Polymer composition for preparing a hard mask and method of manufacturing a semiconductor device

Abstract

Embodiments provide a polymer composition for preparing a hard mask and a method of manufacturing a semiconductor device by etching a semiconductor substrate using the same, and a method of preparing a polymer composition for preparing a hard mask, the polymer composition comprising a polymer including a repeating unit represented by Chemical Formula 1.

Description

Technical Field

[0001] Examples provide polymer compositions for preparing hard masks and methods for manufacturing semiconductor devices using the same. Background Technology

[0002] In the patterning process of conventional semiconductor devices, after a hard mask pattern is formed on the underlying layer (e.g., silicon film, insulating film, or conductive film), the underlying layer is etched using the hard mask pattern as a mask to form the desired pattern.

[0003] Hard mask patterns can be formed by photolithography processes including exposure and development, creating photoresist patterns, or by etching a hard mask film formed on a substrate using the aforementioned photoresist pattern as a mask. In this case, the limitation of the exposure equipment resolution restricts the miniaturization of both the hard mask pattern and the semiconductor device pattern. To overcome this limitation and achieve high integration of semiconductor devices, a scheme using spacer patterning technology to form hard mask patterns has been proposed. Summary of the Invention

[0004] The problem the invention aims to solve The embodiments are intended to provide polymer compositions for preparing hard masks and methods for manufacturing semiconductor devices using the polymer compositions, said polymer compositions having increased coating thickness, increased fill depth and appropriate etching rate.

[0005] means for solving problems The polymer composition for preparing a hard mask in the embodiments comprises a polymer containing repeating units represented by the following chemical formula 1.

[0006] [Chemical Formula 1]

[0007] [Chemical Formula 2]

[0008] [Chemical Formula 3]

[0009] [Chemical Formula 4]

[0010] [Chemical Formula 5]

[0011] [Chemical Formula 6]

[0012] In chemical formula 1, R1 is selected from the group consisting of chemical formula 2 or chemical formula 3; R2 or R3 is independently selected from the group consisting of chemical formulas 4 to 6; R4 and R5 are independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups with 1 to 7 carbon atoms, substituted or unsubstituted aryl groups with 5 to 12 carbon atoms, or aldehyde groups with 1 to 7 carbon atoms; n is a natural number from 1 to 30; and m is a natural number from 1 to 30. In chemical formulas 2, 3, 4, 5, and 6, R6, R7, R8, R9, R10, R11, R12, or R13 are independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 7 carbon atoms, substituted or unsubstituted aryl groups having 5 to 12 carbon atoms, or aldehyde groups having 1 to 7 carbon atoms.

[0013] In one embodiment of the polymer composition for preparing a hard mask, the weight-average molecular weight of the polymer can be from 3250 g / mol to 4200 g / mol.

[0014] In one embodiment of the polymer composition for preparing a hard mask, R4, R6, R7 and R9 may be hydroxyl groups, and R11, R12 and R13 may be hydrogen.

[0015] In one embodiment of the polymer composition for preparing a hard mask, R5, R8, or R10 may be substituted or unsubstituted benzyl groups.

[0016] In one embodiment of the polymer composition for preparing a hard mask, the polymer may have a solubility of more than 30 wt% relative to propylene glycol monomethyl ether acetate.

[0017] In one embodiment of the polymer composition for preparing a hard mask, the coating thickness can exceed 15,000 angstroms.

[0018] In one embodiment of the polymer composition for preparing a hard mask, the filling depth can exceed 300 nm.

[0019] In one embodiment of the polymer composition for preparing a hard mask, the thickness-weighted fill depth of the coating can exceed 0.45 μm. 2 The coating thickness weighted filling depth can be the product of the coating thickness and the filling depth.

[0020] In one embodiment, the polymer composition for preparing a hard mask may contain repeating units represented by the following chemical formula 7.

[0021] [Chemical Formula 7]

[0022] In the chemical formula 7, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0023] In one embodiment, the polymer composition for preparing a hard mask may contain repeating units represented by the following chemical formula 8.

