KR102275344B1 - Organic layer composition, organic layer, and method of forming patterns - Google Patents

Abstract

상기 화학식 1의 정의는 명세서 내에 기재한 바와 같다.An organic polymer, an additive comprising the first structural unit represented by Formula 1, and a solvent,
The thermal decomposition temperature of the additive is lower than the crosslinking temperature of the organic polymer, providing an organic film composition:
[Formula 1]

The definition of Chemical Formula 1 is as described in the specification.

Description

Organic film composition, organic film, and pattern formation method {ORGANIC LAYER COMPOSITION, ORGANIC LAYER, AND METHOD OF FORMING PATTERNS}

An organic film composition, an organic film prepared from the organic film composition, and a method of forming a pattern using the organic film composition.

Since it is difficult to realize a fine pattern required in the semiconductor industry with only a typical lithographic technique, a fine pattern can be formed by forming an organic layer called a hardmask layer between the material layer to be etched and the photoresist layer. have. Accordingly, there is a need to develop an organic film material with improved etch resistance, gap-fill, and planarization characteristics, and there is a growing demand for high quality organic film materials used for semiconductor substrates having various and complex fine patterns.

In particular, in the case of gap-fill properties and planarization properties, the surface tension and surface energy are improved by adjusting the surfactant. In this case, many defects are caused due to the added surfactant.

The reason for the defect is that the surfactant remains in the process of coating and baking the organic film material including the fluorine-based surfactant and volatilizes during the subsequent process to cause voids, and as an example of the subsequent process, silicon-containing This is because the voids form micro bridges with Si-nitride, Si-oxide, etc. in the deposition step of the thin film layer.

One embodiment provides an organic film composition with improved defect generation.

Another embodiment provides an organic film having excellent film flatness.

Another embodiment provides a pattern forming method using the organic film composition.

According to one embodiment, an organic film composition comprising an organic polymer, an additive including a first structural unit represented by the following Chemical Formula 1, and a solvent, wherein the thermal decomposition temperature of the additive is lower than the crosslinking temperature of the organic polymer do.

[Formula 1]

In Formula 1,

R ¹ is hydrogen or a C1 to C3 alkyl group,

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 alkyleneoxy group (-(CH ₂ ) _m -O-, m is an integer from 1 to 4), substituted or unsubstituted a cyclic C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 heterocyclic group,

a is an integer from 1 to 5,

b is an integer from 4 to 20;

The thermal decomposition temperature of the additive may be 100 °C to 220 °C, and the crosslinking temperature of the organic polymer may be 180 °C to 380 °C.

The thermal decomposition temperature of the additive may be 150 °C to 180 °C, and the crosslinking temperature of the organic polymer may be 190 °C to 330 °C.

The first structural unit may be included in an amount of 0.01 mol% to 99.99 mol% based on 100 mol% of the additive.

The additive may further include a second structural unit represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ² is hydrogen or a C1 to C3 alkyl group,

R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

L ² is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 alkyleneoxy group (-(CH ₂ ) _n -O-, n is an integer from 1 to 4), substituted or unsubstituted a cyclic C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 heterocyclic group,

c is an integer from 1 to 5;

The second structural unit may be included in an amount of 0.01 mol% to 99.99 mol% based on 100 mol% of the additive.

The weight average molecular weight of the additive may be 600 to 40,000.

The additive may be included in an amount of 1 ppm to 1 wt % based on the total content of the organic film composition.

The organic polymer comprises at least one substituted or unsubstituted aromatic ring group, a substituted or unsubstituted aliphatic ring group, a substituted or unsubstituted heteroaromatic ring group, a substituted or unsubstituted heteroaliphatic ring group, or a combination thereof. may include

The weight average molecular weight of the organic polymer may be 600 to 20,000.

The organic polymer may be included in an amount of 0.1 wt% to 50 wt% based on the total content of the organic film composition.

The solvent is propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexa Non, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate It may be one or two or more selected from the group consisting of.

According to another embodiment, forming a material layer on a substrate, applying the above-described organic film composition on the material layer, heat-treating the organic film composition to form a hardmask layer, photo on the hardmask layer forming a resist layer; exposing and developing the photoresist layer to form a photoresist pattern; selectively removing the hardmask layer using the photoresist pattern and exposing a portion of the material layer; and etching the exposed portion of the material layer.

The heat treatment temperature of the step of forming the hard mask layer may be 240 °C to 400 °C.

An organic film composition having improved void defect generation may be provided.

