KR20180046236A

KR20180046236A - Polymer, organic layer composition, organic layer, and method of forming patterns

Info

Publication number: KR20180046236A
Application number: KR1020160141244A
Authority: KR
Inventors: 김성환; 박유신; 임재범; 김승현; 정현일
Original assignee: 삼성에스디아이 주식회사
Priority date: 2016-10-27
Filing date: 2016-10-27
Publication date: 2018-05-08
Also published as: WO2018079936A1; TW201816517A; TWI641913B; KR101994367B1

Abstract

There is provided a polymer comprising a structural unit represented by the following general formula (1), and an organic film composition comprising the same.
[Chemical Formula 1]

In the above formula (1), the definitions of A, R ¹ to R ³ are as described in the specification.

Description

POLYMER, ORGANIC LAYER COMPOSITION, ORGANIC LAYER, AND METHOD OF FORMING PATTERNS [0002]

A novel polymer, an organic film composition comprising the polymer, and a pattern forming method using the organic film composition.

Recently, highly integrated design due to the miniaturization and complexity of electronic devices has accelerated the development of more advanced materials and related processes, so that lithography using existing photoresists also requires new patterning materials and techniques .

In the patterning process, an organic film called a hardmask layer, which is a hard interlayer, can be formed in order to transfer a fine pattern of photoresist to a substrate to a sufficient depth without collapse.

The hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Thus, the hardmask layer needs to have corrosion-resisting properties to withstand multiple etching processes. In addition, the hard mask layer is required to have a predetermined absorbance characteristic in order to be usable as an antireflection film.

Meanwhile, it has recently been proposed that the hard mask layer is formed by a spin-on coating method instead of the chemical vapor deposition method. The spin-on coating method can use a hard mask composition having solubility, and the solubility of the hard mask composition also affects the planarization characteristics required in a multi-patterning process and the like.

One embodiment provides a novel polymer capable of forming an organic film having excellent corrosion resistance and at the same time ensuring planarization characteristics.

Another embodiment provides an organic film composition comprising the polymer.

Another embodiment provides a method of pattern formation using an organic film composition comprising the polymer.

According to one embodiment, there is provided a polymer comprising a structural unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

A is a penta- or hexa-heteroaromatic ring containing two or more identical or different hetero atoms,

R ¹ and R ² are each independently an aromatic ring group, a heteroaromatic ring group, or a combination thereof,

R ³ is a divalent organic group,

* Is the connection point.

In Formula 1, A may include two identical or different hetero atoms, and at least one of the two hetero atoms may be a nitrogen atom.

In Formula 1, A is a hexagonal heterocyclic ring containing two nitrogen atoms,

One nitrogen atom, and one of an oxygen atom and a sulfur atom.

In Formula 1, A may be any one of the moieties listed in Group 1 below.

[Group 1]

In the group 1,

X ¹ and X ² are each a nitrogen atom,

X ³ is an oxygen atom, a sulfur atom or NR ^a ,

Wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, Or an unsubstituted C2 to C30 heterocyclic group, a hydroxy group, a halogen atom or a combination thereof,

R ^c is the same as defined above for R ^a .

In Formula 1, R ¹ and R ² may each independently be any one selected from the moieties listed in Groups 2 and 3 below.

[Group 2]

[Group 3]

In the group 3,

Z ¹ to Z ³ are each independently an oxygen atom, a sulfur atom or NR ^a ,

Wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, Or an unsubstituted C2 to C30 heterocyclic group, a hydroxy group, a halogen atom or a combination thereof.

In the above formula (1), R ³ may be represented by the following formula (2).

(2)

In Formula 2,

Y ¹ and Y ² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a hydroxy group, a halogen atom or a combination thereof,

* Is the connection point.

The polymer may have a weight average molecular weight of 500 to 20,000.

According to another embodiment, there is provided an organic film composition comprising a polymer as described above and a solvent.

The polymer may be contained in an amount of 0.1% by weight to 50% by weight based on the total amount of the organic film composition.

