CN116360213A

CN116360213A - Resin composition and photoresist patterning method using the same

Info

Publication number: CN116360213A
Application number: CN202310345418.5A
Authority: CN
Inventors: 马文杰; 晏凯; 刘力铭; 杨遇春; 夏巍; 郑柳瑜
Original assignee: Huizhou City Appearance Photosensitive Technology Co ltd; Shenzhen Rongda Photosensitive Science & Technology Co ltd
Current assignee: Huizhou City Appearance Photosensitive Technology Co ltd; Shenzhen Rongda Photosensitive Science & Technology Co ltd
Priority date: 2023-03-29
Filing date: 2023-03-29
Publication date: 2023-06-30

Abstract

The present invention relates to a resin composition comprising an alkali-soluble resin (a), a dissolution inhibitor (B), a solvent (C), a surfactant (D), and an adhesion promoter (E), a method for forming a pattern using the resin composition in combination with a positive photoresist, and use of the resin composition for metal patterning in semiconductor manufacturing, the composition of the present invention being used in combination with a positive photoresist, enabling the underlying sacrificial layer photoresist to have a reduced alkali dissolution rate during development, and the sidewall angle of the developed underlying sacrificial layer photoresist to be large.

Description

Resin composition and photoresist patterning method using the same

Technical Field

The invention relates to the field of photoresist, in particular to a resin composition for an underlayer sacrificial layer, a method for patterning by using the underlayer sacrificial layer photoresist and application of the resin composition in metal patterning in semiconductor preparation.

Background

In the semiconductor manufacturing process, metal patterns are generally used for manufacturing leads and electrodes of devices, and are generally formed by a method of photolithography followed by wet or dry etching, but some metals are difficult to be patterned by wet etching or dry etching, and chemical substances required for etching the metal patterns have corrosion effects on other parts of the semiconductor devices, so a lift-off process is generally used for manufacturing the patterns of the metals.

In the stripping process using the bilayer adhesive, aiming at the bilayer structure, the angle of the side wall of the bottom layer (the acute angle between the inclined plane of the photoresist of the bottom sacrificial layer and the plane of the substrate) after development is larger is one of the key technical points for realizing the high-resolution process. At present, if a Lift-off resin (LOR) material is thick, the side wall angle of a bottom adhesive film is generally smaller after development, and in this case, the developed top line can be floated due to the fact that the developed top line cannot be held. In addition, in the case where the film layer is relatively thin and the CD requirement is small, it is necessary to further reduce the dissolution rate of the LOR material itself.

Therefore, there is a particular need for an underlayer sacrificial layer photoresist that has a low alkali dissolution rate during development and that provides a high sidewall angle for the developed underlayer film.

Disclosure of Invention

In order to overcome the above-described drawbacks of the prior art, the present inventors have surprisingly found that the alkali dissolution rate of the underlayer sacrificial layer photoresist can be reduced by providing a resin composition added with a dissolution inhibitor as the underlayer sacrificial layer photoresist, so that the sidewall angle of the underlayer sacrificial layer photoresist after development is large, wherein the underlayer sacrificial layer photoresist is used in combination with a positive photoresist.

In one aspect, the resin composition of the present invention comprises:

(A) Alkali-soluble resin, 100 parts by weight;

(B) A dissolution inhibitor, 1 to 25 parts by weight, preferably 2 to 20 parts by weight, more preferably 2 to 15 parts by weight, most preferably 5 to 15 parts by weight, even more preferably 8-12 parts by weight;

(C) Solvent 100 to 1200 parts by weight, preferably 200 to 1000 parts by weight, more preferably 400 to 800 parts by weight;

(D) A surfactant in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, more preferably 0.5 to 1.5 parts by weight;

(E) An adhesion promoter in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, more preferably 1.5 to 2.5 parts by weight;

the components (B) to (E) are each based on 100 parts by weight of the solid content of the component alkali-soluble resin (A).

In another aspect, the present invention also provides a method for forming a pattern on a photoresist, comprising the steps of:

(i) Uniformly coating the resin composition of the present invention on a substrate to form a photoresist of a bottom sacrificial layer, and baking at 90-120 ℃ for 30 seconds to 10 minutes to remove the solvent, wherein the thickness of the baked film is 0.1-8 μm, preferably 0.1-6 μm, more preferably 0.1-4 μm;

(ii) Uniformly coating a positive photoresist on the dried bottom sacrificial layer in (i), preferably baking the coated positive photoresist at a temperature of 90 to 120 ℃;

(iii) Partially irradiating the photoresist formed in (ii) with radiation through a mask;

(iv) Developing the photoresist film obtained in (iii) by using a developing solution, wherein the developing solution is an alkaline solution;

(v) The developed photoresist is optionally baked at less than 200 c, preferably 120 to 180 c, more preferably 120 to 150 c, to make the hardening more complete.

Still another aspect of the present invention provides the use of the resin composition for metal patterning in semiconductor manufacturing.

The bottom sacrificial layer photoresist added with the dissolution inhibitor is matched with the positive photoresist, wherein the dissolution inhibitor and the bottom sacrificial layer photoresist are combined, so that the alkali dissolution rate of the bottom sacrificial layer photoresist in the developing process can be reduced, and the undercut side wall angle of the bottom sacrificial layer photoresist after the developing is larger.

Drawings

Fig. 1 schematically shows an undercut structure obtained using the resin composition of example 3, wherein the undercut angle (angle 1) is about 60 °, which is the acute included angle of the slope of the underlying sacrificial layer photoresist with the plane of the substrate. Where 11 represents a positive photoresist layer, 12 represents an underlying sacrificial layer photoresist layer, and 13 represents a substrate.

Detailed Description

In the present invention, unless otherwise indicated, all operations are carried out at room temperature and pressure.

In the present invention, the term "alkali-soluble resin" is synonymously used with "solid component of alkali-water-soluble resin" unless otherwise indicated. This is because in use, an "alkali-soluble resin" generally contains a solvent component (e.g., for reducing viscosity, ease of handling), however, only components that do not contain a solvent are generally considered when, for example, it is involved in calculating the mass ratio, determining the acid value, and the like, as is well known to those skilled in the art.

In the present invention, unless otherwise indicated, the term "insoluble" refers to the place where the interface between the two film layers of the bottom sacrificial layer photoresist and the top conventional positive photoresist is clear, and where there is no intermixing resulting in an insignificant interface. More specifically, because the top photoresist is liquid (contains a large amount of solvent) when coated on the bottom material, the poor miscibility can cause the top photoresist material to be dissolved by the solvent and to penetrate into the bottom material, so that the characteristic functions of the two layers can be influenced, and the performance of the double-layer structure can be unstable.

As used herein, the term "(n+1) -valent linear alkyl" or "(n+1) -valent cycloalkyl", such as (n+1) -valent linear alkyl or cycloalkyl having 1 to 20 carbon atoms, refers to a group obtained by removing n hydrogen atoms, for example, from a linear or branched alkyl or cycloalkyl having 1 to 20 carbon atoms.

As used herein, the term "undercut structure" refers to a structure formed at the lower edge of the top photoresist when the photoresist is developed after exposure, which is close to a "T" shape in the present invention, i.e., the structure formed by the top photoresist and the bottom photoresist remaining after development is close to a "T" shape, because the dissolution rate of the bottom photoresist is greater than that of the top photoresist when the photoresist is developed after exposure in a photolithography process for manufacturing a semiconductor.

As used herein, the term "film thickness clear time" refers to the time required to properly dissolve the film layer formed by the upper positive photoresist of the present invention and the underlying sacrificial layer photoresist (i.e., the exposed areas of the positive photoresist and the sacrificial layer photoresist thereunder) under a given development medium and mode.

As used herein, the term "resin composition" is used synonymously with "underlying sacrificial layer photoresist".

In addition, other terms used herein have conventional meanings as understood by those skilled in the art unless specifically stated.

The present invention provides a resin composition comprising the following components:

(A) Alkali-soluble resin, 100 parts by weight;

In some embodiments of the present invention, the acid value of the solid component of the alkali-soluble resin (A) is 10 to 300mg KOH/g, preferably 20 to 200mg KOH/g, more preferably 20 to 90mg KOH/g, even more preferably 60 to 90mg KOH/g.

In some embodiments of the present invention, the alkali-soluble resin (a) has a weight average molecular weight of 1,000 to 100,000, preferably 10,000 to 80,000, more preferably 15,000 to 40,000, and a distribution width of molecular weight of 1 to 5, preferably 1 to 3, more preferably 1.5 to 2.5, wherein the weight average molecular weight is determined according to GB/T21863-2008.

Alkali-soluble resin (A)

In some preferred embodiments of the present invention, the alkali-soluble resin (a) of the present invention contains hydroxyl groups and/or carboxyl groups, preferably hydroxyl groups and carboxyl groups.

The alkali-soluble resin in the present invention may be:

the novolak resin is obtained by condensing phenols such as phenol, m-cresol, p-cresol, xylenol, and trimethylphenol with aldehydes such as formaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, and 4-hydroxybenzaldehyde in the presence of an acidic catalyst;

hydroxystyrene resins, for example homopolymers of hydroxystyrene or copolymers of hydroxystyrene with other styrenic monomers, copolymers of hydroxystyrene with acrylic acid or methacrylic acid or derivatives thereof;

acrylic or methacrylic resins, such as copolymers of acrylic or methacrylic acid with derivatives thereof.

