WO2019098493A1 - Photoresist composition - Google Patents

Abstract

The present invention relates to a chemically amplified photoresist composition comprising an alkali-soluble resin comprising a (meth)acrylate-based resin comprising a (meth)acrylate-based repeating unit having a certain heterocyclic compound substituted by means of alkylene sulfide of 1-20 carbons.

Description

 Title of the Invention

 Photoresist composition

 TECHNICAL FIELD

 Cross-reference with related application (s)

₅ This application claims the benefit of priority based on the _{November 14, 2017} Korea Patent Application No. _{10-2017-0151809,} and _{July 23, 2018} Date of Korea Patent Application No. _{10-2018-0085444,} and that of Korea Patent Application The entire contents of which are incorporated herein by reference.

 The present invention relates to a photoresist composition.

_[10] which is the background of the invention described

In addition to expanding the application of microfabrication technology for FAB process, _{there is} also a change in process technology for manufacturing high performance and thin single package (P _{akage) in} the packaging (Pac _kaging) technology. In particular, as semiconductor mouth julryeok terminal increase-chip (F _{l ip} C _hip) uses zoom and F0WLP technique minimizes the introduction and the signal delay purposes to ₁₅ inter-chip direct TSV process connection is possible hear in the expanded, increased Bu _mp demand and forming them The technology development of Bum _{p PR} is very important.

In case of Bum _{p PR} , the sensitivity and resolution in the thick film should be very good from ₁₀ to ₁₀₀ , and since the metal Bu _mp must be formed through the plating process, the pattern performance such as linearity, residue, _{foot ing and} not _ching characteristics should be good And should be resistant to ₂₀ plating solutions.

Accordingly, a chemically amplified photoresist is used in order to increase sensitivity and resolution in a thick film. This composition is composed of a resin dissociated by an acid and increasing in solubility in an alkali developer (hereinafter referred to as an alkali-soluble resin) acid generator water (hereinafter referred to as "acid generator" hereinafter), it is known to include an acid diffusion control agent, corrosion inhibitor ₂₅ and a specific dissolution inhibitor.

On the other hand, a metal substrate is used for the / plating process. If a conventional photoresist composition according to the prior art is used, a scum (S _cum) remains on the exposed portion after development. Therefore, there is a need for research on a technique capable of improving the above disadvantages.

₃₀ [Problem to be solved] SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to improve the compatibility and solubility of an alkali resin to prevent the occurrence of an _exposed portion scum during development, Amplifying type photoresist composition which suppresses the exfoliation phenomenon and does not require the use of a separate corrosion inhibitor.

 MEANS FOR SOLVING THE PROBLEMS

In this specification, the heterocyclic compound comprises an alkali-soluble resin containing a (meth) acrylate-based resin containing a (meth) acrylate-based repeating ₁₀ units substituted with ₂ mediated functional groups, including alkylene sulfide group having ₁ to ₂₀ carbon atoms A photoresist composition is provided.

 The heterocyclic compound may be at least one selected from the group consisting of a triazole compound, an imidazole compound, a thiadial azole compound, a triazine compound, and a benzimidazole compound. )

It may be at least _one member selected from the group consisting of compound _15.

 Further, in this specification, a photoresist pattern made from the chemically amplified photoresist composition is provided.

 Further, in this specification, a method of manufacturing a photoresist pattern using the chemically amplified photoresist composition is provided.

₂₀ or less The chemical amplification type photoresist composition, the photoresist pattern and the method for producing a photoresist pattern according to specific embodiments of the present invention will now be described in more detail. In the present specification, the term "alkylene sulfide having ₁ to ₂₀ carbon atoms" means a functional group in which one element of an alkylene having 1 ₂₅ to ₂₀ carbon atoms is attached with a sulfur ( _S) element.

 In the present specification, the term "alkali-soluble resin" means a resin which is deprotected by light to have alkali-soluble properties. The alkali-soluble resin is a polymer resin having an acid group protected by a protecting group, and the acid group may be, for example, a carboxyl group, a phenolic hydroxyl group, or the like.

_BO According to one embodiment of the invention, the heterocyclic compound is a C ₁ -C ₂₀ alkyl sulfide, including alkali _divalent including (meth) acrylate-based resin containing a (meth) acrylate-based repeating units substituted with a functional group as a medium Soluble resin

The heterocyclic compound may be a triazole-based compound, an imidazole compound, a thiadiazole compound, a tr iazine compound, or a benzimidazole compound. ) is at least _{one member} chemically amplified photoresist composition, selected from the group consisting of compounds can be provided.