According to another embodiment, there is provided a method of manufacturing a semiconductor device, comprising: forming a material layer on a substrate; applying an organic film composition comprising the polymer and the solvent on the material layer; heat treating the organic film composition to form a hard mask layer Containing thin film layer on the hard mask 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 hard mask layer and 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.

And forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.

Provided is a novel polymer capable of forming an organic film having an excellent corrosion resistance and a planarization property and an optical property at the same time.

FIG. 1 is a flow chart for explaining a pattern forming method according to an embodiment,
Fig. 2 is a reference diagram for explaining a method of evaluating the planarization characteristic.

Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, A thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C3 to C30 heteroaryl group, a C3 to C30 heteroaryl group, a C3 to C30 cycloalkyl group, a C3 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C2 to C20 hetero aryl group, Substituted with a substituent selected from a C 1 to C 15 monocycloalkenyl group, a C 6 to C 15 cycloalkynyl group, a C 2 to C 30 heterocycloalkyl group, and combinations thereof.

Also, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S, Se, Te and P.

Polymers according to one embodiment are described below.

The polymer according to one embodiment comprises a structural unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ³ is a divalent organic group,

* Is the connection point.

The polymer includes a heteroaromatic ring containing two or more identical or different hetero atoms in its structural unit (represented by A in the above formula (1)). Here, the hetero atom may be, for example, N, O, S, Te or Se, but is not limited thereto.

In Formula 1, the number of heteroatoms included in A may be, for example, 1, 2, 3, or 4, but is not limited thereto.

Since the polymer contains an aromatic ring group, basically corrosion resistance can be secured. In addition, by including two or more hetero atoms in the aromatic ring group, the hydrogen bond by the hetero atom can be increased to improve the adhesion to the underlying film. Further, by including two or more heteroatoms, heat resistance, solubility, and gap-fill characteristics can be improved.

For example, in Formula 1, A may include two identical or different hetero atoms, and at least one of the two hetero atoms may be a nitrogen atom.

For example, A in the formula (1) may be a hexagonal heterocyclic ring containing two nitrogen atoms, or may be a pentagonal heterocyclic ring containing one nitrogen atom and one of an oxygen atom and a sulfur atom.

For example, in Formula 1, A may be any one of the moieties listed in Group 1 below, but is not limited thereto.

[Group 1]

In the group 1,

X ¹ and X ² are each a nitrogen atom,

X ³ is an oxygen atom, a sulfur atom or NR ^a ,

R ^c is the same as defined above for R ^a .

The position at which each moiety in the group 1 is connected to the formula (1) is not particularly limited.

As described above, the polymer includes a heterocyclic ring represented by A in formula (1), and the heterocyclic ring is, for example, a structure blocked with another ring (in this case, a blocked structure is a structure in which a ring part including a hetero atom is different Ring structure ") but has an open structure.

In formula (1), A representing a heteroaromatic ring is connected to R ¹ and R ² , respectively. Here, each of R ¹ and R ² may independently be any one selected from the moieties listed in Groups 2 and 3, but is not limited thereto.

[Group 2]

[Group 3]

In the group 3,

Z ¹ to Z ³ are each independently an oxygen atom, a sulfur atom or NR ^a ,

The positions at which the respective moieties in the groups 2 and 3 are connected to the formula (1) are not particularly limited.

In the above formula (1), R ³ representing a linking group is not particularly limited as long as it is a divalent organic group. For example, when the moieties listed in Groups 2 and 3 are substituted, at least one hydrogen in the moiety A hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, but is not limited thereto.

For example, R ³ in the formula (2) may be represented by the following formula (2), but is not limited thereto.

(2)

In Formula 2,

* Is the connection point.

For example, in Formula 2, at least one of Y ¹ and Y ² may be any one selected from the ring groups listed in Group 2, or a heterocyclic group listed in Group 3, no.

The above-mentioned polymers may comprise at least one polycyclic ring group. As an example, at least one of R ¹ and R ² in Formula 1 may be a polycyclic ring group including at least two rings. As another example, R ³ in the general formula (1) may be a polycyclic ring group containing two or more rings.

