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

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

[0001] The present invention provides a polymer composition for manufacturing a hard mask and a method for manufacturing a semiconductor device using the same.

[0002] 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.

[0003] The hardmask pattern may be a photoresist pattern formed through a photolithography process including exposure and development processes, or may be formed by etching a hardmask film formed on a substrate using the above-described photoresist pattern as a mask. In this case, due to the limitations of the exposure equipment's resolution, there are limitations in miniaturizing the hardmask pattern and the semiconductor device pattern. To overcome these limitations and achieve high integration of semiconductor devices, a method of forming a hardmask pattern using spacer patterning technology has been proposed.

[0004] 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.

[0005] 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.

[0006] [Chemical Formula 1]

[0007]

[0008] [Chemical Formula 2]

[0009]

[0010] [Chemical Formula 3]

[0011]

[0012] [Chemical Formula 4]

[0013]

[0014] [Chemical Formula 5]

[0015]

[0016] [Chemical Formula 6]

[0017]

[0018] In the above chemical formula 1, the R1 is selected from the group consisting of the chemical formula 2 or the chemical formula 3, the R2 or the R3 are each independently selected from the group consisting of the chemical formulas 4 to 6, the R4 and the 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, the n is one natural number from 1 to 30, the m is one natural number from 1 to 30,

[0019] In the above chemical formula 2, the above chemical formula 3, the above chemical formula 4, the above chemical formula 5 and the above 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 the 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] In a polymer composition for manufacturing a hard mask according to one embodiment, the coating thickness may exceed 15000 Å.

[0025] In a polymer composition for manufacturing a hard mask according to one embodiment, the filling depth may exceed 300 nm.

[0026] In a polymer composition for manufacturing a hard mask according to one embodiment, the coating thickness weighted filling depth is 0.45 μm. 2 , and the weighted filling depth of the coating thickness may be a product of the coating thickness and the filling depth.

[0027] In a polymer composition for manufacturing a hard mask according to one embodiment, a repeating unit represented by the following chemical formula 7 may be included.

[0028] [Chemical Formula 7]

[0029]

[0030] In the above chemical formula 7, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0031] In a polymer composition for manufacturing a hard mask according to one embodiment, a repeating unit represented by the following chemical formula 8 may be included.

[0032] [Chemical Formula 8]

[0033]

[0034] In the above chemical formula 8, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0035] In a polymer composition for manufacturing a hard mask according to one embodiment, a repeating unit represented by the following chemical formula 9 may be included.

[0036] [Chemical Formula 9]

[0037]

[0038] In the above chemical formula 9, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0039] In a polymer composition for manufacturing a hard mask according to one embodiment, a repeating unit represented by the following chemical formula 10 may be included.

[0040] [Chemical Formula 10]

[0041]

[0042] In the above chemical formula 10, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0043] In a polymer composition for manufacturing a hard mask according to one embodiment, a repeating unit represented by the following chemical formula 11 may be included.

[0044] [Chemical Formula 11]

[0045]

[0046] In the above chemical formula 11, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0047] In a polymer composition for manufacturing a hard mask according to one embodiment, a repeating unit represented by the following chemical formula 12 may be included.

[0048] [Chemical Formula 12]

[0049]

[0050] In the above chemical formula 12, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0051] In a polymer composition for manufacturing a hard mask according to one embodiment, a repeating unit represented by the following chemical formula 13 may be included.

[0052] [Chemical Formula 13]

[0053]

[0054] In the above chemical formula 13, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0055] In a polymer composition for manufacturing a hard mask according to one embodiment, a repeating unit represented by the following chemical formula 14 may be included.

[0056] [Chemical Formula 14]

[0057]

[0058] In the above chemical formula 14, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0059] In a polymer composition for manufacturing a hard mask according to one embodiment, a solvent may be further included.

[0060] 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 polymerizing the monomer, wherein the composition for manufacturing a hard mask comprises a polymer including a repeating unit represented by the above-described chemical formula 1.

[0061] 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.

