KR101848343B1 - Polymer, organic layer composition, organic layer, and method of forming patterns - Google Patents

Abstract

There is provided a polymer comprising a first portion represented by Formula 1 and a second portion comprising a substituted or unsubstituted C6 to C60 ring group, a substituted or unsubstituted C6 to C60 heterocyclic group, or a combination thereof .
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, an organic film prepared from the organic film composition, 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 an organic film that simultaneously satisfies both mechanical properties and film flatness.

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

According to one embodiment, a second moiety comprising a first moiety represented by formula 1 and a substituted or unsubstituted C6 to C60 ring group, a substituted or unsubstituted C6 to C60 heterocyclic group, or a combination thereof: ≪ / RTI >

[Chemical Formula 1]

In Formula 1,

X is phosphorus (P), nitrogen (N), boron (B), or P = O,

Y ¹ and Y ² are each independently hydrogen or a moiety comprising at least one substituted or unsubstituted benzene ring, Y ¹ and Y ² Is a moiety comprising at least one substituted or unsubstituted benzene ring,

Y ³ is a moiety comprising at least one substituted or unsubstituted benzene ring,

* Is the connection point.

The polymer may be a substituted or unsubstituted aldehyde compound containing at least one of phosphorus (P), nitrogen (N), and boron (B), and a substituted or unsubstituted C6 to C60 ring group, A C6 to C60 heterocyclic group, and the like.

And the second moiety may be a ring group in which any one selected from the following Group 1 is substituted or unsubstituted.

[Group 1]

However, the connection point in the group 1 is not limited.

The second moiety may be a substituted or unsubstituted heterocyclic group selected from any one of the following Group 2.

[Group 2]

In the group 2,

Z ¹ to Z ³ are each independently C═O, oxygen (O), sulfur (S), CR ^a R ^b , NR ^c , or combinations thereof wherein R ^a to R ^c are each independently hydrogen, Or an unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof.

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

The second moiety may comprise at least two substituted or unsubstituted benzene rings.

When Y ¹ to Y ³ in the general formula (1) are moieties each independently containing a substituted or unsubstituted benzene ring, Y ¹ and Y ³ , Y ² and Y ³ Or Y ¹ and Y ² may be connected to each other to form a ring.

The first moiety may be represented by any one of the following formulas (1-1) to (1-5).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In the above Formulas 1-1 to 1-5,

X is phosphorus (P), nitrogen (N), boron (B), or P = O,

Each of R ¹ to R ³ independently represents 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 C1 to C30 alkoxy Group, or a combination thereof,

* Is the connection point.

The polymer may be represented by any one of the following formulas (2) to (6).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas 2 to 6,

X is phosphorus (P), nitrogen (N), boron (B), or P = O,

Z ³¹ to Z ³⁴ each independently represent C═O, oxygen (O), sulfur (S), CR ^b R ^c , NR ^d , or combinations thereof wherein R ^b to R ^d are each independently hydrogen, Or an unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,

R ⁴ to R ⁸ each independently represents a hydroxyl group, a thionyl 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 C1 to C30 alkoxy Group, or a combination thereof,

n is an integer from 2 to 200,

* 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 an organic film in which the above-mentioned organic film composition is cured to be formed.

The organic layer may include a hard mask layer.

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 present invention provides a novel polymer that has excellent corrosion resistance and good solubility characteristics and is applicable 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 a hydrogen atom in the compound is replaced by a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano 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 cyano group, A C 1 to C 30 arylalkyl group, a C 7 to C 30 arylalkyl group, a C 1 to C 30 alkoxy group, a C 1 to C 20 heteroalkyl group, a C 2 to C 20 heteroaryl group, a C 3 to C 20 heteroarylalkyl group, a C 3 to C 30 cycloalkyl group, C3 to C15 monocyclic alkenyl groups, C6 to C15 cycloalkynyl groups, C2 to C30 heterocycloalkyl groups, and combinations thereof.