[0024] [Chemical Formula 8]

[0025] In the chemical formula 8, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0026] In one embodiment, the polymer composition for preparing a hard mask may contain repeating units represented by the following chemical formula 9.

[0027] [Chemical Formula 9]

[0028] In the chemical formula 9, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0029] In one embodiment, the polymer composition for preparing a hard mask may contain repeating units represented by the following chemical formula 10.

[0030] [Chemical Formula 10]

[0031] In the chemical formula 10, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0032] In one embodiment, the polymer composition for preparing a hard mask may contain repeating units represented by the following chemical formula 11.

[0033] [Chemical Formula 11]

[0034] In the chemical formula 11, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0035] In one embodiment, the polymer composition for preparing a hard mask may contain repeating units represented by the following chemical formula 12.

[0036] [Chemical Formula 12]

[0037] In the chemical formula 12, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0038] In one embodiment, the polymer composition for preparing a hard mask may contain repeating units represented by the following chemical formula 13.

[0039] [Chemical Formula 13]

[0040] In the chemical formula 13, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0041] In one embodiment, the polymer composition for preparing a hard mask may contain repeating units represented by the following chemical formula 14.

[0042] [Chemical Formula 14]

[0043] In the chemical formula 14, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0044] In one embodiment, the polymer composition for preparing a hard mask may also contain a solvent.

[0045] The method for preparing the polymer composition for preparing a hard mask according to the embodiment includes the following steps: preparing at least one monomer selected from the group consisting of pyrene compounds, fluorene compounds, benzene compounds, naphthalene compounds, or phenolic compounds; and polymerizing the monomer, wherein the composition for preparing a hard mask comprises a polymer, the polymer comprising repeating units represented by the above chemical formula 1.

[0046] In one embodiment of the method for preparing a polymer composition for preparing a hard mask, the monomer is polymerized for about 3 hours to about 8 hours at a temperature of about 90°C to about 140°C.

[0047] The method for manufacturing a semiconductor device according to the embodiment includes the following steps: preparing a semiconductor substrate including an etch target layer; forming a hard mask on the semiconductor substrate; patterning the hard mask; and patterning the etch target layer. The step of forming the hard mask includes the following steps: coating a polymer composition on the etch target layer to form a polymer composition layer; and curing the polymer composition, wherein the polymer composition comprises a polymer containing repeating units represented by the above-described chemical formula 1.

[0048] Invention Effects The polymer composition for preparing a hard mask in the embodiments comprises a polymer having the structure of Formula 1. Additionally, the polymer may have an appropriate weight-average molecular weight.

[0049] Furthermore, the polymer can have a solubility exceeding about 30 wt% relative to propylene glycol monomethyl ether acetate. The polymer composition for preparing a hard mask in the examples can have a coating thickness exceeding about 15,000 angstroms. Additionally, the polymer composition for preparing a hard mask in the examples can have a filling depth exceeding about 300 nm. Furthermore, the polymer composition for preparing a hard mask in the examples can have a coating thickness exceeding about 0.45 μm. 2 Coating thickness weighted filling depth.

[0050] Therefore, the polymer composition used for preparing a hard mask in the embodiments can be uniformly and thickly coated on a semiconductor substrate. Furthermore, the polymer composition used for preparing a hard mask in the embodiments can uniformly fill even fine patterns.

[0051] Therefore, the polymer composition used in the embodiments for preparing hard masks can appropriately protect the etchable layer and precisely etch the etchable layer. Furthermore, the hard mask prepared from the polymer composition of the embodiments can have an appropriate selectivity for the etchable layer. Attached Figure Description

[0052] Figures 1 to 5 This is a diagram illustrating the process of manufacturing a semiconductor device according to an embodiment. Detailed Implementation

[0053] The invention will now be described in detail through implementation examples. These implementation examples are not limited to those disclosed below, and various modifications can be made without altering the spirit of the invention.

[0054] In this specification, when a part is referred to as "including" a constituent element, it does not exclude other constituent elements, but rather indicates that other constituent elements may also be included, unless otherwise stated to the contrary.