1 is a SEM photograph showing a cross section of a hard mask layer prepared with the composition of each Example / Comparative Example.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Unless otherwise defined herein, "substituted" means that a hydrogen atom in a compound is a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, A hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alky nyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 It means substituted with a substituent selected from a cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof.

In addition, unless otherwise defined herein, 'hetero' means containing 1 to 3 heteroatoms selected from N, O, S and P.

As used herein, the term “aryl group” refers to a group having one or more hydrocarbon aromatic moieties, and broadly refers to a form in which hydrocarbon aromatic moieties are connected by a single bond and a non-aromatic group in which hydrocarbon aromatic moieties are directly or indirectly fused. Also included are fused rings. Aryl groups include monocyclic, polycyclic or fused polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

In the present specification, "heterocyclic group" is a concept including a heteroaryl group, in addition to carbon (C) in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof. It means containing at least one hetero atom selected from N, O, S, P and Si. When the heterocyclic group is a fused ring, the entire heterocyclic group or each ring may include one or more heteroatoms.

In the present specification, the heterocyclic group is a concept including both a monovalent substituent and a divalent linking group.

More specifically, a substituted or unsubstituted aryl group and/or a substituted or unsubstituted heterocyclic group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted A substituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted A substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted Or an unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazole Diyl, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted Or an unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted qui Nolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, A substituted or unsubstituted benzthiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted A substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a pyridoindolyl group, a benzopyridooxazinyl group, a benzopyridothia Jinil group, 9,9-dimethyl 9,10 dihydroacridinyl, a combination thereof, or a combination thereof may be in a fused form, but limited thereto it doesn't happen In one embodiment of the present invention, the heterocyclic group or the heteroaryl group may be an imidazolyl group, a thiophenyl group, a pyridyl group, a pyrimidinyl group or an indolyl group.

In the present specification, a substituted or unsubstituted arylene group or a substituted or unsubstituted heterocyclic group means that there are two linking groups in the substituted or unsubstituted aryl group or substituted or unsubstituted heterocyclic group as defined above, for example For example, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted naphthacenylene group, a substituted or unsubstituted pyrenylene group, substituted or unsubstituted biphenylene group, substituted or unsubstituted terphenylene group, substituted or unsubstituted quarterphenylene group, substituted or unsubstituted chrysenylene group, substituted or unsubstituted triphenylenylene group , substituted or unsubstituted perylenylene group, substituted or unsubstituted indenylene group, substituted or unsubstituted furanylene group, substituted or unsubstituted thiophenylene group, substituted or unsubstituted pyrrolylene group, substituted or unsubstituted A substituted pyrazolylene group, a substituted or unsubstituted imidazolylene group, a substituted or unsubstituted triazolylene group, a substituted or unsubstituted oxazolylene group, a substituted or unsubstituted thiazolylene group, a substituted or unsubstituted oxadia A zolylene group, a substituted or unsubstituted thiadiazolylene group, a substituted or unsubstituted pyridinylene group, a substituted or unsubstituted pyrimidinylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted triazinylene group, A substituted or unsubstituted benzofuranylene group, a substituted or unsubstituted benzothiophenylene group, a substituted or unsubstituted benzimidazolylene group, a substituted or unsubstituted indolylene group, a substituted or unsubstituted quinolinylene group, A substituted or unsubstituted isoquinolinylene group, a substituted or unsubstituted quinazolinylene group, a substituted or unsubstituted quinoxalinylene group, a substituted or unsubstituted naphthyridinylene group, a substituted or unsubstituted benzoxazinyl Rene group, substituted or unsubstituted benzthiazinylene group, substituted or unsubstituted acridinylene group, substituted or unsubstituted phenazinylene group, substituted or unsubstituted phenothiazinylene group, substituted or unsubstituted phenoxazinyl Rene group, substituted or unsubstituted fluorenylene group, substituted or unsubstituted dibenzofuranylene group, substituted or unsubstituted dibenzo A thiophenylene group, a substituted or unsubstituted carbazolene group, a combination thereof, or a combination thereof may be in a fused form, but is not limited thereto.

Hereinafter, an organic film composition according to an embodiment will be described.

The organic film composition according to an embodiment includes an organic polymer, an additive, and a solvent.

The additive may include a first structural unit represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ¹ is hydrogen or a C1 to C3 alkyl group,

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 alkyleneoxy group (-(CH ₂ ) _m -O-, m is an integer from 1 to 4), substituted or unsubstituted a cyclic C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 heterocyclic group,

a is an integer from 1 to 5,

b is an integer from 4 to 20;

For example, L ¹ may be a substituted or unsubstituted C2 to C10 alkylene group.

