WO2025053656A1 - Polymer composition for manufacturing hard mask and method for manufacturing semiconductor device - Google Patents

Abstract

An embodiment provides: a polymer composition for manufacturing a hard mask, the polymer composition comprising a polymer containing a repeating unit represented by chemical formula 1; a method for manufacturing a semiconductor device by etching a semiconductor substrate using same; and a method for preparing a polymer composition for manufacturing a hard mask.

Description

Polymer composition for manufacturing hard mask and method for manufacturing semiconductor device

The present invention provides a polymer composition for manufacturing a hard mask and a method for manufacturing a semiconductor device using the same.

In a typical semiconductor device pattern formation process, a hard mask pattern is formed on an underlying layer (e.g., a silicon film, an insulating film, or a conductive film), and then the underlying layer is etched using the hard mask pattern as a mask to form a desired pattern.

The hard mask pattern may be a photoresist pattern formed through a photolithography process including an exposure and development process, or may be formed by etching a hard mask film formed on a substrate using the above-described photoresist pattern as a mask. In this case, due to the limitation of the resolution of the exposure equipment, there are limitations in miniaturizing the hard mask pattern and the pattern of the semiconductor device. In order to overcome this limitation and achieve high integration of the semiconductor device, a method of forming a hard mask pattern using a spacer patterning technique has been proposed.

The present invention provides a polymer composition for manufacturing a hard mask having an improved coating thickness, an improved filling depth, and an appropriate etching rate, and a method for manufacturing a semiconductor device using the same.

A polymer composition for manufacturing a hard mask according to an embodiment comprises a polymer including a repeating unit represented by the following chemical formula 1.

[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical formula 6]

In the chemical formula 1, R1 is selected from the group consisting of the chemical formula 2 or the chemical formula 3, R2 or R3 are each independently selected from the group consisting of the chemical formulas 4 to 6, R4 and R5 are each independently selected from the group consisting of hydrogen, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms, or an aldehyde group having 1 to 7 carbon atoms, n is one natural number from 1 to 30, m is one natural number from 1 to 30,

In the chemical formula 2, the chemical formula 3, the chemical formula 4, the chemical formula 5 and the chemical formula 6, the R6, the R7, the R8, the R9, the R10, the R11, the R12 or the R13 are each independently selected from a group consisting of hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms or an aldehyde group having 1 to 7 carbon atoms.

In a polymer composition for manufacturing a hard mask according to one embodiment, the weight average molecular weight of the polymer may be 3250 g/mol to 4200 g/mol.

In a polymer composition for manufacturing a hard mask according to one embodiment, R4, R6, R7 and R9 may be hydroxy groups, and R11, R12 and R13 may be hydrogen.

In a polymer composition for manufacturing a hard mask according to one embodiment, R5, R8 or R10 may be a substituted or unsubstituted benzyl group.

In a polymer composition for manufacturing a hard mask according to one embodiment, the polymer may have a solubility of 30 wt% or more in propylene glycol monomethyl ether acetate.

In a polymer composition for manufacturing a hard mask according to one embodiment, the coating thickness may exceed 15,000 Å.

In a polymer composition for manufacturing a hard mask according to one embodiment, the filling depth may exceed 300 nm.

In a polymer composition for manufacturing a hard mask according to one embodiment, a coating thickness weighted filling depth exceeds 0.45 μm ² , and the coating thickness weighted filling depth may be a value obtained by multiplying the coating thickness and the filling depth.

In a polymer composition for manufacturing a hard mask according to one embodiment, the polymer composition may include a repeating unit represented by the following chemical formula 7.

[Chemical formula 7]

In the chemical formula 7 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In a polymer composition for manufacturing a hard mask according to one embodiment, the polymer composition may include a repeating unit represented by the following chemical formula 8.

[Chemical formula 8]

In the chemical formula 8 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In a polymer composition for manufacturing a hard mask according to one embodiment, the polymer composition may include a repeating unit represented by the following chemical formula 9.

[Chemical formula 9]

In the chemical formula 9 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In a polymer composition for manufacturing a hard mask according to one embodiment, the polymer composition may include a repeating unit represented by the following chemical formula 10.

[Chemical Formula 10]

In the chemical formula 10 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In one embodiment, a polymer composition for manufacturing a hard mask may include a repeating unit represented by the following chemical formula 11.

[Chemical Formula 11]

In the chemical formula 11 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In a polymer composition for manufacturing a hard mask according to one embodiment, the polymer composition may include a repeating unit represented by the following chemical formula 12.

[Chemical Formula 12]

In the chemical formula 12 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In a polymer composition for manufacturing a hard mask according to one embodiment, the polymer composition may include a repeating unit represented by the following chemical formula 13.

[Chemical Formula 13]

In the chemical formula 13, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In one embodiment, a polymer composition for manufacturing a hard mask may include a repeating unit represented by the following chemical formula 14.

[Chemical Formula 14]

In the chemical formula 14 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In a polymer composition for manufacturing a hard mask according to one embodiment, a solvent may be further included.