For example, the polymer may have a weight average molecular weight of about 500 to 20,000. By having a weight average molecular weight in the above range, it is possible to optimize by controlling the carbon content of the organic film composition (for example, hard mask composition) containing the polymer and the solubility in solvents.

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 deteriorate thickness scattering in the baking process, or when a step is present in the lower substrate (or film) It is possible to provide excellent gap-fill and planarization characteristics.

The solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the polymer. Examples of the solvent include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) But are not limited to, methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylformamide, , Methyl pyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate.

The polymer may be included in an amount of about 0.1 to 50% by weight based on the total amount of the organic film composition. By including the polymer in the above range, the thickness, surface roughness, and leveling 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, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.

Examples of the cross-linking agent include melamine-based, substitution-based, or polymer-based ones. Preferably, the crosslinking agent having at least two crosslinking substituents is, for example, a methoxymethylated glycerol, a butoxymethylated glyceryl, a methoxymethylated melamine, a butoxymethylated melamine, a methoxymethylated benzoguanamine, a butoxy Methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea can be used.

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

The acid generator may be an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid or naphthalenecarboxylic acid and / , 4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters, but are 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 film composition. By including it in the above range, the solubility can be improved without changing the optical properties of the organic film composition.

According to another embodiment, there is provided an organic film produced using the organic film composition described above. The organic layer may be in the form of a hardened layer, for example, a hard mask layer, a planarization layer, a sacrificial layer, a filler, etc., and an organic thin film used for electronic devices, .

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

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

The pattern forming method according to one embodiment includes the steps of forming a material layer on a substrate (S1), applying (S2) an organic film composition including the above-mentioned polymer and a solvent on the material layer, Forming a hard mask layer (S3) on the hard mask layer, 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) (S6) selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern and exposing a part of the material layer using the photoresist pattern, 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 a metal layer such as aluminum, copper, or the like, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like. The material layer may be formed by, for example, 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. At this time, the coating thickness of the organic film composition is not particularly limited, but may be applied to a thickness of about 50 to 10,000 ANGSTROM.

The heat treatment of the organic film composition may be performed at about 100 to 500 DEG C for about 10 seconds to 1 hour.

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

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

The step of exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV. Further, after the exposure, the heat treatment process may be performed at about 100 to 500 ° C.

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, for example, 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 a metal pattern, a semiconductor pattern, an insulation pattern, or the like, and may be applied to various patterns in a semiconductor integrated circuit device, for example.

Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Polymerization Example

Polymerization Example One

To the flask was dissolved malonyl chloride (14.1 g, 0.1 mol) and hydroxypyrrole (43.7 g, 0.2 mol) in 1,2-dichloroethane (319 g) and stirred at room temperature with aluminum chloride mol) is added slowly and stirred for an additional 1 hour.

After the reaction is complete, the reaction is slowly added dropwise to DIW (1 L) and the organic layer is discarded. The organic layer was washed twice with DIW (100 mL), and then the organic solvent was removed under reduced pressure to obtain the following compound 1a.

The obtained compound 1a (25.0 g, 0.05 mol) and hydrazine hydrochloride (6.9 g, 0.1 mol) were dissolved in 150 ml of ethanol, followed by stirring at 80 ° C for 5 hours.

After the reaction was completed, the solution was slowly added dropwise to a cold DIW (500 mL), and the resulting solid was filtered and the residual organic solvent was removed under reduced pressure to obtain the following compound 1b.

To the flask, Compound 1b (20.0 g, 0.04 mol) obtained, hydroxypyranecarboxaldehyde (9.9 g, 0.04 mol) and propylene glycol monomethyl ether acetate 120 g were added to prepare a solution. Diethylsulfate (0.31 g) was added to the solution, followed by stirring at 100 占 폚 for 10 hours. When the polymerization was completed, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer containing the structural unit represented by the following formula (1-1).

[Formula 1-1]

Polymerization Example 2

To the flask, compound 1b (20.0 g, 0.04 mol), triethylamine (40.5 g, 0.4 mol), magnesium chloride (28.6 g, 0.3 mol) and paraformaldehyde (14.4 g) And the mixture was stirred at 60 ° C for 24 hours.

