KR102151674B1 - Polymer, organic layer composition, and method of forming patterns - Google Patents

Abstract

상기 화학식 1에서,
A는 하기 화학식 2로 표현되는 모이어티이고,
B는 하기 화학식 3으로 표현되는 모이어티이고,
*은 연결지점이다:
[화학식 2]

[화학식 3]

상기 화학식 2 및 3의 정의는 명세서 내에 기재한 바와 같다.It relates to a polymer comprising a structural unit represented by the following Formula 1, an organic film composition comprising the polymer, and a pattern formation method using the organic film composition.
[Formula 1]

In Formula 1,
A is a moiety represented by the following formula (2),
B is a moiety represented by the following formula (3),
* Is the connection point:
[Formula 2]

[Formula 3]

The definitions of Formulas 2 and 3 are as described in the specification.

Description

Polymer, organic film composition, and pattern forming method {POLYMER, ORGANIC LAYER COMPOSITION, AND METHOD OF FORMING PATTERNS}

The present invention relates to a novel polymer, an organic film composition comprising the polymer, and a pattern forming method using the organic film composition.

Recently, the semiconductor industry is developing from a pattern of several hundred nanometers to an ultra-fine technology having a pattern of several to tens of nanometers. Effective lithographic techniques are essential to realize such ultra-fine technology.

A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing to form a photoresist pattern, and then etching the material layer using the photoresist pattern as a mask. do.

In recent years, as the size of a pattern to be formed decreases, it is difficult to form a fine pattern having a good profile using only the above-described typical lithographic technique. Accordingly, 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.

The hard mask layer serves as an interlayer that transfers the fine pattern of photoresist to the material layer through a selective etching process. Therefore, the hard mask layer needs properties of heat resistance and etch resistance to withstand multiple etching processes.

On the other hand, in recent years, it has been proposed to form a hardmask layer by a spin-on coating method instead of a chemical vapor deposition method. The spin-on coating method is easy to process and can improve planarization properties. In order to realize a fine pattern, it is essential to form multiple patterns, and at this time, a gap-fill property is required to fill the inside of the pattern with a film without voids.

In addition, when there is a step difference in the substrate to be processed, or when a pattern dense portion and an area without a pattern exist together on the wafer, it is necessary to flatten the film surface using a hard mask layer. However, the above-described properties required for the hardmask layer are in conflict with each other, so a hardmask composition capable of satisfying all of them is required.

One embodiment provides a novel polymer capable of securing not only excellent etch resistance, but also gap-fill properties and planarization properties.

Another embodiment provides an organic film composition comprising the polymer.

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

According to an embodiment, a polymer including a structural unit represented by Formula 1 below is provided.

[Formula 1]

In Formula 1,

A is a moiety represented by the following formula (2),

B is a moiety represented by the following formula (3),

* Is the connection point:

[Formula 2]

In Chemical Formula 2,

Z is NR ⁰ , O or S, wherein R ⁰ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ¹ is a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group , A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

a is an integer from 0 to 3,

* Is the connection point:

[Formula 3]

In Chemical Formula 3,

L ¹ and L ² are each independently O, S, SO ₂ , or carbonyl,

R ² to R ⁵ are each independently a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted A C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

b to e are each independently an integer of 0 to 4,

R ⁶ to R ¹¹ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

n is an integer from 0 to 5,

* Is the connection point.

The weight average molecular weight of the polymer may be 1,000 to 200,000.

According to another embodiment, an organic film composition including the above-described polymer and a solvent is provided.

The polymer may be included in an amount of 0.1% to 30% by weight based on the total content of the organic film composition.

According to another embodiment, forming a material layer on a substrate, applying an organic film composition including the above-described polymer and a solvent on the material layer, and forming a hardmask layer by heat treating the organic film composition , Forming a silicon-containing thin film layer on the hardmask layer, forming a photoresist layer on the silicon-containing thin film layer, exposing and developing the photoresist layer to form a photoresist pattern, using the photoresist pattern Thus, it provides a pattern forming method comprising the step of selectively removing the silicon-containing thin film layer and the hardmask layer, exposing a portion of the material layer, and etching the exposed portion of the material layer.