₁₀ The chemically amplified photoresist composition is characterized in that the heterocyclic compound has a carbon number

From ₁ to ₂₀ alkylene sulfide, including _divalent as substituted functional groups borne (meth) include acrylate-based repeating unit (meth) comprises an alkali-soluble resin containing an acrylate-based resin according commercially in an alkaline resin properties and solubility Since the improved can be prevented from occurring phenomenon when the exposed portion ₁₅ scum _(scum) that occurred during the prior use preservatives, and also inhibit the leaching phenomenon that low-molecular substances leaking into the plating liquid to, and also represents corrosion protection separate corrosion inhibitor Can be used _.

Specifically, as the (meth) there is an acrylate-based (meth) acrylate-based repeating unit contained in the resin, the _second heterocyclic compound containing an alkyl sulfide having a carbon number of _{20, 1} and ₂₀ substituting the functional group as a medium described above the heterocyclic compound to form a optionally substituted on the (meth) acrylate-based repeating unit bulky _(bulky), a structure of the _two not only indicate the corrosion protection, including alkylene sulfide of the carbon number of ₁ to ₂₀ functional groups as a medium and it can be carried out ₂₅ serves to suppress the leaching phenomenon that low-molecular substances leaking into the plating liquid.

Moreover, the heterocyclic compound has the carbon number of _one to ₂₀ alkyl sulfide ₂ mediated functional groups including the (meth) Therefore, the implementation As substituted for an acrylate-based repeating unit embodiment a chemically amplified photoresist composition compatibility and solubility Can be improved and even with a relatively small amount, it is possible to achieve an effect equivalent to or better than the addition of ₃₀ extra corrosion inhibitors 2019/098493 1 ^» (: 1 ^ {2018/008366

It can be implemented.

More specifically, when a specific heterocyclic compound is substituted at the terminal of a (meth) acrylate-based repeating unit contained in the (meth) acrylate-based resin through an alkylene sulfide having 1 to ₂₀ carbon atoms, When _{0.5 % by} weight of paper is added to the chemical amplification type photoresist composition weight, the degree of occurrence of scum generation is greatly reduced, thereby realizing a further improved effect. On the other hand, the heterocyclic compound is a (meth) acrylate-based repeating units substituted with a _bivalent functional group that contains an alkylene sulfide group having ₁ to _{10 20} as a medium is to be able to contain a repeating unit represented by the formula shows.

 [Chemical formula

 In the above formula, R is hydrogen or methyl,

¾ ¾ ₁₅ and are each a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms and the _ring,

_X is a heterocyclic compound. On the other hand, the (meth) acrylate-based resin can comprise a (meth) _{from 1} to _50% by weight of an acrylate-based repeating unit is substituted by a _divalent mediate the functional group including an alkylene sulfide of the heterocyclic compound ₂₀ having ₁ to ₂₀ carbon atoms have. 2019/098493 1 ^» (: 1/10/01 018/008366

Resins wherein the heterocyclic compound is _2, including alkylene sulfide group having ₁ to ₂₀ to prevent the (meth) acrylate-based repeating units substituted with a functional group as a medium for scum _(Scum) occurs if included within the above range more effectively have. On the other hand, in some cases when the (meth) acrylate-based resin comprises a (meth) acrylate-based repeating high content of units substituted with ₂ mediated functional groups wherein the heterocyclic compound containing an alkylene sulfide group having ₁ to ₂₀ carbon atoms After the pattern development, the lower _CD ( _{Critical Dimension} ) may be excessively widened or _notching may occur at the bottom of the pattern. In addition, the (meth) acrylate-based resin is a compound of the heterocyclic compound having ₁ the _2-containing alkylene sulfide to ₂₀ substituting the functional group-borne (meth) to a non-acrylate-based repeating unit of Formula ₁ to ₈ And a repeating unit derived from _one kind of compound selected from the group consisting of

 [Chemical Formula 1]

[Chem 2]

2019/098493 1 ^» (: 1/10/01 018/008366

[Chemical Formula 6] 2019/098493 1 ^» (: 1/10/01 018/008366

In the above Chemical Formulas ₁ to ₈ , ¾ is hydrogen, halogen or an aliphatic group having 1 to 10 carbon atoms; _111, and _{¾ is a} constant, and 1 £ _{111 <18} and 1 £ _{¾ 18} . On the other hand, the heterocyclic compound is selected from the group consisting of triazole, imidazole, thiadiazole, triazine, and benzimidazole compounds _It can be more than _one kind Specifically, the heterocyclic compound may include one kind of functional group selected from a thiol and an alkylene _thiol, and the thiol may be a methacrylate (meth) acrylate as a part of an alkali- Reacts with a double bond contained at the end of a methacrylate repeating unit contained in the rate-based resin and forms a thiol-ene-click reaction to form an alkylene sulfide having ₁ to ₂₀ carbon atoms, Acrylate-based resin.

More specifically, the heterocyclic compound may be derived from one selected from among compounds represented by the following general formulas ( ₉₎ to ( ₁₄ ).