A method for manufacturing a composition for manufacturing a hard mask according to an embodiment comprises the steps of preparing at least one monomer selected from the group consisting of a pyrene-based compound, a fluorene-based compound, a benzene-based compound, a naphthalene-based compound, or a phenol-based compound; and a step of polymerizing the monomer, wherein the composition for manufacturing a hard mask comprises a polymer including a repeating unit represented by the chemical formula 1.

In a method for manufacturing a polymer composition for manufacturing a hard mask according to one embodiment, the monomer can be polymerized at a temperature of about 90° C. to about 140° C. for about 3 hours to about 8 hours.

A method for manufacturing a semiconductor device according to an embodiment comprises the steps of: preparing a semiconductor substrate including an etching target layer; forming a hard mask on the semiconductor substrate; patterning the hard mask; and patterning the etching target layer, wherein the step of forming the hard mask comprises the steps of coating a polymer composition on the etching target layer to form a polymer composition layer; and curing the polymer composition, wherein the polymer composition comprises a polymer including a repeating unit represented by the chemical formula 1 above.

A polymer composition for manufacturing a hard mask according to an embodiment comprises a polymer having a structure represented by chemical formula 1. In addition, the polymer may have an appropriate weight average molecular weight.

In addition, the polymer can have a solubility in propylene glycol monomethyl ether acetate of greater than about 30 wt %. The polymer composition for manufacturing a hard mask according to the embodiment can have a coating thickness of greater than about 15000 Å. In addition, the polymer composition for manufacturing a hard mask according to the embodiment can have a filling depth of greater than about 300 nm. In addition, the polymer composition for manufacturing a hard mask according to the embodiment can have a coating thickness weighted filling depth of greater than about 0.45 μm ² .

Accordingly, the polymer composition for manufacturing a hard mask according to the embodiment can be uniformly and thickly coated on a semiconductor substrate. In addition, the polymer composition for manufacturing a hard mask according to the embodiment can be uniformly filled even in a fine pattern.

Therefore, the polymer composition for manufacturing a hard mask according to the embodiment can accurately etch the etching target layer while appropriately protecting the etching target layer. In addition, the hard mask manufactured by the polymer composition according to the embodiment can have an appropriate selectivity with respect to the etching target layer.

Figures 1 to 5 are drawings illustrating a process for manufacturing a semiconductor device according to an embodiment.

Hereinafter, the invention will be described in detail through implementation examples. The implementation examples are not limited to the contents disclosed below and may be modified in various forms as long as the gist of the invention is not changed.

In this specification, when a part is said to "include" a certain component, this does not mean that other components are excluded, but rather that other components may be included, unless otherwise specifically stated.

In addition, it should be understood that all numerical ranges indicating the physical property values, dimensions, etc. of the components described in this specification are modified by the term “about” in all cases unless otherwise specified.

In this specification, the terms first, second, primary, secondary, etc. are used to describe various components, and the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

A polymer composition for manufacturing a hard mask according to an embodiment comprises an aromatic ring-containing polymer.

The above aromatic ring-containing polymer can be represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1, R1 can be selected from a group consisting of the following chemical formula 2 or the following chemical formula 3.

In the above chemical formula 1, the R2 or the R3 can be independently selected from the group consisting of the following chemical formula 4, the following chemical formula 5, or the following chemical formula 6.

In addition, in the chemical formula 1, R4 and R5 may be independently selected from a group consisting of hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms, or an aldehyde group having 1 to 7 carbon atoms.

In the above chemical formula 1, R4 may be a hydroxy group. In the above chemical formula 1, R5 may be hydrogen or a benzyl group.

In the chemical formula 1 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In the chemical formula 1 above, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

In the chemical formula 1 above, n may be a natural number from 1 to 15, and m may be a natural number from 1 to 15.

[Chemical formula 2]

In the above chemical formula 2, the R6, the R7 or the R8 may be independently selected from a group consisting of hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms or an aldehyde group having 1 to 7 carbon atoms.

In the above chemical formula 2, R6 and R7 may be hydroxy groups. In the above chemical formula 2, R8 may be hydrogen or a benzyl group.

[Chemical Formula 3]

In the above chemical formula 3, the R9 or the R10 can be independently selected from a group consisting of hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms, or an aldehyde group having 1 to 7 carbon atoms.

In the above chemical formula 3, R9 may be a hydroxy group. In the above chemical formula 3, R10 may be hydrogen or a benzyl group.

Additionally, in the chemical formula 1, the chemical formula 2 or the chemical formula 3, R5, R8 or R10 may be a substituted or unsubstituted benzyl group.

[Chemical Formula 4]

In the above chemical formula 4, R11 can be independently selected from a group consisting of hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms, or an aldehyde group having 1 to 7 carbon atoms.

In the above chemical formula 4, R11 can be hydrogen or a benzyl group.

[Chemical Formula 5]

In the above chemical formula 5, R12 can be independently selected from a group consisting of hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms, or an aldehyde group having 1 to 7 carbon atoms.

In the above chemical formula 5, R12 can be hydrogen or a benzyl group.

[Chemical formula 6]

In the above chemical formula 6, R13 can be independently selected from a group consisting of hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms, or an aldehyde group having 1 to 7 carbon atoms.