The step of applying the organic film composition may be performed by a spin-on coating method.

It may further include forming a bottom anti-reflection layer (BARC) before forming the photoresist layer.

The polymer according to an embodiment includes a heterocyclic group moiety and an aromatic cyclic group moiety connected by a predetermined linker. Accordingly, the polymer can simultaneously secure a gap-fill property and a planarization property along with etch resistance, and when the polymer is used as an organic film material, an organic film having excellent etch resistance and flatness can be provided.

1 is a flow chart for explaining a pattern forming method according to an embodiment,
2 is a reference diagram for explaining the calculation formula 2 related to the planarization characteristic,
3 is a reference diagram for explaining the calculation equation 3 related to the step characteristic.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the embodiments of the present invention. However, the present invention may be implemented in various different forms, and is not limited to the embodiments described herein.

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

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

In addition, unless otherwise defined in the specification,'*' refers to a connection point of a compound or a compound moiety.

Hereinafter, a polymer according to an embodiment will be described.

A polymer according to an embodiment includes a structural unit represented by Formula 1 below.

[Formula 1]

In Formula 1,

A is a moiety represented by the following formula (2),

B is a moiety represented by the following formula (3),

* Is the connection point:

[Formula 2]

In Chemical Formula 2,

Z is NR ⁰ , O or S, wherein R ⁰ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ¹ is a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group , A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

a is an integer from 0 to 3,

* Is the connection point:

[Formula 3]

In Chemical Formula 3,

L ¹ and L ² are each independently O, S, SO ₂ , or carbonyl,

R ² to R ⁵ are each independently a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted A C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

b to e are each independently an integer of 0 to 4,

R ⁶ to R ¹¹ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

n is an integer from 0 to 5,

* Is the connection point.

The polymer includes the structural units represented by Formula 1, wherein the number and arrangement of these structural units are not limited.

The structural unit represented by Formula 1 includes a heterocyclic group moiety (A) and a predetermined linker, that is, an aromatic cyclic group moiety (B) linked by O, S, SO ₂ , or carbonyl.

The heterocyclic group moiety (A) is represented by Formula 2, and the aromatic cyclic group moiety (B) connected by a predetermined linker is represented by Formula 3 above. For example, the pentagonal ring portion in the heterocyclic group portion (A) may be connected to the aromatic ring group portion (B) connected by the predetermined linker.

The hetero atom included in the pentagonal ring in Formula 2 is N, O, or S. The hexagonal ring in Formula 2 is, for example, a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted It may be substituted with a functional group such as a C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, or a substituted or unsubstituted C2 to C30 heteroaryl group. It may be in a circular shape.

As described above, since the polymer includes the structure represented by Chemical Formula 2 in its structural unit, it is basically excellent in corrosion resistance.

The moiety (B) represented by Formula 3 has a structure in which two benzene rings are connected by a linker of O, S, SO ₂ , or carbonyl, and this structure may be one (ie, the formula 3 In the case of n=0), it may be 2 to 6 (that is, when n is 1 to 5 in Formula 3).

For example, in Formula 3, L ¹ and L ² may each be O, that is, an ether linker, but are not limited thereto.

The polymer may increase the flexibility of the polymer by including a predetermined linking group represented by Formula 3 in its structural unit. Such a flexible structure not only improves solubility by increasing the free volume of the polymer, but also lowers the glass transition temperature (Tg), thereby improving gap-fill performance and planarization during the baking process.

The polymer may have a weight average molecular weight of about 500 to 200,000. More specifically, the polymer may have a weight average molecular weight of about 1,000 to 20,000. By having a weight average molecular weight in the above range, the carbon content of the organic film composition (eg, hard mask composition) including the polymer and the solubility in a solvent can be adjusted to optimize.

When the polymer is used as an organic film material, it is possible to form a uniform thin film without forming pin-holes and voids or deteriorating the thickness distribution during the baking process, as well as when there is a step difference or a pattern on the lower substrate (or film). When formed, excellent gap-fill and planarization properties may be provided.

According to another embodiment, an organic film composition including the above-described polymer and a solvent is provided.

The solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the polymer, for example, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) mono Methyl 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.