[Chemical Formula ₉ ]

[Chemical Formula ₁₃ ] 2 _019/098493 1 »(: _{1/10/01 018/008366}

In Formula ₉ to _{14, ¾} to _¾◦ are each independently from each other hydrogen, halogen, thiol (e), amine _(? ), Hydroxy (E), alkylene having ₁ to ₂₀ carbon atoms ( _{Si1 6116} ) or alkoxy group having 1 to 20 carbon atoms,

A functional group containing thiol (eg), or a functional group containing an alkylene thiol having ₁ to ₂ carbon atoms, which is _¾ and _{¾ of the} number, and 1 < _¾ <2 and 1 ≦ ₁₁₄ ≦ 4.

(Meth) acrylate-based repeating unit to form an alkylene sulfide having ₁ to ₂₀ carbon atoms.

In the chemically amplified photoresist composition, the heterocyclic compound capable of performing the thiol-enclosure reaction may be included in an amount of ₅ to ₂₀ parts by weight based on ₁₀₀ parts by weight of the total alkali-soluble resin. When the heterocyclic compound is contained in the above-described weight range, the sensitivity can be effectively increased with only a small equivalent, and the occurrence of the scum ratio of the exposed portion in development due to excessive use of the heterocyclic compound can be prevented. Specifically, when the amount is less than ₅ parts by weight, the effect of preventing corrosion is little or insignificant. When the amount exceeds ₂₀ parts by weight, adherence to the substrate is poor and the photoresist film may not be properly formed. Specifically, the alkali-soluble resin according to one embodiment of the present invention comprises 2019/098493 1 ^» (: 1 ^ {2018/008366

(Meth) acrylate-based resin containing a (meth) acrylate-based repeating unit in which the heterocyclic compound is bonded via an alkylene sulfide having ₁ to ₂₀ carbon atoms.

In the alkali-soluble resin according to another embodiment of the present invention, the 5-heterocyclic compound is a (meth) acrylate-based (meth) acrylate-based resin having an alkylene sulfide having ₁ to ₂₀ carbon atoms, (Meth) acrylate-based resin different from the resin other than the resin; a novolac-based resin; And polyester can be further comprising at least _{one member} selected from the group consisting of a hydroxystyrene-based resin.

In more _{detail. 10,} the chemical amplification according to the invention form in the photoresist composition is part of doedoe the alkali-soluble resin include an alkali-soluble resin has a specific heterocyclic compound combination of an alkylene sulfide group having ₁ to ₂ ◦ mediated (Meth) acrylate-based repeating units

(Meth) acrylate based resin.

₁₅ Specifically, the (meth) acrylate based resin is thiol because it contains a double bond in the (meth) acrylate-based repeating unit terminal (:比比₁₎ and an alkylene

Terminal thiol reacts with the thiol of the heterocyclic compound - this en click ₍₁ ^ ₀₁ reaction taking place, whereby the alkylene sulfide group having ₁ to _{20 20} formed by them is coupled to both parameters. On the other hand, the alkali-soluble resin is normally in other than the (meth) including acrylate-based repeating unit (meth) acrylate-based resin ₂₅ is substituted by the _two said heterocyclic compound containing an alkylene sulfide group having 1 to ₂₀ functional groups mediated And may further comprise known alkali soluble resins.

Specifically, the alkali-soluble resin is different from the (meth) acrylate-based resin containing a (meth) acrylate-based repeating unit is substituted by mediating the ₂ The heterocyclic compound containing an alkylene sulfide group having ₁ to ₂₀ functional groups ( Methacrylate resin; Novolac resins; And

₃₀ poly further at least _one element selected from the group consisting of a hydroxystyrene-based resin You can include it. In addition, the chemically amplified photoresist composition for a thick film in one embodiment may further include at least _one selected from a photoacid generator and a photoinitiator.

The photoacid generators may be those generally used in the art, and are not particularly limited. Examples of the photoacid generator include an iodonium salt, a sulfonium salt, a diazonium salt, an ammonium salt, a pyridinium salt and the like, and in the halogen-containing compound, a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound Halomethyltriazine derivatives, etc.). Diazoketone compounds include _1,3- diketo- _2- diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds and the like.

Alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, iminosulfonate, and the like. In the naphthalimide compound, _N-

(Trifluoromethyl sulfonyloxy) - _{1,8-naphthalimide, N- (p-} toluenesulfonyloxy) _ _{1, 8-naphthalimide, N-} (methyl-sulfonyloxy) - _{1, 8} -naphthalimide, _N-

(Campo sulfonyloxy) - _{1, 8-naphthalimide} may include imide and the like. These may be used alone or in combination of _two or more.