In the above chemical formula 6, R13 can be hydrogen or a benzyl group.

The above aromatic ring-containing polymer can be represented by the following chemical formula 7.

[Chemical formula 7]

In the chemical formula 7 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In the chemical formula 7 above, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

In the chemical formula 7 above, n may be a natural number from 1 to 15, and m may be a natural number from 1 to 15.

The above aromatic ring-containing polymer can be represented by the following chemical formula 8.

[Chemical formula 8]

In the chemical formula 8 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In the chemical formula 8 above, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

In the chemical formula 8 above, n may be a natural number from 1 to 15, and m may be a natural number from 1 to 15.

The above aromatic ring-containing polymer can be represented by the following chemical formula 9.

[Chemical formula 9]

In the chemical formula 9 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In the chemical formula 9 above, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

In the chemical formula 9, n may be a natural number from 1 to 15, and m may be a natural number from 1 to 15.

The above aromatic ring-containing polymer can be represented by the following chemical formula 10.

[Chemical Formula 10]

In the chemical formula 10 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In the chemical formula 10 above, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

In the chemical formula 10, n may be a natural number from 1 to 15, and m may be a natural number from 1 to 15.

The above aromatic ring-containing polymer can be represented by the following chemical formula 11.

[Chemical Formula 11]

In the chemical formula 11 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In the chemical formula 11 above, n may be a natural number from 1 to 25, and m may be a natural number from 1 to 25.

In the chemical formula 11 above, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

The above aromatic ring-containing polymer can be represented by the following chemical formula 12.

[Chemical Formula 12]

In the chemical formula 12 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In the chemical formula 12 above, n may be a natural number from 1 to 25, and m may be a natural number from 1 to 25.

In the chemical formula 12 above, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

The above aromatic ring-containing polymer can be represented by the following chemical formula 13.

[Chemical Formula 13]

In the chemical formula 13, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In the chemical formula 13, n may be a natural number from 1 to 25, and m may be a natural number from 1 to 25.

In the chemical formula 13 above, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

The above aromatic ring-containing polymer can be represented by the following chemical formula 14.

[Chemical Formula 14]

In the chemical formula 14 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

In the chemical formula 14, n may be a natural number from 1 to 25, and m may be a natural number from 1 to 25.

In the chemical formula 14 above, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

The weight average molecular weight of the aromatic ring-containing polymer may be from about 3250 g/mol to about 4200 g/mol. The weight average molecular weight of the aromatic ring-containing polymer may be from about 2500 g/mol to about 8000 g/mol. The weight average molecular weight of the aromatic ring-containing polymer may be from about 3000 g/mol to about 5000 g/mol. The weight average molecular weight of the aromatic ring-containing polymer may be from about 3250 g/mol to about 5000 g/mol. The weight average molecular weight of the aromatic ring-containing polymer may be from about 3400 g/mol to about 4200 g/mol. The weight average molecular weight of the aromatic ring-containing polymer may be from about 3500 g/mol to about 4200 g/mol.

The above weight average molecular weight can be measured by gel permeation chromatography (GPC). The above weight average molecular weight can be measured and converted based on polystyrene. The gel permeation chromatography equipment can be Waters E2695 separations module W/SHC (blue). The above polymers are dissolved in tetrahydrofuran (THF), and can be measured and converted into a polystyrene-converted weight average molecular weight.

Since the aromatic ring-containing polymer has a weight average molecular weight within the above range, the polymer composition for manufacturing a hard mask according to the embodiment can have improved coating properties. In addition, since the aromatic ring-containing polymer has a weight average molecular weight within the above range, the polymer composition for manufacturing a hard mask according to the embodiment can have improved filling properties.

The above aromatic ring-containing polymer can be produced by the following process.

First, in order to manufacture the aromatic ring-containing polymer, a monomer is prepared. The monomer may be selected from at least one of a group consisting of a pyrene-based compound, a fluorene-based compound, a benzene-based compound, a naphthalene-based compound, or a phenol-based compound.

The above monomers may include 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxy Pyrene, and Benzaldehyde.

The above monomers may include 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxy Pyrene, and 2-Naphthaldehyde.

The above monomers may include 4-phenylphenol, 1-hydroxy pyrene, and benzaldehyde.

The above monomers may include 4-phenylphenol, 1-hydroxy pyrene and benzaldehyde.

The above monomers may include 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxypyrene, benzaldehyde, and benzylalcohol.

The above monomers may include 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxypyrene, 2-naphthalaldehyde, and benzyl alcohol.

The above monomers may include 4-phenylphenol, 1-hydroxy pyrene, benzaldehyde and benzyl alcohol.

The above monomers may include 4-phenylphenol, 1-hydroxy pyrene, naphthalaldehyde and benzyl alcohol.

The above monomer can be polymerized in the presence of a thermal oxidizer. The thermal oxidizer can include p-toluenesulfonic acid monohydrate.

The above monomer can be polymerized for about 3 hours to about 8 hours. The above monomer can be polymerized at a temperature of about 90° C. to about 140° C.

The polymer formed through the above polymerization process can be neutralized by pyridine or the like.

Additionally, the neutralized polymer can be purified by using an aqueous hydrochloric acid solution or distilled water, and extracted by using heptane or the like.