In some embodiments, the resins of the present invention are prepared from monofunctional unsaturated monomers by initiating free radical polymerization of the monomers in a solvent system via a thermal initiator at a temperature. The specific preparation modes of the resin disclosed by the invention are as follows: one is to raise the temperature of the selected proper solvent to a certain temperature, and drop the monomer and the free radical initiator mixed in a specified proportion into the solvent; the other is that after mixing the selected monomers according to the specified proportion, the mixture and the free radical initiator are completely dissolved in the selected proper solvent and then dripped into the selected solvent at a certain temperature; and the other is to mix part of the monomer with the selected solvent, raise the temperature to a certain level and then drop the residual monomer and free radical initiator mixed solution into the inside. The three methods mainly solve the problems of heat release, dissolution, molecular weight regulation and reaction control in the synthesis process, and are selected according to monomers with different properties, different combination ratios, different free radical initiators and different solvent systems. The present invention illustrates three synthetic methods of the resins of the present invention, but is not limited to these three methods.

In one embodiment of the present invention, the alkali-soluble resin of the present invention is preferably polymerized from a plurality of monomers, and the alkali-soluble resin comprises at least one of the compounds shown in the following 1a and 1b, and the compounds 1a and 1b together account for 20 to 60% by weight, based on the weight of the alkali-soluble resin, and the monomers for synthesizing 1a and 1b are the monomers for synthesizing the alkali-soluble resin of the present invention.

Wherein in (1 a) and (1 b), each R is independently a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group or a trifluoromethyl group. R is R ¹ R is as follows ² Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Wherein the alkyl group having 1 to 4 carbon atoms is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. R is R ³ R is as follows ⁴ Each independently is an (n+1) -valent organic group selected from a (n+1) -valent chain hydrocarbon group having 1 to 20 carbon atoms, an (n+1) -valent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a (n+1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof. Further, some or all of hydrogen atoms included in these groups may be substituted. Each n is independently an integer from 1 to 3. In the case where n is greater than 2, R ¹ R is as follows ² Each may be the same or different Different from each other.

In one embodiment of the present invention, the (n+1) -valent linear or branched alkyl group having 1 to 20 carbon atoms may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl.

In one embodiment of the present invention, the (n+1) -valent alicyclic hydrocarbon group having 3 to 20 carbon atoms may be, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl.

In one embodiment of the present invention, the (n+1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms may be, for example, a group obtained by removing n hydrogen atoms from a 1-valent aromatic hydrocarbon group having 6 to 20 carbon atoms.

In one embodiment of the invention, R ³ Preferably, propylene such as methylene, ethylene, 1, 3-propylene or 1, 2-propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecylmethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecenethylene, nonadecamethylene, eicosylene, 1-methyl-1, 3-propylene, 2-methyl-1, 2-propylene, 1-methyl-1, 4-butylene, 2-methyl-1, 4-butylene, metabolylene such as metabolylene, cyclohexylene such as 2-metabolylene, cyclooctylene such as 1, 5-cyclooctylene, norbornylene such as 1, 4-norbornylene, 2, 5-norbornylene or 2, 6-norbornylene, 1, 5-alkylene or 2, 6-phenylene, 1, 3-phenylene, 1, 4-phenylene, or an aromatic hydrocarbon group such as adamantylene, or a combination thereof. In addition, R ⁶ Preferably 1, 3-phenylene or 1, 4-phenylene, more preferably 1, 4-phenylene.

In a preferred embodiment of the invention, for compounds 1a, n is preferably 1,

R ¹ and R is ² Identical and preferably methyl, and R ³ Preferably methylene, ethylene, 1, 2-propylene or 1, 4-propylenePhenyl.

In a preferred embodiment of the invention, for compound 1b, n is preferably 1,

R ¹ and R is ² Identical and preferably methyl, R ⁴ Preferably 1, 4-phenylene.

In some preferred embodiments of the present invention, the alkali-soluble resin (a) is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer with a hydroxyl group-containing ethylenically unsaturated monomer. Wherein the carboxyl-containing ethylenically unsaturated monomer comprises acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid and other acrylic monomers; the hydroxyl-containing ethylenically unsaturated monomer includes hydroxyl C acrylate ₂ -C ₆ Alkyl esters and/or hydroxy methacrylates C ₂ -C ₆ Alkyl esters; preferably, the monomer for preparing the alkali-soluble resin (A) may further comprise acrylic acid C ₁ -C ₆ Alkyl esters, acrylic acid C ₃ -C ₈ Cycloalkyl esters, methacrylic acid C ₁ -C ₆ Alkyl esters, methacrylic acid C ₃ -C ₈ Cycloalkyl esters.

In some preferred embodiments of the present invention, the alkali-soluble resin (A) is an acrylic or methacrylic resin obtained by polymerizing an acrylic or methacrylic monomer, methacrylic acid C ₁ -C ₈ Alkyl ester monomer and hydroxy group C methacrylate ₂ -C ₆ And (3) copolymerizing alkyl ester monomers.

In some preferred embodiments of the present invention, the alkali-soluble resin (A) is prepared by reacting methacrylic acid, hydroxy methacrylic acid C ₂ -C ₆ Alkyl esters with methacrylic acid C ₁ -C ₆ And (3) copolymerizing alkyl ester.

In other preferred embodiments of the present invention, the alkali-soluble resin (A) is prepared by reacting methacrylic acid, hydroxy methacrylic acid C ₂ -C ₆ Alkyl esters with methacrylic acid C ₃ -C ₈ And (3) copolymerizing cycloalkyl ester.

In some preferred embodiments of the present invention, the alkali-soluble resin (a) of the present invention is more preferably a combination of at least two methacrylic resins having different solid acid values. More preferably, the absolute value of the difference in acid values of the two methacrylic resins used for the alkali-soluble resin (A) is 5mg KOH/g or more, even more preferably 10mg KOH/g or more. More preferably, the absolute value of the difference in acid values of the two methacrylic resins for the alkali-soluble resin (A) is 40mg KOH/g or less, preferably 30mg KOH/g or less.

In some preferred embodiments of the present invention, the absolute value of the difference in acid values of the two methacrylic resins for the alkali-soluble resin (A) is 5mg KOH/g or more and 40mg KOH/g or less, preferably 10mg KOH/g or more and 30mg KOH/g or less.

In some preferred embodiments of the present invention, it is preferred that the acid value of the alkali-soluble resin (a) is provided by monomeric methacrylic acid.

In some embodiments of the present invention, wherein the methacrylic resin of the present invention is prepared by copolymerizing at least three monomers of methacrylic acid, methyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate monomers.

In some embodiments of the present invention, wherein the methacrylic resin of the present invention is prepared by copolymerizing methacrylic acid, methyl methacrylate and any one selected from hydroxyethyl methacrylate, hydroxypropyl methacrylate, and also preferably by copolymerizing methacrylic acid, cyclohexyl methacrylate, hydroxyethyl methacrylate.

In some embodiments of the present invention, the weight ratio of monomers methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate used to prepare the alkali-soluble resins of the present invention is from 1.0:10.0:5.0 to 1.0:2.5:1.5, preferably from 1.0:6.0:3.0 to 1.0:4.5:2.0.

In some preferred embodiments of the present invention, wherein the monomer used to prepare the acrylic or methacrylic resin comprises 5 to 20 wt%, preferably 8 to 15 wt%, more preferably 8.5 to 14 wt% of the monomer with carboxyl groups, based on the total weight of the monomers used to prepare the acrylic or methacrylic resin. In a preferred embodiment of the present invention, wherein the monomer with a carboxyl group is acrylic acid or methacrylic acid or a combination thereof, preferably methacrylic acid.

In some preferred embodiments of the present invention, wherein the monomer methacrylic acid and monomer methacrylic acid C used to prepare the methacrylic resin ₁ -C ₈ The weight ratio of the alkyl ester is 1: (1-15), preferably 1: (2-10), more preferably 1: (4-8), more preferably methacrylic acid C as described above ₁ -C ₈ The alkyl ester is methyl methacrylate or cyclohexyl methacrylate.

In some preferred embodiments of the present invention, wherein the monomer methacrylic acid and monomer hydroxy methacrylic acid C used to prepare the methacrylic resin ₂ -C ₆ The weight ratio of the alkyl ester is 1:

(1.0-10.0), preferably 1: (1.2-6.0), more preferably 1: (1.5-4.0), more preferably, the above-mentioned hydroxy group C methacrylate ₂ -C ₆ The alkyl ester is hydroxyethyl methacrylate or hydroxypropyl methacrylate.

In the present invention, the non-functional monomer is a (meth) acrylic monomer having a carbon chain number of 4 to 20 in the composition of the resin monomer; aromatic styrene monomers such as o-vinyltoluene, m-vinyltoluene, and o-chlorostyrene; an ethylene (propylene) compound such as (meth) acrylamide, (meth) acrylamides, (meth) acrylonitrile and vinyl toluene. These polymerizable monomers may be used alone or in combination of two or more, but the proportion of the nonfunctional monomer to the resin monomer is 5 to 90%, preferably 10 to 80%, more preferably 20 to 70%, based on the weight of the alkali-soluble resin. The nonfunctional monomers are reasonably selected for the desired properties of the synthetic resin.

In the present invention, the radical initiator used for preparing the alkali-soluble resin is usually an organic peroxide initiator (e.g., t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, cyclohexyl peroxide, t-butyl peroxybenzoate); azo-based initiators (e.g., azobisisobutyronitrile, azobisisoheptonitrile, methyl azobisisobutyrate), among which dibenzoyl peroxide, di-t-butyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile are preferably used. The initiator may be used alone or in combination of plural kinds.