The polymer may be included in an amount of about 0.1 to 50% by weight, about 0.1 to 30% by weight, or about 0.1 to 15% by weight based on the total content of the organic film composition. By including the polymer in the above range, the thickness, surface roughness, and degree of planarization of the organic film can be controlled.

The organic film composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.

The surfactant may be, for example, a fluoroalkyl-based compound, an alkylbenzene sulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.

The crosslinking agent may be, for example, melamine-based, substituted urea-based, or these polymers. Preferably, a crosslinking agent having at least two crosslinking substituents, for example, methoxymethylated glycoruryl, butoxymethylated glycoruryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy Compounds such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea may be used.

Further, as the crosslinking agent, a crosslinking agent having high heat resistance may be used. As a crosslinking agent having high heat resistance, a compound containing a crosslinking substituent having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule can be used.

The thermal acid generator is an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, or/and 2,4 ,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, and other organic fonate alkyl esters may be used, but the present invention is not limited thereto.

The additive may be included in an amount of about 0.001 to 40 parts by weight based on 100 parts by weight of the organic layer composition. By including in the above range, solubility can be improved without changing the optical properties of the organic film composition.

According to another embodiment, an organic film prepared 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 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 with reference to FIG. 1.

1 is a flowchart illustrating a method of forming a pattern according to an exemplary embodiment.

The pattern formation method according to an embodiment includes the steps of forming a material layer on a substrate (S1), applying an organic film composition including the above-described polymer and solvent on the material layer (S2), and heat treatment of the organic film composition. Forming a hard mask layer (S3), forming a silicon-containing thin film layer on the hard mask layer (S4), forming a photoresist layer on the silicon-containing thin film layer (S5), and exposing the photoresist layer And developing to form a photoresist pattern (S6), selectively removing the silicon-containing thin film layer and the hardmask layer using the photoresist pattern, and exposing a portion of the material layer (S7), and the And etching the exposed portion of the material layer (S8).

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 can be formed, for example, by a chemical vapor deposition method.

The organic film composition is as described above, and may be prepared in a solution form and applied by a spin-on coating method. In this case, the coating thickness of the organic film composition is not particularly limited, but may be applied to a thickness of, for example, about 50 to 200,000Å or about 50 to 10,000Å.

The step of heat-treating the organic film composition may be performed at, for example, about 100 to 700° C. for about 10 seconds to 1 hour.

The silicon-containing thin film layer may be formed of, for example, a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and/or SiN.

In addition, before forming the photoresist layer, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer.

The step of exposing 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 step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be CHF ₃ , CF ₄ , Cl ₂ , BCl _3, and a mixed gas 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, and an insulating pattern, and 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.

Synthesis example

Synthesis Example 1

In a flask, 6-hydroxyindole (26.6 g, 0.2 mol), 4,4'-bismethoxymethyl diphenyl ether (51.6 g, 0.2 mol), diethyl sulfate (0.9 g, 6 mmol) and propylene glycol monomethyl ether After 78.2 g of acetate (PGMEA) was added, the mixture was stirred at 100° C. for 2 to 15 hours to perform a polymerization reaction. Samples were taken from the polymerization reaction product at 1 hour intervals, and the reaction was completed when the weight average molecular weight was 2,000 to 3,500. After the polymerization reaction was completed, the reaction product was gradually cooled to room temperature, the reaction product was added to 40 g of distilled water and 400 g of methanol, stirred vigorously, and allowed to stand to form a precipitate. The formed precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and then stirred vigorously with 320 g of methanol and 320 g of water to form a precipitate. The precipitate obtained at this time was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA). The purification process of forming a precipitate twice was performed a total of three times. After dissolving the purified polymer in 80 g of propylene glycol monomethyl ether acetate (PGMEA), methanol and distilled water remaining in the solution were removed under reduced pressure to obtain a polymer containing a structural unit represented by the following Formula 1-1 (Mw: 2,900).

[Formula 1-1]

Synthesis Example 2

Cyanaphthene (26.8 g, 0.2 mol), 4,4'-bismethoxymethyl diphenyl ether (51.6 g, 0.2 mol), propylene glycol monomethyl ether acetate 78.4 g and diethyl sulfate (0.9 g, 6 mmol) Using the same synthesis procedure as in Synthesis Example 1, a polymer including the structural unit represented by Formula 1-2 was obtained (Mw: 2,700).