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

Further, a group derived from any compound herein refers to a group formed by substitution of at least one hydrogen in the compound. For example, a monovalent group derived from a compound A means a monovalent group formed by substituting one hydrogen in the A compound. For example, a monovalent group derived from a benzene group is a phenyl group. Further, the term "bivalent group derived from A compound" means a bivalent group in which two hydrogen atoms in A compound are substituted to form two connecting points. For example, a divalent group derived from a benzene group becomes a phenylene group.

Polymers according to one embodiment are described below.

The polymer according to one embodiment comprises a first portion represented by Formula 1 below and a second portion comprising a substituted or unsubstituted C6 to C60 ring group, a substituted or unsubstituted C6 to C60 heterocyclic group, ≪ / RTI >

[Chemical Formula 1]

In Formula 1,

X is phosphorus (P), nitrogen (N), boron (B), or P = O,

Y ¹ and Y ² are each independently hydrogen or a moiety comprising at least one substituted or unsubstituted benzene ring, Y ¹ and Y ² Is a moiety comprising at least one substituted or unsubstituted benzene ring,

Y ³ is a moiety comprising at least one substituted or unsubstituted benzene ring,

* Is the connection point.

First, the first part will be described.

The first portion represented by Formula 1 has a structure in which X is a hetero atom and two or three substituents (Y ¹ , Y ² , and Y ³ ) are connected to the core portion.

In Formula 1, Y ¹ , Y ² , and Y ³ each independently represent a moiety including at least one substituted or unsubstituted benzene ring. Here, the term " moiety including at least one substituted or unsubstituted benzene ring " includes not only a substituted or unsubstituted aromatic ring group, but also a ring group formed by bonding substituted or unsubstituted aromatic ring groups.

In one embodiment, Y ¹ , Y ² , and Y ³ are each independently selected from substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted Substituted or unsubstituted pyrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted benzopyrilylene, substituted or unsubstituted coronene, substituted or unsubstituted triphenylene, substituted or unsubstituted phenanthrene, Corannulene, and substituted or unsubstituted chrysene. However, the present invention is not limited thereto.

As another example, when Y ¹ to Y ³ in the general formula (1) are moieties each independently including a substituted or unsubstituted benzene ring, Y ¹ and Y ³ , Y ² and Y ³ Or Y ¹ and Y ² may be connected to each other to form a ring, for example, Y ¹ and Y ³ , Y ² and Y ³ Or Y ¹ and Y ² may be connected to each other to form a ring. ^Two different groups selected from Y ¹ , Y ² and Y ³ which are connected to each other to form a ring may be a ring group formed by bonding together aromatic ring groups. Herein, "ring group formed by bonding aromatic ring groups to each other" means that either one of the aromatic rings is directly or indirectly connected to any one of the other aromatic rings.

The first portion may be a monovalent group derived from a substituted or unsubstituted aldehyde compound containing at least one of phosphorus (P), nitrogen (N), and boron (B). The aldehyde compound refers to a compound containing an aldehyde group in its structure.

For example, the polymer may be a substituted or unsubstituted aldehyde compound (also referred to as a first compound) comprising at least one of phosphorus (P), nitrogen (N), and boron (B) To C60 cyclic group, and a substituted or unsubstituted C6 to C60 heterocyclic group (also referred to as a second compound). In the polymer, the first portion may be derived from the first compound, and the second portion may be derived from the second compound.

The heteroatom such as phosphorus (P), nitrogen (N), or boron (B) contained in the first compound not only acts as a reducing agent during the condensation reaction but also acts as a flame retardant after the formation of the polymer, It is possible to improve the alertness. In addition, since the polymer contains a hetero atom such as nitrogen or oxygen, the polarity is increased, and excellent solubility can be ensured.

For example, the first moiety may be represented by any one of the following formulas (1-1) to (1-5), but is not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In the above Formulas 1-1 to 1-5,

X is phosphorus (P), nitrogen (N), boron (B), or P = O,

Each of R ¹ to R ³ independently represents 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 C1 to C30 alkoxy Group, or a combination thereof,

* Is the connection point.