In some embodiments of the present invention, the solvent used to prepare the alkali-soluble resin of the present invention is typically an ether solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, or the like; ketone solvents such as methanone, butanone, cyclohexanone, heptanone, and the like; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as N-methylpyrrolidone, N-dimethylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide.

Here, it is important to note that since the alkali-soluble resin in the present invention is resistant to an ester solvent, that is, ensures that the synthesized resin compound is not dissolved in the ester solvent, which is the basis for realizing a bilayer structure, the ester solvent is not suitable for the synthesis of the alkali-soluble resin of the present invention. The total amount of the solvent used in the polymerization reaction of the alkali-soluble resin in the present invention is not particularly limited, and is generally selected to be 10 to 80 parts by weight, preferably 30 to 60 parts by weight (based on 100 parts by weight of the total resin).

In the present invention, the alkali-soluble resin is synthesized by initiating polymerization of various monofunctional unsaturated monomers in a solvent system through a radical thermal initiator at a certain temperature. The specific synthetic routes are as follows: one is to raise the temperature of the proper solvent to certain temperature and drop the mixed monomer and free radical initiator in certain proportion into the solvent; the other is that after the selected monomers are mixed according to the specified proportion, the mixture and the free radical initiator are completely dissolved in the selected proper solvent and then dripped into the selected solvent at a certain temperature; and the other is to mix part of the monomer with the selected solvent, raise the temperature to a certain level and then drop the residual monomer and free radical initiator mixed solution into the inside. The three methods mainly solve the problems of heat release, dissolution, molecular weight regulation, reaction control and the like in the synthesis process, and are selected according to different character monomers, different combination ratios, different free radical initiators and different solvent systems. The invention describes three synthetic methods of the resin, but is not limited to the three methods.

In a specific embodiment of the present invention, the reaction temperature, the dropping time, and the reaction time for synthesizing the alkali-soluble resin of the present invention are selected according to the kind of the polymerization monomer, the radical initiator, and the solvent used. The reaction temperature is 30 to 200 ℃, preferably 40 to 180 ℃, more preferably 50 to 150 ℃. The dropping time is 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 hour to 5 hours. The reaction time after completion of the dropping is 1 to 20 hours, preferably 3 to 15 hours, more preferably 5 to 10 hours. In addition, the dripping mode can be single-mouth single-position dripping, multi-mouth multi-position dripping or dipping dripping.

In the present invention, it is important to say that the carboxyl group in the alkali-soluble resin is provided by a monofunctional unsaturated monomer having a carboxyl group such as (meth) acrylic acid, and the acid value of the solid component of the resin is 10 to 300mg KOH/g, preferably 20 to 200mg KOH/g, more preferably 20 to 90mg KOH/g, even more preferably 60 to 90mg KOH/g, as measured according to GB/T2895-2008.

In some embodiments of the present invention, in the resin composition of the present invention, wherein the alkali-soluble resin (a) has a weight average molecular weight of 1,000 to 100,000, preferably 2,000 to 80,000, more preferably 3,000 to 50,000, and a distribution width of molecular weight of 1 to 5, preferably 1 to 3, more preferably 1.5 to 2.5, the weight average molecular weight is determined according to GB/T21863-2008.

In the present invention, it is important to note that the hydroxyl groups in the resin may be provided by monomers selected from the group consisting of: hydroxy (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; the hydroxyethyl (meth) acrylate is ethoxylated and the solid content of the alkali-soluble resin has a hydroxyl value of 10 to 800mg KOH/g, preferably 30 to 500mg KOH/g, more preferably 50 to 300mg KOH/g, as determined from the determination of the hydroxyl value in HG/T2709-95 polyester polyol.

In a preferred embodiment of the present invention, the alkali dissolution rate of the resin composition of the present invention is 75nm/s or less, preferably 50nm/s or less, more preferably 10 nm/s or more and 50nm/s or less, most preferably 20 nm/s or more and 50nm/s or less.

The alkali-soluble resin (A) of the present invention has a suitable acid value, average molecular weight and dispersibility, so that the dissolution rate of the resin composition in an alkaline aqueous solution is controllable, and certain Tg characteristics (glass transition temperature) and control of profile undercut are ensured. And ensures that the resin composition has a certain adhesion to the substrate.

In some preferred embodiments of the present invention, the resin composition of the present invention does not include an unsaturated compound containing a curing group (excluding unsaturated carboxylic acids), for example, does not include an unsaturated compound containing an epoxy group and an unsaturated compound of oxetane, for example, glycidyl (meth) acrylate.

Dissolution inhibitor (B)

In the present invention, a suitable dissolution inhibitor is a compound that chemically reacts under irradiation of ultraviolet rays (light of one or more wavelengths including g-Line, h-Line, i-Line, krF rays, arF rays) or other rays.

In some embodiments of the invention, the dissolution inhibitor (B) is a compound that reacts under irradiation with ultraviolet rays or radiation.

In some embodiments of the present invention, the dissolution inhibitor (B) may be a compound that generates an acid upon irradiation with ultraviolet rays or radiation, also referred to as photoacid generator (B1). The photoacid generator comprises an onium salt compound (B1-1), a halogen-containing compound (B1-2), a sulfonic acid compound and a sulfonyl compound (B1-3) or a combination of the above compounds.

In the present invention, the cationic moiety of the onium salt compound (B1-1) may be an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, a pyridinium salt or the like. The sulfonium cation moiety preferably has a structure represented by the following formula (1)

Wherein R is ⁵ 、R ⁶ And R is ⁷ Each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, an aryl group which may have an unsubstituted or substituted group, a hydroxyl group, or a linear or branched alkoxy group having 1 to 4 carbon atoms; or R is ⁵ 、R ⁶ And R is ⁷ Each independently represents a straight or branched alkylene group having 1 to 4 carbon atoms, and their terminals may be linked to form a ring; or R is ⁵ 、R ⁶ And R is ⁷ In the case where each is independently an unsubstituted or substituted aryl group, the number of carbon atoms is preferably 6 to 15, and specific examples are alkylphenyl groups such as phenyl group, tert-butylphenyl group and the like.

R ⁵ 、R ⁶ And R is ⁷ Each independently represents a straight or branched alkylene group having 1 to 4 carbon atoms, and their terminals may be linked to form a ring. In this case, the two alkylene groups mentioned above form a 3-to 9-membered ring containing a sulfur atom. The number of atoms constituting the ring (including sulfur atoms) is preferably 5 to 6.

In view of acid production efficiency, the preferable anion moiety is an anion capable of forming a sulfonium salt, and particularly preferable is an alkylsulfonate ion or an allylsulfonate ion in which part or all of hydrogen atoms are substituted with fluorine atoms.

The alkyl group in the fluoroalkylsulfonate ion may be a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms. In view of the bulkiness of the acid produced and the chain length thereof, the number of carbon atoms is preferably 1 to 10. Branched or cyclic alkyl groups are particularly preferred due to the short chain length.

Specific examples of such alkyl groups are methyl, ethyl, propyl, butyl and octyl, since they can all be synthesized at low cost.

Examples of the aryl group in the allylsulfonic acid include aryl groups having 6 to 20 carbon atoms, such as phenyl and naphthyl groups, which may be substituted or unsubstituted with an alkyl group or a halogen atom. Aryl groups having 6 to 10 carbon atoms are preferred because they can be synthesized at low cost.

Specific examples of preferred aryl groups include phenyl, tosyl, ethylphenyl, naphthyl and methylnaphthyl.

The degree of fluorination is preferably 10 to 100%, and more preferably 50 to 100%. Sulfonates in which all hydrogen atoms are replaced by fluorine atoms are preferred because of the increased acidity. Specific examples thereof include trifluoromethane sulfonate, perfluorobutane sulfonate, perfluorooctane sulfonate and perfluorobenzene sulfonate.

As the anionic moiety, a nitrogen-containing anionic moiety having the formula (2) can also be used

Wherein Y is ⁰ And Z ⁰ Each independently is a fluoro-substituted alkyl, fluoro-substituted alkyl ether, fluoro-substituted aryl, fluoro-substituted acyl, or fluoro-substituted alkoxyaryl, and further Y ⁰ And Z ⁰ Are not linked or are linked to each other to form a fluorine substituted heterocyclic structure. Here Y ⁰ And Z ⁰ The number of carbon atoms contained in (a) is preferably 1 to 10. Also, Y ⁰ And Z ⁰ Is fluorinated in which at least one hydrogen is substituted by fluorine. In particular at Y ⁰ And Z ⁰ In the case of a fluorinated alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 2 to 6, and is preferably a perfluoroalkyl group in which hydrogen is entirely substituted with fluorine. Specific examples thereof include triphenylsulfonium hexafluorophosphate, 4-methoxyphenyl diphenylsulfonium trifluoromethanesulfonic acid and p-tert-butylphenyl diphenylsulfonium trifluoromethanesulfonic acid.

In the present invention, the halogen-containing compound (B1-2) may be a halogen-containing triazine compound of the formula (3),

wherein R is ⁸ To R ¹⁰ Each of which may be the same or different, and represents a chloroalkyl group.