Also, the photoacid generator may be, for example, triarylsulfonium salts, diaryl iodonium salts, sulfonate (1 0116) compounds, triphenylsulfonium triflate (1: 1 Triflate), triphenylsulfonium antimonate (1: 1 1), diphenyl iodonium triflate (1011111111), diphenyl iodide Diphenyl iodonium antimonate, methoxydiphenyl iodonium trifrate, di-t-butyliodonium trifrate, 2,6- In the group consisting of 2,6-dinitobenzyl sulfonate, pyrogallol tris (alkylsulfonate), and succinimidyl triflate, It may be at least _one selected.

The photoinitiator may be one commonly used in the art, and is not particularly limited. The photoinitiator may be, for example, benzophenone, aromatic-hydroxy ketone, benzyl ketal aromatic-amino ketone, phenylglyoxalic acid ester, monoacylphosphine oxide, bis-acylphosphine oxides trisacylphosphine oxide, And / or oxime esters of carbazole type. Meanwhile, in one embodiment of the present invention, the photoinitiator may be one used in the preparation of the photoacid generator, may be used after being polymerized with the alkali-soluble resin and then charged with the photoacid generator . On the other hand, the chemical amplification type photoresist composition of the embodiment may further include an acid diffusion controlling agent _{, a} dissolution inhibitor, a solvent, and the like in addition to the above components.

The acid diffusion control agent may be included for improving the resist pattern shape, post exposure stability, and the like. However, the acid diffusion control agent is not particularly limited and includes, for example, triethylamine, tripropylamine, And may be at least _one selected from the group consisting of benzylamine, tribenzylamine, tr ihydroxyethylamine, and ethylene diamine.

 On the other hand, the dissolution inhibitor may be a dissolution inhibitor commonly known in the art and is not particularly limited.

On the other hand, the solvent may be included to control the viscosity of the photoresist composition, but is not particularly limited, and includes, for example, acetone, methyl ethyl ketone cyclohexanone, methyl isoamyl ketone, ketones such as ₂ -heptanone; Ethylene glycol ethylene glycol monoacetate diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, monomethyl ether of dipropylene glycol monoacetate, monoethyl ether monopropyl ether monobutyl ether monophenyl ether Polyhydric alcohols and derivatives thereof; Cyclic ethers such as dioxane; Ethyl formate, methyl lactate, 2019/098493 1 ^» (: 1 ^ {2018/008366

Ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethoxy _ethyl, methoxy methyl propionate, ethyl ethoxy propionate, _{2-hydroxy-propionic} acid methyl _{2-hydroxy-propionic} acid ethyl, _{2-hydroxy-5-methyl-2-propionate,} ethyl _{2-hydroxy-esters} such as _{3-methoxybutyl acetate-3-methyl-butanoic} acid _{methyl-3-methoxybutyl} acetate, _3-methyl; Aromatic hydrocarbons such as toluene and xylene; Lt; / RTI &gt; These may be used alone or in combination of _two or more.

₁₀ On the other hand, according to another embodiment of the invention, the photoresist pattern is prepared from the chemically amplified photoresist composition can be provided.

 The photoresist pattern may be formed by using a conventionally known photoresist patterning method and associated apparatus, etc., with no particular limitation, except that the chemically amplified photoresist composition described above is used.

₁₅

 According to another embodiment of the present invention, a method of manufacturing a photoresist pattern using a chemically amplified photoresist composition may be provided.

Such as the photoresist _20. The photoresist pattern method, the method for producing a pattern, except using the above-described chemically amplified photoresist composition conventionally known and related apparatus may be used without any other restriction.

Specifically, the photoresist pattern manufacturing method includes: a laminating step of laminating a thick film photoresist layer made of the chemically amplified photoresist composition of one embodiment on a support; An exposure step of irradiating the thick film photoresist layer with radiation containing ₂₅ electromagnetic waves or pressure lines, and a developing step of developing the thick film photoresist layer after exposure to obtain a thick film resist pattern.

【Effects of the Invention】

30 The photoresist composition of the present invention is characterized in that the alkali Certain heterocyclic compounds in soluble resin including a methacrylate-based repeating unit is substituted by mediating an alkylene sulfide group having ₁ to _{20 (meth)} by containing an acrylate resin compatible in an alkali resin of the hetero ring compound And solubility can be improved, so that it _is possible to prevent the occurrence of an exposure _{bum (scum)} when the conventional corrosion inhibitor is used.

In addition, the photoresist composition suppresses the leaching phenomenon in which a low-molecular substance leaks into a plating solution by forming a bulky structure by bonding a heterocyclic compound with an alkali-soluble resin containing a specific repeating unit, and exhibits an anti-corrosion effect. there is no need to use preservatives _10.

 BRIEF DESCRIPTION OF THE DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure ₁ shows a process for forming bumps using the photoresist composition of the present invention.