[0062] 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: coating a polymer composition on the etching target layer to form a polymer composition layer; and curing the polymer composition, wherein the polymer composition includes a polymer including a repeating unit represented by the above-described chemical formula 1.

[0063] 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.

[0064] In addition, the polymer may 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 an embodiment may have a coating thickness exceeding about 15,000 Å. In addition, the polymer composition for manufacturing a hard mask according to an embodiment may have a filling depth exceeding about 300 nm. In addition, the polymer composition for manufacturing a hard mask according to an embodiment may have a filling depth of about 0.45 μm. 2 The coating thickness may have a weighted fill depth exceeding .

[0065] 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 in a fine pattern.

[0066] 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 using the polymer composition according to the embodiment can have an appropriate selectivity with respect to the etching target layer.

[0067] Figures 1 to 5 are drawings illustrating a process for manufacturing a semiconductor device according to an embodiment.

[0068] The invention is described in detail below through implementation examples. The implementation examples are not limited to the content disclosed below and may be modified in various ways as long as the spirit of the invention remains unchanged.

[0069] In this specification, when a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0070] In addition, all numerical ranges indicating the physical properties, dimensions, etc. of the components described in this specification should be understood to be modified by the term “about” in all cases unless otherwise specified.

[0071] In this specification, the terms "first," "second," "primary," and "secondary" are used to describe various components, and the components are not limited by the terms. The terms are used solely to distinguish one component from another.

[0072] A polymer composition for manufacturing a hard mask according to an embodiment comprises an aromatic ring-containing polymer.

[0073] The above aromatic ring-containing polymer can be represented by the following chemical formula 1.

[0074] [Chemical Formula 1]

[0075]

[0076] In the above chemical formula 1, R1 may be selected from a group consisting of the following chemical formula 2 or the following chemical formula 3.

[0077] 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.

[0078] In addition, in the above chemical formula 1, the R4 and the R5 may be independently selected from a 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.

[0079] 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.

[0080] In the above chemical formula 1, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0081] In the above chemical formula 1, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

[0082] In the above chemical formula 1, n may be a natural number from 1 to 15, and m may be a natural number from 1 to 15.

[0083] [Chemical Formula 2]

[0084]

[0085] In the above chemical formula 2, the R6, the R7 or the R8 may be independently selected from a 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.

[0086] 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.

[0087] [Chemical Formula 3]

[0088]

[0089] In the above chemical formula 3, R9 or R10 may be independently selected from a 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.

[0090] 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.

[0091] Additionally, in the chemical formula 1, the chemical formula 2 or the chemical formula 3, the R5, the R8 or the R10 may be a substituted or unsubstituted benzyl group.

[0092] [Chemical Formula 4]

[0093]

[0094] In the above chemical formula 4, R11 can be independently selected from a 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.

[0095] In the above chemical formula 4, R11 may be hydrogen or a benzyl group.

[0096] [Chemical Formula 5]

[0097]

[0098] In the above chemical formula 5, R12 can be independently selected from a 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.

[0099] In the above chemical formula 5, R12 may be hydrogen or a benzyl group.

[0100] [Chemical Formula 6]

[0101]

[0102] In the above chemical formula 6, R13 can be independently selected from a 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.

[0103] In the above chemical formula 6, R13 may be hydrogen or a benzyl group.

[0104] The above aromatic ring-containing polymer can be represented by the following chemical formula 7.

[0105] [Chemical Formula 7]

[0106]

[0107] In the above chemical formula 7, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0108] In the above chemical formula 7, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

[0109] In the above chemical formula 7, n may be a natural number from 1 to 15, and m may be a natural number from 1 to 15.

[0110] The above aromatic ring-containing polymer can be represented by the following chemical formula 8.

[0111] [Chemical Formula 8]

[0112]

[0113] In the above chemical formula 8, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0114] In the above chemical formula 8, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

[0115] In the above chemical formula 8, n may be a natural number from 1 to 15, and m may be a natural number from 1 to 15.

[0116] The above aromatic ring-containing polymer can be represented by the following chemical formula 9.