[0055] In addition, all numerical ranges of physical properties, dimensions, etc. of the constituent elements described in this specification shall, in all cases, be understood to be modified by the term “about” unless otherwise specified.

[0056] In this specification, the terms "first," "second," "primary," "secondary," etc., are used to describe various constituent elements, and the constituent elements are not limited by the terms used. The terms are used only for the purpose of distinguishing one constituent element from other constituent elements.

[0057] The polymer composition used in the examples for preparing hard masks comprises a polymer containing aromatic rings.

[0058] The aromatic ring-containing polymer can be represented by the following chemical formula 1.

[0059] [Chemical Formula 1]

[0060] In the chemical formula 1, R1 can be selected from the group consisting of the following chemical formulas 2 or 3.

[0061] In the chemical formula 1, R2 or R3 can be independently selected from the group consisting of the following chemical formulas 4, 5, or 6.

[0062] In addition, in the chemical formula 1, R4 and R5 can be independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 7 carbon atoms, substituted or unsubstituted aryl groups having 5 to 12 carbon atoms, or aldehyde groups having 1 to 7 carbon atoms.

[0063] In Chemical Formula 1, R4 can be a hydroxyl group. In Chemical Formula 1, R5 can be hydrogen or benzyl.

[0064] In the chemical formula 1, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0065] In the chemical formula 1, n can be a natural number from 1 to 20, and m can be a natural number from 1 to 20.

[0066] In the chemical formula 1, n can be a natural number from 1 to 15, and m can be a natural number from 1 to 15.

[0067] [Chemical Formula 2]

[0068] In the chemical formula 2, R6, R7, or R8 can be independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 7 carbon atoms, substituted or unsubstituted aryl groups having 5 to 12 carbon atoms, or aldehyde groups having 1 to 7 carbon atoms.

[0069] In the chemical formula 2, R6 and R7 can be hydroxyl groups, and R8 can be hydrogen or benzyl.

[0070] [Chemical Formula 3]

[0071] In the chemical formula 3, R9 or R10 can be independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 7 carbon atoms, substituted or unsubstituted aryl groups having 5 to 12 carbon atoms, or aldehyde groups having 1 to 7 carbon atoms.

[0072] In chemical formula 3, R9 can be a hydroxyl group. In chemical formula 3, R10 can be hydrogen or benzyl.

[0073] Additionally, in chemical formula 1, chemical formula 2, or chemical formula 3, R5, R8, or R10 can be substituted or unsubstituted benzyl groups.

[0074] [Chemical Formula 4]

[0075] In the chemical formula 4, R11 can be independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 7 carbon atoms, substituted or unsubstituted aryl groups having 5 to 12 carbon atoms, or aldehyde groups having 1 to 7 carbon atoms.

[0076] In the chemical formula 4, R11 can be hydrogen or benzyl.

[0077] [Chemical Formula 5]

[0078] In the chemical formula 5, R12 can be independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 7 carbon atoms, substituted or unsubstituted aryl groups having 5 to 12 carbon atoms, or aldehyde groups having 1 to 7 carbon atoms.

[0079] In the chemical formula 5, R12 can be hydrogen or benzyl.

[0080] [Chemical Formula 6]

[0081] In the chemical formula 6, R13 can be independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 7 carbon atoms, substituted or unsubstituted aryl groups having 5 to 12 carbon atoms, or aldehyde groups having 1 to 7 carbon atoms.

[0082] In the chemical formula 6, R13 can be hydrogen or benzyl.

[0083] The aromatic ring-containing polymer can be represented by the following chemical formula 7.

[0084] [Chemical Formula 7]

[0085] In the chemical formula 7, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0086] In the chemical formula 7, n can be a natural number from 1 to 20, and m can be a natural number from 1 to 20.

[0087] In the chemical formula 7, n can be a natural number from 1 to 15, and m can be a natural number from 1 to 15.

[0088] The aromatic ring-containing polymer can be represented by the following chemical formula 8.

[0089] [Chemical Formula 8]

[0090] In the chemical formula 8, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0091] In the chemical formula 8, n can be a natural number from 1 to 20, and m can be a natural number from 1 to 20.

