KR101895908B1 - Polymer, organic layer composition, organic layer, and method of forming patterns - Google Patents

Abstract

상기 화학식 1의 정의는 명세서 내에서 설명한 바와 같다.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]

The definition of the above formula (1) is 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.

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. Generally, heat resistance and corrosion resistance are required to be compatible with spin-on characteristics, and an organic film material that can satisfy all of these properties.

One embodiment provides a polymer having good corrosion resistance and good solubility characteristics.

Another embodiment provides an organic film composition comprising the polymer.

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

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 carbon ring group containing at least one hetero atom,

B is any one of the groups listed in Group 1 below,

* Is the connection point.

Provided that when the carbon ring group includes a pentagonal ring portion and the nitrogen atom (N) is contained as a hetero atom in the pentagonal ring, the carbon ring group includes at least two hetero atoms.

[Group 1]

In the group 1,

Ar ¹ to Ar ⁴ each independently represent a substituted or unsubstituted C6 to C30 aryl group,

R ¹¹ to R ¹⁴ each independently represent a hydroxyl group, a thioyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted 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, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted A C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,

g to j are each independently an integer of 0 to 2,

L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,

m is an integer of 1 to 3,

* Is the connection point.

In Formula 1, the hetero atom may be N, O, S, Te, or Se.

In Formula 1, A may be a substituted or unsubstituted cyclic group selected from Group 2 below.

[Group 2]

In the group 2,

Z ¹ and Z ¹² are O, S, Te or Se,

Z ² , Z ⁵ , Z ⁶ and Z ⁹ are NR ^a , O, S, Te or Se,

Z ³ to Z ⁴ , Z ⁷ to Z ⁸ , Z ¹⁰ to Z ¹¹ and Z ¹³ to Z ²³ are N,

R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted Or a substituted or unsubstituted C2 to C30 heteroalkoxy group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 alkenyl group, A C2 to C30 alkynyl group, a hydroxyl group, a halogen atom or a combination thereof.

However, the connection point in the group 2 is not limited.

In the group 1, Ar ¹ to Ar ⁴ may each independently be a substituted or unsubstituted cyclic group selected from the following group 3.

[Group 3]

However, the connection point in the group 3 is not limited.

The polymer may include any one of structural units represented by the following formulas (1-1) to (1-8).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

In the above formulas 1-1 to 1-8,

Z ¹⁰¹ and Z ¹⁰⁴ are N,

Z ¹⁰² is O, S, Te or Se,

Z ¹⁰³ is NR ^a , O, S, Te or Se,

Wherein R ^a and R ¹⁰¹ are selected from the group consisting of hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aryl A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 alkenyl group, An unsubstituted C2 to C30 alkynyl group, a hydroxyl 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: providing a material layer on a substrate; applying the organic film composition on the material layer; heat treating the organic film composition to form a hard mask layer; Containing thin film 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 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.

The heat treatment may be performed at a temperature of 100 ° C to 500 ° C.

A novel polymer that has excellent corrosion resistance and heat resistance, and at the same time has good solubility characteristics and can be applied to a spin-on coating system.

Fig. 1 is a reference diagram for explaining calculation formula 2 for evaluating planarization characteristics.

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,

A is a carbon ring group containing at least one hetero atom,

B is any one of the groups listed in Group 1 below,

* Is the connection point.

Provided that when the carbon ring group includes a pentagonal ring portion and the nitrogen atom (N) is contained as a hetero atom in the pentagonal ring, the carbon ring group includes at least two hetero atoms.

[Group 1]

In the group 1,

Ar ¹ to Ar ⁴ each independently represent a substituted or unsubstituted C6 to C30 aryl group,

R ¹¹ to R ¹⁴ each independently represent a hydroxyl group, a thioyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted 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, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted A C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,

g to j are each independently an integer of 0 to 2,

L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,

m is an integer of 1 to 3,

* Is the connection point.

The polymer may include a carbon ring group (A) containing a hetero atom and a high carbon-based aromatic ring group (B) to ensure rigid characteristics.

In addition, since the polymer contains tertiary carbon or quaternary carbon in the structural unit (the part B in the above formula (1)), the benzylic hydrogen of the benzene is minimized and the ring parameter is maximized, Can be further strengthened.