[0117] [Chemical Formula 9]

[0118]

[0119] In the above chemical formula 9, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0120] In the above chemical formula 9, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

[0121] In the above chemical formula 9, n may be a natural number from 1 to 15, and m may be a natural number from 1 to 15.

[0122] The above aromatic ring-containing polymer can be represented by the following chemical formula 10.

[0123] [Chemical Formula 10]

[0124]

[0125] In the above chemical formula 10, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0126] In the above chemical formula 10, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

[0127] In the above chemical formula 10, n may be a natural number from 1 to 15, and m may be a natural number from 1 to 15.

[0128] The above aromatic ring-containing polymer can be represented by the following chemical formula 11.

[0129] [Chemical Formula 11]

[0130]

[0131] In the above chemical formula 11, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0132] In the above chemical formula 11, n may be a natural number from 1 to 25, and m may be a natural number from 1 to 25.

[0133] In the above chemical formula 11, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

[0134] The above aromatic ring-containing polymer can be represented by the following chemical formula 12.

[0135] [Chemical Formula 12]

[0136]

[0137] In the above chemical formula 12, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0138] In the above chemical formula 12, n may be a natural number from 1 to 25, and m may be a natural number from 1 to 25.

[0139] In the above chemical formula 12, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

[0140] The above aromatic ring-containing polymer can be represented by the following chemical formula 13.

[0141] [Chemical Formula 13]

[0142]

[0143] In the above chemical formula 13, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0144] In the above chemical formula 13, n may be a natural number from 1 to 25, and m may be a natural number from 1 to 25.

[0145] In the above chemical formula 13, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

[0146] The above aromatic ring-containing polymer can be represented by the following chemical formula 14.

[0147] [Chemical Formula 14]

[0148]

[0149] In the above chemical formula 14, n may be a natural number from 1 to 30, and m may be a natural number from 1 to 30.

[0150] In the above chemical formula 14, n may be a natural number from 1 to 25, and m may be a natural number from 1 to 25.

[0151] In the above chemical formula 14, n may be a natural number from 1 to 20, and m may be a natural number from 1 to 20.

[0152] The weight average molecular weight of the aromatic ring-containing polymer may be about 3250 g / mol to about 4200 g / mol. The weight average molecular weight of the aromatic ring-containing polymer may be about 2500 g / mol to about 8000 g / mol. The weight average molecular weight of the aromatic ring-containing polymer may be about 3000 g / mol to about 5000 g / mol. The weight average molecular weight of the aromatic ring-containing polymer may be about 3250 g / mol to about 5000 g / mol. The weight average molecular weight of the aromatic ring-containing polymer may be about 3400 g / mol to about 4200 g / mol. The weight average molecular weight of the aromatic ring-containing polymer may be about 3500 g / mol to about 4200 g / mol.

[0153] The above weight average molecular weight can be measured by gel permeation chromatography (GPC). The 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 polymers are dissolved in tetrahydrofuran (THF), and can be measured and converted to a polystyrene-equivalent weight average molecular weight.

[0154] 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.

[0155] The above aromatic ring-containing polymer can be prepared by the following process.

[0156] First, in order to manufacture the aromatic ring-containing polymer, a monomer is prepared. The monomer may be selected from at least one group consisting of a pyrene-based compound, a fluorene-based compound, a benzene-based compound, a naphthalene-based compound, or a phenol-based compound.

[0157] The monomer may include 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxy pyrene, and benzaldehyde.

[0158] The monomer may include 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxy Pyrene, and 2-Naphthaldehyde.

[0159] The above monomer may include 4-phenylphenol, 1-hydroxy pyrene, and benzaldehyde.

[0160] The above monomers may include 4-phenylphenol, 1-hydroxypyrene and benzaldehyde.

[0161] The above monomer may include 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxypyrene, benzaldehyde, and benzylalcohol.

[0162] The above monomer may include 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxypyrene, 2-naphthalaldehyde, and benzyl alcohol.

[0163] The above monomers may include 4-phenylphenol, 1-hydroxypyrene, benzaldehyde, and benzyl alcohol.

