. The dimensions of the resist pattern were a line width of 450 μm, a space width between lines of 100 μm, and a thickness of 40 μm.
The cell provided with the resist pattern was immersed for 10 minutes in an etchant containing ozone at a concentration of 40 mass ppm and hydrofluoric acid at a concentration of 7 mass %.
After the immersion, the state of the p-layer was confirmed with a scanning electron microscope (SEM), and the resistance to ozone and hydrofluoric acid of the resist pattern was evaluated based on the following evaluation criteria.
Good: Line width of p-layer is 400 μm or more and 450 μm or less Acceptable: Line width of p-layer is 350 μm or more and less than 400 μm Poor: Line width of p-layer is less than 350 μm

(Removability of resist pattern)
The above-mentioned ozone/hydrofluoric acid-treated cell is rocked in an aqueous solution of 0.4% by mass of potassium hydroxide and 1.0% by mass of borax (rocking width = 3 cm, speed = 60 rpm) and immersed for 10 minutes, and the peeled state of the resist pattern after immersion was observed with an optical microscope.
A: Completely peeled off by immersion for 10 minutes.
B: Mostly peeled off by immersion for 10 minutes, peeling residue can be removed by additional immersion or ultrasonic irradiation.
C: No or little peeling after 10 minutes of immersion.

Resin compositions for resist pattern formation of Examples 1 to 7 and Comparative Example 1 were prepared according to the following formulations, and various properties were evaluated using the obtained resin compositions according to the methods described above.

[Example 1]
In a container dedicated to blending (φ89×φ98×94 mm, content 470 cc, made of polypropylene), 55 g of maleic acid-modified rosin ester resin (trade name: Marquid No. 6, manufactured by Arakawa Chemical Industries, Ltd.) as a binder component, and an interface 1 g of sodium polyoxyethylene lauryl ether sulfate (trade name: Emar 270J, manufactured by Kao Corporation) as an activator, and pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxy Phenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF Japan Co., Ltd.) 2 g, spherical silica powder as a filler (trade name: SFP-30M, manufactured by Denki Kagaku Kogyo Co., Ltd.) 15 g, and solvent 1-( 2-Methoxy-2-methylethoxy)-2-propanol (dipropylene glycol monomethyl ether) 27 g was added, and after manual stirring using a spoon, a dedicated stirring and defoaming device (product number: foam removal The mixture was sheared and stirred using Taro ARV-310 (manufactured by Thinky Co., Ltd.).
Mixing, stirring and defoaming were carried out to obtain a resin composition for forming a resist pattern. The viscosity, printability, resistance to ozone and hydrofluoric acid, and resist peelability of the obtained etching resist composition were evaluated by the measurement methods described above. Table 1 shows the results obtained.

[Example 2]
Using 1 g of polyoxyethylene alkylene ether (trade name: Emulgen LS-110, manufactured by Kao Corporation) instead of sodium polyoxyethylene lauryl ether sulfate, and pentaerythritol tetra[3-(3,5-di-tert -Butyl-4-hydroxyphenyl)propionate] using 2 g of 4,4′-bis(α,α-dimethylbenzyl)diphenylamine (trade name: Naugard 445, Informatica Japan Co., Ltd.); -(2-Methoxy-2-methylethoxy)-2-propanol was changed to 15 g, and 12 g of diethylene glycol monoethyl ether acetate was added. A resin composition for forming was prepared and evaluated for characteristics. Table 1 shows the results obtained.

[Example 3]
Changing the amount of maleic acid-modified rosin ester resin used to 30 g, changing the amount of granular silica used to 5 g, and talc (compound name: hydrous magnesium silicate, manufactured by Wako Pure Chemical Industries, Ltd.) 35 g , and 2 g of carbon black (trade name: MA-100, manufactured by Mitsubishi Chemical Corporation), and 15 g of 1-(2-methoxy-2-methylethoxy)-2-propanol to 10 g of diethylene glycol monoethyl ether acetate. A resin composition for forming a resist pattern was produced in the same manner as in Example 1, except that the composition was changed, and its properties were evaluated. Table 1 shows the results obtained.

[Example 4]
Changing the amount of maleic acid-modified rosin ester resin added to 15 g, using 15 g of acidic acrylic resin (ZAH-110, carboxylic acid functional group amount = 96 mg KOH / g, manufactured by Soken Chemical Co., Ltd.), Erythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is changed to 1 g of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, and an acid anhydride compound A resin composition for forming a resist pattern was prepared in the same manner as in Example 3, except that 1 g of 2-octenylsuccinic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the resin composition, and the characteristics were evaluated. Table 1 shows the results obtained.