The thermal decomposition temperature of the additive is lower than the crosslinking temperature of the organic polymer.

For example, the thermal decomposition temperature of the additive may be 100°C to 220°C, and the crosslinking temperature of the organic polymer may be 180°C to 380°C.

As a specific example, the thermal decomposition temperature of the additive may be 100 °C to 200 °C, and the crosslinking temperature of the organic polymer may be 180 °C to 330 °C.

For example, the thermal decomposition temperature of the additive may be 150 °C to 180 °C, and the crosslinking temperature of the organic polymer may be 190 °C to 330 °C.

In general, a fluorine-based surfactant containing a perfluoro group is used as an additive to improve gap-fill properties and planarization properties, and hydrophilicity and hydrophobicity are reduced by controlling the surface energy by changing the fluorine content, substituent, molecular weight, etc. of the surfactant. It can be controlled to improve the gap-fill properties and the planarization properties. In this case, a structural change for controlling the surface energy is accompanied, and as a result, the thermal decomposition temperature of the surfactant is rapidly changed, and thus, the residual aspect of the surfactant according to the curing temperature during the curing process may be changed. In particular, if the thermal decomposition temperature of the surfactant increases, the possibility of causing trapping voids during the curing process increases, which may affect the film quality of other layers applied to the subsequent process of the multiple patterning process. For example, when a silicon-containing thin film layer is applied, micro bridges such as Si-nitride, Si-oxide, etc. are formed in the voids to cause defects, which may cause a decrease in yield.

In one embodiment of the present invention, void generation can be controlled by adjusting the thermal decomposition temperature of the additive to a specific value in relation to the organic polymer applied to the organic film formation, and thus the formation of defects can be suppressed.

Meanwhile, b in Formula 1 may be 4 to 15, or 5 to 15, but is not limited thereto.

The first structural unit may be included in an amount of 0.01 mol% to 99.99 mol%, specifically 20 mol% to 80 mol%, for example, 30 mol% to 70 mol% based on 100 mol% of the additive.

The additive may further include a second structural unit represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ² is hydrogen or a C1 to C3 alkyl group,

R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

L ² is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 alkyleneoxy group (-(CH ₂ ) _n -O-, n is an integer from 1 to 4), substituted or unsubstituted a cyclic C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 heterocyclic group,

c is an integer from 1 to 5;

For example, L ² may be a substituted or unsubstituted C1 to C10 alkylene group.

The second structural unit may be included in an amount of 0.01 mol% to 99.99 mol%, specifically 20 mol% to 80 mol%, for example, 30 mol% to 70 mol% based on 100 mol% of the additive.

The additive may be included in an amount of 1 ppm to 1 wt %, specifically 1 ppm to 1000 ppm, such as 10 ppm to 100 ppm, based on the total content of the organic film composition, but the content may be adjusted in consideration of the coatability and flatness of the film. .

The additive may further include at least one of a perfluoro alkyl alcohol, a perfluoro alkyl carboxylic acid, a perfluoro alkyl sulfonic acid, a perfluor ester, a perfluor acrylate perfluor ether, and combinations thereof.

The weight average molecular weight of the additive may be 600 to 40,000.

Hereinafter, the organic polymer included in the organic film composition will be described.

The organic polymer comprises at least one substituted or unsubstituted aromatic ring group, a substituted or unsubstituted aliphatic ring group, a substituted or unsubstituted heteroaromatic ring group, a substituted or unsubstituted heteroaliphatic ring group, or a combination thereof. may include

The organic polymer may be a mixture of organic polymers having different molecular weights or a mixture of an organic polymer and a monomolecular compound.

The weight average molecular weight of the organic polymer may be about 600 to 20,000, or about 1,000 to 10,000, but is not limited thereto.

For example, the organic polymer may include a monovalent or divalent organic group derived from a substituted or unsubstituted functional group selected from Group 1 below.

[Group 1]

In group 1,

Z ¹ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroaryl a lene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, C=O, NR ^a , oxygen (O), sulfur (S), or a combination thereof, wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom, or a combination thereof;

Z ^{3 To} Z ¹⁸ are each independently C=O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c or a combination thereof, wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heteroarylene group , a halogen atom, a halogen-containing group, or a combination thereof.