Accordingly, the aromatic-containing polymer can be formed.

The polymer composition for manufacturing a hard mask according to an embodiment comprises an organic solvent. The organic solvent may be at least one selected from the group consisting of tetrahydronaphthalene, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, ethyl lactate, propylene glycol n-propyl ether, dimethyl formamide (DMF), gamma-butyrolactone, ethoxyethanol, methoxyethanol, menyl-3-methoxypropionate (MMP), or ethyl-3-ethoxypropionate (EEP).

The content of the organic solvent may be from about 40 wt% to about 90 wt% based on the entire composition. The content of the organic solvent may be from about 50 wt% to about 80 wt% based on the entire composition. The content of the organic solvent may be from about 55 wt% to about 75 wt% based on the entire composition.

The polymer composition for manufacturing a hard mask according to the embodiment may further include a curing agent. The curing agent may include a compound having two or more cross-linking functional groups. The cross-linking functional groups may be at least one selected from the group consisting of an oxetanyl group, an oxazoline group, a cyclocarbonate group, an alcoholisiryl group, an amino methion group or an alkoxymethyl group, an aziridinyl group, a methion group, an isocyanate group, an alkoxymethylamino group or a polyfunctional epoxy group.

The polymer composition for manufacturing a hard mask according to the embodiment may further include a crosslinking agent. The crosslinking agent is capable of crosslinking repeating units of the polymer of the aromatic compound, and may react with, for example, a hydroxyl group of the polymer. By the crosslinking agent, the curing characteristics of the composition for a hard mask may be further enhanced.

Examples of the crosslinking agent include melamine, amino resin, glycoluril compound, or bisepoxy compound.

The crosslinking agent may include, for example, an etherified amino resin, for example, a methylated or butylated melamine (a specific example is N-methoxymethyl-melamine or N-butoxymethyl-melamine) and a methylated or butylated urea resin (a specific example is Cymel U-65 Resin or UFR 80 Resin), a glycoluril derivative, a bis(hydroxymethyl)-p-cresol compound, and the like. In addition, a bisepoxy series compound and a melamine series compound can also be used as a crosslinking agent.

The polymer composition for manufacturing a hard mask according to an embodiment may further include a catalyst.

The catalyst may include an acid catalyst or a basic catalyst.

The acid catalyst may be a heat-activated acid catalyst. An example of the acid catalyst may be an organic acid such as p-toluene sulfonic acid. A compound of the thermal acid generator (TAG) system may also be used as the acid catalyst.

Examples of the above thermal acid generator system catalysts include pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.

As the above basic catalyst, any one selected from among ammonium hydroxide represented by NH ₄ OH or NR ₄ OH (R is an alkyl group) can be used.

When the polymer composition for manufacturing a hard mask according to the embodiment includes the crosslinking agent, the content of the crosslinking agent may be about 1 part by weight to about 30 parts by weight, preferably about 5 parts by weight to about 20 parts by weight, and more preferably about 5 parts by weight to about 10 parts by weight, relative to about 100 parts by weight of the aromatic ring-containing polymer.

When the polymer composition for manufacturing a hard mask according to an embodiment includes the catalyst, the content of the catalyst may be about 0.001 part by weight to about 5 parts by weight, preferably about 0.1 part by weight to about 2 parts by weight, and more preferably about 0.1 part by weight to about 1 part by weight, based on about 100 parts by weight of the aromatic ring-containing polymer.

Within the content range of the crosslinking agent and the catalyst, the polymer composition for manufacturing a hard mask according to the embodiment can obtain appropriate crosslinking properties without deteriorating etching resistance, heat resistance, and flatness.

The composition for manufacturing a hard mask according to the embodiment may further include a surfactant to improve the surface properties and adhesiveness of the hard mask. As the surfactant, alkylbenzenesulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, etc. may be used, but are not limited thereto. The content of the surfactant may be, for example, about 0.1 part by weight to about 10 parts by weight based on about 100 parts by weight of the aromatic ring-containing polymer.

The above aromatic ring-containing polymer may have solubility in an organic solvent. The aromatic ring-containing polymer may have a solubility of about 30 wt% or more in propylene glycol monomethyl ether acetate. The aromatic ring-containing polymer may have a solubility of about 35 wt% or more in propylene glycol monomethyl ether acetate. The aromatic ring-containing polymer may have a solubility of about 40 wt% or more in propylene glycol monomethyl ether acetate. The aromatic ring-containing polymer may have a solubility of about 44 wt% or more in propylene glycol monomethyl ether acetate. The aromatic ring-containing polymer may have a solubility of about 49 wt% or more in propylene glycol monomethyl ether acetate. The aromatic ring-containing polymer may have a solubility of about 55 wt% or more in propylene glycol monomethyl ether acetate. The above aromatic ring-containing polymer can have a solubility of about 59 wt% or more in propylene glycol monomethyl ether acetate. The above aromatic ring-containing polymer can have a maximum solubility value of about 80 wt% in propylene glycol monomethyl ether acetate.

The above solubility can be measured by the following method.