In the present specification, a tertiary carbon is a carbon in which three positions of four hydrogens bonded to a carbon are substituted with groups other than hydrogen, and a quaternary carbon is a carbon in which all four of four hydrogen bonded to the carbon are hydrogen Is a carbon in a form substituted with another group.

When a polymer containing this type of carbon is used in an organic film composition, the solubility can be improved and it is advantageous to form a film by a spin-on coating method. Part of the compound containing the tertiary carbon or the quaternary carbon is as listed in the above group 1.

In the above formula (1), A is a carbon ring group containing a hetero atom, and the hetero atom is collectively referred to as atoms other than carbon or hydrogen. A may include, but is not limited to, a heteroatom such as N, O, S, Te or Se. In Formula 1, the number of heteroatoms included in A may be, for example, 1, 2, 3, or 4, but is not limited thereto. For example, when the carbon ring group (A) contains a pentagonal ring portion and the nitrogen atom (N) is contained as a hetero atom in the pentagonal ring, the carbon ring group (A) may contain at least two heteroatoms .

For example, when a plurality of heteroatoms are included in the A moiety, these heteroatoms may be homologous or heterogeneous. For example, when the carbon ring group (A) includes a pentagonal ring portion, the carbon ring group may include, for example, two nitrogen atoms as a hetero atom.

The polymer can thus improve solubility and gap-fill properties by including heteroatoms within the structural units.

In Formula 1, A may include at least one substituted or unsubstituted benzene ring. For example, A may be a substituted or unsubstituted cyclic group selected from the following group 2, but is not limited thereto.

[Group 2]

In the group 2,

Z ¹ and Z ¹² are O, S, Te or Se,

Z ² , Z ⁵ , Z ⁶ and Z ⁹ are NR ^a , O, S, Te or Se,

Z ³ to Z ⁴ , Z ⁷ to Z ⁸ , Z ¹⁰ to Z ¹¹ and Z ¹³ to Z ²³ are N,

R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted Or a substituted or unsubstituted C2 to C30 heteroalkoxy group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 alkenyl group, A C2 to C30 alkynyl group, a hydroxyl group, a halogen atom or a combination thereof.

However, the connection point in the group 2 is not limited.

In the above formula (1), Ar ¹ to Ar ⁴ of Group 1 may independently be a polymer which is a substituted or unsubstituted cyclic group selected from the following Group 3, but is not limited thereto.

[Group 3]

However, the connection point in the group 3 is not limited.

For example, when the compounds listed in Groups 2 and 3 are of the substituted form, one hydrogen in the compound may be substituted with 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, the polymer may include any one of structural units represented by the following general formulas (1-1) to (1-8), but is not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

In the above formulas 1-1 to 1-8,

Z ¹⁰¹ and Z ¹⁰⁴ are N,

Z ¹⁰² is O, S, Te or Se,

Z ¹⁰³ is NR ^a , O, S, Te or Se,

Wherein R ^a and R ¹⁰¹ are selected from the group consisting of hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aryl A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 alkenyl group, An unsubstituted C2 to C30 alkynyl group, a hydroxyl group, a halogen atom or a combination thereof,

* Is the connection point.

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.

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

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 organic film composition described above will be described.

The method of forming a pattern according to one embodiment includes the steps of providing 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 using a mask to 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 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.

Synthetic example

Synthetic example  One

(12.9 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4-Dioxane (94 g) was added thereto, followed by stirring at 100 ° C for 8 hours. After completion of the reaction, 100 g of hexane was added to extract 1,4-dioxane. Methanol was added to the mixture to precipitate a precipitate. The remaining monomer was removed using methanol to obtain a polymer represented by the following formula (1a).

[Formula 1a]

Synthetic example  2

To the flask was added 9-methylacridine (19.3 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) , And 4-dioxane (98 g) were added thereto, followed by stirring at 100 ° C for 12 hours. After the reaction was completed, 100 g of hexane was added to extract 1,4-dioxane. The residue was recrystallized using acetonitrile and methanol, and the remaining monomer was removed using acetonitrile and methanol to obtain a polymer represented by Formula 2a .