Hereinafter, the second part will be described.

The second moiety comprises a substituted or unsubstituted C6 to C60 ring group, a substituted or unsubstituted C6 to C60 heterocyclic group, or a combination thereof.

For example, the second moiety may be a ring group in which any one of the following Group 1 is substituted or unsubstituted, but is not limited thereto.

[Group 1]

However, the connection point in the group 1 is not limited.

For example, the second moiety may be a polycyclic ring system comprising at least two substituted or unsubstituted benzene rings. Thereby further securing the rigid characteristics of the polymer.

For example, the second moiety may be a substituted or unsubstituted heterocyclic group selected from the following Group 2, but is not limited thereto.

[Group 2]

In the group 2,

Z ¹ to Z ³ are each independently C═O, oxygen (O), sulfur (S), CR ^a R ^b , NR ^c , or combinations thereof wherein R ^a to R ^c are each independently hydrogen, Or an unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof.

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

For example, the second moiety may comprise at least one nitrogen atom, for example in the group 2 Z ¹ is NRc, wherein each R ^c is independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, A halogen atom, or a combination thereof, but is not limited thereto.

The polymer according to one embodiment includes the above-described first and second portions, and may be represented by, for example, any one of the following Formulas (2) to (6), but is not limited thereto.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas 2 to 6,

X is phosphorus (P), nitrogen (N), boron (B), or P = O,

Z ³¹ to Z ³⁴ each independently represent C═O, oxygen (O), sulfur (S), CR ^b R ^c , NR ^d , or combinations thereof wherein R ^b to R ^d are each independently hydrogen, Or an unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,

R ⁴ to R ⁸ each independently represents a hydroxyl group, a thionyl 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 C1 to C30 alkoxy Group, or a combination thereof,

n is an integer from 2 to 200,

* 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, as the crosslinking agent having at least two crosslinking substituents, for example, methoxymethylated glycoluril, butoxymethylated glyceryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy Methylated benzoguanamine, a methoxymethylated urea, a butoxymethylated urea, a methoxymethylated thioether, or a methoxymethylated thioether.

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

(21.84 g, 0.1 mol), 6- (phenylamino) -2-naphthaldehyde (24.75 g, 0.1 mol) and p-toluenesulfonic acid monohydrate (19.04 g, 0.1 mol) were added to a 500 ml flask equipped with a thermometer, a condenser and a mechanical stirrer. mol), and 1,4-dioxane (196.9 g) were added thereto, followed by stirring at 120 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,000 to 3,000. When the reaction was completed, the procedure of adding tetrahydrofuran and ethyl acetate and removing the acid catalyst with distilled water was repeated three times. Ethyl acetate was then added to extract and decompress the organic layer. Then 50 g of tetrahydrofuran was added and precipitated into 300 g of hexane to remove the 1,4-dioxane and the remaining monomers to give the polymer represented by formula (Ia) (Mw: 2,300).

[Formula 1a]

Synthetic example  2

5.11-dihydroindolo [3,2-b] carbazole (25.65 g, 0.1 mol), 4- (phenylphosphino) benzaldehyde (29.06 g, 0.1 mol), p-toluenesulfonic acid acid monohydrate (19.04 g, 0.1 mol) and 1,4-dioxane (221.2 g) were added thereto, followed by stirring at 120 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,000 to 3,000. When the reaction was completed, the procedure of adding tetrahydrofuran and ethyl acetate and removing the acid catalyst with distilled water was repeated three times. Ethyl acetate was then added to extract the organic layer and decompression. Then 50 g of tetrahydrofuran was added and precipitated into 300 g of hexane, 1,4-dioxane and the remaining monomer were removed to obtain the polymer represented by formula (1b) (Mw: 2150).