The aromatic ring-containing polymer is continuously added to propylene glycol monomethyl ether acetate (PGMEA) at room temperature and stirred. When the aromatic ring-containing polymer is precipitated, the added solid content can be derived from the solubility.

Since the above aromatic ring-containing polymer has the increased solubility as described above, the polymer composition for manufacturing a hard mask according to the embodiment can have an increased coating thickness.

In the polymer composition for manufacturing a hard mask according to an embodiment, the coating thickness may exceed 15,000 Å. In the polymer composition for manufacturing a hard mask according to an embodiment, the coating thickness may exceed 20,000 Å. In the polymer composition for manufacturing a hard mask according to an embodiment, the coating thickness may exceed 25,000 Å. In the polymer composition for manufacturing a hard mask according to an embodiment, the maximum value of the coating thickness may be 250,000 Å.

The above coating thickness can be measured by the following method. The polymer composition for manufacturing a hard mask according to the embodiment is spin-coated on a 30-inch silicon wafer, dried, and cured. The average thickness of the hard mask formed in this manner is the above coating thickness. That is, the thickness of the hard mask formed under the following conditions can be the coating thickness.

The above coating conditions may be a wafer rotation speed of about 1000 rpm and a coating time of about 10 seconds.

Additionally, the drying conditions may be a temperature of about 250°C and a drying time of about 1 minute.

Additionally, the curing conditions may be a temperature of about 400°C and a baking time of about 2 minutes.

Since the polymer composition for manufacturing a hard mask according to the embodiment has a coating thickness in the above range, a thick hard mask can be implemented. Accordingly, the polymer composition for manufacturing a hard mask according to the embodiment can efficiently protect an etching target layer and effectively implement a fine pattern.

The polymer composition for manufacturing a hard mask according to an embodiment can have a filling depth. In the polymer composition for manufacturing a hard mask according to an embodiment, the filling depth can exceed about 300 nm. In the polymer composition for manufacturing a hard mask according to an embodiment, the filling depth can exceed about 330 nm. In the polymer composition for manufacturing a hard mask according to an embodiment, the filling depth can exceed about 360 nm. In the polymer composition for manufacturing a hard mask according to an embodiment, the filling depth can exceed about 390 nm. The maximum value of the filling depth can be about 5000 nm.

The above filling depth can be measured by the following method.

First, a silicon wafer is prepared that includes a line pattern having a width of approximately 40 nm, a spacing of 195 nm, and a depth of at least 400 nm.

A polymer composition for manufacturing a hard mask according to an embodiment is coated on the silicon wafer under the above coating conditions. Thereafter, the coated polymer composition is dried under the above drying conditions. Thereafter, the dried polymer composition is baked under the above curing conditions.

At this time, the filling depth is the depth of the hard mask filled in the line pattern.

Since the polymer composition for manufacturing a hard mask according to the embodiment has the above range, the hard mask can be uniformly formed even in a fine pattern.

The polymer composition for manufacturing a hard mask according to an embodiment may have a coating thickness weighted filling depth.

In the polymer composition for manufacturing a hard mask according to an embodiment, the coating thickness weighted filling depth may exceed 0.45 μm ² . In the polymer composition for manufacturing a hard mask according to an embodiment, the coating thickness weighted filling depth may exceed 0.45 μm ² . In the polymer composition for manufacturing a hard mask according to an embodiment, the coating thickness weighted filling depth may exceed 0.55 μm ² . In the polymer composition for manufacturing a hard mask according to an embodiment, the coating thickness weighted filling depth may exceed 0.6 μm ² .

The above coating thickness weighted filling depth may be a value obtained by multiplying the coating thickness and the filling depth.

The above coating thickness weighted filling depth can be expressed by the following mathematical formula 1.

[Formula 1]

Coating thickness weighted fill depth = Coating thickness × Fill depth

Since the polymer composition for manufacturing a hard mask according to the embodiment has a coating thickness weighted filling depth in the range as described above, a thick hard mask can be formed while being uniformly coated on a fine pattern.

A method for manufacturing a semiconductor device according to an embodiment comprises the steps of: preparing a semiconductor substrate including an etching target layer; forming a hard mask on the semiconductor substrate; patterning the hard mask; and patterning the etching target layer.

In addition, the step of forming the hard mask includes the step of coating a polymer composition on the etching target layer to form a polymer composition layer; and the step of curing the polymer composition.

Figures 1 to 5 are drawings illustrating a manufacturing process of a semiconductor device according to an embodiment.

Referring to FIGS. 1 to 5, a polymer composition for manufacturing a hard mask according to an embodiment can be used to manufacture a semiconductor device.

As illustrated in FIG. 1, an etching target layer (11) is formed on a semiconductor substrate (10). Thereafter, a polymer composition for manufacturing a hard mask according to an embodiment is coated on the etching target layer (11), dried, and baked, thereby forming a hard mask (12). Thereafter, a photoresist composition is coated on the hard mask (12). Accordingly, a photoresist film (13) is formed.

The polymer composition is coated on the etching target layer by one selected from spin coating, air spray, electrospray, dip coating, spray coating, doctor blade method, or bar coating.