After the reaction is completed, cool to room temperature and slowly add the reactant to DIW (500 g) under stirring. Filter the resulting solids and wash them three times with DIW (300 g). The solid was then dissolved in diethyl ether (300 g), filtered again, and the residual solvent was removed under reduced pressure to obtain the following compound 2a.

The obtained compound 2a (11.1 g, 0.02 mol), indole (2.3 g, 0.02 mol) and propylene glycol monomethyl ether acetate (68 g) were added to prepare a solution. Diethylsulfate (0.15 g) was added to the solution, followed by stirring at 100 占 폚 for 10 hours. When the polymerization was completed, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer containing the structural unit represented by the following formula (1-2).

[Formula 1-2]

Polymerization Example 3

The compound 1a (25.0 g, 0.05 mol), 4-hydroxybenzamidine hydrochloride (8.6 g, 0.05 mol) and potassium carbonate (6.9 g, 0.05 mol) were dissolved in 150 ml of dimethylformamide and stirred at 80 ° C for 5 hours .

After the reaction is completed, cool to room temperature and slowly add the reactant to DIW (800 g) under stirring. Filter the resulting solids and wash them three times with DIW (300 g). The solid was then dissolved in ethanol (300 g), filtered again, and the residual solvent was removed under reduced pressure to obtain the following compound 3a.

A solution was prepared by adding the obtained compound 3a (18.1 g, 0.03 mol), pyrencarboxaldehyde (6.9 g, 0.03 mol) and propylene glycol monomethyl ether acetate (100 g). Diethylsulfate (0.23 g) was added to the solution and the mixture was stirred at 100 占 폚 for 20 hours. When the polymerization was completed, the polymer was precipitated in methanol to remove the monomer and the low molecular weight to obtain a polymer containing the structural unit represented by the following Formula 1-3.

[Formula 1-3]

Polymerization Example 4

Compound 1a (25.2 g, 0.05 mol) and hydroxylamine hydrochloride (6.9 g, 0.10 mol) were placed in a flask and dissolved in ethanol (150 g), followed by stirring at 80 ° C for 5 hours.

After the reaction is completed, cool to room temperature and slowly add the reactant to DIW (500 g) under stirring. The resulting solids were filtered and dissolved in diethyl ether (200 g), filtered again, and the residual solvent was removed under reduced pressure to obtain the following compound 4a.

A solution was prepared by adding the obtained compound 4a (15.0 g, 0.03 mol), pyrencarboxaldehyde (6.9 g, 0.03 mol) and propylene glycol monomethyl ether acetate (100 g). Diethylsulfate (0.23 g) was added to the solution, and the mixture was stirred at 100 占 폚 for 10 hours. Upon completion of the polymerization, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer containing the structural unit represented by the following formula (1-4).

[Formula 1-4]

Polymerization Example 5

After dissolving malonyl chloride (28.2 g, 0.2 mol) and indole (46.9 g, 0.4 mol) in 1,2-dichloroethane (400 g) and stirring at room temperature, aluminum chloride (53.3 g, 0.4 mol) The mixture was stirred for an additional hour.

After the reaction is complete, the reaction is slowly added dropwise to DIW (1 L) and the organic layer is discarded. The organic layer was washed twice with DIW (100 mL), and then the organic solvent was removed under reduced pressure to obtain the following compound 5a.

The obtained compound 5a (32.0 g, 0.10 mol) and hydrazine hydrochloride (13.7 g, 0.20 mol) were dissolved in 250 ml of ethanol, followed by stirring at 80 ° C for 5 hours.

After the reaction was completed, the solution was slowly added dropwise to a cold DIW (500 mL), and the resultant solid was filtered and the residual organic solvent was removed under reduced pressure to obtain the following compound 5b.