[Chemical Formula 1b]

Synthetic example  3

2-naphthol (14.43 g, 0.1 mol), 6 - (6-methoxynaphthalen-2-yl) (phenyl) amino) -2-naphthaldehyde (40.38 g, 0.1 mol) in a 500 ml flask equipped with a thermometer, condenser and mechanical stirrer ), p-toluenesulfonic acid monohydrate (19.04 g, 0.1 mol) and 1,4-dioxane (221.6 g) were added and stirred at 120 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,000 to 3,000. When the reaction was completed, the procedure of adding tetrahydrofuran and ethyl acetate and removing the acid catalyst with distilled water was repeated three times. Ethyl acetate was then added to extract the organic layer and decompression. Then, 50 g of tetrahydrofuran was added and precipitated in 300 g of hexane, 1,4-dioxane and the remaining monomer were removed to obtain the polymer represented by formula (1c) (Mw: 2930).

[Chemical Formula 1c]

Synthetic example  4

Benzo [g] naphtho [2,1-b] carbazole (15.88 g, 0.05 mol) and 4- (naphthalen-2-yl (phenyl) phosphoryl) benzaldehyde were added to a 500 ml flask equipped with a thermometer, a condenser and a mechanical stirrer 17.83 g, 0.05 mol), p-toluenesulfonic acid monohydrate (9.52 g, 0.05 mol) and 1,4-dioxane (129.7 g) were added and stirred at 120 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,000 to 3,000. When the reaction was completed, the procedure of adding tetrahydrofuran and ethyl acetate and removing the acid catalyst with distilled water was repeated three times. Ethyl acetate was then added to extract the organic layer and decompression. Then 30 g of tetrahydrofuran was added and precipitated in 200 g of hexane to remove the 1,4-dioxane and the remaining monomer to obtain a polymer represented by the formula (1d) (Mw: 2410).

≪ RTI ID = 0.0 &

Synthetic example  5

(8.37 g, 0.05 mol), 12,12-dimethyl-7- (naphthalen-1-yl) -7,12-dihydrobenzo [a] acridine-3- After adding carbaldehyde (20.69 g, 0.05 mol), p-toluenesulfonic acid monohydrate (9.52 g, 0.05 mol) and 1,4-dioxane (115.7 g), the mixture was stirred at 120 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,000 to 3,000. When the reaction was completed, the procedure of adding tetrahydrofuran and ethyl acetate and removing the acid catalyst with distilled water was repeated three times. Ethyl acetate was then added to extract the organic layer and decompression. Then 30 g of tetrahydrofuran was added and precipitated in 200 g of hexane to remove 1,4-dioxane and the remaining monomer to obtain a polymer represented by the formula (1e) (Mw: 2000).

[Formula 1e]

Comparative Synthetic Example  One

(21.84 g, 0.1 mol), anthracene-9-carbaldehyde (20.64 g, 0.1 mol), p-toluenesulfonic acid monohydrate (19.04 g, 0.1 mol), and a mixture of water and ethanol were placed in a 500 ml flask equipped with a thermometer, a condenser and a mechanical stirrer 1,4-Dioxane (184.6 g) was added and the mixture was stirred at 120 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,000 to 3,000. When the reaction was completed, the process of removing the acid catalyst with distilled water after adding tetrahydrofuran and ethyl acetate was repeated three times. Ethyl acetate was then added to extract the organic layer and decompression. Then 50 g of tetrahydrofuran was added and precipitated into 300 g of hexane and 1,4-dioxane and the remaining monomer were removed to give the polymer represented by formula A (Mw: 2480).

(A)

Comparative Synthetic Example  2

(25.65 g, 0.1 mol), anthracene-9-carbaldehyde (20.64 g, 0.1 mol) and p-toluenesulfonic acid (25.0 g) were added to a 500 ml flask equipped with a thermometer, condenser and mechanical stirrer monohydrate (19.04 g, 0.1 mol), and 1,4-dioxane (196 g) were added, followed by stirring at 120 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,000 to 3,000. When the reaction was completed, the procedure of adding tetrahydrofuran and ethyl acetate and removing the acid catalyst with distilled water was repeated three times. Ethyl acetate was then added to extract the organic layer and decompression. Then 50 g of tetrahydrofuran was added and precipitated into 300 g of hexane and 1,4-dioxane and the remaining monomer were removed to obtain the polymer represented by the formula (B) (Mw: 2180).