 DETAILED DESCRIPTION OF THE INVENTION

_The present invention is capable of various modifications and various forms, and specific embodiments are illustrated and described in detail below. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

₂₀ or less The operation and effect of the invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and do not thereby imply the scope of the invention. Example 1: Preparation of a chemically amplified photoresist composition containing an alkali-soluble resin in which the heterocyclic compound is substituted with an alkylene ₂₅ sulfide having 1 to 20 carbon atoms

_{t ert-Butyl methacrylate, M ethacryl} i c a cid, 2- (Al lyloxy) ethyl met hacrylate, Di cyclopentanyl Met hacrylate (FA-513M), 1-Dodecanethiol, respectively _{95.58g, 28.94g} of PGMEA _(solvent) into the reactor _{, 85.86 g, 37.05 g, 2.19 g, and 30 320.09 g} were added to prepare a homogeneous solution. 2019/098493 1 ^» (: 1/10/01 018/008366

The inside temperature of the solution was _adjusted to ₆₅₁ :

1 _Dissolve AIB _{N 1.62 §} in _{4.58 §} and _add to this solution. After the reaction was carried out for ₁₈ hours, the polymerization reaction was terminated to obtain a resin phase represented by the following formula ( ₁₅ ): _25.2 .

In addition to the reactor to the simyo for _137.8 represented by the formula ₍₁₆₎

₆₅ (: thiol for ₃ h at-yen to click on the mutual reaction to the combined structure of the compound of formula ₁₇ as a medium for the acrylic resin and the anti-corrosion agent functional groups, including alkylene sulfide was _prepared.

To the acrylic resin represented by the general formula ₃₂ 0 ^: _25.比), for ₄₀ to thiols of the formula ₁₇ - _4§ a yen to which the click reaction _{compound,的1火4 - 11 1} ) 1 1101) 25 _.比) in addition to mixed, and as a further additive for ₆

 The mixture was stirred at room temperature to prepare a homogeneous solution to obtain a chemically amplified photoresist composition.

[Chemical Formula _15]

2019/098493 1 ^» (: 1/10/01 018/008366

[Chemical Formula 17]

Example 2

Embodiment obtained a resin represented by the general formula ₍₁₅₎ in the same manner as in Example _1. Next, into the O to the reactor, adding a corrosion inhibitor to be ssae as AIBN of ₁₃₇ represented by formula ₍₁₈₎ in-put the比比1 _{10.0 £} - greater. _651, such as a polymerization temperature: ₃ hours thiol while in-yen to the click reaction to the mutual coupling with the functional group mediating the anti-corrosion agent, and the acrylic resin containing the alkylene sulfide to prepare a compound of the formula ₍₁₉₎ structure. When the reaction is completed,

Filter and dry in a _{40 ° 0} oven for one day.

To the acrylic resin represented by the general formula per ₃₂ :: _(25.1 urine _{1) 6 (¾}細_{25.1 40} seedlings, to thiol represented by the formula ₍₁₉₎ - _{\ 1} 1 _61101-yen to which the click reaction _4§ the _compound) And as an additional additive in addition to 2019/098493 1 ^» (: 1/10/01 018/008366

3 _¾ the acid diffusion inhibitors, the photo acid generator in _{§ 0.5,} the solvent of 0: 50 shows _§ mixed to thereby prepare a homogeneous solution by stirring at room temperature to give a chemically amplified photoresist composition.

 [Chemical Formula 18]

Example 3

Example 1 and obtained a resin represented by the general formula (15) in the same way, then was put into a reactor, and to add to simyo for 137.8 corrosion inhibitor represented by the formula (20) 1- _{11161: 1171-4, 5; 17 ( 110-1} 1Ni 1} 1 _{32016-2-1: 11101 11.6 The} sugar is added and the acrylic resin and the corrosion inhibitor are reacted with a functional group containing an alkylene sulfide by a thiol- A compound of the structure of the following formula (21) 2019/098493 1 ^» (: 1/10/01 018/008366

The poured precipitate is collected and filtered and dried in a _{40 0} oven for one day.

To the acrylic resin represented by the formula _{32 (¾: 25.1} to, ₄₀ per thiol represented by the formula ₂₁ - _4g to the click reaction in which the compound _{yen, 01火4 - 1 1 1} ?) 1½1101) eobang: _25.比) ₆ , and a photoacid generator ₃₈ as an additional additive, _{0.5 parts of an} acid diffusion inhibitor, and Myo _{Sho 502 as a} solvent were mixed and stirred at room temperature to prepare a homogeneous solution to obtain a chemically amplified photoresist composition.

 [Chemical Formula 20]

_{2019/098493 1 »} (: ₁ ^ _{2018/008366

Example ₄

Example 1 and obtained a resin represented by the general formula (15) in the same way, then was put into a reactor, adding preservative is _{4,6-11161 31} to 137 and a show犯represented by the general formula 22 _{in) 1; 0-1} , 3,5-1; ₁ ^ _{11-2-01-16 1} sugar was added.