[Example 5]
changing the amount of acidic acrylic resin added to 10 g; changing the amount of rosin ester resin added to 20 g; changing sodium polyoxyethylene lauryl ether sulfate to 2 g of polyoxyethylene alkyl ether; A resin composition for forming a resist pattern was prepared in the same manner as in Example 4, except that no octenylsuccinic anhydride was added, and its properties were evaluated. Table 1 shows the results obtained.

[Example 6]
Polyoxyethylene lauryl ether sodium sulfate is replaced with polyoxyethylene alkyl ether potassium phosphate (trade name: Nucalgen TG-100, manufactured by Takemoto Yushi Co., Ltd.), and pentaerythritol tetra[3-(3,5-di -tert-butyl-4-hydroxyphenyl) propionate] to 2,4-bis(octylthiomethyl)-6-methylphenol (trade name: IRGANOX1520L, manufactured by BASF Japan Co., Ltd.) A resin composition for forming a resist pattern was prepared in the same manner as in Example 1, and its properties were evaluated. Table 1 shows the results obtained.

[Example 7]
Changing the amount of rosin ester resin used to 45 g, not using surfactants and antioxidants, talc (hydrous magnesium silicate, Wako Pure Chemical Industries, Ltd.) 25 g, silica powder (Denki Kagaku Kogyo Co., Ltd.) 2 g of carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation) and 2 g of carbon black (manufactured by Mitsubishi Chemical Corporation), and the amount of 1-(2-methoxy-2-methylethoxy)-2-propanol used. was changed to 20 g, and 5 g of diethylene glycol monoethyl ether acetate was added. Table 1 shows the results obtained.

[Comparative Example 1]
55 g of rosin ester resin is changed to 30 g of acidic acrylic resin (ZAH-110, carboxylic acid functional group content = 96 mg KOH / g, manufactured by Soken Chemical Co., Ltd.), and silica powder (Denki Kagaku Kogyo Co., Ltd.) is used as a filler. "SFP-30M" manufactured by Wako Pure Chemical Industries, Ltd.) 20 g, and talc (hydrous magnesium silicate, Wako Pure Chemical Industries, Ltd.) 30 g, and 2-octenylsuccinic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) is not used. The same method as in Example 1 except that the amount of 1-(2-methoxy-2-methylethoxy)-2-propanol used and the amount of diethylene glycol monoethyl ether acetate used were each changed to 10 g. A resin composition for forming a resist pattern was prepared and evaluated for its characteristics. Table 1 shows the results obtained.

The resin compositions of Examples and Comparative Examples, and the resist patterns formed using the resin compositions, had no problem in terms of viscosity, printability, resistance to ozone and hydrofluoric acid.
On the other hand, it can be seen from Comparative Example 1 that when the resin composition does not contain a rosin ester resin, the strippability of the resist pattern with a basic stripper after the resist pattern comes into contact with the oxidizing agent is significantly impaired.
According to Example 7, when the resin composition does not contain a combination of a surfactant, an antioxidant, and a filler, after the resist pattern comes into contact with an oxidizing agent, the basic stripping solution of the resist pattern Although the peelability is good, it can be seen that it is slightly inferior.

REFERENCE SIGNS LIST 10 crystalline silicon substrate 11 intrinsic semiconductor layer 12 first semiconductor layer 13 second semiconductor layer 14 insulating layer 15 lift-off layer 16 resist pattern

Claims (16)