Halogen-containing compounds are, for example, tris (2, 3-bromopropyl) phosphate, tris (2, 3-dibromo-3-chloropropyl) phosphate, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethane) -s-triazine, 2- [2- (4-methoxyphenyl-2-yl) vinyl ] -4, 6-bis (trichloromethane) -s-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (2-furyl) vinyl ] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) vinyl ] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-ethyl-2-furyl) vinyl ] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) vinyl ] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3-furyl) vinyl ] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 5-diethoxyphenyl) vinyl ] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 5-dipropoxyphenyl) vinyl ] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3-methoxy-5-ethoxyphenyl) vinyl ] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) vinyl ] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-methylenedioxyphenyl) vinyl ] -s-triazine, 2, 4-bis (trichloromethyl) -6- (3, 4-methylenedioxyphenyl) -s-triazine, 2, 4-bis trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2, 4-bis trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2, 4-bis (trichloromethyl) -6- (2-bromo-4-methoxy) phenyl-s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (2-furyl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (5-methyl-2-furyl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (3, 5-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4-methylenedioxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, tris (3, 3-dibromo) -1,3, 5-triazine, and combinations thereof.

In the present invention, the sulfonic acid-based and sulfonyl-based compounds (B1-3) are sulfonic acid-based and sulfonyl-based compounds of the formula (4)

Wherein R is ¹¹ Represents a monovalent, divalent or trivalent organic radical, R ¹² Represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group or aromatic compound group, n represents a natural number of 1 to 3, examples of the aromatic compound group used herein include aromatic hydrocarbon groups such as phenyl and naphthyl, and heterocyclic groups such as furyl and thienyl, and these groups may further have one or more suitable substituents on the ring such as halogen atom, alkyl group, alkoxy group and nitro group, R ¹² Particularly preferred are alkyl groups having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl and butyl groups, particularly preferred wherein R is ¹¹ Is an aromatic compound group and R ¹² Compounds which are lower alkyl.

Specific examples of the sulfonic acid compound include benzoin tosylate, o-nitrophenyl trichloromethane sulfonate, o-nitrophenyl p-toluenesulfonate, or a combination of the foregoing.

Specific examples of the sulfonylimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) -1, 8-naphthalenedicarboximide, alpha- (p-toluenesulfonyloxy imino) -phenylacetonitrile, alpha- (benzenesulfonyloxy imino) -2, 4-dichlorophenylacetonitrile, alpha- (benzenesulfonyloxy imino) -2, 6-dichlorophenylacetonitrile, alpha- (2-chlorobenzenesulfonyloxy imino) -4-methoxyphenylacetonitrile, alpha- (ethylsulfonyloxy imino) -1-cyclopentenylacetone, (5-p-toluenesulfonate imine-5H-thiophene-2-imine) -phenylacetonitrile, (5-p-trifluoromethylsulfonate imine-5H-thiophene-2-imine) -phenylacetonitrile, (4-methylsulfonate imine-cyclohexanol-2, 5-diimine) - (2-phenyl) -acetonitrile, (4-p-toluenesulfonate imine-2, 5-diimine) - (2-phenyl) -acetonitrile, or a combination thereof.

Bis-sulfonyldiazomethanes such as bis (p-toluenesulfonyl) diazomethane, bis (1, 1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane and bis (2, 4-dimethylphenylsulfonyl) diazomethane;

nitrobenzyl derivatives, such as 2-nitrobenzyl p-toluenesulfonate, 2, 6-dinitrophenyl p-toluenesulfonate, nitrobenzyl toluenesulfonate, dinitrobenzyl toluenesulfonate, nitrophenyl sulfonate, nitrobenzyl carbonate and dinitrobenzyl carbonate;

sulfonates such as pyrogallol trimethylsulfonate, pyrogallol trimethylbenzenesulfonate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxy succinimide, N-trichloromethylsulfonyloxy succinimide, N-phenylsulfonyloxy maleimide and N-methylsulfonyloxy phthalimide; trifluoromethane sulfonates such as N-hydroxyphthalimide and N-hydroxynaphthalimide;

onium salts such as diphenyliodonium hexafluorophosphate, 4-methoxyphenyl phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, 4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate and (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate;

Benzoin (benzoin) tosylate esters, such as benzoin tosylate and a-methylbenzin tosylate;

and other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, and benzyl carbonates.

In the present invention, component (B1) is preferably a compound having at least two oxime sulfonate groups represented by the general formula (5):

wherein R is ¹³ Represents a substituted or unsubstituted alkyl or allyl radical having from 1 to 8 carbon atomsAnd particularly preferred are compounds of formula (6):

wherein A represents a divalent substituted or unsubstituted alkylene or aromatic compound group having 1 to 8 carbon atoms, and R ¹⁴ And R is ¹⁵ Represents a substituted or unsubstituted alkyl or allyl group having 1 to 8 carbon atoms. An aromatic compound group as used herein refers to a group of a compound exhibiting physical and chemical properties possessed by an aromatic compound, and examples thereof include aromatic hydrocarbon groups such as phenyl and naphthyl, and heterocyclic groups such as furyl and thienyl. These aromatic compound groups may have at least one suitable substituent on the ring, such as a halogen atom, an alkyl group, an alkoxy group or a nitro group. It is further preferred that A represents phenylene and R represents a lower alkyl group having 1 to 4 carbon atoms.

Component (B1) may be used alone or in combination.

The content of the component (B1) is 0.1 to 20 parts by weight, and preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the component (a). When the content is 0.1 parts by weight or more, it becomes possible to obtain sufficient sensitivity. On the other hand, when the content is 20 parts by weight or less, a uniform solution is obtained due to good solubility in a solvent, and thus storage stability can be improved.

The component (B1) is preferably a 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, sulfonium salt compound, and the photoacid generator may be used alone or in combination of two or more.

Component (B2)

In some embodiments of the present invention, component (B2) is a compound that reacts chemically under irradiation with ultraviolet rays or radiation, specifically, component (B2) is an esterified compound of the 1, 2-naphthoquinone diazide sulfonic acid type. In a preferred embodiment of the present invention, the ester (B2) of 1, 2-naphthoquinone diazide sulfonic acid may be an ester of 1, 2-naphthoquinone diazide sulfonic acid with a hydroxyl compound, such as 1, 2-naphthoquinone diazide-4-sulfonate, 1, 2-naphthoquinone diazide-5-sulfonate, and 1, 2-naphthoquinone diazide-6-sulfonate, and more preferably an ester of the above-mentioned 1, 2-naphthoquinone diazide sulfonic acid with a polyhydroxy compound. The esters of the above 1, 2-naphthoquinone diazide sulfonic acids may be fully or partially esterified. The kind of the aforementioned hydroxyl compound (hereinafter also referred to as b 2) may be, for example: hydroxybenzophenones (b 2-1), hydroxyaryl compounds (b 2-2) of the formula (7), and (hydroxyphenyl) hydrocarbon compounds (b 2-3) of the formula (8) as well as other aromatic hydroxy compounds (b 2-4).

In some embodiments of the present invention, the hydroxybenzophenones (b 2-1) may be 2,3, 4-trihydroxybenzophenone, 2, 4' -trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2',3, 4-tetrahydroxybenzophenone, 2',3, 4-tetrahydroxybenzophenone, 2,3', 4', 6-pentahydroxybenzophenone, 2',3, 4' -pentahydroxybenzophenone, 2',3,4,5' -pentahydroxybenzophenone.

In some embodiments of the invention, hydroxyaryl compound (b 2-2) is a compound of formula (7):

/>

r in formula (7) ¹⁶ To R ¹⁸ Represents a hydrogen atom or C ₁ -C ₄ An alkyl group; r is R ¹⁹ To R ²⁴ Represents a hydrogen atom, a halogen atom, C ₁ -C ₄ Alkyl, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ Alkenyl and C ₃ -C ₈ Cycloalkyl; r is R ²⁵ R is R ²⁶ Represents a hydrogen atom, a halogen atom, and C ₁ -C ₄ An alkyl group; x, y and z represent integers from 1 to 3.

In some preferred embodiments of the present invention, the hydroxyaryl compound of formula (7) may be tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -3-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -3-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -3, 4-dihydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -2, 4-dihydroxyphenyl methane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenyl methane, bis (4-hydroxyphenyl-2, 5-dimethylphenyl) -4-hydroxy-5-methoxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -3-hydroxyphenyl methane, bis (4-hydroxy-cyclohexyl-3-hydroxyphenyl methane, bis (4-hydroxy-phenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylaryl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylaryl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylaryl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylaryl) -3, 4-dihydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) -3, 4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene or 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (3-methyl-4-hydroxyphenyl) ethyl ] benzene.

In some embodiments of the invention, (hydroxyphenyl) hydrocarbon (b 2-3) is a compound of formula (8):

wherein R is ²⁷ R is R ²⁸ Represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms; and x 'and y' represent integers from 1 to 3.

In some preferred embodiments of the present invention, the hydrocarbon compound having the structure represented by the general formula (8) is 2- (2, 3, 4-trihydroxyphenyl) -2- (2 ',3',4 '-trihydroxyphenyl) propane, 2- (2, 4-dihydroxyphenyl) -2- (2', 4 '-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4' -hydroxyphenyl) propane, bis (2, 3, 4-trihydroxyphenyl) methane or bis (2, 4-dihydroxyphenyl) methane, 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene, more preferably 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene.