To the flask, a solution was prepared by adding the obtained compound 5b (14.9 g, 0.05 mol), pyrencarboxaldehyde (11.5 g, 0.05 mol) and propylene glycol monomethyl ether acetate 120 g. Diethylsulfate (0.39 g) was added to the solution, followed by stirring at 100 占 폚 for 10 hours. When the polymerization was completed, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer containing the structural unit represented by the following formula (1-5).

[Formula 1-5]

Comparative Polymerization Example One

After the addition of 28.83 g (0.2 mol) of 1-naphthol, 41.4 g (0.15 mol) of benzoperrylene and 12.0 g (0.34 mol) of paraformaldehyde, 162 g of propylene glycol monomethyl ether acetate (PGMEA) was added to the flask. Next, 0.19 g of p -toluenesulfonic acid monohydrate was added, followed by stirring at 90 to 100 캜 for 5 to 12 hours.

Samples were taken from the polymerization reactants at intervals of 1 hour, and the weight average molecular weight of the sample was measured. When the weight average molecular weight was 1,800 to 2,500, the reaction was completed.

polymerization After completion of the reaction, the reaction product was slowly cooled to room temperature, and the reaction product was added to 40 g of distilled water and 400 g of methanol, stirred vigorously, and allowed to stand. The supernatant was removed, and the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA). After stirring vigorously using 320 g of methanol, the solution was allowed to stand (first step). The resulting supernatant was again removed and the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA) (second order). The primary and secondary processes were referred to as a one-time purification process, and this purification process was performed three times in total. The purified polymer was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and 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 (A).

(A)

Comparative Polymerization Example 2

(0.143 mol) of 9,9'-bis (4-hydroxyphenyl) fluorene, 23.7 g (0.143 mol) of 1,4-bis (methoxymethyl) benzene and 50 g of propylene glycol monomethyl ether acetate To prepare a solution. To the solution was added 1.10 g (7.13 mmol) of diethylsulfate and the mixture was stirred at 100 DEG C for 24 hours. Upon completion of the polymerization, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer containing the structural unit represented by the following formula (B).

[Chemical Formula B]

Comparative Polymerization Example 3

To the flask was added a solution of Phyrol 5b (3.4 g, 0.05 mol), pyrene carbodaldehyde (11.5 g, 0.05 mol) and propylene glycol monomethyl ether acetate 100 g. Diethylsulfate (0.39 g) was added to the solution, followed by stirring at 100 占 폚 for 5 hours. After the polymerization was completed, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer containing the structural unit represented by the following formula (C).

&Lt; RTI ID = 0.0 &

Hard mask Preparation of composition

Example One

The polymer obtained in Polymerization Example 1 was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)) and then filtered to obtain a hard mask composition . The weight of the polymer was adjusted to 5.0 wt.% To 15.0 wt.% Based on the total thickness of the hard mask composition, depending on the intended thickness.

Example 2

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Polymerization Example 2 was used in place of the polymer obtained in Polymerization Example 1.

Example 3

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Polymerization Example 3 was used in place of the polymer obtained in Polymerization Example 1.

Example 4

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Polymerization Example 4 was used in place of the polymer obtained in Polymerization Example 1.

Example 5

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Polymerization Example 5 was used in place of the polymer obtained in Polymerization Example 1.

Comparative Example One

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

Comparative Example 2

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Polymerization Example 2 was used in place of the polymer obtained in Polymerization Example 1.

Comparative Example 3

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Polymerization Example 3 was used in place of the polymer obtained in Polymerization Example 1.

Evaluation 1: Evaluation of heat resistance

A hard mask composition (polymer content: 10.0 wt%) according to Examples 1 to 5 and Comparative Example 1 was spin-coated on a silicon wafer, followed by heat treatment at 240 ° C for 2 minutes to form a thin film, The thickness of the thin film formed by MAC thin film thickness gauge was measured.

Further, a hard mask composition (polymer content: 10.0% by weight) according to Examples 1 to 5 was spin-coated on a silicon wafer, followed by heat treatment at 400 DEG C for 5 minutes to form a thin film. Thickness of thin film formed by thin film thickness gauge was measured again.

The results are shown in Table 1.