[0092] In the chemical formula 8, n can be a natural number from 1 to 15, and m can be a natural number from 1 to 15.

[0093] The aromatic ring-containing polymer can be represented by the following chemical formula 9.

[0094] [Chemical Formula 9]

[0095] In the chemical formula 9, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0096] In the chemical formula 9, n can be a natural number from 1 to 20, and m can be a natural number from 1 to 20.

[0097] In the chemical formula 9, n can be a natural number from 1 to 15, and m can be a natural number from 1 to 15.

[0098] The aromatic ring-containing polymer can be represented by the following chemical formula 10.

[0099] [Chemical Formula 10]

[0100] In the chemical formula 10, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0101] In the chemical formula 10, n can be a natural number from 1 to 20, and m can be a natural number from 1 to 20.

[0102] In the chemical formula 10, n can be a natural number from 1 to 15, and m can be a natural number from 1 to 15.

[0103] The aromatic ring-containing polymer can be represented by the following chemical formula 11.

[0104] [Chemical Formula 11]

[0105] In the chemical formula 11, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0106] In the chemical formula 11, n can be a natural number from 1 to 25, and m can be a natural number from 1 to 25.

[0107] In the chemical formula 11, n can be a natural number from 1 to 20, and m can be a natural number from 1 to 20.

[0108] The aromatic ring-containing polymer can be represented by the following chemical formula 12.

[0109] [Chemical Formula 12]

[0110] In the chemical formula 12, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0111] In the chemical formula 12, n can be a natural number from 1 to 25, and m can be a natural number from 1 to 25.

[0112] In the chemical formula 12, n can be a natural number from 1 to 20, and m can be a natural number from 1 to 20.

[0113] The aromatic ring-containing polymer can be represented by the following chemical formula 13.

[0114] [Chemical Formula 13]

[0115] In the chemical formula 13, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0116] In the chemical formula 13, n can be a natural number from 1 to 25, and m can be a natural number from 1 to 25.

[0117] In the chemical formula 13, n can be a natural number from 1 to 20, and m can be a natural number from 1 to 20.

[0118] The aromatic ring-containing polymer can be represented by the following chemical formula 14.

[0119] [Chemical Formula 14]

[0120] In the chemical formula 14, n can be a natural number from 1 to 30, and m can be a natural number from 1 to 30.

[0121] In the chemical formula 14, n can be a natural number from 1 to 25, and m can be a natural number from 1 to 25.

[0122] In the chemical formula 14, n can be a natural number from 1 to 20, and m can be a natural number from 1 to 20.

[0123] The weight-average molecular weight of the aromatic ring-containing polymer can be from about 3250 g / mol to about 4200 g / mol. The weight-average molecular weight of the aromatic ring-containing polymer can be from about 2500 g / mol to about 8000 g / mol. The weight-average molecular weight of the aromatic ring-containing polymer can be from about 3000 g / mol to about 5000 g / mol. The weight-average molecular weight of the aromatic ring-containing polymer can be from about 3250 g / mol to about 5000 g / mol. The weight-average molecular weight of the aromatic ring-containing polymer can be from about 3400 g / mol to about 4200 g / mol. The weight-average molecular weight of the aromatic ring-containing polymer can be from about 3500 g / mol to about 4200 g / mol.

[0124] The weight-average molecular weight can be determined by gel permeation chromatography (GPC). The weight-average molecular weight can be determined and converted based on polystyrene. The gel permeation chromatograph can be a Waters E2695 separation module W / SHC (blue). The polymer is soluble in tetrahydrofuran (THF), and the weight-average molecular weight is determined and converted based on polystyrene.

[0125] Since the weight-average molecular weight of the aromatic ring-containing polymer is within the aforementioned range, the polymer composition for preparing a hard mask in the embodiments can have improved coating properties. Furthermore, since the weight-average molecular weight of the aromatic ring-containing polymer is within the aforementioned range, the polymer composition for preparing a hard mask in the embodiments can have improved filling properties.

[0126] The aromatic ring-containing polymer can be prepared by the following process.