Specific examples of other aromatic hydroxy compounds (b 2-4) in the present invention are phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, catechol, phenolphthalein, 1,2, 3-phloroglucinol methyl ether, 1,2, 3-phloroglucinol-1, 3-dimethyl ether, 3,4, 5-trihydroxybenzoic acid or partially esterified 3,4, 5-trihydroxybenzoic acid, 2, 4-bis (3, 5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol, 2, 6-bis (2, 5-dimethyl-4-hydroxybenzyl) -4 methylphenol and other linear trinuclear compounds; bis [2, 5-dimethyl-3- (4-hydroxy-5-methylbenzyl) -4-hydroxyphenyl ] methane, bis [2, 5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl ] methane, bis [3- (3, 5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl ] methane, bis [3- (3, 5-dimethyl-4-hydroxybenzyl) -4-hydroxybenzyl ] -4-hydroxybenzoyl ] methane, bis [3- (3, 5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl ] methane, bis [3- (3, 5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl ] methane, bis [ 2-hydroxy-3- (3, 5-dimethyl-4-hydroxybenzyl) -5-methylphenyl ] methane, bis [ 2-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl ] methane, bis [ 4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl ] methane, and linear compounds thereof; linear pentanuclear compounds such as 2, 4-bis [ 2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl ] -6-cyclohexylphenol, 2, 4-bis [ 4-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl ] -6-cyclohexylphenol; and other linear polyphenols.

The above-mentioned hydroxy compound is preferably 2,3, 4-trihydroxybenzophenone, 2',3, 4-tetrahydroxybenzophenone, 2, 6-bis (2, 5-dimethyl-4-hydroxy-3-hydroxymethylbenzyl) -4-methylphenol, 3, 5-bis [2, 5-dimethyl-3- (2, 4-dimethyl-5-hydroxybenzyl) -4-hydroxybenzyl ] -4-methylphenol or 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene, more preferably 2,2', 4 '-tetrahydroxybenzophenone and 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene, most preferably 2,3, 4-trihydroxybenzophenone, 2',3, 4-tetrahydroxybenzophenone or 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene. The aforementioned hydroxyl compounds may be used singly or in combination of several.

The esterified product of the 1, 2-naphthoquinone-diazide sulfonic acid-based compound as component B2 of the present invention can be obtained by condensation reaction of a quinone diazide group-containing compound such as 1, 2-naphthoquinone diazide-4 (or 5) -sulfonic acid halide salt with the above-mentioned hydroxy compound of (B2-1) to (B2-4), and can be completely esterified or partially esterified. The condensation reaction is usually carried out in an organic solvent such as dioxane, N-pyrrolidone, or acetamide, preferably in the presence of a basic condensing agent such as triethanolamine, an alkali metal carbonate, or an alkali metal hydrogencarbonate.

In a preferred embodiment of the present invention, more preferably 50 mol% or more, particularly preferably 60 mol% or more of hydroxyl groups are condensed with 1, 2-naphthoquinone-diazide-4 (or 5) sulfonate, i.e., the degree of esterification is 50% or more, more preferably 60% or more, based on 100 mol% of the total hydroxyl groups in the hydroxyl compound.

In the embodiment of the present invention, the ester (B2) of the 1, 2-naphthoquinone-diazide sulfonic acid compound of the present invention is used in an amount of usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 60 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).

In some preferred embodiments of the present invention, the weight ratio of the solid component of the resin composition used in the present invention to the dissolution inhibitor is 5:1 to 19:1, preferably 6:1 to 16:1, more preferably 6:1 to 14:1, and most preferably 8:1 to 12:1.

In some preferred embodiments of the present invention, the dissolution inhibitor of the present invention is used in an amount of 1 to 25 parts by weight, preferably 2 to 20 parts by weight, more preferably 2 to 15 parts by weight, most preferably 5 to 15 parts by weight, particularly preferably 8 to 12 parts by weight, based on 100 parts by weight of the solid content of the alkali-soluble resin (a).

In some embodiments of the present invention, the amount relationship between the alkali-soluble resin (A) (denoted as m), the dissolution inhibitor (denoted as n), and the adhesion promoter (denoted as q) used in the present invention satisfies the formula

1≤n/[mq/(m+q)]≤10；

Preferably

3≤n/[mq/(m+q)]≤8；

More preferably

3≤n/[mq/(m+q)]≤7；

Most preferably

4≤n/[mq/(m+q)]≤6；

m, n and q are the weight parts of the alkali-soluble resin A, the dissolution inhibitor and the bonding aid respectively.

Solvent (C)

Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, and hydrocarbon solvents, and examples of the alcohol solvents include ethylene glycol, propylene glycol, diethylene glycol, 3-methoxybutanol, 2-methylpentanol, 2-ethylbutanol, 2, 6-dimethyl-4-heptanol, sec-undecanol, 3, 5-trimethylcyclohexanol, benzyl alcohol, diethylene glycol, and triethylene glycol. Examples of the ether solvent include monoacids, or polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether, and the like, and derivatives thereof, dipropyl ether, dibutyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether, and tetrahydrofuran; examples of the ketone solvent include acetone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2, 4-pentanedione, acetophenone, and the like; examples of the amide-based solvent include N, N' -dimethylimidazolidone, N-methylformamide, N-dimethylformamide, N-diethylformamide, acetamide, N-methylacetamide, N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; ethylene glycol monoacetate, propylene glycol monoacetate, and diethylene glycol as the above-mentioned ester solvents; cyclic ethers such as dioxane; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate.

In view of the excellent coating uniformity and the strong coverage of the step on the chip epitaxy, it is preferable to use a mixture containing at least 1 or 2 or more selected from propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, alkyl lactate and gamma-butyrolactone without mutual dissolution with the top layer conventional positive photoresist or negative photoresist.

Among the above solvents, propylene glycol methyl ether is particularly preferred, which has a better polarity, i.e., hydrophilicity, than propylene glycol methyl ether acetate in conventional photoresist systems. The resin (A) preferred in the invention has excellent solubility and also has immiscibility with the traditional photoresist system, so that the phenomenon of dissolution and doping at the interface between the wet film and the adjacent layer can not exist when two or more layers are coated.

In some preferred embodiments of the present invention, the solvent is used in an amount of 100 to 1200 parts by weight, preferably 200 to 1000 parts by weight, more preferably 400 to 800 parts by weight, based on 100 parts by weight of the solid content of the alkali-soluble resin (a).

Surfactant (D)

In some preferred embodiments of the present invention, the above-described resin composition of the present invention further comprises a component (D) surfactant component. In some preferred embodiments, the surfactant is selected from organofluorine modified surfactants, (poly) siloxane-based surfactants, and other surfactants.

The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluoroalkylene group in at least one of the terminal, main chain and side chain, examples thereof include 1, 2-tetrafluoro-n-octyl (1, 2-tetrafluoro-n-propyl) ether, 1, 2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethyleneglycol di (1, 2, 3-hexafluoro-n-pentyl) ether, octaethyleneglycol di (1, 2-tetrafluoro-n-butyl) ether hexapropylene glycol bis (1,1,2,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol bis (1, 2-tetrafluoro-n-butyl) ether, sodium perfluoro-n-dodecanesulfonate, 1,2, 3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane and/or, sodium fluoroalkyl benzenesulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carboxylate, diglycerol tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylene alcohol, perfluoroalkyl alkoxylates, fluoroalkyl carboxylates, and the like. Examples of the commercial products of the fluorine-based surfactant include BM-1000, BM01100 (manufactured by BM CHEMIE), megaface F142D, F172, F173, F183, F178, F191, F471, F476 (manufactured by Dainippon Ink and Chemicals Inc.), surflon S-112, SC-102, SC-103, SC104 (manufactured by Asahi Kazaku-Nitro), eftop EF301, EF303, EF352 (manufactured by Santa Clara), ftergent FT-100, FT-110, FT-140A, FT-150, FTX-218, and FTX-251 (manufactured by NEOS).

Examples of the commercial products of the (poly) siloxane surfactant include Toray silicone DC PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, DC-57, and DC-190 (manufactured by Dow Corning Toray Silicone co., ltd.) and organosiloxane polymer KP341 (manufactured by siemens chemical Co., ltd.), and BYK-310, 320, 322, 323, 330, 333, 377, 378, and 3760 (manufactured by BYK).

Examples of the other surfactants include ammonium salts and organic amine salts of alkyl diphenyl ether disulfonic acid; ammonium salts and organic amine salts of alkyl diphenyl ether sulfonic acids; ammonium salts and organic amine salts of alkylbenzenesulfonic acids; ammonium salts and organic amine salts of polyoxyethylene alkyl ether sulfuric acid; and ammonium salts and organic amine salts of alkyl sulfuric acid.

In one embodiment of the present invention, the resin composition of the present invention may contain a surfactant, which may be used alone or in combination of two or more thereof, in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, more preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the solid content of the alkali-soluble resin.

Bonding aid (E)

(E) The adhesion promoter is a component that improves the adhesion of the obtained film to the substrate. The (E) adhesion promoter is preferably a functional silane coupling agent having a reactive functional group such as styrene, methacrylic, methacryloyl, vinyl, isocyanate, oxirane, amino, ureido, or the like.

Examples of the functional silane coupling agent include vinyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, 3-methacrylonitrile propyltrimethoxysilane, 3-methacrylonitrile propyltriethoxysilane, hydrolysis condensate of 3-3 ethoxysilane-N- (1, 3-dimethyl-butylene) propylamino, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, γ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ -isocyanatopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

In the present invention, the adhesion promoter (D) may be used alone or two or more thereof may be used in combination, and the adhesion promoter (D) is used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).