[0164] The above monomers may include 4-phenylphenol, 1-hydroxypyrene, naphthalaldehyde, and benzyl alcohol.

[0165] The above monomer can be polymerized in the presence of a thermal oxidizer. The thermal oxidizer can include p-toluenesulfonic acid monohydrate.

[0166] 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.

[0167] The polymer formed through the above polymerization process can be neutralized by pyridine or the like.

[0168] 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.

[0169] Accordingly, the aromatic-containing polymer can be formed.

[0170] A 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, methyl-3-methoxypropionate (MMP), or ethyl-3-ethoxypropionate (EEP).

[0171] The content of the organic solvent may be about 40 wt% to about 90 wt% based on the entire composition. The content of the organic solvent may be about 50 wt% to about 80 wt% based on the entire composition. The content of the organic solvent may be about 55 wt% to about 75 wt% based on the entire composition.

[0172] 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 selected from the group consisting of an oxetanyl group, an oxazoline group, a cyclocarbonate group, an alcohol silyl group, an amino methyl group, an alkoxymethyl group, an aziridinyl group, a methyl group, an isocyanate group, an alkoxymethylamino group, or a polyfunctional epoxy group.

[0173] 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, hydroxyl groups of the polymer. The curing properties of the hard mask composition may be further enhanced by the crosslinking agent.

[0174] Examples of the crosslinking agent include melamine, amino resin, glycoluril compound, or bisepoxy compound.

[0175] 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), 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 compound and a melamine compound may also be used as a crosslinking agent.

[0176] The polymer composition for manufacturing a hard mask according to the embodiment may further include a catalyst.

[0177] The catalyst may include an acid catalyst or a basic catalyst.

[0178] The above acid catalyst may be a thermally activated acid catalyst. An example of an acid catalyst may be an organic acid such as p-toluene sulfonic acid. A thermal acid generator (TAG) compound may also be used as the acid catalyst.

[0179] Examples of the above thermal acid generator system catalyst include pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.

[0180] As the above basic catalyst, any one selected from among ammonium hydroxide represented by NH4OH or NR4OH (R is an alkyl group) can be used.

[0181] 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, based on about 100 parts by weight of the aromatic ring-containing polymer.

[0182] When the polymer composition for manufacturing a hard mask according to the embodiment includes the catalyst, the content of the catalyst may be about 0.001 parts by weight to about 5 parts by weight, preferably about 0.1 parts by weight to about 2 parts by weight, and more preferably about 0.1 parts by weight to about 1 part by weight, based on about 100 parts by weight of the aromatic ring-containing polymer.

[0183] 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.

[0184] 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. Examples of the surfactant include, but are not limited to, alkylbenzenesulfonates, alkylpyridinium salts, polyethylene glycols, and quaternary ammonium salts. The content of the surfactant may be, for example, about 0.1 to about 10 parts by weight based on about 100 parts by weight of the aromatic ring-containing polymer.

[0185] The 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 aromatic ring-containing polymer may have a solubility of about 59 wt% or more in propylene glycol monomethyl ether acetate. The aromatic ring-containing polymer may have a maximum solubility of about 80 wt% in propylene glycol monomethyl ether acetate.

[0186] The above solubility can be measured by the following method.

[0187] 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 precipitates, the added solid content can be derived from the solubility.

[0188] Since the 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.

[0189] 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.

[0190] 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 thus formed is the coating thickness. In other words, the thickness of the hard mask formed under the following conditions can be the coating thickness.

[0191] The above coating conditions may be a wafer rotation speed of about 1000 rpm and a coating time of about 10 seconds.

[0192] Additionally, the drying conditions may be a temperature of about 250°C and a drying time of about 1 minute.

[0193] Additionally, the above curing conditions may be a temperature of about 400°C and a baking time of about 2 minutes.

[0194] Since the polymer composition for manufacturing a hard mask according to the embodiment has a coating thickness within 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.