The above polymer composition can be applied by a spin-on coating method. The coating thickness of the polymer composition is not limited, but may be, for example, from about 10 nm to about 10,000 nm, specifically from about 10 nm to about 1,000 nm.

Additionally, the semiconductor substrate may be selected from the group consisting of a silicon substrate, a glass substrate, a GaN substrate, a silica substrate, a metal substrate, or a polymer substrate.

Additionally, the etching target layer may be selected from at least one of a group consisting of an oxide film, a nitride film, a silicon film, or a metal film.

As shown in Fig. 2, the photoresist film (13) is patterned by a photolithography and development process, and a photoresist pattern (13a) is formed on the hard mask.

The step of exposing the above photoresist film can be performed using, for example, ArF, KrF, or EUV. Then, a heat treatment process can be performed at about 200 to 500°C after exposure. In the development process, a developer such as a tetramethyl ammonium hydroxide (TMAH) aqueous solution can be used.

As shown in Fig. 3, the photoresist pattern (13a) is used as an etching mask, and the hard mask (12) is patterned. Accordingly, a hard mask pattern (12a) is formed on the etching target layer (11).

The thickness of the above hard mask pattern can be from about 10 nm to about 10,000 nm.

In the etching process for forming the above hard mask, an etching gas may be used. The etching gas may be selected from at least one selected from the group consisting of CF ₄ , CHF ₃ , SF ₆ , Cl ₂ , BCl ₃ and O ₂ . According to one embodiment, a mixed gas of C4F8 and CHF3 is used as the etching gas, and the mixing ratio thereof may be a volume ratio of 1:10 to 10:1.

The above etching target layer can be formed into a plurality of patterns. The plurality of patterns can be diverse, such as a metal pattern, a semiconductor pattern, an insulator pattern, etc. For example, it can be applied as various patterns in a semiconductor integrated circuit device.

The above etching target layer contains a material to be ultimately patterned, and may be, for example, a metal layer such as aluminum or copper, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide or silicon nitride. The etching film may be formed by various methods such as sputtering, electron beam deposition, chemical vapor deposition, or physical vapor deposition. The etching film may be formed by, for example, a chemical vapor deposition method.

As shown in Fig. 4, the hard mask pattern (12a) is used as an etching mask, and the etching target layer (11) is patterned. Accordingly, an etching pattern (11a) is formed on the semiconductor substrate (10).

As shown in Fig. 5, the hard mask pattern (12a) is removed.

Accordingly, an etching pattern (11a) is formed on the semiconductor substrate (10), and a semiconductor device can be manufactured through a subsequent process.

The polymer composition for manufacturing a hard mask according to the embodiment comprises a polymer having a structure of chemical formula 1 as described above. In addition, the polymer may have an appropriate weight average molecular weight.

In addition, the polymer can have a solubility in propylene glycol monomethyl ether acetate of greater than about 30 wt %. The polymer composition for manufacturing a hard mask according to the embodiment can have a coating thickness of greater than about 15000 Å. In addition, the polymer composition for manufacturing a hard mask according to the embodiment can have a filling depth of greater than about 300 nm. In addition, the polymer composition for manufacturing a hard mask according to the embodiment can have a coating thickness weighted filling depth of greater than about 0.45 μm ² .

Accordingly, the polymer composition for manufacturing a hard mask according to the embodiment can be uniformly and thickly coated on a semiconductor substrate. In addition, the polymer composition for manufacturing a hard mask according to the embodiment can be uniformly filled even in a fine pattern.

Therefore, the polymer composition for manufacturing a hard mask according to the embodiment can accurately etch the etching target layer while appropriately protecting the etching target layer. In addition, the hard mask manufactured by the polymer composition according to the embodiment can have an appropriate selectivity with respect to the etching target layer.

In addition, since the polymer composition for manufacturing a hard mask according to the embodiment forms a thick hard mask, a thick etching target layer can be easily patterned.

The above contents are explained in more detail by the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited to these examples.

Manufacturing example

A1: 9,9-bis(4-hydroxyphenyl)fluorene

A2: 4-phenylphenol

B: 1-hydroxy pyrene

C1: Benzaldehyde

C2: 2-Naphthaldehyde

D: Benzyl alcohol

E: 1,4-Benzenedimethanol

Manufacturing example 1

About 10 parts by weight of 9,9-bis(4-hydroxyphenyl)fluorene, about 3.74 parts by weight of 1-hydroxypyrene, about 2.7 parts by weight of benzaldehyde, about 8.5 parts by weight of toluene, and about 25 parts by weight of tetralin are charged into a flask and stirred sufficiently at a temperature of about 120°C. Then, about 0.27 parts by weight of p-toluenesulfonic monohydrate is added to the flask and reacted at a temperature of about 120°C for about 5 hours. The reactant is neutralized with pyridine and purified with about 1 wt% aqueous hydrochloric acid solution and distilled water. Thereafter, the purified reactant is extracted with heptane, and an aromatic ring-containing polymer is obtained.