[0127] First, in order to prepare the polymer containing the aromatic ring, a monomer is prepared. The monomer may be selected from at least one of the group consisting of pyrene compounds, fluorene compounds, benzene compounds, naphthalene compounds, or phenolic compounds.

[0128] The monomer may contain 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxypyrene, and benzaldehyde.

[0129] The monomer may contain 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxypyrene, and 2-naphthaldehyde.

[0130] The monomer may contain 4-phenylphenol, 1-hydroxypyrene, and benzaldehyde.

[0131] The monomer may contain 4-phenylphenol, 1-hydroxypyrene, and benzaldehyde.

[0132] The monomer may contain 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxypyrene, benzaldehyde, and benzyl alcohol.

[0133] The monomer may contain 9,9-bis(4-hydroxyphenyl)fluorene, 1-hydroxypyrene, 2-naphthaldehyde and benzyl alcohol.

[0134] The monomer may contain 4-phenylphenol, 1-hydroxypyrene, benzaldehyde, and benzyl alcohol.

[0135] The monomer may contain 4-phenylphenol, 1-hydroxypyrene, naphthaldehyde, and benzyl alcohol.

[0136] The monomer can be polymerized in the presence of a hot acid generating agent. The hot acid generating agent may contain p-toluenesulfonic monohydrate.

[0137] The monomer can polymerize for about 3 hours to about 8 hours. The monomer can polymerize at a temperature of about 90°C to about 140°C.

[0138] The polymer formed by the polymerization process can be neutralized by pyridine or the like.

[0139] In addition, the neutralized polymer can be purified by aqueous hydrochloric acid or distilled water, and can be extracted by heptane or the like.

[0140] Thus, the aromatic ring-containing polymer can be formed.

[0141] The polymer composition for preparing a hard mask in the examples comprises an organic solvent. The organic solvent may be selected from at least one group consisting of tetrahydronaphthalene, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, ethyl lactate, propylene glycol n-propyl ether, dimethylformamide (DMF), γ-butyrolactone, ethoxyethanol, methoxyethanol, methyl 3-methoxypropionate (MMP), or ethyl 3-ethoxypropionate (EEP).

[0142] Based on the overall composition, the content of the organic solvent can be from about 40 wt% to about 90 wt%. Based on the overall composition, the content of the organic solvent can be from about 50 wt% to about 80 wt%. Based on the overall composition, the content of the organic solvent can be from about 55 wt% to about 75 wt%.

[0143] The polymer composition for preparing a hard mask in the embodiments may further include a curing agent. The curing agent may include a compound having two or more crosslinking functional groups. The crosslinking functional groups may be selected from at least one group selected from the group consisting of oxacyclobutyl, oxazolinyl, cyclic carbonate, alkoxysilyl group, aminomethiol group, or alkoxymethyl, aziridinyl, methiol group, isocyanate group, alkoxymethylamino, or polyfunctional epoxy groups.

[0144] The polymer composition for preparing a hard mask in the embodiments may further include a crosslinking agent. The crosslinking agent can crosslink the repeating units of the aromatic compound polymer, for example, by reacting with the hydroxyl groups of the polymer. The crosslinking agent can further enhance the curing properties of the composition for hard masks.

[0145] Examples of crosslinking agents include melamine, amino resins, glycolamide compounds, or diepoxide compounds.

[0146] Specific examples of the crosslinking agent may include: etherified amino resins, such as methylated or butylated melamine (specifically N-methoxymethyl-melamine or N-butoxymethyl-melamine) and methylated or butylated urea resins (specifically Cymel U-65 resin or UFR 80 resin), glycourea derivatives, bis(hydroxymethyl)-p-cresol compounds, etc. Additionally, diepoxide compounds and melamine compounds may also be used as crosslinking agents.

[0147] The polymer composition used in the examples for preparing hard masks may also contain a catalyst.

[0148] The catalyst may include an acid catalyst or a basic catalyst.

[0149] The acid catalyst may be a thermally activated acid catalyst. Examples of acid catalysts include organic acids such as p-toluenesulfonic acid. Thermal acid generator (TAG) compounds may also be used as the acid catalyst.