A thiol-enclosure reaction was carried out at _{65 °} C for ₃ hours to produce a compound of the following formula ( ₂₃₎ wherein the acrylic resin and the corrosion inhibitor were mutually bonded via a functional group containing an alkylene sulfide. this

₄ a to which the click reaction yen compound - _{25. lt),} to ₄₀ for the thiol represented by the formula _(23): To an acrylic resin represented by the general formula ₃₂

Of 25.1 urine) 6 were mixed, and in addition the 3 _§, acid diffusion inhibitors of photo-acid generating agent as an additional additive _{§ 0.5,} solvent: 1 ³ ₀₁ (4 _\ ^ _{11 711)} 161 101) (1}

_Were mixed and stirred at room temperature to prepare a homogeneous solution to obtain a chemically amplified photoresist composition.

 [Chemical Formula 22]

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Example 5

 In the same manner as in Example 1, a resin represented by the formula (15) was obtained. The resin was then charged into a reactor, and further, 137.1 AIBN and the corrosion inhibitor represented by the following formula (24) -1 ^ 321116-2,4 - (^ 01 14.5 sugars were added.

And subjected to a thiol-enclit reaction at 65: 3, which is the same as the polymerization temperature, to prepare a compound having the structure of the formula (25), wherein the acrylic resin and the corrosion inhibitor are mutually bonded via a functional group containing an alkylene sulfide.

,

Poured into a mixed solvent, sedimented, filtered and dried in a 400 oven for one day.

¹³ 01, per the following that the yen Click reaction Compound ₄ (4-to to 25.110 4 (地, an acrylic resin represented by the general formula 32-thiol represented by the formula ₂₅ 11711 61101) (¾½: 25.1 urine) 6 , And photoacid generators (30) _, acid diffusion inhibitors (0.52) _{, and} solvents ( _6, 2019/098493 1 ^{»(Manufacture} as a homogeneous solution by stirring at room temperature to give a 1/10公018/008366 chemically amplified photoresist composition.

 &Lt; EMI ID =

Example 6

Example 1 and obtained a resin represented by the general formula (15) in the same way, then was put into a reactor, and to add AIBN of 137 as a corrosion inhibitor represented by the formula 26 1,3,4- ₁ ± _{1 2016-2- 1; 11101} 11.8 sugars.

And then subjected to a thiol-enclit reaction at 65 ₁₀ for 3 hours 2019/098493 1 ^» (: 1 ^ {2018/008366

A compound having a structure of the following formula ( ₂₇₎ wherein the acrylic resin and the corrosion inhibitor are mutually bonded via a functional group including an alkylene sulfide. The reaction

To open the acrylic resin represented by the formula _{32 25.}比) _4¾, to a formula ₂₇ shown dwa is thiol-ene to the click reaction in which the compound _{4 1 ¾1 (4 - ^ 117111161101} ) (:! 25.110 6 and mixed for In addition, as a cost-effective additive

The mixture was stirred at room temperature to prepare a homogeneous solution to obtain a chemically amplified photoresist composition.

 (26)

(27)

2019/098493 1 ^» (: 1 ^ {2018/008366

Example 7

Example 1 and obtained a resin represented by the general formula (15) in the same way, then was put into a reactor, adding to and AIBN of 137. preservatives 5_ (17 _61171-1, 3, 4 of the formula 28 _{1 ; 11} ( _{113216-2-1; 01 14.6} sugar was added.

And subjected to a thiol-enclit reaction at 651: the same temperature as the polymerization temperature to prepare a compound of the following formula (29) wherein the acrylic resin and the corrosion inhibitor are mutually bonded via a functional group containing an alkylene sulfide. When the reaction was completed, the temperature was lowered to room temperature, diluted with ShoWashimyo Sho, and poured into water to remove the precipitate. Then, the polymer obtained by the filtration is re-

Poured into a mixed solvent, sedimented, filtered, and dried in a 40 ° 0 oven for one day.

To the acrylic resin represented by the formula 32: 25.比) below, for the 40-thiol of the formula 29-a to which the click reaction yen _g Compound _A, 2019/098493 1 ^»(: 1/10公018/008366 between - _{11 711 - 161 101) (1:} 25) 6 mixed, and in addition as further additives

The mixture was stirred at room temperature to prepare a homogeneous solution to obtain a chemically amplified photoresist composition.

 (28)

Example 8

In the same manner as in Example 1, the resin represented by the formula ( ₁₅₎ was obtained 2019/098493 1 ^» (: 1/10/01 018/008366

And then it was put into a reactor, and to show比of _137.8 for an additional corrosion inhibitor represented by the formula _{30 1, 3,4-比(1 2016-2,5-} 1; _{01 15.0 §} .