In another aspect, the invention also provides a method of patterning a photoresist, comprising the steps of,

(i) Uniformly coating the resin composition according to any one of claims 1 to 9 on a substrate to form an underlying sacrificial layer photoresist, and pre-baking at 90 to 150 ℃ for 30 seconds to 10 minutes to remove the solvent, the thickness of the baked film being 0.1 to 8 μm, preferably 0.1 to 6 μm, more preferably 0.1 to 4 μm;

(ii) Uniformly coating a positive photoresist on the dried bottom sacrificial layer in (i), preferably pre-baking the coated positive photoresist at a temperature of 90 to 150 ℃;

In a preferred embodiment of the present invention, in step (i), a coating film is formed on a substrate using the resin composition of the present invention. Specifically, the solution of the resin composition is applied to the surface of a substrate, and preferably baked to remove the solvent, thereby forming a coating film. Suitable substrates include glass substrates, silicon substrates, sapphire substrates, silicon carbide substrates, compound semiconductor substrates, and substrates obtained by forming various metal thin films on their surfaces.

Examples of the coating method include a spray coating method, a roll coating method, a spin coating method, a slit coating method, a bar coating method, and an inkjet method. As the conditions for the above-mentioned prebaking (for the purpose of physically evaporating the organic solvent to reduce the internal stress), it is possible to adjust according to the kind and the use ratio of each component, and for example, it is possible to prebake on a contact hotplate at 90℃to 150℃for 30 seconds to 10 minutes. The thickness of the adhesive film after the pre-baking is 0.1 to 8. Mu.m, preferably 0.1 to 6. Mu.m, more preferably 0.1 to 4. Mu.m.

In a preferred embodiment of the present invention, in step (ii), a positive photoresist is coated on the resin composition completing step (ii) to form a coating film. Specifically, a photoresist that can be patterned using photosensitive characteristics is coated on the underlying sacrificial layer, and preferably prebaked to remove the solvent to form a coating film.

In a preferred embodiment of the present invention, a positive photoresist model RD-2700 (available from Shenzhen City photosensitive technologies Co., ltd.) is used.

As a method for applying the positive photoresist, for example, a spray coating method, a roll coating method, a spin coating method, a slit coating method, a bar coating method, and an inkjet method can be used.

In step (ii), the positive photoresist coating film described above is baked by heating. The heating method is not particularly limited, but may be, for example, heating using a heating device such as an oven and/or a hot plate. The heating temperature in this step is preferably 200℃or lower. The heating may be performed at such a low temperature, and thus the photoresist film forming method may be preferably used for the underlying sacrificial layer of the Lift-off double-layer process for electrode metal deposition on the glass substrate, the sapphire substrate of the MiniLED, and the III-V film layer of the compound semiconductor power device. The heating temperature is more preferably 100 to 200 ℃, still more preferably 110 to 150 ℃. The heating time may be, for example, 5 to 40 minutes in the case of performing the heating treatment on the hot plate, 30 to 80 minutes in the case of performing the heating treatment in the oven, and more preferably 30 minutes or less in the case of performing the heating treatment on the hot plate, and 60 minutes or less in the case of performing the heating treatment in the oven, depending on the kind of heating equipment. By doing so, a photosensitive chemical film that can be patterned can be formed on the substrate.

In step (iii), a part of the photosensitive resist film is irradiated with radiation, specifically, the radiation is irradiated through the coating film formed in step (iii) by means of a mask having a predetermined pattern. Examples of the radiation used in this case include ultraviolet rays, extreme ultraviolet rays, X-rays, charged particle rays, and the like.

Examples of the ultraviolet rays include g-line (wavelength 436 nm) and i-line (wavelength 365 nm). Examples of the deep ultraviolet rays include KrF excimer laser. Examples of the X-ray include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these rays, ultraviolet rays are preferable, and rays including g-rays, h-rays, and/or i-rays are more preferable among ultraviolet rays. As the exposure amount of the radiation, it is generally preferably 0.1J/m, which is classified according to the kind of the top photoresist ² To 10000J/m ² 。

In the step (iv), the coating film irradiated with the radiation is developed. Specifically, the coating film irradiated with the radiation in the step (iii) is formed. The irradiated portion of the radiation is removed by development with a developer (positive photoresist). Examples of the developer include: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1, 8-diazabis [5,4,0] -7-undecene, 1, 5-diazabicyclo [4,3,0] -5-nonane, and the like. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant to the aqueous solution of the above base, or an aqueous alkali solution containing a small amount of various organic solvents capable of dissolving the positive or negative photoresist and the resin composition of the present invention may be used as a developer.

As the developing method, for example, a spin coating immersing method, an immersing method, a shaking immersing method, a spraying method, or the like can be suitably used. The development time may be, for example, 30 seconds to 120 seconds, depending on the alkali dissolution rate of the resin composition. Preferably, after the development step, the patterned coating film is subjected to a cleaning treatment by running water washing.

In the step (v), the developed coating film is heated. Specifically, a heating device such as a hot plate or an oven is used to heat the coating film after development in step (iv), and the coating film is subjected to a heat treatment (post baking, also called hard baking) to make the photoresist film layer denser, i.e., to form hydrogen bonds between the hydroxyl groups of the resin and the DNQ groups (diazonaphthoquinone groups) of the dissolution inhibitor after mixing the materials, and to form a diazonium coupling reaction between the DNQ, TMAH and the resin groups, including a phenomenon such as electrostatic action, such that the alkali dissolution rate of the bottom sacrificial layer is lowered. The heating temperature in this step is preferably 200℃or lower. The heating temperature is more preferably 120 to 180 ℃, still more preferably 120 to 150 ℃. The heating time varies depending on the type of heating equipment, and may be, for example, 5 minutes to 40 minutes in the case of performing the heating treatment on a hot plate, or 30 minutes to 80 minutes in the case of performing the heating treatment in an oven, and more preferably, 30 minutes or less in the case of performing the heating treatment on a hot plate, or 60 minutes or less in the case of performing the heating treatment in an oven. By doing so, a patterned coating film corresponding to the mask as a target can be formed on the substrate.

In some preferred embodiments of the present invention, the sidewall angle of the underlying sacrificial layer obtained after photolithographic development using the composition of the present invention is 32 ° to 45 °, preferably 45 ° to 60 °, more preferably 60 ° or more.

In yet another aspect, the present invention also provides the use of the above resin composition for metal patterning in semiconductor manufacturing.

The semiconductor element manufacturing process of the present invention uses the resin composition and a positive photoresist double-layer coating film. The resin composition is used as an underlying sacrificial release layer in, for example, a metal electrode manufacturing lift-off process in the manufacture of semiconductor devices. The semiconductor element can be formed by using a known method. The semiconductor element is preferably used for electronic devices such as display elements, LEDs, solar thin film batteries, and the like because the semiconductor element needs to be processed by using the material.

The bottom sacrificial layer photoresist added with the dissolution inhibitor is matched with the positive photoresist, wherein the dissolution inhibitor and the bottom sacrificial layer photoresist are combined, so that the alkali dissolution rate of the bottom sacrificial layer photoresist in the developing process can be reduced, and the angle of the undercut side wall of the bottom sacrificial layer photoresist after development (the acute included angle between the slope surface of the bottom sacrificial layer photoresist after development and the plane of the substrate) is larger.

Examples

Preparation of alkali-soluble resin A-1

100g of propylene glycol monomethyl ether (available from Dow solvent Co., USA) was added to a four-necked flask equipped with a stirring device, thermometer, gas-guide tube, condenser, and the flask was placed in a constant temperature oil bath and held stationary with an iron stand. Nitrogen was introduced, stirring was turned on, and the temperature was raised to 110 ℃.

A mixed solution of 10g of methacrylic acid (from Sadoma Co., ltd.), 76g of methyl methacrylate (from Sadoma Co., ltd.), 30g of hydroxyethyl methacrylate (from Mitsubishi chemical Co., japan) and 3g of azobisisobutyronitrile (from Shanghai Ala Biochemical technologies Co., ltd.) with 80g of propylene glycol monomethyl ether (from Dow solvent Co., USA) was completely dissolved, and the mixture was dropped from a dropping funnel into the above flask containing 100g of propylene glycol monomethyl ether over 2 hours. After the dripping is finished, the reaction is carried out for two hours at the constant temperature of 110 ℃, the polymerization is carried out, and finally, the temperature is reduced to 50 ℃ and the polymerized materials are poured out. The resin solution containing hydroxyl groups, which had a weight average molecular weight of 15,000, a solid acid value of 59.7KOH mg/g, a solids content of 40% and a hydroxyl value of 107.5KOH mg/g, was obtained by detection.

Preparation of alkali-soluble resins A-2 to A-5

The preparation of alkali-soluble resins A-2 to A-5 was carried out similarly to the preparation of alkali-soluble resin 1, except that different monomers were used, and the kinds and amounts of the monomers used are shown in Table 1.

Preparation of dissolution inhibitor B2-1

The hydroxy compound (b 2-1) 2,3, 4-trihydroxybenzophenone (available from national pharmaceutical systems chemical Co., ltd.) may be all esterified with naphthoquinone diazide sulfonic acid by a usual method. Specifically, 11.5g of 2,3, 4-trihydroxybenzophenone and 36.54g of naphthoquinone-1, 2-diazide-5-sulfonyl chloride (purchased from Shanghai Baishun Biotechnology Co., ltd.) were dissolved in 450ml of an aqueous acetone solution (the volume ratio of acetone to water was 85:15) at room temperature, reacted for 0.5h under stirring, 18.76ml of triethylamine was slowly added dropwise, and the dropwise addition time was controlled to 1h. After the dripping is finished, stirring and reacting for 4 hours, pouring the reacted solution into ultrapure water with the volume of 10 times, repeatedly washing the solution with the ultrapure water until the solution is neutral after the solid is completely separated out, carrying out suction filtration, and drying at the constant temperature of 40 ℃ until the solid product is constant in weight, thus obtaining 46.33g of yellow solid.