Here, the 'monovalent group derived from compound A' means a monovalent group formed by substituting one hydrogen in compound A. For example, a monovalent group derived from a benzene group becomes a phenyl group. In addition, the 'divalent group derived from compound A' refers to a divalent group in which two connection points are formed by substituted two hydrogens in compound A. For example, a divalent group derived from a benzene group becomes a phenylene group.

The physical properties of the organic film composition can be controlled by selecting the type and number of functional groups included in the organic polymer, and the functional groups are hydroxyl group, halogen atom, halogen-containing group, thionyl group, thiol group, cyano group, substituted or unsubstituted. substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted A substituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or Unsubstituted C1 to C4 alkyl ether, substituted or unsubstituted C7 to C20 arylalkylene ether, substituted or unsubstituted C1 to C30 haloalkyl group, substituted or unsubstituted C1 to C20 alkylborane group, and substituted or unsubstituted It may be selected from the group consisting of a C6 to C30 arylborane group, but is not limited thereto.

The organic polymer may be included in an amount of about 0.1 to 50 wt% based on the total content of the organic film composition. When the organic polymer is included in the above range, the thickness and planarization degree of the organic layer can be controlled.

On the other hand, the solvent included in the organic film composition is not particularly limited as long as it has sufficient solubility or dispersibility for the organic polymer, for example, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol Butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N -Dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate may be one or two or more selected from the group consisting of.

The organic film composition may further include a plasticizer, a crosslinking agent, a thermal acid generator (TAG), a photo acid generator (PAG), etc. in addition to the above-described additives.

The plasticizer is, for example, DOP (dioctyl phthalate), DOA (dioctyl adipate), TCP (tricresyl phosphate), DIOP (Diisocctyl phthalate), DL79P (diheptyl, nonyl phthalate) , DINP (diisononyl phthalate), DUP (diunedcyl) phthalate), BBP(butyl benzyl phthalate), DOA(di-2-ethyl hexyl adipate), DIDA(diisodecyl adipate), DOZ(di-2-ethylhexyl Sebacate), DIOZ(Diisooctyl Azelate), DOS(Di-2-ethylhexyl) Sebacate), TOP(tri-2ethylhexyl phosphate), TTP(triphenyl phosphate), CDP(Cresyldephenyl phosphate), TCP(tircresyl phosphate), TXP(Trixylyl phosphate), TOTM(tri-2-ethylhexyl trimellitate), polyethylene gpycol ester, ASE (alkylsulphonic acid phenyl ester), 3G6 (triethylene glycol dihexanoate), 4g7 (tetraethyleneglycol diheptanoate), ATEC (acetyl triethyl citrate), TBC (tributyl citrate), TOC (trioctyl citrate), ATOC (acetyl trioctyl citrate), ATHC (acetyl trihexyl citrate) citrate), TMC(trimethyl citrate), DMAD(dimethyl adipate_, MMAD(monomethyl adipate), DBM(dibutyl maleate), DIBM(diisobutyl maleate), BDNPF(bis(2,2-dinitropropyl)formal), TNEN(2,2) ,2-trinitroethyl 2-nitrox yethyl ether) , polyethylene glycol, polypropylene, or a combination thereof may be used, but is not limited thereto.

The crosslinking agent may be, for example, a melamine-based, substituted urea-based, or polymer-based agent. Preferably, crosslinking agents having at least two crosslinking substituents are, for example, methoxymethylated glycouryl, butoxymethylated glycouryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy Methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, methoxymethylated thiourea, methoxymethylated benzene, butoxymethylated benzene, methoxymethylated phenol, butoxymethylated phenol, or a combination thereof can be used, but is not limited thereto.

Examples of the thermal acid generator include organic sulfonic acid alkyl ester compounds such as benzointosylate and 2-nitrobenzyl tosylate, diphenyliodonium trifluoromethane sulfonate, and diphenyliodonium dodecylbenzenesulfonate. , Bis(4-tert-butyl phenyl) iodonium camphorsulfonate, bis(4-tert-butyl phenyl) iodonium nonafluoro n-butane sulfonate, bis(4-tert-butyl phenyl) iodonium and onium salt compounds such as trifluoromethane sulfonate and triphenylsulfonium trifluoromethane sulfonate. Also, 2,4,4,6-tetrabromocyclohexadienone, phenyl-bis(trichloromethyl)-s-triazine and N-hydroxysuccinimide trifluoromethane sulfonate, pyridinium p- Toluenesulfonate (Pyridinium p-toluenesulfonate), or a combination thereof may be used, but is not limited thereto.