(2a)

Synthetic example  3

To the flask was added 9-methylacridine (19.3 g, 0.1 mol), Benzophenone (18.2 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol), and 1,4- ) Was added, followed by stirring at 100 ° C for 12 hours. After completion of the reaction, 100 g of hexane was added to extract 1,4-dioxane. The residue was recrystallized using acetonitrile and methanol, and the remaining monomer was removed using acetonitrile and methanol to obtain a polymer represented by Formula 3a .

[Chemical Formula 3]

Synthetic example  4

To the flask was added Thianaphthene (13.4 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol), and 1,4- Followed by stirring at 100 ° C for 8 hours. When the reaction was completed, 100 g of hexane was added to extract 1,4-dioxane. Methanol was added thereto, and the resulting precipitate was filtered, and the remaining monomer was removed using methanol to obtain a polymer represented by Formula 4a.

[Chemical Formula 4a]

Synthesis Example 5

To the flask was added benzothiazole (13.5 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4- Followed by stirring at 100 ° C for 14 hours. When the reaction was completed, 100 g of hexane was added to extract 1,4-dioxane. Methanol was added thereto, and the resulting precipitate was filtered, and the remaining monomer was removed using methanol to obtain a polymer represented by Formula 5a.

[Chemical Formula 5a]

Synthetic example  6

To the flask was added benzoxazole (11.9 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4- Followed by stirring at 100 ° C for 14 hours. When the reaction was completed, 100 g of hexane was added to extract 1,4-dioxane. Methanol was added thereto, and the resulting precipitate was filtered and the remaining monomer was removed using methanol to obtain a polymer represented by the formula 6a.

[Chemical Formula 6a]

Synthesis Example 7

To the flask was added indazole (11.8 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol), and 1,4- Followed by stirring at 100 ° C for 14 hours. When the reaction was completed, 100 g of hexane was added to extract 1,4-dioxane. Methanol was added to the reaction mixture, and the resulting precipitate was filtered. The remaining monomer was removed using methanol to obtain a polymer represented by the formula (7a).

[Formula 7a]

Synthetic example  8

To the flask was added 7-azaindole (11.8 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol), and 1,4- Followed by stirring at 100 ° C for 8 hours. After completion of the reaction, 100 g of hexane was added to extract 1,4-dioxane. Methanol was added to the reaction mixture, and the resulting precipitate was filtered. The remaining monomer was removed using methanol to obtain a polymer represented by Formula 8a.

[Chemical Formula 8a]

Synthesis Example 9

After adding Thianaphthene (20.1 g, 0.15 mol), Anthrone (17.5 g, 0.09 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol), and 1,4-dioxane (152 g) Followed by stirring at 100 占 폚 for 8 hours. After completion of the reaction, 100 g of hexane was added to extract 1,4-dioxane. Methanol was added thereto, and the resulting precipitate was filtered, and the remaining monomer was removed using methanol to obtain a polymer represented by Formula 9a.

[Formula 9a]

Comparative Synthesis Example 1

(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. When the polymerization was completed, the polymer was precipitated in methanol to remove the monomer and low molecular weight to obtain a polymer represented by the following formula (10a).

[Chemical Formula 10a]

Hard mask  Preparation of composition

Example  One

The polymer obtained in Synthesis Example 1 was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)), . 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 Synthesis Example 2 was used in place of the polymer obtained in Synthesis Example 1.

Example  3

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

Example  4

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

* Example 5

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

Example  6

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 6 was used in place of the polymer obtained in Synthesis Example 1.

Example  7

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 7 was used in place of the polymer obtained in Synthesis Example 1.

Example  8

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 8 was used in place of the polymer obtained in Synthesis Example 1.

Example  9

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 9 was used in place of the polymer obtained in Synthesis 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 Synthesis Example 1 was used instead of the polymer obtained in Synthesis Example 1.

Rating 1: Awareness of corrosion  evaluation

Hard mask compositions (polymer content: 9.5%) according to Examples 1 to 9 and Comparative Example 1 were coated on a silicon wafer by a spin-on coating method on a patterned silicon wafer. Then, a thin film was formed by heat treatment at 400 ° C for 120 seconds, and then the thickness of the thin film formed 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 1.