[Chemical Formula B]

Comparative Synthetic Example  3

2-naphthol (14.43 g, 0.1 mol), Perylene-1-carbaldehyde (28.06 g, 0.1 mol), p-toluenesulfonic acid monohydrate (19.04 g, 0.1 mol), 1 , And 4-dioxane (184.57 g) were added thereto, followed by stirring at 120 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,000 to 3,000. When the reaction was completed, the procedure of adding tetrahydrofuran and ethyl acetate and removing the acid catalyst with distilled water was repeated three times. Ethyl acetate was then added to extract the organic layer and decompression. Then 50 g of tetrahydrofuran was added and precipitated into 300 g of hexane and 1,4-dioxane and the remaining monomer were removed to give the polymer represented by formula C (Mw: 2810).

≪ RTI ID = 0.0 &

Comparative Synthetic Example  4

Benzo [g] naphtho [2,1-b] carbazole (15.88 g, 0.05 mol), Pyrene-1-carbaldehyde (11.52 g, 0.05 mol), p- toluenesulfonic acid monohydrate (9.52 g, 0.05 mol) and 1,4-dioxane (110.77 g) were added, followed by stirring at 120 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,000 to 3,000. When the reaction was completed, the procedure of adding tetrahydrofuran and ethyl acetate and removing the acid catalyst with distilled water was repeated three times. Ethyl acetate was then added to extract the organic layer and decompression. Then 30 g of tetrahydrofuran was added and precipitated into 200 g of hexane and the 1,4-dioxane and the remaining monomer were removed to obtain the polymer represented by the formula (D) (Mw: 2220).

[Chemical Formula D]

Comparative Synthetic Example  5

Carbazole (8.37 g, 0.05 mol), perylene-3-carbaldehyde (14.03 g, 0.05 mol), p-toluenesulfonic acid monohydrate (9.52 g, 0.05 mol), 1, 4-Dioxane (95.74 g) was added and the mixture was stirred at 120 占 폚. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,000 to 3,000. When the reaction was completed, the procedure of adding tetrahydrofuran and ethyl acetate and removing the acid catalyst with distilled water was repeated three times. Ethyl acetate was then added to extract the organic layer and decompression. 30 g of tetrahydrofuran was then added and precipitated into 200 g of hexane and 1,4-dioxane and the remaining monomer were removed to give the polymer represented by formula E (Mw: 2190).

(E)

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 resin was adjusted to 1.0 wt% to 15.0 wt% with respect to the total weight of the hard mask composition, depending on the desired 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.

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.

Comparative Example  2

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 2 was used in place of the polymer obtained in Synthesis 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 Synthesis Example 3 was used in place of the polymer obtained in Synthesis Example 1.

Comparative Example  4

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

Comparative Example  5

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

Rating 1: Awareness of corrosion  evaluation

The hard mask composition according to Examples 1 to 5 and Comparative Examples 1 to 5 was applied on a silicon wafer to a thickness of 4,000 Å by a spin-on coating method, and then heat-treated at 400 ° C. for 2 minutes on a hot plate to form a thin film The thickness of the formed thin film was measured.

Subsequently, the thin film was dry-etched for 60 seconds using a N ₂ / O ₂ mixed gas, and then the thickness of the thin film was measured again. 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).

[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 mixed gas) Example 1 20.18 Example 2 19.85 Example 3 22.06 Example 4 20.27 Example 5 21.33 Comparative Example 1 22.49 Comparative Example 2 25.42 Comparative Example 3 24.37 Comparative Example 4 23.56 Comparative Example 5 24.8

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 lower etching rate than the thin film formed from the hard mask composition according to Comparative Examples 1 to 5.