As an example of the photo-acid generator, triphenylsulfonium triflate, triphenylsulfonium antimonate, diphenyliodonium triflate, diphenyliodonium antimonate (diphenyliodonium antimonate), methoxydiphenyliodonium triflate, di-t-butyldiphenyliodonium triflate, 2,6-dinitrobenzyl sulfonate (2) ,6-dinitrobenzyl sulfonates), pyrogallol tris(alkylsulfonates), N-hydroxysuccinimide triflate, norbornene-dicarboximide-triflate (norbornene-dicarboximide-triflate), triphenylsulfonium nonaflate, diphenyliodonium nonaflate, methoxydiphenyliodonium nonaflate, di-t-butyldi Phenyliodonium nonaflate (di-t-butyldiphenyliodonium nonaflate), N-hydroxysuccinimide nonaflate (N-hydroxysuccinimide nonaflate), norbornene-dicarboximide-nonaflate (norbornene-dicarboximide-nonaflate), triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate, diphenyliodonium PFOS (diphenyliodonium PFOS) ), methoxydiphenyliodonium PFOS, di-t-butyldiphenyliodonium triflate, N-hydroxysuccinimide PFOS, Norbornene-dicarboximide PFOS (norbornene-dicarboximide PFOS), or a combination thereof may be used, but is not limited thereto.

According to another embodiment, an organic film prepared by using the above-described organic film composition is provided. The organic film may be in a form cured through a heat treatment process after coating the above-described organic film composition on a substrate, for example, and may include, for example, an organic thin film used in electronic devices such as a hard mask layer, a planarization film, a sacrificial film, and a filler. have.

Hereinafter, a method of forming a pattern using the above-described organic film composition will be described.

The method for forming a pattern according to an exemplary embodiment includes providing a material layer on a substrate, applying the above-described organic film composition on the material layer, heat-treating the organic film composition to form a hard mask layer, the hard mask forming a photoresist layer over the layer, exposing and developing the photoresist layer to form a photoresist pattern, using the photoresist pattern to selectively remove the hardmask layer and expose a portion of the material layer and etching the exposed portion of the material layer.

The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.

The material layer is a material to be finally patterned, and may be, for example, a metal layer such as aluminum or copper, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide or silicon nitride. The material layer may be formed, for example, by a chemical vapor deposition method.

The organic film composition is the same as described above, and may be prepared in a solution form and applied by a spin-on 　 coating method. At this time, the coating thickness of the organic film composition is not particularly limited, but may be applied, for example, to a thickness of about 50 to 200,000 Å.

The temperature for heat-treating the organic film composition may be about 100 to 700° C., or about 240 to 400° C., for example, the heat treatment may be performed for 10 seconds to 1 hour.

By heat-treating the organic film composition, a film density is improved, etch resistance is enhanced, and a planarized film can be formed.

As an example, the method may further include forming a silicon-containing thin film layer on the hardmask layer. The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and/or SiN.

For example, before the step of forming the photoresist layer, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer or on the hard mask layer.

The exposing of the photoresist layer may be performed using, for example, ArF, KrF, or EUV. In addition, a heat treatment process may be performed at about 100 to 700° C. after exposure.

The etching of the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl _{3 ,} or a mixture thereof.

The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be various, such as a metal pattern, a semiconductor pattern, an insulating pattern, and for example, may be applied as various patterns in a semiconductor integrated circuit device.

The embodiments of the present invention described above will be described in more detail through the following examples. However, the following examples are for illustrative purposes only and do not limit the scope of the present invention.

Example : organic film Produce

Example One

1 kg of a polymer having a weight average molecular weight of 4,500 measured by GPC was dissolved in 9 kg of propylene glycol monomethyl ether acetate (PGMEA), and DIC's An organic film composition was prepared by mixing F444 surfactant in a weight ratio of 0.01%. This organic film composition was packaged in a gallon bottle after 20 cycles of circulation filtration using Entergris' 5nm UPE capsule filter. After spin-on coating by mounting the gallon bottle on a 12" auto track, baking was performed at 240° C. for 2 minutes to form an organic film.

Example 2

An organic film was formed in the same manner as in Example 1, except that DIC's F444 surfactant was changed to DIC's F554 surfactant.

Example 3

An organic film was formed in the same manner as in Example 1, except that DIC's F444 surfactant was changed to DIC's DS21 surfactant.

Example 4

An organic film was formed in the same manner as in Example 1, except that the baking was performed at 400° C. for 2 minutes instead of baking at 240° C. for 2 minutes.

Example 5

An organic layer was formed in the same manner as in Example 2, except for baking at 400° C. for 2 minutes instead of baking at 240° C. for 2 minutes.