_651, such as a polymerization temperature: ₃ hours thiol-ene reaction by clicking to the cross-coupled to mediate the functional group is an acrylic resin and a corrosion inhibitor including an alkylene sulfide to prepare a compound of the structure of formula _31. After the reaction was completed, the temperature was lowered to room temperature, diluted with water, and poured into water to remove precipitate. Then, the polymer obtained by the filtration was re-

To the acrylic resin represented by the formula _{32: 25.}比) _40§, to thiols of the formula _31-N to a reaction in which the compound _{4-click ¾1} 1 (for _{4 - 11; 71 61 101)} (! _{: 25.1} urine) mixing sugar and _6, in addition to a solvent of _{0.5 3§)} an acid diffusion inhibitor the photo-acid generating agent as an additional additive _6¾促show _50g were mixed to prepare a homogeneous solution by stirring at room temperature for a chemically amplified photoresist composition &Lt; / RTI &gt;

 (30)

(31)

2019/098493 1 ^» (: 1 ^ {2018/008366

Comparative Example 1

As the alkali-soluble resin, an acrylic resin represented by the following general formula (32) _{01 (4 - 1¾ ^ 11)} 1 ½1101) (]: 25.1 urine) for a 6, a photo-acid generator ₁ ^ _{£ luoromethylsul} fon _yloxy represented by the formula 33) - _{l, 8-}

To obtain a chemically amplified photoresist composition.

(32) 2019/098493 1 ^» (: 1 ^ {2018/008366

<Experimental Example>

Using the respective photoresist compositions according to the embodiments and the comparative examples, semiconductor devices were patterned by the following method. A photoresist composition was spin-coated on a _4- inch screen of copper (() having a coating thickness of about ₂₀₀₀ shots, and then dried at _{120 X} : for ₄ minutes to form a photoresist layer having a thickness of about ₅₀占 퐉. The wafer was exposed using a ₁₆ stepper (with a photomask having hole patterns of about _{10, 20, 30, 40 and 50} size formed therein). The exposed wafer was dried at ₉₀₁ : ₃ for ₃ minutes, and then the wafer was developed for ₂₄₀ seconds using a developing solution (about _{2.38 %} by weight of tetramethylammonium hydroxide aqueous solution).

After the patterning, the physical properties of the photoresist composition were evaluated in the following manner (1) Sensitivity (exposure dose, mJ / cnf)

 The photoresist compositions prepared in Examples 1 to 8 and Comparative Example 1 were spin-coated on a substrate, dried at 120 ° C for 4 minutes on a hot plate, exposed using a step mask and hot-coated at 90 ° C for 3 minutes in

₅ After further drying, it was developed in an aqueous solution of tetramethyl _ammonium hydroxide (TMAH). The exposure amount with the same CD size of the step mask pattern and the photoresist (PR) pattern was evaluated with sensitivity.

(2) footing ( _g) occurs under the pattern

₁₀ substrates were spin-coated with the photoresist compositions prepared in Examples 1 to 8 and Comparative Example 1, and dried on a hot plate at 120 ° C for 4 minutes, exposed using a step mask, and hot-coated at 100 ° C for 2 minutes then further dried in a phenomenon was in TMAH (tetrameth _{yl ammonium ydroxide h)} aqueous solution. The value obtained by reducing the diameter of the hole _{15 at the} bottom from the hole diameter at the top of the thick resist pattern was measured as the footing length. The putting characteristics of PR were evaluated based on the following criteria.

◎: Putting length exceeding 0 nm and less than 200 run

 O: Footing length more than 200 nm and less than 500 nm

2 _{0 A:} Footing length exceeding 500 nm and less than 1 _m

_X : Footing length exceeded ₁

₃ scum (Scu _m) generated Evaluation (residues or not)

A thick film resist pattern _{25 was} prepared in the same manner as the occurrence of _{footing under the} pattern, and the presence or absence of scumming on the developed portion was observed to be an index of developability. Developability was evaluated based on the following criteria.

◎: No scum occurred

 S: Some scum around pattern

30 X: Generation failure occurs chesscom 2019/098493 1 ^» (: 1 ^ {2018/008366

( ₄ ) Resistance of plating solution

The photoresist compositions prepared in Examples ₁ to ₈ and Comparative Example ₁ were applied on a substrate using a spin coater, and then a resist film formed by a process such as pre-baking (post baking After immersing for ₂₄ hours, the thickness of the resist film was examined for change. The thickness change rate was evaluated based on the following criteria.

_◎: Thickness change rate within _1%

◦ _: Thickness change _ratio exceeding _{1% and} below _3%

·. Thickness change rate more than 3 _{% and} less than 10 _%

 X: Thickness change rate exceeding 10%

[Table 1]

As can be seen from the results of Table _1, the (meth) acrylate-based resin containing a (meth) acrylate-based repeating unit in which the specific heterocyclic compound is substituted with an alkylene sulfide having ₁ to ₂₀ carbon atoms 2019/098493 1 ^» (: 1 ^ {2018/008366

In the case of the photoresist compositions of Examples 1 to 8 of the present invention, which were included as part of the alkali-soluble resin, the sensitivity to Comparative Example ₁ was excellent, and no typing and scum ratio occurred. I was able to confirm that the resistance was excellent.