[0150] Examples of catalysts that generate hot acids include pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.

[0151] The alkaline catalyst may be any one of ammonium hydroxide selected from NH4OH or NR4OH (R being alkyl).

[0152] When the polymer composition for preparing a hard mask in the embodiments contains the crosslinking agent, the content of the crosslinking agent may be from about 1 part by weight to about 30 parts by weight, preferably from about 5 parts by weight to about 20 parts by weight, and more preferably from about 5 parts by weight to about 10 parts by weight, relative to about 100 parts by weight of the aromatic ring-containing polymer.

[0153] When the polymer composition for preparing a hard mask in the embodiments contains the catalyst, the content of the catalyst may be from about 0.001 parts by weight to about 5 parts by weight, preferably from about 0.1 parts by weight to about 2 parts by weight, and more preferably from about 0.1 parts by weight to about 1 part by weight, relative to about 100 parts by weight of the aromatic ring-containing polymer.

[0154] Within the content range of the crosslinking agent and the catalyst, the polymer composition used to prepare the hard mask in the embodiments can obtain appropriate crosslinking properties without reducing the etch resistance, heat resistance, and flatness.

[0155] The polymer composition for preparing a hard mask in the embodiments may further include a surfactant to improve the surface properties and adhesion of the hard mask. The surfactant may be an alkylbenzene sulfonate, an alkylpyridinium salt, a polyethylene glycol, a quaternary ammonium salt, etc., but is not limited thereto. For example, the surfactant content may be from about 0.1 parts by weight to about 10 parts by weight relative to about 100 parts by weight of the aromatic ring-containing polymer.

[0156] The aromatic ring-containing polymer may have solubility relative to organic solvents. Relative to propylene glycol monomethyl ether acetate, the aromatic ring-containing polymer may have a solubility of about 30 wt% or more. Relative to propylene glycol monomethyl ether acetate, the aromatic ring-containing polymer may have a solubility of about 35 wt% or more. Relative to propylene glycol monomethyl ether acetate, the aromatic ring-containing polymer may have a solubility of about 40 wt% or more. Relative to propylene glycol monomethyl ether acetate, the aromatic ring-containing polymer may have a solubility of about 44 wt% or more. Relative to propylene glycol monomethyl ether acetate, the aromatic ring-containing polymer may have a solubility of about 49 wt% or more. Relative to propylene glycol monomethyl ether acetate, the aromatic ring-containing polymer may have a solubility of about 55 wt% or more. Relative to propylene glycol monomethyl ether acetate, the aromatic ring-containing polymer may have a solubility of about 59 wt% or more. Relative to propylene glycol monomethyl ether acetate, the aromatic ring-containing polymer may have a maximum solubility of about 80 wt%.

[0157] The solubility can be determined by the following methods.

[0158] Under ambient temperature conditions, the aromatic-ring-containing polymer is continuously added to propylene glycol monomethyl ether acetate (PGMEA) while stirring. When the aromatic-ring-containing polymer precipitates, the amount of solids added can be derived from the solubility.

[0159] Because the aromatic ring-containing polymer has the increased solubility described above, the polymer composition used in the embodiments for preparing hard masks can have an increased coating thickness.

[0160] In the polymer composition for preparing a hard mask in the embodiments, the coating thickness can exceed 15,000 angstroms. In the polymer composition for preparing a hard mask in the embodiments, the coating thickness can exceed 20,000 angstroms. In the polymer composition for preparing a hard mask in the embodiments, the coating thickness can exceed 25,000 angstroms. In the polymer composition for preparing a hard mask in the embodiments, the maximum coating thickness can be 250,000 angstroms.

[0161] The coating thickness can be determined by the following method. In the embodiment, the polymer composition used to prepare the hard mask was spin-coated, dried, and cured on a 30-inch silicon wafer. The average thickness of the hard mask formed in this manner is the coating thickness. That is, the thickness of the hard mask formed under the following conditions can be the coating thickness.

[0162] The coating conditions are as follows: the wafer rotation speed can be about 1000 rpm, and the coating time can be about 10 seconds.