Manufacturing examples 2 to 10

As described in Table 1 below, the monomer content was changed. The remaining process was referenced to Manufacturing Example 1.

division A1
(weight) A2
(weight) B
(weight) C1
(weight) C2
(weight) D
(weight) E
(weight) Manufacturing example 1 10 3.74 2.7 Manufacturing example 2 10 3.74 6.68 Manufacturing example 3 10 7.69 9.35 Manufacturing example 4 10 7.69 13.76 Manufacturing example 5 10 3.74 9.34 3.17 Manufacturing example 6 10 3.74 13.74 3.17 Manufacturing example 7 10 7.69 9.52 3.17 Manufacturing example 8 10 7.69 13.74 3.17 Manufacturing example 9 10 12.17 Manufacturing example 10 7.69 13.7

Example 1

About 70 parts by weight of the polymer obtained in Manufacturing Example 1 and about 30 parts by weight of propylene glycol monomethyl ether acetate were uniformly mixed to produce a polymer composition for manufacturing a hard mask.

Examples 2 to 8 and Comparative Examples 1 and 2

As described in Table 2 of the present invention, the contents of polymer and organic solvent were varied.

division Type of polymer Polymer content
(weight) PGMEA
(weight) Example 1 Manufacturing example 1 70 30 Example 2 Manufacturing example 2 70 30 Example 3 Manufacturing example 3 70 30 Example 4 Manufacturing example 4 70 30 Example 5 Manufacturing example 5 70 30 Example 6 Manufacturing example 6 70 30 Example 7 Manufacturing example 7 70 30 Example 8 Manufacturing example 8 70 30 Comparative Example 1 Manufacturing example 9 70 30 Comparative Example 2 Manufacturing example 10 70 30

Evaluation example

Evaluation Example 1. Solubility

The polymers prepared in the manufacturing examples were continuously added to propylene glycol monomethyl ether acetate (PGMEA) at room temperature and stirred. The solid content when the polymer precipitated was derived from the solubility.

Evaluation Example 2. Weight average molecular weight

The weight average molecular weight of the polymers manufactured in the manufacturing examples was measured by gel permeation chromatography (GPC, Waters E2695 separations module W/SHC (blue)). The polymers were dissolved in tetrahydrofuran (THF) and measured as the polystyrene-converted weight average molecular weight.

Evaluation Example 3. Coating Thickness

While a 30-inch silicon wafer was rotated at about 1000 rpm, polymer compositions according to examples and comparative examples were coated on the upper surface of the silicon wafer using the material coating track equipment (TEL-MARK 8 / 8 inch Wafer, Tokyo Electron Co.), and then baked at 400°C. The thickness of the hard mask formed on the silicon wafer was measured as the coating thickness by VM-120, DNS Co., Japan.

Evaluation Example 4. Filling Depth

In the same manner as Evaluation Example 3, the polymer composition for the hard mask was coated on a pattern si wafer having an L/S Depth of 4000Å and a CD size of 40nm, and then baked, and the filling depth within the pattern was measured.

Evaluation Example 5. Etching Speed

The substrate on which the hard mask was formed was mounted on a dry etching device, and the hard mask was etched with an etching gas. Under the same conditions, a silicon wafer including an amorphous carbon layer was etched. The etching speed was relatively compared based on an etching speed of 100% of the amorphous carbon layer.

The above etching rate measurement was performed using the Nano Comprehensive Technology Institute’s dry etch equipment (Oxford, ICP380) according to the Nano Comprehensive Technology Institute’s standards.

As shown in Table 3 below, the weight average molecular weight and solubility of the polymers manufactured in the manufacturing examples were derived.

division Weight average molecular weight
(g/mol) Solubility
(wt%) Manufacturing example 1 3770 50 Manufacturing example 2 3740 50 Manufacturing example 3 3690 45 Manufacturing example 4 3760 45 Manufacturing example 5 3930 60 Manufacturing example 6 3990 60 Manufacturing example 7 3810 50 Manufacturing example 8 3650 50 Manufacturing example 9 3200 10 Manufacturing example 10 2840 5

As shown in Table 4 below, the coating thickness, filling depth, and etching rate of the polymer compositions manufactured in the examples and comparative examples were derived.

division Coating thickness
(Å) Filling depth
(nm) Etching speed
(%) Example 1 23000 400 80 Example 2 22010 400 75 Example 3 19360 400 79 Example 4 18990 400 72 Example 5 25910 400 84 Example 6 24100 400 80 Example 7 23450 400 83 Example 8 22180 400 86 Comparative Example 1 2350 250 82 Comparative Example 2 680 230 73

As described in Tables 3 and 4 above, the polymer compositions according to the examples have improved coatability and etching speed.