Thickness (Å) measured after 2 min annealing at 240 ℃ Thin film thickness (Å) measured after heat treatment at 400 ° C for 5 minutes Thin film thickness
Decrease (%) Comparative Example 1 2021 1415 -30.0 Example 1 2007 1662 -17.2 Example 2 1999 1807 -9.6 Example 3 1983 1715 -13.5 Example 4 2013 1838 -8.7 Example 5 1832 1701 -7.2

Referring to Table 1, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 5 has a smaller thickness reduction rate at the heat treatment of 400 degrees Celsius than the thin film formed from the hard mask composition according to Comparative Example 1. [

From this, it can be seen that the hard mask composition according to Examples 1 to 5 has higher heat resistance than the hard mask composition according to the comparative example.

Evaluation 2: Awareness of corrosion evaluation

Hard mask compositions (polymer content: 10% by weight) according to Examples 1 to 5 and Comparative Examples 1 to 3 were coated on a silicon wafer by a spin-on coating method on a patterned silicon wafer. Subsequently, the thin film was formed by heat treatment at 400 ° C for 2 minutes, and the thickness of the thin film was measured using a ST-5000 thin film thickness meter of K-MAC.

Then, after performing dry etching for 60 seconds each using N ₂ / O ₂ mixed gas _{(50mT / 300W / 10O 2 /} 50N 2) to the thin film was further measured the thickness of the thin film. The bulk etch rate (BER) was calculated from the thin film thickness before and after the dry etching and the etching time according to the following equation (1).

N ₂ / O ₂ using a gas mixture instead of CFx gas _{(100mT / 600W / 42CF 4 /} 600Ar / 15O 2) removal rate was calculated by the following formula 1 similarly subjected to dry etching for 120 seconds.

[Equation 1]

Bulk etch rate (BER) = (initial thin film thickness - thin film thickness after etching) / etching time (Å / sec)

The results are shown in Table 2.

Bulk etch rate (Å / sec) N ₂ O ₂ etch CFx etch Example 1 26.4 24.7 Example 2 24.9 22.5 Example 3 23.3 24.6 Example 4 27.5 25.6 Example 5 25.1 21.9 Comparative Example 1 31.2 27.0 Comparative Example 2 33.0 26.1 Comparative Example 3 29.4 23.1

Referring to Table 1, the thin films formed from the hard mask compositions according to Examples 1 to 5 had an etching rate for the N ₂ / O ₂ mixed gas as compared with the thin films formed from the hard mask composition according to Comparative Examples 1 to 3 Low. In addition, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 5 has a lower etching rate with respect to the CFx gas as compared with the thin film formed from the hard mask composition according to Comparative Examples 1 and 2. [

From this, it can be confirmed that the hard mask composition according to Examples 1 to 5 can secure excellent corrosion resistance.

Evaluation 3: Evaluation of planarization characteristics

The hard mask composition (polymer content: 5% by weight) according to Examples 1 to 5 and Comparative Examples 1 to 3 was spin-on coated on a patterned silicon wafer (trench width 10 탆, trench depth 100 nm) For 120 seconds to observe the planarization characteristics of the thin film.

The planarization characteristics were measured by measuring the thickness of the hard mask layer from the image of the pattern cross section observed with SEM and numerically expressed by the formula 2 shown in FIG. Referring to FIG. 2, h ₁ denotes a value obtained by averaging thicknesses of thin films measured at arbitrary three points where no pattern is formed in the substrate, h ₂ denotes a value measured at any three points where a pattern is formed on the substrate Means the thickness of one thin film. Referring to FIG. 2, since the planarization characteristic is superior as the difference between h ₁ and h ₂ is small, the smaller the planarization value, the better the planarization characteristic.

On the other hand, the gap-fill characteristic was observed by observing the cross section of the pattern with a scanning electron microscope (SEM) to determine whether or not a void occurred.

The results are shown in Table 3.