Bulk etch rate (Å / sec) N ₂ / O ₂ etch CFx etch Example 1 23.6 25.1 Example 2 23.5 25.3 Example 3 23.2 25.3 Example 4 23.6 25.4 Example 5 23.5 25.2 Example 6 23.4 25.4 Example 7 23.7 25.5 Example 8 23.3 25.4 Example 9 23.7 25.7 Comparative Example 1 28.4 30.2

Referring to Table 1, the thin films formed from the hard mask compositions according to Examples 1 to 9 had a low etching rate for N ₂ / O ₂ mixed gas and CF x gas as compared with the thin films formed from the hard mask composition according to Comparative Example 1 .

From these results, it can be seen that the hard mask composition according to Examples 1 to 9 has higher corrosion resistance than the hard mask composition according to Comparative Example 1.

Evaluation 2: Evaluation of planarization characteristics

A hard mask composition (polymer content: 5%) according to Examples 1 to 9 and Comparative Example 1 was spin-on-coated on a patterned silicon wafer and heat treatment was performed at 400 ° C for 120 seconds to observe a planarization property Respectively.

The planarization characteristics were measured by measuring the thickness of the hard mask layer from the image of the pattern cross section observed with the SEM and numerically represented by the formula 2 shown in Figure 1. The planarization characteristic is better as the difference between h1 and h2 is smaller, And the planarization characteristic is excellent.

The results are shown in Table 2.

Planarization characteristics Example 1 9.8 Example 2 10.2 Example 3 10.6 Example 4 9.9 Example 5 10.2 Example 6 9.8 Example 7 9.7 Example 8 10.1 Example 9 10.4 Comparative Example 1 13.2

Referring to Table 1, the thin film formed from the hard mask composition according to Examples 1 to 9 has a low level of the planarization characteristic according to Equation 2, as compared with the thin film formed from the hard mask composition according to Comparative Example 1, .

Evaluation 3: Evaluation of heat resistance

The hard mask composition (10.0% by weight) according to Examples 1 to 9 and Comparative Example 1 was spin-coated on a silicon wafer, and then heat-treated at 240 캜 for 1 minute to measure the thickness of a thin film thickness meter of K- Respectively. Thereafter, the substrate was heat-treated at 400 ° C for 2 minutes, and then its thickness was measured again. From the thickness of the film measured at the two temperatures, the degree of relative heat resistance of the hard mask film was numerically calculated by calculating the thin film thickness reduction ratio based on the following equation (3).

The results are shown in Table 3.

[Equation 3]

Thin film thickness reduction ratio = (thin film thickness after baking at 240 占 폚 - thin film thickness after baking at 400 占 폚) / (thin film thickness after baking at 240 占 폚) X100 (%)

Thin film thickness reduction rate (%) Example 1 15.7 Example 2 12.3 Example 3 12.1 Example 4 18.7 Example 5 17.5 Example 6 17.2 Example 7 15.9 Example 8 16.5 Example 9 16.9 Comparative Example 1 32

Referring to Table 1, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 9 has a smaller thickness reduction rate at 400 ° C than the thin film formed from the hard mask composition according to Comparative Example 1.

From the results, it can be seen that the hard mask composition according to Examples 1 to 9 has a high heat resistance even at a high temperature of 400 ° C because of the high degree of crosslinking of the thin film as compared with the hard mask composition according to Comparative Example 1.

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 (17)

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

In Formula 1,
A is a substituted or unsubstituted carbon ring group selected from the following Group 2,
B is any one of the groups listed in Group 1 below,
* Is the connection point.
Provided that when the carbon ring group includes a pentagonal ring portion and the nitrogen atom (N) is contained as a hetero atom in the pentagonal ring, the carbon ring group includes at least two hetero atoms.
[Group 1]

In the group 1,
Ar ¹ to Ar ⁴ each independently represent a substituted or unsubstituted C6 to C30 aryl group,
R ¹¹ to R ¹⁴ each independently represent a hydroxyl group, a thioyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted 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, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted A C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,
g to j are each independently an integer of 0 to 2,
L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,
m is an integer of 1 to 3,
* Is the connection point.
[Group 2]