[0195] The polymer composition for manufacturing a hard mask according to an embodiment may have a filling depth. In the polymer composition for manufacturing a hard mask according to an embodiment, the filling depth may exceed about 300 nm. In the polymer composition for manufacturing a hard mask according to an embodiment, the filling depth may exceed about 330 nm. In the polymer composition for manufacturing a hard mask according to an embodiment, the filling depth may exceed about 360 nm. In the polymer composition for manufacturing a hard mask according to an embodiment, the filling depth may exceed about 390 nm. The maximum value of the filling depth may be about 5000 nm.

[0196] The above filling depth can be measured by the following method.

[0197] 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.

[0198] 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.

[0199] At this time, the filling depth is the depth of the hard mask filled in the line pattern.

[0200] 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.

[0201] The polymer composition for manufacturing a hard mask according to the embodiment may have a coating thickness weighted filling depth.

[0202] In a polymer composition for manufacturing a hard mask according to an embodiment, the coating thickness weighted filling depth is 0.45 μm. 2In the polymer composition for manufacturing a hard mask according to an embodiment, the coating thickness weighted filling depth is 0.45 μm. 2 In the polymer composition for manufacturing a hard mask according to an embodiment, the coating thickness weighted filling depth is 0.55 μm. 2 In the polymer composition for manufacturing a hard mask according to an embodiment, the coating thickness weighted filling depth is 0.6 μm. 2 may exceed.

[0203] The above coating thickness weighted filling depth may be a value obtained by multiplying the coating thickness and the filling depth.

[0204] The above coating thickness weighted filling depth can be expressed by the following equation 1.

[0205] [Formula 1]

[0206] Coating thickness weighted fill depth = Coating thickness × Fill depth

[0207] 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, it can be uniformly coated on a fine pattern while forming a thick hard mask.

[0208] A method for manufacturing a semiconductor device according to an embodiment includes 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.

[0209] In addition, the step of forming the hard mask includes a step of coating a polymer composition on the etching target layer to form a polymer composition layer; and a step of curing the polymer composition.

[0210] Figures 1 to 5 are drawings illustrating a manufacturing process of a semiconductor device according to an embodiment.

[0211] 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.

[0212] 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.

[0213] 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.

[0214] The polymer composition may 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.

[0215] 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.

[0216] Additionally, the etching target layer may be selected from at least one group consisting of an oxide film, a nitride film, a silicon film, or a metal film.

[0217] 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.

[0218] The step of exposing the above photoresist film can be performed using, for example, ArF, KrF, or EUV. After exposure, a heat treatment process can be performed at about 200 to 500°C. In the development process, a developer such as a tetramethyl ammonium hydroxide (TMAH) aqueous solution can be used.

[0219] As illustrated 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).

[0220] The thickness of the above hard mask pattern may be from about 10 nm to about 10,000 nm.

[0221] 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 group consisting of CF4, CHF3, SF6, Cl2, BCl3, and O2. 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.

[0222] The above etching target layer can be formed into a plurality of patterns. The plurality of patterns can be diverse, such as metal patterns, semiconductor patterns, and insulator patterns. For example, it can be applied as various patterns in a semiconductor integrated circuit device.

[0223] The above etching target layer contains the 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 target film may be formed by various methods such as sputtering, electron beam deposition, chemical vapor deposition, or physical vapor deposition. The etching target film may be formed by, for example, chemical vapor deposition.

[0224] As illustrated 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).

[0225] As shown in Fig. 5, the hard mask pattern (12a) is removed.

[0226] Accordingly, an etching pattern (11a) is formed on the semiconductor substrate (10), and a semiconductor device can be manufactured through a subsequent process.

[0227] The polymer composition for manufacturing a hard mask according to the embodiment comprises a polymer having a structure represented by Chemical Formula 1 as described above. In addition, the polymer may have an appropriate weight average molecular weight.

[0228] In addition, the polymer may 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 an embodiment may have a coating thickness exceeding about 15,000 Å. In addition, the polymer composition for manufacturing a hard mask according to an embodiment may have a filling depth exceeding about 300 nm. In addition, the polymer composition for manufacturing a hard mask according to an embodiment may have a filling depth of about 0.45 μm. 2 The coating thickness may have a weighted fill depth exceeding .