Planarization characteristics (| h ₁ -h ₂ |, Å) Gap Fill Character
(with or without void) aspect ratio
(1: 2) aspect ratio
(1:10) Example 1 87 193 void None Example 2 79 175 void None Example 3 78 159 void None Example 4 88 184 void None Example 5 94 220 void None Comparative Example 1 120 370 void occurrence Comparative Example 2 113 312 void occurrence Comparative Example 3 104 350 void occurrence

Referring to Table 3, in the case of Comparative Examples 1 to 3, the difference between h1 and h2 is large, so that the flatness is not very good, and voids are also observed in the pattern, and the gap-fill performance is also deteriorated.

On the other hand, it was confirmed that the thin films according to Examples 1 to 5 had a good gap-fill performance to such an extent that no voids were observed, and that the difference between h1 and h2 was small as compared with Comparative Examples 1 and 2, .

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims

A polymer comprising a structural unit represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

In Formula 1,
A is a penta- or hexa-heteroaromatic ring containing two or more identical or different hetero atoms,
R ¹ and R ² are each independently an aromatic ring group, a heteroaromatic ring group, or a combination thereof,
R ³ is a divalent organic group,
* Is the connection point.

The method of claim 1,
In formula (1), A includes two identical or different hetero atoms,
Wherein at least one of the two heteroatoms is a nitrogen atom
polymer.

3. The method of claim 2,
In the above formula (1), A is a hexagonal heterocyclic ring containing two nitrogen atoms, or a pentagonal heterocyclic ring containing one nitrogen atom and one of an oxygen atom and a sulfur atom.

4. The method of claim 3,
Wherein A in Formula 1 is any one of the moieties listed in Group 1 below:
[Group 1]

In the group 1,
X ¹ and X ² are each a nitrogen atom,
X ³ is an oxygen atom, a sulfur atom or NR ^a ,
Wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, Or an unsubstituted C2 to C30 heterocyclic group, a hydroxy group, a halogen atom or a combination thereof,
R ^c is the same as defined above for R ^a .

The method of claim 1,
Wherein R ¹ and R ² are each independently any one selected from the moieties listed in Groups 2 and 3 below:
[Group 2]

[Group 3]

In the group 3,
Z ¹ to Z ³ are each independently an oxygen atom, a sulfur atom or NR ^a ,
Wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, Or an unsubstituted C2 to C30 heterocyclic group, a hydroxy group, a halogen atom or a combination thereof.

The method of claim 1,
Wherein R < ³ > is a polymer represented by the following formula (2): < EMI ID =
(2)

In Formula 2,
Y ¹ and Y ² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a hydroxy group, a halogen atom or a combination thereof,
* Is the connection point.

The method of claim 1,
A polymer having a weight average molecular weight of 500 to 20,000.

A polymer comprising a structural unit represented by the following formula (1), and
menstruum
: &Lt; / RTI >
[Chemical Formula 1]

9. The method of claim 8,
In formula (1), A includes two identical or different hetero atoms,
Wherein at least one of the two heteroatoms is a nitrogen atom
Organic film composition.

The method of claim 9,
Wherein A is a hexagonal heterocyclic ring containing two nitrogen atoms, or a pentagonal heterocyclic ring containing one nitrogen atom and one of an oxygen atom and a sulfur atom.

11. The method of claim 10,
Wherein A in Formula 1 is any one of the moieties listed in Group 1:
[Group 1]

9. The method of claim 8,
Wherein R ¹ and R ² are each independently any one selected from the moieties listed in Groups 2 and 3 below:
[Group 2]

[Group 3]

9. The method of claim 8,
Wherein R ³ in Formula 1 is represented by Formula 2:
(2)

9. The method of claim 8,
And a weight average molecular weight of 500 to 20,000.

Providing a layer of material over the substrate,
Applying the organic film composition according to any one of claims 8 to 14 on the material layer,
Heat treating the organic film composition to form a hard mask layer,
Forming a silicon-containing thin film layer on the hard mask 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 hard mask layer using the photoresist pattern and exposing a portion of the material layer, and
Etching the exposed portion of the material layer
&Lt; / RTI >

16. The method of claim 15,
Wherein the step of applying the organic film composition is performed by a spin-on coating method.

16. The method of claim 15,
Further comprising forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.