[Formula 1-2]

Synthesis Example 3

Synthesis using indole (23.4 g, 0.2 mol), 4,4'-bismethoxymethyl diphenyl ether (51.6 g, 0.2 mol), propylene glycol monomethyl ether acetate 75 g and diethyl sulfate (0.9 g, 6 mmol) A polymer containing the structural unit represented by Chemical Formula 1-3 was obtained through the same synthesis process as in Example 1 (Mw: 2,700).

[Formula 1-3]

Synthesis Example 4

Indole (23.4 g, 0.2 mol), 2,2'-bis[4-(4-methoxymethylphenoxy)phenyl]propane (94.4 g, 0.2 mol), propylene glycol monomethyl ether acetate 117.8 g and diethyl sulfate (0.9g, 6mmol) was used to obtain a polymer including the structural unit represented by Formula 1-4 through the same synthesis process as in Synthesis Example 1 (Mw: 3,800).

[Formula 1-4]

Comparative Synthesis Example 1

In a flask, 4,4'-9H-fluorene-9,9-diyl diphenol (70 g, 0.2 mol), 1,4-bismethoxymethylbenzene (34 g, 0.2 mol), propylene glycol monomethyl ether acetate 104 g And diethyl sulfate (0.9 g, 6 mmol) to obtain a polymer including the structural unit represented by Formula A through the same synthesis process as in Synthesis Example 1 (Mw: 3,700).

[Formula A]

Comparative Synthesis Example 2

4,4'-9H-fluorene-9,9-diyl diphenol (70 g, 0.2 mol), 4,4'-bismethoxymethyl diphenyl ether (51.6 g, 0.2 mol), propylene glycol monomethyl ether Using 121.6 g of acetate and diethyl sulfate (0.9 g, 6 mmol), a polymer containing the structural unit represented by Formula B was obtained through the same synthesis procedure as in Synthesis Example 1 (Mw: 3,800).

[Formula B]

Comparative Synthesis Example 3

6-hydroxyindole (26.6 g, 0.2 mol), 1,4-bismethoxymethylbenzene (34 g, 0.2 mol), propylene glycol monomethyl ether acetate 60.6 g and diethyl sulfate (0.9 g, 6 mmol) were added to the flask. Using the same synthesis procedure as in Synthesis Example 1, a polymer containing the structural unit represented by Chemical Formula C was obtained (Mw: 2,500).

[Formula C]

Comparative Synthesis Example 4

In a flask, 1-naphthol (28.8 g, 0.2 mol), 3,5-bis (methoxymethyl) biphenyl (48.4 g, 0.2 mol), propylene glycol monomethyl ether acetate 77.2 g and diethyl sulfate (0.9 g, 6 mmol) ) To obtain a polymer containing the structural unit represented by Formula D through the same synthesis process as in Synthesis Example 1 (Mw: 2,800).

[Formula D]

Comparative Synthesis Example 5

In a flask, 1-hydroxypyrene (43.6 g, 0.2 mol), 1,4-bismethoxymethylbenzene (34 g, 0.2 mol), propylene glycol monomethyl ether acetate 77.6 g and diethyl sulfate (0.9 g, 6 mmol) To obtain a polymer containing the structural unit represented by Formula E through the same synthesis process as in Synthesis Example 1 (Mw: 3,000).

[Formula E]

Preparation of hard mask composition

Example 1

1 g of the polymer obtained in Synthesis Example 1 was dissolved in 10 g of a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3 (v/v)), Filtration through a Teflon filter to prepare a hard mask composition.

Example 2

A hardmask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 2 was used instead of the polymer obtained in Synthesis Example 1.

Example 3

A hardmask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 3 was used instead of the polymer obtained in Synthesis Example 1.

Example 4

A hardmask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 4 was used instead of the polymer obtained in Synthesis Example 1.

Comparative Example 1

A hardmask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 1 was used instead of the polymer obtained in Synthesis Example 1.

Comparative Example 2

A hardmask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 2 was used instead of the polymer obtained in Synthesis Example 1.