[0163] In addition, the drying conditions are as follows: the temperature can be about 250°C and the drying time can be about 1 minute.

[0164] In addition, the curing conditions are as follows: the temperature can be about 400°C and the baking time can be about 2 minutes.

[0165] Since the coating thickness of the polymer composition used in the embodiments for preparing hard masks is within the aforementioned range, thick hard masks can be achieved. Therefore, the polymer composition used in the embodiments for preparing hard masks can effectively protect the etched target layer and effectively achieve fine patterning.

[0166] The polymer compositions used in the embodiments for preparing hard masks may have a filling depth. In the polymer compositions used in the embodiments for preparing hard masks, the filling depth may exceed about 300 nm. In the polymer compositions used in the embodiments for preparing hard masks, the filling depth may exceed about 330 nm. In the polymer compositions used in the embodiments for preparing hard masks, the filling depth may exceed about 360 nm. In the polymer compositions used in the embodiments for preparing hard masks, the filling depth may exceed about 390 nm. The maximum value of the filling depth may be about 5000 nm.

[0167] The filling depth can be determined by the following methods.

[0168] First, prepare a silicon wafer, which includes a line pattern with a width of about 40nm, a spacing of 195nm, and a depth of more than 400nm.

[0169] The polymer composition used for preparing a hard mask in the embodiment is coated onto the silicon wafer according to the coating conditions described. Then, the coated polymer composition is dried according to the drying conditions described. Finally, the dried polymer composition is baked according to the curing conditions described.

[0170] At this point, the fill depth is the depth of the hard mask filling the line pattern.

[0171] Because the polymer composition used in the embodiments for preparing hard masks has the above-described range, the hard mask can be uniformly formed even in fine patterns.

[0172] The polymer composition used in the examples for preparing hard masks may have a coating thickness-weighted fill depth.

[0173] In the polymer composition used for preparing a hard mask in the examples, the thickness-weighted fill depth of the coating can exceed 0.45 μm. 2 In the polymer composition used to prepare a hard mask in the examples, the thickness-weighted fill depth of the coating can exceed 0.45 μm. 2 In the polymer composition used to prepare a hard mask in the examples, the thickness-weighted fill depth of the coating can exceed 0.55 μm. 2 In the polymer composition used to prepare a hard mask in the examples, the thickness-weighted fill depth of the coating can exceed 0.6 μm. 2 .

[0174] The coating thickness weighted filling depth can be the product of the coating thickness and the filling depth.

[0175] The coating thickness weighted filling depth can be represented by the following formula 1.

[0176] [Formula 1] Coating thickness weighted filling depth = coating thickness × filling depth.

[0177] Since the coating thickness weighted fill depth of the polymer composition used in the embodiments for preparing hard masks is within the above-mentioned range, a thick hard mask can be formed and uniformly coated on the fine pattern.

[0178] The semiconductor device manufacturing method of the embodiment includes the following steps: preparing a semiconductor substrate including an etch target layer; forming a hard mask on the semiconductor substrate; patterning the hard mask; and patterning the etch target layer.

[0179] Additionally, the step of forming the hard mask includes the following steps: coating a polymer composition onto the etched object layer to form a polymer composition layer; and curing the polymer composition.

[0180] Figures 1 to 5 This is a diagram illustrating the manufacturing process of a semiconductor device according to an embodiment.

[0181] Reference Figures 1 to 5 Semiconductor devices can be manufactured using the polymer composition for preparing hard masks as described in the examples.

[0182] like Figure 1 As shown, an etch target layer 11 is formed on the semiconductor substrate 10. Then, a polymer composition for preparing a hard mask in this embodiment is coated on the etch target layer 11, and after drying and baking, a hard mask 12 is formed. Then, a photoresist composition is coated on the hard mask 12. Thus, a photoresist film 13 is formed.

[0183] The polymer composition is applied to the etched object layer by a method selected from spin coating, air spraying, electrospraying, dip coating, spray coating, doctor blade coating, or bar coating.

[0184] The polymer composition can be applied by spin-on coating. The coating thickness of the polymer composition is not limited, for example, it can be from about 10 nm to about 10,000 nm, specifically from about 10 nm to about 1,000 nm.