Preparation of dissolution inhibitor B2-2

12.3g of 2,2',3, 4-tetrahydroxybenzophenone (from the company of Chemie, inc. of the group of Chinese medicine) and 51.43g of naphthoquinone-1, 2-diazide-5-sulfonyl chloride were dissolved in 450ml of an aqueous acetone solution (the volume ratio of acetone to water: 85:15) at room temperature, and after stirring, 26.41ml of triethylamine was slowly added dropwise, and the dropwise addition time was controlled to 1 hour. After the dripping is finished, stirring and reacting for 4 hours, pouring the reacted solution into ultrapure water with the volume of 10 times, repeatedly washing the solution with the ultrapure water until the solution is neutral after the solid is completely separated out, carrying out suction filtration, and drying at the constant temperature of 40 ℃ until the solid product has constant weight, thus obtaining 58.75g of yellow solid.

Preparation of dissolution inhibitor B2-3

21.2g of 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene (available from Shanghai Ala Biotechnology Co., ltd.) and 40.60g of naphthoquinone-1, 2-diazide-5-sulfonyl chloride were dissolved in 450ml of an aqueous acetone solution (the volume ratio of acetone to water: 85:15) at room temperature, and after stirring, 20.85ml of triethylamine was slowly added dropwise thereto, and the dropwise addition time was controlled for 1 hour. After the dripping is finished, stirring and reacting for 4 hours, pouring the reacted solution into ultrapure water with the volume of 10 times, repeatedly washing the solution with the ultrapure water until the solution is neutral after the solid is completely separated out, carrying out suction filtration, and drying at the constant temperature of 40 ℃ until the solid product has constant weight, thus obtaining 55.96g of yellow solid.

EXAMPLE 1 preparation of resin composition 1

50 parts by weight of an alkali-soluble resin (A-1), 50 parts by weight of an alkali-soluble resin (A-2), 10 parts by weight of an ester of 2,3, 4-trihydroxybenzophenone with 1, 2-naphthoquinone diazide-5-sulfonyl chloride as the dissolution inhibitor (B2-1), 550 parts by weight of a solvent (C) propylene glycol monomethyl ether, 1 part by weight of a high-polymer organosiloxane polymer (BYK-333) as a surfactant (D), and 2 parts by weight of a 3-glycidyltrimethoxysilane (KBM-403) as an adhesion promoter (E) as a bonding aid were mixed and stirred uniformly by a shaker, and then filtered by a membrane (PTFE polytetrafluoroethylene) filter having a pore size of 0.1. Mu.m, thereby preparing a resin composition 1.

EXAMPLE 2 preparation of resin composition 2

50 parts by weight of an alkali-soluble resin (A-1), 50 parts by weight of an alkali-soluble resin (A-3), 10 parts by weight of an ester of 2,3, 4-trihydroxybenzophenone with 1, 2-naphthoquinone diazide-5-sulfonyl chloride as the dissolution inhibitor (B2-1), 580 parts by weight of a solvent (C) propylene glycol monomethyl ether, 0.1 parts by weight of a high-polymer organosiloxane polymer (BYK-333 of Pick chemical) as the surfactant (D), and 2 parts by weight of 3-glycidyltrimethoxysilane (KBM-403 of Xinyue chemical) as the adhesion promoter (E) were mixed and stirred uniformly by a shaking stirrer, and then filtered by a membrane (PTFE polytetrafluoroethylene) filter having a pore size of 0.1. Mu.m, to prepare a resin composition 2.

EXAMPLE 3 preparation of resin composition 3

50 parts by weight of an alkali-soluble resin (A-1), 50 parts by weight of an alkali-soluble resin (A-3), 10 parts by weight of an ester of 2,2',3, 4-tetrahydroxybenzophenone, which is the dissolution inhibitor (B2-2) prepared above, with 1, 2-naphthoquinone diazide-5-sulfonyl chloride, 650 parts by weight of a solvent (C) propylene glycol monomethyl ether, 1 part by weight of a high-polymer organosiloxane polymer (BYK-333 of Pick chemistry) as a surfactant (D), and 2 parts by weight of a 3-glycidyltrimethoxysilane (KBM-403 of Xingzhi chemistry) as an adhesion promoter (E) were mixed and stirred uniformly by a shaking stirrer, and then filtered by a membrane (PTFE polytetrafluoroethylene) filter having a pore diameter of 0.1. Mu.m, thereby preparing a resin composition 4.

EXAMPLE 4 preparation of resin composition 4

50 parts by weight of an alkali-soluble resin (A-1), 50 parts by weight of an alkali-soluble resin (A-2), 10 parts by weight of an ester of 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene and 1, 2-naphthoquinone diazide-5-sulfonyl chloride as the dissolution inhibitor (B2-3) prepared above, 650 parts by weight of a solvent (C) propylene glycol monomethyl ether, 1 part by weight of a high-polymer organosiloxane polymer (BYK-333 of Pick chemistry) as a surfactant (D), and 2 parts by weight of a KBM-403 of 3-glycidyltrimethoxysilane (KBM-403 of Xinyue chemistry) as an adhesion aid (E) were mixed uniformly by a shaking stirrer, and then filtered with a membrane (PTFE polytetrafluoroethylene) filter having a pore size of 0.1. Mu.m, to prepare a resin composition 4.

Comparative example 1

50 parts by weight of an alkali-soluble resin (A-1), 50 parts by weight of a polymer solution of an alkali-soluble resin (A-2), 525 parts by weight of a solvent (C) propylene glycol monomethyl ether, 1 part by weight of a high-polymer organosiloxane polymer (BYK-333 of Pick chemical) as a surfactant (D), and 2 parts by weight of 3-glycidylpropyltrimethoxysilane (KBM-403 of Xinyue chemical) as an adhesion promoter (E) were mixed and stirred uniformly by a shaking stirrer, and then filtered by a membrane (PTFE polytetrafluoroethylene) filter having a pore size of 0.1. Mu.m, to thereby prepare a resin composition of comparative example 1.

Comparative example 2

50 parts by weight of an alkali-soluble resin (A-1), 50 parts by weight of a polymer solution of an alkali-soluble resin (A-3), 525 parts by weight of a solvent (C) propylene glycol monomethyl ether, 1 part by weight of a high-polymer organosiloxane polymer (BYK-333 of Pick chemical) as a surfactant (D), and 2 parts by weight of 3-glycidylpropyltrimethoxysilane (KBM-403 of Xinyue chemical) as an adhesion promoter (E) were mixed and stirred uniformly by a shaking stirrer, and then filtered by a membrane (PTFE polytetrafluoroethylene) filter having a pore size of 0.1. Mu.m, to thereby prepare a resin composition of comparative example 2.

Comparative example 3

100 parts by weight of a polymer solution of an alkali-soluble resin (A-2), 10 parts by weight of an ester of a dissolution inhibitor (B2-1) prepared as described above, namely, 2,3, 4-trihydroxybenzophenone with 1, 2-naphthoquinone diazide-5-sulfonyl chloride, 630 parts by weight of a solvent (C) propylene glycol monomethyl ether, 1 part by weight of a high-polymer organosiloxane polymer (BYK-333 of Pick chemical) as a surfactant (D), and 2 parts by weight of a 3-glycidyltrimethoxysilane (KBM-403 of Xingzhi chemical) as an adhesion aid (E) were mixed and stirred uniformly by a shaker, and then filtered by a membrane (PTFE polytetrafluoroethylene) filter having a pore size of 0.1. Mu.m, to prepare a resin composition of comparative example 3.

Comparative example 4

The resin composition of comparative example 4 was prepared by mixing 100 parts by weight of the polymer solution of alkali-soluble resin (A-3), 25 parts by weight of the ester of dissolution inhibitor (B2-2) prepared above, namely 2,2',3, 4-tetrahydroxybenzophenone with 1, 2-naphthoquinone diazide-5-sulfonyl chloride, 660 parts by weight of solvent (C) propylene glycol monomethyl ether, 1 part by weight of high-polymer organosiloxane polymer (BYK-333 of Pick chemical) as surfactant (D), and 2 parts by weight of KBM-403 as adhesion promoter (E) which was 3-glycidyltrimethoxysilane (KBM-403 of Xinyue chemical) with a shaking stirrer, and then filtering with a membrane (PTFE polytetrafluoroethylene material) filter having a pore size of 0.1. Mu.m.

Comparative example 5

After 50 parts by weight of the alkali-soluble resin (A-1), 50 parts by weight of the polymer solution of the alkali-soluble resin (A-2), 5 parts by weight of the dissolution inhibitor (B2-2) prepared above, that is, the ester of 2,2',3, 4-tetrahydroxybenzophenone with 1, 2-naphthoquinone diazide-5-sulfonyl chloride, 600 parts by weight of the solvent (C) propylene glycol monomethyl ether, 1 part by weight of the high-polymer organosiloxane polymer (BYK-333 of Pick chemistry) as the surfactant (D), and 2 parts by weight of the 3-glycidyltrimethoxysilane (KBM-403 of Xinyue chemistry) as the adhesion promoter (E) were mixed and stirred uniformly in a shaking mixer, they were filtered with a membrane (PTFE polytetrafluoroethylene material) filter having a pore size of 0.1. Mu.m, to prepare the resin composition of comparative example 5.