Example 6

An organic layer was formed in the same manner as in Example 3 except that the baking was performed at 400° C. for 2 minutes instead of baking at 240° C. for 2 minutes.

comparative example One

An organic layer was formed in the same manner as in Example 1, except that DIC's F444 surfactant was changed to DIC's R40 surfactant.

comparative example 2

An organic film was formed in the same manner as in Comparative Example 1, except that the baking was performed at 400° C. for 2 minutes instead of baking at 240° C. for 2 minutes.

evaluation example : void defect observe

After setting the center, middle, and edge positions of the organic films formed from Examples 1 to 6 and Comparative Examples 1 and 2, and cutting each position vertically using a dicing facility, V-SEM (side) was measured and center, middle , the frequency of void defects when observed 10 times each at the edge position is shown in Table 1 below for a total of 30 observations.

of surfactant
pyrolysis temperature
(℃) of organic polymers
crosslinking temperature
(℃) bake temperature
(℃) Void Defect Example 1 161 180 240 None Example 2 178 180 240 None Example 3 165 180 240 None Example 4 161 180 400 None Example 5 178 180 400 None Example 6 165 180 400 None Comparative Example 1 207 180 240 10ea Comparative Example 2 207 180 400 20ea

Referring to Table 1, it can be seen that the frequency of occurrence of void defects in the organic layer according to the embodiment is significantly reduced compared to the comparative example.

Accordingly, in the case of the organic film according to the embodiment, it can be predicted that the characteristics of the organic film introduced in a subsequent process will be improved.

Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also presented. It belongs to the scope of the invention.

Claims (14)

organic polymers,
An additive comprising a first structural unit represented by the following formula (1), and
menstruum
including,
The thermal decomposition temperature of the additive is lower than the crosslinking temperature of the organic polymer,
The thermal decomposition temperature of the additive is 150 ℃ to 180 ℃,
The crosslinking temperature of the organic polymer is 190 ℃ to 330 ℃,
The additive is contained in an amount of 1 ppm to 1% by weight based on the total content of the organic film composition, the organic film composition:
[Formula 1]

In Formula 1,
R ¹ is hydrogen or a C1 to C3 alkyl group,
L ¹ is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 alkyleneoxy group (-(CH ₂ ) _m -O-, m is an integer from 1 to 4), substituted or unsubstituted a cyclic C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 heterocyclic group,
a is an integer from 1 to 5,
b is an integer from 4 to 20; delete delete In claim 1,
The organic film composition in which the first structural unit is contained in an amount of 0.01 mol% to 99.99 mol% based on 100 mol% of the additive. In claim 1,
The additive is an organic film composition further comprising a second structural unit represented by the following Chemical Formula 2:
[Formula 2]

In Formula 2,
R ² is hydrogen or a C1 to C3 alkyl group,
R ³ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,
L ² is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 alkyleneoxy group (-(CH ₂ ) _n -O-, n is an integer from 1 to 4), substituted or unsubstituted a cyclic C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 heterocyclic group,
c is an integer from 1 to 5; In claim 5,
The organic film composition in which the second structural unit is contained in an amount of 0.01 mol% to 99.99 mol% based on 100 mol% of the additive. In claim 1,
The weight average molecular weight of the additive is 600 to 40,000, the organic film composition. delete In claim 1,
The organic polymer comprises at least one substituted or unsubstituted aromatic ring group, a substituted or unsubstituted aliphatic ring group, a substituted or unsubstituted heteroaromatic ring group, a substituted or unsubstituted heteroaliphatic ring group, or a combination thereof. An organic film composition comprising. In claim 1,
The weight average molecular weight of the organic polymer is 600 to 20,000 organic film composition. In claim 1,
The organic polymer is contained in an amount of 0.1% to 50% by weight based on the total amount of the organic film composition. In claim 1,
The solvent is propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexa Non, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate One or two or more organic film compositions selected from the group consisting of. forming a material layer over the substrate;
Applying the organic film composition according to any one of claims 1, 4 to 7 and 9 to 12 on the material layer,
forming a hard mask layer by heat-treating the organic film composition;
forming a photoresist layer over the hardmask layer;
exposing and developing the photoresist layer to form a photoresist pattern
selectively removing the hardmask layer using the photoresist pattern and exposing a portion of the material layer; and
etching the exposed portion of the material layer;
A pattern forming method comprising a. In claim 13,
The temperature for heat-treating the organic film composition is a pattern forming method of 240 ℃ to 400 ℃.

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