[0229] 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 in a fine pattern.

[0230] 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 using the polymer composition according to the embodiment can have an appropriate selectivity with respect to the etching target layer.

[0231] 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.

[0232] The above contents are explained in more detail with the following examples. However, the following examples are only intended to illustrate the present invention, and the scope of the examples is not limited to these examples.

[0233] Manufacturing example

[0234] A1: 9,9-bis(4-hydroxyphenyl)fluorene

[0235] A2: 4-phenylphenol

[0236] B: 1-hydroxy pyrene

[0237] C1: Benzaldehyde

[0238] C2: 2-Naphthaldehyde

[0239] D: Benzyl alcohol

[0240] E: 1,4-Benzenedimethanol

[0241] Manufacturing Example 1

[0242] 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 acid 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.

[0243] Manufacturing Examples 2 to 10

[0244] As described in Table 1 below, the monomer content was varied. The remaining process was referenced to Manufacturing Example 1.

[0245] Classification A1 (parts by weight) A2 (parts by weight) B (parts by weight) C1 (parts by weight) C2 (parts by weight) D (parts by weight) E (parts by weight) Manufacturing example 1103.742.7 Manufacturing example 2103.746.68 Manufacturing example 3107.699.35 Manufacturing example 4107.6913.76 Manufacturing example 5103.749.343.17 Manufacturing example 6103.7413.743.17 Manufacturing example 7107.699.523.17 Manufacturing example 8107.6913.743.17 Manufacturing example 91012.17 Manufacturing example 107.6913.7

[0246] Example 1

[0247] 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.

[0248] Examples 2 to 8 and Comparative Examples 1 and 2

[0249] As described in Table 2 of the higi, the contents of polymer and organic solvent were varied.

[0250] Classification Polymer type Polymer content (weight parts) PGMEA (weight parts) Example 1 Manufacturing example 17030 Example 2 Manufacturing example 27030 Example 3 Manufacturing example 37030 Example 4 Manufacturing example 47030 Example 5 Manufacturing example 57030 Example 6 Manufacturing example 67030 Example 7 Manufacturing example 77030 Example 8 Manufacturing example 87030 Comparative example 1 Manufacturing example 97030 Comparative example 2 Manufacturing example 107030

[0251] Evaluation example

[0252] Evaluation Example 1. Solubility

[0253] The polymers prepared in the manufacturing examples were continuously added to propylene glycol monomethyl ether acetate (PGMEA) at room temperature and stirred. The solids content at the time of precipitation of the polymer was derived from the solubility.

[0254] Evaluation Example 2. Weight average molecular weight

[0255] 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 polystyrene-converted weight average molecular weights.

[0256] Evaluation Example 3. Coating Thickness

[0257] While a 30-inch silicon wafer was rotating at about 1000 rpm, the polymer compositions according to the examples and comparative examples were coated on the upper surface of the silicon wafer using the material coating track equipment (Tokyo Electron Co., Ltd. TEL-MARK 8 / 8 inch Wafer), and then baked at 400°C. The thickness of the hard mask formed on the silicon wafer was measured as the coating thickness using VM-120 of DNS Co., Japan.

[0258] Evaluation Example 4. Filling Depth

[0259] In the same manner as Evaluation Example 3, the polymer composition for the hard mask was coated on a pattern si wafer having a L / S Depth of 4000Å and a CD size of 40nm, and then baked, and the filling depth within the pattern was measured.

[0260] Evaluation Example 5. Etching Speed

[0261] The substrate on which the hard mask was formed was mounted on a dry etching device, and the hard mask was etched using an etching gas. Under the same conditions, a silicon wafer including an amorphous carbon layer was etched. The etching rates were compared relative to the 100% etching rate of the amorphous carbon layer.

[0262] 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.

[0263] As shown in Table 3 below, the weight average molecular weight and solubility of the polymers manufactured in the manufacturing examples were derived.