From this, it can be seen that the hard mask composition according to Examples 1 to 5 has higher corrosion resistance of the thin film as compared with the hard mask composition according to Comparative Examples 1 to 5.

Evaluation 2: Evaluation of gap-fill and planarization characteristics

The hard mask composition according to Examples 1 to 5 and Comparative Examples 1 to 5 was spin-on-coated on the patterned silicon wafer and heat-treated at 400 ° C for 120 seconds, and then the gap-fill characteristic And planarization characteristics were observed. The hard mask compositions according to Examples 1 to 5 and Comparative Examples 1 to 5 were adjusted to have a solid content of 1700 Å in thickness on a bare wafer.

The gap-fill characteristic was determined by observing the pattern section with a scanning electron microscope (SEM) to determine whether voids were generated. The planarization characteristic was measured by measuring the thickness of the hard mask layer from the image of the pattern section observed by SEM, And expressed by the following formula 2. The planarization characteristic is better as the difference between h1 and h2 is smaller, and the smaller the value is, the better the planarization characteristic is.

The results are shown in Table 2.

_{Gapfil  characteristic
( aspect ratio
(1: 5)) aspect ratio
(1: 2) aspect ratio
(1:15)} Example 1 4.28 66.43 void None Example 2 5.15 74.32 void None Example 3 5.73 76.55 void None Example 4 4.64 70.70 void None Example 5 6.68 78.11 void None Comparative Example 1 10.61 89.44 void occurrence Comparative Example 2 10.87 88.18 void None Comparative Example 3 11.51 90.65 void occurrence Comparative Example 4 12.47 93.28 void occurrence Comparative Example 5 14.06 98.83 void occurrence

 Referring to Table 2, when the hard mask composition according to Examples 1 to 5 was used, the degree of planarization was excellent and the pattern depth was deep (aspect ratio 1 : ≪ / RTI > 5), voids were not observed, indicating excellent gap-fill characteristics.

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 (24)

A polymer represented by any one of the following formulas (2) to (6):
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas 2 to 6,
X is phosphorus (P), nitrogen (N), boron (B), or P = O,
Z ³¹ to Z ³⁴ each independently represent C═O, oxygen (O), sulfur (S), CR ^b R ^c , NR ^d , or combinations thereof wherein R ^b to R ^d are each independently hydrogen, Or an unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
R ⁴ to R ⁸ each independently represents a hydroxyl group, a thionyl 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 C1 to C30 alkoxy Group, or a combination thereof,
n is an integer from 2 to 200,
* Is the connection point. delete delete delete delete delete delete delete The method of claim 1,
Wherein the polymer has a weight average molecular weight of 500 to 20,000. A polymer represented by any one of the following formulas (2) to (6), and
menstruum
≪ / RTI >
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas 2 to 6,
X is phosphorus (P), nitrogen (N), boron (B), or P = O,
Z ³¹ to Z ³⁴ each independently represent C═O, oxygen (O), sulfur (S), CR ^b R ^c , NR ^d , or combinations thereof wherein R ^b to R ^d are each independently hydrogen, Or an unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
R ⁴ to R ⁸ each independently represents a hydroxyl group, a thionyl 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 C1 to C30 alkoxy Group, or a combination thereof,
n is an integer from 2 to 200,
* Is the connection point. delete delete delete delete delete delete delete 11. The method of claim 10,
Wherein the polymer has a weight average molecular weight of 500 to 20,000. 11. The method of claim 10,
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. An organic film formed by curing an organic film composition according to any one of claims 10, 18 and 19. 20. The method of claim 20,
Wherein the organic film comprises a hard mask layer. Providing a layer of material over the substrate,
Applying the organic film composition according to any one of claims 10, 18 and 19 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 22,
Wherein the step of applying the organic film composition is performed by a spin-on coating method. The method of claim 22,
Further comprising forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.

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