Comparative Example 3

A hardmask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 3 was used instead of the polymer obtained in Synthesis Example 1.

Comparative Example 4

A hardmask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 4 was used instead of the polymer obtained in Synthesis Example 1.

Comparative Example 5

A hardmask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 5 was used instead of the polymer obtained in Synthesis Example 1.

evaluation

Evaluation 1: corrosion resistance

After spin-on coating the hardmask compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 on a silicon wafer, heat treatment on a hot plate at 400° C. for 120 seconds to form a thin film, and then K-MAC The thickness of the formed thin film was measured with the ST5000 thin film thickness meter. Subsequently, dry etching was performed for 60 seconds each using an N ₂ /O ₂ mixed gas (50mT/300W/O ₂ 10sccm/N ₂ 50sccm) on the thin film, and then the thickness of the thin film was measured, and the following calculation formula 1 Etch rate (bulk etch rate, BER) was calculated by. In addition, after dry etching was performed for 120 seconds using CF _x gas (100mT/600W/CF ₄ 42sccm/Ar 600sccm/O ₂ 15sccm), the thickness of the thin film was measured, and the etch rate (bulk etch rate, BER) was calculated.

[Calculation 1]

(Initial thin film thickness-Thin film thickness after etching)/Etching time (Å/sec)

The results are shown in Table 1.

Bulk etch rate(Å/s ec ) N ₂ /O ₂ etch CF _x etch Example 1 23.6 25.1 Example 2 23.5 25.5 Example 3 24.2 26.3 Example 4 25.7 27.3 Comparative Example 1 28.2 31.3 Comparative Example 2 28.6 30.6 Comparative Example 3 23.5 25.2 Comparative Example 4 28.8 30.9 Comparative Example 5 23.4 25.6

Referring to Table 1, the thin film formed from the hardmask composition according to Examples 1 to 4 has sufficient etch resistance to the etching gas compared to the thin film formed from the hardmask composition according to Comparative Examples 1 to 5, and the bulk etch characteristics are improved. can confirm.

Evaluation 2: Gap-fill and planarization properties

After applying the hardmask compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 to the patterned wafer and forming a thin film through a baking process using a hot plate, gap-fill characteristics and planarization characteristics were observed.

The gap-fill characteristics were determined by the presence or absence of voids by observing the cross section of the pattern with an FE-SEM facility (Hitachi, S-4800). The thickness of the thin film was measured and quantified by the formula 2 shown in FIG. 2.

The results are shown in Table 2.

Planarity (%) Gap-Fill characteristics Example 1 5.72 No Void Example 2 6.39 No Void Example 3 5.25 No Void Example 4 7.72 No Void Comparative Example 1 51.68 No Void Comparative Example 2 5.94 No Void Comparative Example 3 63.28 No Void Comparative Example 4 48.7 No Void Comparative Example 5 58.1 No Void

The planarization characteristic is superior as the difference in thickness of the thin film formed on the space pattern in the line/space pattern, that is, the difference between h1 and h2 in FIG. 2 is not large.

Referring to Table 2, it can be seen that the thin film formed from the hardmask composition according to Examples 1 to 4 can simultaneously secure the planarization characteristics and the gap-fill characteristics compared to the thin film formed from the hardmask composition according to Comparative Examples 1 to 5. have.

Evaluation 3: step characteristics

After applying the hardmask compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 on the patterned wafer and going through a bake process, the step characteristics were observed using FE-SEM equipment.

The step characteristics were quantified by the following calculation formula 3. 3 is a reference diagram for explaining the calculation formula 3 for calculating the total step difference. Referring to FIG. 3, since the film thickness at the cell portion varies according to the distance to the ferry, four cells are selected in an order close to the ferry, and the step difference characteristic as the sum of the steps between the cell and the ferry region at four points decreases. Let this be excellent.

[Calculation 3]

Total step difference (nm) = (h0-h1) + (h0-h2) + (h0-h3) + (h0-h4)

The results are shown in Table 3.