Claims (20)

A polymer composition for manufacturing a hard mask, comprising a polymer comprising a repeating unit represented by the following chemical formula 1. [Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical formula 6]

In the chemical formula 1, R1 is selected from the group consisting of the chemical formula 2 or the chemical formula 3, R2 or R3 are each independently selected from the group consisting of the chemical formulas 4 to 6, R4 and R5 are each independently selected from the group consisting of hydrogen, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms, or an aldehyde group having 1 to 7 carbon atoms, n is one natural number from 1 to 30, m is one natural number from 1 to 30, In the chemical formula 2, the chemical formula 3, the chemical formula 4, the chemical formula 5 and the chemical formula 6, the R6, the R7, the R8, the R9, the R10, the R11, the R12 or the R13 are each independently selected from a group consisting of hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms or an aldehyde group having 1 to 7 carbon atoms. A polymer composition for manufacturing a hard mask, wherein the weight average molecular weight of the polymer in claim 1 is 3250 g/mol to 4200 g/mol. A polymer composition for manufacturing a hard mask, wherein in claim 1, R4, R6, R7 and R9 are hydroxy groups, and R11, R12 and R13 are hydrogen. A polymer composition for manufacturing a hard mask, wherein in claim 3, R5, R8 or R10 is a substituted or unsubstituted benzyl group. A polymer composition for manufacturing a hard mask, wherein in claim 1, the polymer has a solubility of 30 wt% or more in propylene glycol monomethyl ether acetate. A polymer composition for manufacturing a hard mask having a coating thickness exceeding 15,000 Å in the first paragraph. A polymer composition for manufacturing a hard mask having a filling depth exceeding 300 nm in claim 6. In the 7th paragraph, the coating thickness weighted filling depth exceeds 0.45 ㎛ ² , A polymer composition for manufacturing a hard mask, wherein the weighted filling depth of the coating thickness is a product of the coating thickness and the filling depth. A polymer composition for manufacturing a hard mask, comprising a repeating unit represented by the following chemical formula 7 in claim 1. [Chemical formula 7]

In the chemical formula 7 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30. A polymer composition for manufacturing a hard mask, comprising a repeating unit represented by the following chemical formula 8 in claim 1. [Chemical formula 8]

In the chemical formula 8 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30. A polymer composition for manufacturing a hard mask, comprising a repeating unit represented by the following chemical formula 9 in claim 1. [Chemical formula 9]

In the chemical formula 9 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30. A polymer composition for manufacturing a hard mask, comprising a repeating unit represented by the following chemical formula 10 in claim 1. [Chemical Formula 10]

In the chemical formula 10 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30. A polymer composition for manufacturing a hard mask, comprising a repeating unit represented by the following chemical formula 11 in claim 1. [Chemical Formula 11]

In the chemical formula 11 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30. A polymer composition for manufacturing a hard mask, comprising a repeating unit represented by the following chemical formula 12 in claim 1. [Chemical Formula 12]

In the chemical formula 12 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30. A polymer composition for manufacturing a hard mask, comprising a repeating unit represented by the following chemical formula 13 in claim 1. [Chemical Formula 13]

In the chemical formula 13, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30. A polymer composition for manufacturing a hard mask, comprising a repeating unit represented by the following chemical formula 14 in claim 1. [Chemical Formula 14]

In the chemical formula 14 above, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30. In claim 1, a composition for manufacturing a hard mask further comprising a solvent A step of preparing at least one monomer selected from the group consisting of a pyrene compound, a fluorene compound, a benzene compound, a naphthalene compound or a phenol compound; and Comprising a step of polymerizing the above monomer, A method for producing a polymer composition for manufacturing a hard mask, comprising a polymer comprising a repeating unit represented by the following chemical formula 1. [Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical formula 6]

In the chemical formula 1, R1 is selected from the group consisting of the chemical formula 2 or the chemical formula 3, R2 or R3 are each independently selected from the group consisting of the chemical formulas 4 to 6, R4 and R5 are each independently selected from the group consisting of hydrogen, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms, or an aldehyde group having 1 to 7 carbon atoms, n is one natural number from 1 to 30, m is one natural number from 1 to 30, In the chemical formula 2, the chemical formula 3, the chemical formula 4, the chemical formula 5 and the chemical formula 6, the R6, the R7, the R8, the R9, the R10, the R11, the R12 or the R13 are each independently selected from a group consisting of hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms or an aldehyde group having 1 to 7 carbon atoms. A method for producing a polymer composition for manufacturing a hard mask, wherein the monomer is polymerized at a temperature of about 90° C. to about 140° C. for about 3 hours to about 8 hours in the 18th paragraph. A step of preparing a semiconductor substrate including an etching target layer; A step of forming a hard mask on the semiconductor substrate; a step of patterning the above hard mask; and Comprising a step of patterning the above etching target layer, The step of forming the above hard mask is A step of forming a polymer composition layer by coating a polymer composition on the etching target layer; and Comprising a step of curing the above polymer composition, The above polymer composition A method for manufacturing a semiconductor device comprising a polymer comprising a repeating unit represented by the following chemical formula 1. [Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical formula 6]

In the chemical formula 1, R1 is selected from the group consisting of the chemical formula 2 or the chemical formula 3, R2 or R3 are each independently selected from the group consisting of the chemical formulas 4 to 6, R4 and R5 are each independently selected from the group consisting of hydrogen, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms, or an aldehyde group having 1 to 7 carbon atoms, n is one natural number from 1 to 30, m is one natural number from 1 to 30, In the chemical formula 2, the chemical formula 3, the chemical formula 4, the chemical formula 5 and the chemical formula 6, the R6, the R7, the R8, the R9, the R10, the R11, the R12 or the R13 are each independently selected from a group consisting of hydrogen, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 carbon atoms or an aldehyde group having 1 to 7 carbon atoms.

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