Claims

Claims:

 [Claim 1]

The heterocyclic compound includes an alkali-soluble resin containing a (meth) acrylate-based resin ₂ containing alkylene sulfide group having ₁ to ₂₀ carbon atoms containing a (meth) acrylate-based repeating units substituted with a functional group as a medium

The heterocyclic compound may be at least one selected from the group consisting of a triazole compound, an imidazole compound, a thiadial azole compound, a triazine compound, and a benzimidazole compound. ) _one member selected from the group consisting of compounds or more chemically amplified photoresist composition.

[Claim _2]

 The method according to claim 1,

The (meth) acrylate-based resin wherein the heterocyclic compound having ₁ to _20-2 contains an alkyl sulfide substitution of functional groups as a medium methacrylate-based repeating unit _1, a chemically amplified photoresist containing to _50% by weight Composition.

[ _3]

The method of claim ₁ , wherein

The heterocyclic compound having ₁ to ₂ ◦ _divalent alkylene sulfide to the (meth) acrylate-based repeating units substituted with a functional group as a medium, including chemically-amplified photoresist compositions comprising the formula _{(A) of:}

( _A) 2019/098493 1 ^» (: 1 ^ {2018/008366

In the above formula, _¾ is hydrogen or methyl,

 And each of R &lt; 3 &gt; and R &lt; 4 &gt; is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

_{5 X} is the aforementioned heterocyclic compound.

Claim ₄

 The method of claim 1, wherein

 The (meth) acrylate-based resin

1 chemically amplified further comprising the repeating units derived from a compound of _one member selected from the group consisting of compounds of formula ₁ to _{8 0} to photoresist composition:

[Chemical Formula 1] 2019/098493 1 ^» (: 1/10/01 018/008366

2019/098493 1 ^» (: 1/10/01 018/008366

[Chemical Formula _4]

[Chemical Formula _6] 2019/098493 1 ^» (: 1/10/01 018/008366

[Chemical Formula 8]

2019/098493 1 ^» (: 1/10/01 018/008366

In the above Chemical Formulas 1 to ₈ ,

_¾ is hydrogen, halogen or an aliphatic group having a carbon number of ₁ to _10;

11 ₁ and _{¾ are} constant, and 1 £ 11 ₁ £ 18 and 1 £ _¾ £ 18.

[Claim _5]

 The method according to claim 1,

Wherein said heterocyclic compound is derived from one selected from the following chemical formulas ( ₉₎ to ( ₁₄ ):

 [Chemical Formula 9]

_[Chemical Formula _11] 2019/098493 1 ^» (: 1 ^ {2018/008366

 In the above formulas (9) to (14)

¾ to ¾ ₀ are each independently hydrogen, halogen, thiol each other (YES), the amine (), hydroxy (0, an alkoxy group having 1 to 20 alkylene (on 1 1 _61½) or having 1 to 20 carbon atoms and ,

Functional group including thiol,

_¾ and _{¾ ¾,} and 1 ¼ _{¾ 2 and} 1 _{¾ 4} .

[Claim 6]

The method according to claim 1, 2019/098493 1 ^» (: 1 ^ {2018/008366

Alkylene sulfide of the above ₁ to ₂₀ carbon atoms is a thiol-ene click 0 ^ _{01 - 1}

_7.

_5. The method of claim ₁ ,

 The alkali-soluble resin

The heterocyclic compound is a (meth) acrylate resins different from the (meth) acrylate-based resin ₂ containing alkylene sulfide group having ₁ to ₂₀ carbon atoms, including the (meth) acrylate-based repeating units substituted with a functional group as a medium; ₁₀ novolac resin; And polyhydroxy chemically amplified further comprising at least _one element selected from the group consisting of styrene-based resin-type photoresist composition.

[ _8]

 The method according to claim 1,

_15, a photo-acid generator and a chemically amplified photoresist composition further comprises at least _one member selected from a photoinitiator.

_9]

_{20. A} photoresist pattern made from the chemically amplified photoresist composition of claim ₁ .

Claim ₁₀

The photo-resist pattern using a chemically amplified photoresist composition _of claim ₁ method.

 25

 Claim 11

 11. The method of claim 10,

 The photoresist pattern manufacturing method includes:

On a support, a lamination step of laminating a ₃₀ thick film photoresist layer consisting of a _first term a chemically amplified photoresist composition; 2019/098493 1 ^» (: 1 ^ {2018/008366

An exposure step of irradiating the thick film photoresist layer with radiation including electromagnetic waves or particle beams,

 And developing the thick film photoresist layer after exposure to obtain a thick film resist pattern.