including a binder and an acid anhydride compound,
The binder includes a binder resin containing a rosin ester resin,
A resin composition used for forming a resist pattern, wherein the acid anhydride compound has an aliphatic hydrocarbon group having 6 or more carbon atoms and a carboxylic acid anhydride group. 2. The resin composition according to claim 1, comprising one or more selected from the group consisting of fillers, surfactants, and antioxidants. 3. The resin composition according to claim 2, comprising said filler, said surfactant, and said antioxidant. 4. The resin composition according to claim 2, wherein the surfactant comprises an anionic surfactant, and the anionic surfactant comprises a polyoxyethylene alkyl ether derivative. 5. The polyoxyethylene alkyl ether derivative according to claim 4, wherein the polyoxyethylene alkyl ether derivative has one or more groups selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphate group, a sulfonic acid group, a carboxylic acid group, and a phosphate group. The described resin composition. The surfactant according to any one of claims 2 to 5, which contains 0.1 parts by mass or more and 10 parts by mass or less of the surfactant with respect to a total of 100 parts by mass of components other than the solvent contained in the resin composition. of the resin composition. Any one of claims 2 to 6, comprising as the antioxidant one or more selected from the group consisting of hindered phenol antioxidants, aromatic amine antioxidants, and sulfur antioxidants. The resin composition according to . Any one of claims 2 to 7, comprising 0.1 parts by mass or more and 5 parts by mass or less of the antioxidant with respect to the total 100 parts by mass of the mass of components other than the solvent contained in the resin composition. The resin composition according to . The resin composition according to any one of claims 1 to 8, which is used for forming a resist pattern by printing. The resin composition according to any one of claims 1 to 9, wherein said resist pattern is used in contact with an oxidizing agent. an oxidant contact step of contacting the semiconductor substrate provided with the resist pattern with the oxidant;
11. The resist pattern according to claim 10, which is used for forming the resist pattern in a method for manufacturing a semiconductor product comprising a stripping step of stripping the resist pattern after contact with the oxidizing agent from the semiconductor substrate with a basic stripping solution. of the resin composition. wherein the semiconductor product is a back-contact solar cell,
The semiconductor substrate has, on at least one surface, a p-type semiconductor layer or an n-type semiconductor layer as a first semiconductor layer on the outermost surface, and an intrinsic semiconductor layer in contact with the first semiconductor layer,
the resist pattern is formed directly on the first semiconductor layer;
The semiconductor substrate provided with the resist pattern is brought into contact with an etchant containing an oxidant to remove the first semiconductor layer and the intrinsic semiconductor layer at positions corresponding to positions of openings of the resist pattern. ,
After removing the first semiconductor layer and the intrinsic semiconductor layer, the resist pattern is removed,
After removing the resist pattern, the intrinsic semiconductor layer is formed in the space from which the first semiconductor layer and the intrinsic semiconductor layer have been removed, and then a second semiconductor layer having a polarity opposite to that of the first semiconductor layer is formed. The resin composition according to claim 11, which forms a semiconductor layer. wherein the semiconductor product is a back-contact solar cell,
the semiconductor substrate comprises a p-type semiconductor layer or an n-type semiconductor layer as a first semiconductor layer on at least one surface side, and an intrinsic semiconductor layer in contact with the first semiconductor layer;
the resist pattern is formed on the first semiconductor layer via a lift-off layer;
removing the lift-off layer at positions corresponding to positions of openings of the resist pattern by contacting the semiconductor substrate provided with the resist pattern with an etchant containing an oxidant;
After the lift-off layer is removed, the resist pattern is stripped, and the first semiconductor layer at a position corresponding to the position of the opening of the resist pattern is removed by etching,
forming a second semiconductor layer having a polarity opposite to that of the first semiconductor layer so as to cover the bottom and side surfaces of the space from which the first semiconductor layer has been removed and the lift-off layer;
12. The resin composition according to claim 11, wherein the second semiconductor layer in contact with the lift-off layer is removed along with the removal of the lift-off layer. a resist pattern forming step of forming a resist pattern on the surface of a semiconductor substrate by a printing method or a photolithography method using a resin composition containing a binder resin containing a rosin ester resin as a binder;
an oxidant contact step of contacting the semiconductor substrate provided with the resist pattern with an oxidant;
and a stripping step of stripping the resist pattern after contact with the oxidizing agent with a basic stripping solution. A method for manufacturing a semiconductor product, wherein a back contact solar cell is manufactured as the semiconductor product,
The semiconductor substrate has, on at least one surface, a p-type semiconductor layer or an n-type semiconductor layer as a first semiconductor layer on the outermost surface, and an intrinsic semiconductor layer in contact with the first semiconductor layer,
the resist pattern is formed directly on the first semiconductor layer;
The semiconductor substrate provided with the resist pattern is brought into contact with an etchant containing an oxidant to remove the first semiconductor layer and the intrinsic semiconductor layer at positions corresponding to positions of openings of the resist pattern. ,
After removing the first semiconductor layer and the intrinsic semiconductor layer, the resist pattern is removed,
After removing the resist pattern, the intrinsic semiconductor layer is formed in the space from which the first semiconductor layer and the intrinsic semiconductor layer have been removed, and then a second semiconductor layer having a polarity opposite to that of the first semiconductor layer is formed. 15. The method of manufacturing a semiconductor product according to claim 14, comprising forming a semiconductor layer. A method for manufacturing a semiconductor product, wherein a back contact solar cell is manufactured as the semiconductor product,
the semiconductor substrate comprises, on at least one surface side, a p-type semiconductor layer or an n-type semiconductor layer as a first semiconductor layer, and an intrinsic semiconductor layer in contact with the first semiconductor layer;
the resist pattern is formed on the first semiconductor layer via a lift-off layer;
removing the lift-off layer at positions corresponding to positions of openings of the resist pattern by contacting the semiconductor substrate provided with the resist pattern with an etchant containing an oxidant;
After the lift-off layer is removed, the resist pattern is stripped, and the first semiconductor layer at a position corresponding to the position of the opening of the resist pattern is removed by etching,
forming a second semiconductor layer having a polarity opposite to that of the first semiconductor layer so as to cover the bottom and side surfaces of the space from which the first semiconductor layer has been removed and the lift-off layer;
15. The method of manufacturing a semiconductor product according to claim 14, wherein along with the removal of the lift-off layer, the second semiconductor layer in contact with the lift-off layer is removed.

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