TABLE 1 monomer and solvent amounts for the preparation examples

TABLE 2 composition of the resin composition of the invention and results of performance test

Development adhesion test

The resin composition was spin-coated on a monocrystalline silicon substrate to form a coating film. Then, the coating film was baked at 115℃for 180 seconds to form a film having a thickness of about 1.0. Mu.m. Subsequently, a positive photosensitive resin (RD-2700, made by Shenzhen Kagaku photosensitive technologies Co., ltd.) was applied on the formed resin composition film by spin coating to form a photoresist coating film. The coating film was then baked at 100℃for 90 seconds to finally form a resist film having a thickness of 3.5. Mu.m. Then, using a line and space (line and space) mask, 120mJ/cm was used ² Is subjected to patterning exposure on the photoresist film. Next, the substrate having the exposed resist film thereon was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (tetramethylammonium hydroxide, TMAH) at a temperature of 23 ℃ for 60 seconds.

After the developed resist was washed with ultrapure water for 1 minute with running water, the presence or absence of peeling of the line having a width of 10 μm from the line space pattern was observed with a microscope, and the resultant was used as an index of development adhesion. At this time, the following was set according to the degree of peeling, a: no peeling, B: slightly peeled off, C: part of the material was peeled off, D: the entire surface was peeled off, and the development adhesion was evaluated as good in the case of a or B, and as poor in the case of C or D, and the test results were recorded in table 2 above.

Evaluation of T-shaped section morphology

After the photoresist developed in the photolithography development step was washed with ultrapure water for 1 minute with running water, the formed "T" shape was observed with a scanning electron microscope (S4700, hitachi company), and the size of the sidewall angle of the underlayer sacrificial layer was used as an index of the "T" shape, and specific evaluation criteria were as follows:

when the side wall angle of the bottom sacrificial layer reaches more than 60 degrees, evaluating the result as A; the sidewall angle was 45 ° to 60 °, with a result of evaluation B; the sidewall angle was 32 ° to 45 °, with the result being evaluated as C; the sidewall angle was less than 32 deg., and the result was rated D, and the sidewall angles of the examples of the present invention and the comparative examples and the "T" profile evaluations thereof are shown in table 2.

Fig. 1 schematically shows the results obtained with the glue of example 3, showing an undercut window, wherein the undercut angle (angle 1) is about 60 °, which is the acute included angle of the sloped surface of the underlying sacrificial layer photoresist to the substrate plane. Where 11 represents a positive photoresist layer, 12 represents an underlying sacrificial layer photoresist layer, and 13 represents a substrate.

Alkali dissolution rate determination

Spin coating and pre-baking the examples, then measuring the alkali dissolution rate of the underlying sacrificial layer, recording the development time of the examples, observing the undercut window width by microscopy, and calculating the alkali dissolution rate by the following formula

Wherein, the liquid crystal display device comprises a liquid crystal display device,

the film thickness of the underlying sacrificial layer glue was obtained by optical film thickness meter Filmetrics F20,

the clear time of the thickness of the underlying sacrificial layer photoresist was obtained by a stopwatch timer.

The results of the measured alkali dissolution rates are recorded in table 2.

As can be seen from a comparison of tables 1 and 2, the examples of the present invention can also be compared with each other, for example, example 1 and example 2, except that the alkali-soluble resin composition: example 1 used alkali-soluble resins a-1 and a-2, example 2 used alkali-soluble resins a-1 and a-3, and example 2 had a significantly greater alkali dissolution rate than example 1, and it was apparent that example 1 gave a greater sidewall angle.

Examples 1 and 4 and comparative examples 1 and 5 use the same alkali-soluble resin combinations (50 parts by weight each of A-1 and A-2), and a relatively small amount of dissolution inhibitor was added to comparative example 5 to obtain substantially unchanged sidewall angles, while examples 1 and 4 each had an increased sidewall angle, and the dissolution inhibitor type and content affected both dissolution rate and sidewall angle. Next, examples 2 and 3 and example 2 used the same alkali-soluble resins (50 parts by weight each of a-1 and a-3), examples 2 and 3 each had an increased sidewall angle relative to comparative example 2, and the dissolution rates were reduced by 24.5% and 53.4%, respectively. Both a reduction in dissolution rate and an increase in sidewall angle (as in example 3 and example 4) are optimized.

Therefore, the needed bottom sacrificial layer resin composition is obtained by adjusting the type and the dosage of the alkali-soluble resin and the type and the dosage of the dissolution inhibitor, so that the bottom sacrificial layer photoresist has lower alkali dissolution rate in the developing process, and the side wall angle of the developed bottom sacrificial layer photoresist is larger.

Claims

1. A resin composition comprising the following components:

(A) Alkali-soluble resin, 100 parts by weight;

(B) A dissolution inhibitor, 1 to 25 parts by weight, preferably 2 to 20 parts by weight, more preferably 2 to 15 parts by weight, most preferably 5 to 15 parts by weight, even more preferably 8 to 12 parts by weight;

2. The resin composition according to claim 1, wherein the dissolution inhibitor is a compound that reacts under irradiation of radiation such as ultraviolet rays, preferably wherein the dissolution inhibitor is selected from an onium salt compound, a halogen-containing compound, a sulfonic acid compound, a sulfonyl compound, or an esterified product of a 1, 2-naphthoquinone diazide sulfonic acid compound, or a combination thereof.

3. The resin composition according to claim 2, wherein the esterified product of the 1, 2-naphthoquinone diazide sulfonic acid compound is an esterified product of a 1, 2-naphthoquinone diazide sulfonic acid compound and a hydroxyl compound, preferably wherein the 1, 2-naphthoquinone diazide sulfonic acid compound is 1, 2-naphthoquinone diazide-4-sulfonate, 1, 2-naphthoquinone diazide-5-sulfonate or 1, 2-naphthoquinone diazide-6-sulfonate, more preferably 1, 2-naphthoquinone diazide-5-sulfonate.

4. The resin composition of claim 3, wherein the hydroxy compound is selected from the group consisting of hydroxybenzophenones, hydroxyaryl compounds of formula (7), (hydroxyphenyl) hydrocarbons of formula (8), and other aromatic hydroxy compounds, or combinations thereof.

Wherein R in formula (7) ¹⁶ To R ¹⁸ Represents a hydrogen atom or C ₁ -C ₄ An alkyl group; r is R ¹⁹ To R ²⁴ Represents a hydrogen atom, a halogen atom, C ₁ -C ₄ Alkyl, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ Alkenyl and C ₃ -C ₈ Cycloalkyl; r is R ²⁵ R is R ²⁶ Represents a hydrogen atom, a halogen atom, and C ₁ -C ₄ An alkyl group; x, y and z represent integers from 1 to 3,

wherein R in formula (8) ²⁷ R is R ²⁸ Represents a hydrogen atom or C ₁ -C ₄ An alkyl group; and x 'and y' represent integers from 1 to 3.

5. The resin composition of claim 4, wherein the hydroxy compound is selected from 2,3, 4-trihydroxybenzophenone, 2',3, 4-tetrahydroxybenzophenone, 2, 6-bis (2, 5-dimethyl-4-hydroxy-3-hydroxymethylbenzyl) -4-methylphenol, 3, 5-bis [2, 5-dimethyl-3- (2, 4-dimethyl-5-hydroxybenzyl) -4-hydroxybenzyl ] -4-methylphenol or 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene or a combination thereof, preferably 2,3, 4-trihydroxybenzophenone, 2',3, 4-tetrahydroxybenzophenone or 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene.

6. The resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (a) comprises hydroxyl groups and/or carboxyl groups, preferably hydroxyl groups and carboxyl groups.

7. The resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (a) is selected from novolac resins, hydroxystyrene resins, acrylic or methacrylic resins, preferably acrylic or methacrylic resins; preferably, wherein the alkali-soluble resin has a weight average molecular weight of 1,000 to 100,000, preferably 10,000 to 80,000, more preferably 15,000 to 40,000, and a distribution width of the molecular weight of 1 to 5, preferably 1 to 3, more preferably 1.5 to 2.5; preferably wherein the acid value of the alkali-soluble resin solid component is 10 to 300mg KOH/g, preferably 20 to 200mg KOH/g, more preferably 20 to 90mg KOH/g, even more preferably 60 to 90mg KOH/g.

8. The resin composition according to claim 7, wherein the acrylic or methacrylic resin is obtained by polymerizing an acrylic or methacrylic monomer, methacrylic acid C ₁ -C ₈ Alkyl ester monomer and hydroxy group C methacrylate ₂ -C ₆ The alkali-soluble resin (a) is more preferably a combination of at least two methacrylic resins having different solid acid values.

9. The resin composition according to any one of claims 1 to 8, wherein the weight ratio of the solid component of the alkali soluble resin (a) to dissolution inhibitor is from 5:1 to 19:1, preferably from 6:1 to 16:1, more preferably from 6:1 to 14:1, most preferably from 8:1 to 12:1.

10. A method of patterning a photoresist comprising the steps of:

(i) Uniformly coating the resin composition according to any one of claims 1 to 9 on a substrate to form an underlying sacrificial layer photoresist, and baking at 90-150 ℃ for 30 seconds to 10 minutes to remove the solvent, the thickness of the baked film being 0.1-8 μm, preferably 0.1-6 μm, more preferably 0.1-4 μm;

(ii) Uniformly coating a positive photoresist on the dried bottom sacrificial layer in (i), preferably baking the coated positive photoresist at a temperature of 90 to 150 ℃;

11. Use of the resin composition according to any one of claims 1 to 9 for metal patterning in semiconductor manufacturing.