Step (A) Example 1 72 Example 2 95 Example 3 57 Example 4 168 Comparative Example 1 529 Comparative Example 2 91 Comparative Example 3 692 Comparative Example 4 453 Comparative Example 5 569

Referring to Table 3, the thin film formed from the hardmask composition according to Examples 1 to 4 was compared with the thin film formed from the hardmask composition according to Comparative Examples 1 to 5, and the total step difference according to Formula 3 was relatively small. It can be seen that the film has flatness.

Referring to Tables 1 to 3, it can be seen that the thin film formed from the hardmask composition according to Examples 1 to 4 has overall excellent etch resistance, gap-fill and planarization properties, and step characteristics. On the other hand, the thin film formed from the hardmask composition according to Comparative Examples 1 to 5 has poor overall thin film properties, or when the etch resistance is satisfied, the flatness is very poor, or when the step characteristics are satisfied, the etch resistance is very poor. It can be seen that the properties required for thin films such as hard masks, etc. are not evenly satisfied.

Although the 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 defined in the following claims are also present. It belongs to the scope of the invention.

Claims (14)

Polymer consisting of a structural unit represented by the following formula (1):
[Formula 1]

In Formula 1,
A is a moiety represented by the following formula (2),
B is a moiety represented by the following formula (3),
* Is the connection point:
[Formula 2]

In Chemical Formula 2,
Z is NR ⁰ , O or S, wherein R ⁰ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
R ¹ is a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group , A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
a is an integer from 0 to 3,
* Is the connection point:
[Formula 3]

In Chemical Formula 3,
L ¹ and L ² are each independently O, S, SO ₂ , or carbonyl,
R ² to R ⁵ are each independently a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted A C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
b to e are each independently an integer of 0 to 4,
R ⁶ to R ¹¹ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
n is an integer from 0 to 5,
* Is the connection point. In claim 1,
In Formula 3, n is 0 or 1 polymer. In claim 1,
In Chemical Formula 3, L ¹ and L ² are each O. In claim 1,
A polymer wherein the pentagonal ring moiety of the moiety represented by Chemical Formula 2 is connected to the B moiety of Chemical Formula 1. In claim 1,
A polymer having a weight average molecular weight of 1,000 to 200,000. A polymer consisting of a structural unit represented by the following formula (1), and
menstruum
Including
Organic film composition:
[Formula 1]

In Formula 1,
A is a moiety represented by the following formula (2),
B is a moiety represented by the following formula (3),
* Is the connection point:
[Formula 2]

In Chemical Formula 2,
Z is NR ⁰ , O or S, wherein R ⁰ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
R ¹ is a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group , A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
a is an integer from 0 to 3,
* Is the connection point:
[Formula 3]

In Chemical Formula 3,
L ¹ and L ² are each independently O, S, SO ₂ , or carbonyl,
R ² to R ⁵ are each independently a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted A C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
b to e are each independently an integer of 0 to 4,
R ⁶ to R ¹¹ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
n is an integer from 0 to 5,
* Is the connection point. In paragraph 6,
In Formula 3, n is 0 or 1 organic film composition. In paragraph 6,
In Chemical Formula 3, L ¹ and L ² are each O. An organic film composition. In paragraph 6,
An organic film composition wherein the pentagonal ring moiety of the moiety represented by Formula 2 is connected to the B moiety of Formula 1. In paragraph 6,
An organic film composition having a weight average molecular weight of 1,000 to 200,000 of the polymer. In paragraph 6,
The polymer is an organic film composition containing 0.1% to 30% by weight based on the total content of the organic film composition. Providing a layer of material over the substrate,
Applying the organic film composition according to any one of claims 6 to 11 on the material layer,
Forming a hard mask layer by heat treating the organic film composition,
Forming a silicon-containing thin film layer on the hardmask layer,
Forming a photoresist layer on the silicon-containing thin film layer,
Exposing and developing the photoresist layer to form a photoresist pattern,
Selectively removing the silicon-containing thin film layer and the hardmask layer using the photoresist pattern and exposing a portion of the material layer, and
Etching the exposed portion of the material layer
Pattern forming method comprising a. In claim 12,
The step of applying the organic layer composition is a pattern forming method performed by a spin-on coating method. In claim 12,
Forming a bottom anti-reflection layer (BARC) prior to forming the photoresist layer.

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