In the group 2,
Z ¹ and Z ¹² are O, S, Te or Se,
Z ² , Z ⁵ , Z ⁶ and Z ⁹ are NR ^a , O, S, Te or Se,
Z ³ to Z ⁴ , Z ⁷ to Z ⁸ , Z ¹⁰ to Z ¹¹ and Z ¹³ to Z ²³ are N,
R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxyl group, a halogen atom, or a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 alkenyl group, .
However, the connection point in the group 2 is not limited. The method of claim 1,
Wherein said heteroatom is N, O, S, Te or Se. delete The method of claim 1,
In the group 1, Ar ¹ to Ar ⁴ each independently represent a substituted or unsubstituted ring group selected from the following Group 3:
[Group 3]

However, the connection point in the group 3 is not limited. The method of claim 1,
A polymer comprising any one of the structural units represented by the following formulas (1-1) to (1-8)
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

In the above formulas 1-1 to 1-8,
Z ¹⁰¹ and Z ¹⁰⁴ are N,
Z ¹⁰² is O, S, Te or Se,
Z ¹⁰³ is NR ^a , O, S, Te or Se,
Wherein R ^a and R ¹⁰¹ are selected from the group consisting of hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aryl An alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxy group, a halogen Atoms or combinations thereof,
* Is the connection point. The method of claim 1,
Wherein the polymer has a weight average molecular weight of 500 to 20,000. A polymer comprising a structural unit represented by the following formula (1), and
menstruum
: ≪ / RTI >
[Chemical Formula 1]

In Formula 1,
A is a substituted or unsubstituted carbon ring group selected from the following Group 2,
B is any one of the groups listed in Group 1 below,
* Is the connection point.
Provided that when the carbon ring group includes a pentagonal ring portion and the nitrogen atom (N) is contained as a hetero atom in the pentagonal ring, the carbon ring group includes at least two hetero atoms.
[Group 1]

In the group 1,
Ar ¹ to Ar ⁴ each independently represent a substituted or unsubstituted C6 to C30 aryl group,
R ¹¹ to R ¹⁴ each independently represent a hydroxyl group, a thioyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted 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, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted A C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,
g to j are each independently an integer of 0 to 2,
L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,
m is an integer of 1 to 3,
* Is the connection point.
[Group 2]

In the group 2,
Z ¹ and Z ¹² are O, S, Te or Se,
Z ² , Z ⁵ , Z ⁶ and Z ⁹ are NR ^a , O, S, Te or Se,
Z ³ to Z ⁴ , Z ⁷ to Z ⁸ , Z ¹⁰ to Z ¹¹ and Z ¹³ to Z ²³ are N,
R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxyl group, a halogen atom, or a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 alkenyl group, .
However, the connection point in the group 2 is not limited. 8. The method of claim 7,
Wherein said heteroatom is N, O, S, Te or Se. delete 8. The method of claim 7,
Wherein Ar ¹ to Ar ⁴ in the group 1 are each independently a substituted or unsubstituted ring group selected from the following group 3:
[Group 3]

However, the connection point in the group 3 is not limited. 8. The method of claim 7,
Wherein the polymer comprises any one of structural units represented by the following Formulas 1-1 to 1-8:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

In the above formulas 1-1 to 1-8,
Z ¹⁰¹ and Z ¹⁰⁴ are N,
Z ¹⁰² is O, S, Te or Se,
Z ¹⁰³ is NR ^a , O, S, Te or Se,
Wherein R ^a and R ¹⁰¹ are selected from the group consisting of hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aryl An alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxy group, a halogen Atoms or combinations thereof,
* Is the connection point. 8. The method of claim 7,
Wherein the polymer has a weight average molecular weight of 500 to 20,000. 8. The method of claim 7,
Wherein the polymer is contained in an amount of 0.1% by weight to 50% by weight based on the total amount of the organic film composition. Providing a layer of material over the substrate,
Applying the organic film composition according to any one of claims 7, 8 and 10 to 13 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
≪ / RTI > The method of claim 14,
Wherein the step of applying the organic film composition is performed by a spin-on coating method. The method of claim 14,
Further comprising forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer. The method of claim 14,
Wherein the heat treatment is performed at a temperature of 100 ° C to 500 ° C.

Images