[0264] ClassificationWeight average molecular weight (g / mol)Solubility (wt%)Manufacturing example 1377050Manufacturing example 2374050Manufacturing example 3369045Manufacturing example 4376045Manufacturing example 5393060Manufacturing example 6399060Manufacturing example 7381050Manufacturing example 8365050Manufacturing example 9320010Manufacturing example 1028405

[0265] 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.

[0266] Division Coating thickness (Å) Filling depth (nm) Etching rate (%) Example 1 2 3 0 0 4 0 0 8 0 Example 2 2 2 0 1 0 4 0 0 7 5 Example 3 1 9 3 6 0 4 0 0 7 9 Example 4 1 8 9 9 0 4 0 0 7 2 Example 5 2 5 9 1 0 4 0 0 8 4 Example 6 2 4 1 0 4 0 0 8 0 Example 7 2 3 4 5 0 4 0 0 8 3 Example 8 2 2 1 8 0 4 0 0 8 6 Comparative example 1 2 3 5 0 2 5 0 8 2 Comparative example 2 6 8 0 2 3 0 7 3

[0267] As described in Tables 3 and 4 above, the polymer compositions according to the examples have improved coatability and etching speed.

Claims

1. 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 above chemical formula 1, the R1 is selected from the group consisting of the chemical formula 2 or the chemical formula 3, the R2 or the R3 are each independently selected from the group consisting of the chemical formulas 4 to 6, the R4 and the 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, the n is one natural number from 1 to 30, the m is one natural number from 1 to 30, In the above chemical formula 2, the above chemical formula 3, the above chemical formula 4, the above chemical formula 5 and the above 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 the 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.

2. A polymer composition for manufacturing a hard mask, wherein the polymer has a weight average molecular weight of 3250 g / mol to 4200 g / mol in the first paragraph.

3. A polymer composition for manufacturing a hard mask in claim 1, wherein R4, R6, R7 and R9 are hydroxy groups, and R11, R12 and R13 are hydrogen.

4. A polymer composition for manufacturing a hard mask, wherein in the third paragraph, R5, R8 or R10 is a substituted or unsubstituted benzyl group.

5. A polymer composition for manufacturing a hard mask, wherein the polymer has a solubility of 30 wt% or more in propylene glycol monomethyl ether acetate in the first paragraph.

6. A polymer composition for manufacturing a hard mask having a coating thickness exceeding 15,000 Å in the first paragraph.

7. A polymer composition for manufacturing a hard mask having a filling depth exceeding 300 nm in the 6th paragraph.

8. In paragraph 7, the coating thickness weighted filling depth is 0.45㎛ 2 exceeds, A polymer composition for manufacturing a hard mask, wherein the above coating thickness weighted filling depth is a value obtained by multiplying the above coating thickness and the above filling depth.

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

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

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

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

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

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

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

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

17. A composition for manufacturing a hard mask further comprising a solvent according to claim 1.

18. A step of preparing at least one monomer selected from the group consisting of pyrene compounds, fluorene compounds, benzene compounds, naphthalene compounds, or phenol compounds; 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 above chemical formula 1, the R1 is selected from the group consisting of the chemical formula 2 or the chemical formula 3, the R2 or the R3 are each independently selected from the group consisting of the chemical formulas 4 to 6, the R4 and the 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, the n is one natural number from 1 to 30, the m is one natural number from 1 to 30, In the above chemical formula 2, the above chemical formula 3, the above chemical formula 4, the above chemical formula 5 and the above 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 the 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.

19. 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 to about 8 hours in the 18th paragraph.

20. 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 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 above chemical formula 1, the R1 is selected from the group consisting of the chemical formula 2 or the chemical formula 3, the R2 or the R3 are each independently selected from the group consisting of the chemical formulas 4 to 6, the R4 and the 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, the n is one natural number from 1 to 30, the m is one natural number from 1 to 30, In the above chemical formula 2, the above chemical formula 3, the above chemical formula 4, the above chemical formula 5 and the above 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 the 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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