[0185] In addition, the semiconductor substrate may be selected from the group consisting of a silicon substrate, a glass substrate, a GaN substrate, a silicon dioxide substrate, a metal substrate, or a polymer substrate.

[0186] In addition, the etched target layer can be selected from at least one of the group consisting of an oxide film, a nitride film, a silicon film, or a metal film.

[0187] like Figure 2 As shown, the photoresist film 13 is patterned through exposure and development processes, and a photoresist pattern 13a is formed on the hard mask.

[0188] The step of exposing the photoresist film can be performed, for example, using ArF, KrF, or EUV. After exposure, a heat treatment process is performed at a temperature of approximately 200-500°C. In the developing process, a developer such as an aqueous solution of tetramethylammonium hydroxide (TMAH) can be used.

[0189] like Figure 3 As shown, the photoresist pattern 13a is used as an etching mask to pattern the hard mask 12. Thus, a hard mask pattern 12a is formed on the etch target layer 11.

[0190] The thickness of the hard mask pattern can be from about 10 nm to about 10,000 nm.

[0191] In the etching process used to form the hard mask, an etching gas can be used. The etching gas can be selected from at least one of the group consisting of CF4, CHF3, SF6, Cl2, BCl3, and O2. According to one embodiment, a mixture of C4F8 and CHF3 can be used as the etching gas, and their mixing ratio can be from 1:10 to 10:1 by volume.

[0192] The etched layer can be formed from multiple patterns. These multiple patterns can be various types, such as metal patterns, semiconductor patterns, and insulator patterns. For example, they can be applied to various patterns used in semiconductor integrated circuit devices.

[0193] The etched layer may contain the material to be patterned, such as a metal layer like aluminum or copper; a semiconductor layer like silicon; or an insulating layer like silicon oxide or silicon nitride. The etched film can be formed using various methods such as sputtering, electron beam deposition, chemical vapor deposition, and physical vapor deposition. For example, the etched film can be formed using chemical vapor deposition.

[0194] like Figure 4 As shown, the hard mask pattern 12a is used as an etching mask to pattern the etch target layer 11. Thus, the etched pattern 11a is formed on the semiconductor substrate 10.

[0195] like Figure 5 As shown, the hard mask pattern 12a is removed.

[0196] Thus, an etched pattern 11a is formed on the semiconductor substrate 10, and a semiconductor device can be manufactured through subsequent processes.

[0197] As described above, the polymer composition for preparing a hard mask in the embodiments comprises a polymer having a structure of Formula 1. Additionally, the polymer may have an appropriate weight-average molecular weight.

[0198] Furthermore, the solubility of the polymer relative to propylene glycol monomethyl ether acetate can exceed about 30 wt%. The coating thickness of the polymer composition used in the examples for preparing hard masks can exceed about 15,000 angstroms. Additionally, the filling depth of the polymer composition used in the examples for preparing hard masks can exceed about 300 nm. Furthermore, the thickness-weighted filling depth of the polymer composition used in the examples for preparing hard masks can exceed about 0.45 μm. 2 .

[0199] Therefore, the polymer composition used for preparing a hard mask in the embodiments can be uniformly and thickly coated on a semiconductor substrate. Furthermore, the polymer composition used for preparing a hard mask in the embodiments can uniformly fill even fine patterns.

[0200] Therefore, the polymer composition used in the embodiments for preparing hard masks can appropriately protect the etchable layer and precisely etch the etchable layer. Furthermore, the hard mask prepared from the polymer composition of the embodiments can have an appropriate selectivity for the etchable layer.

[0201] In addition, since the polymer composition used in the embodiments for preparing hard masks can form thick hard masks, thick etched object layers can be easily patterned.

[0202] The following embodiments illustrate the content in more detail. However, these embodiments are merely illustrative of the invention, and the scope of the embodiments is not limited thereto.

[0203] Preparation Example A1: 9,9-bis(4-hydroxyphenyl)fluorene A2: 4-Phenylephrol B: 1-hydroxypyrene C1: Benzaldehyde C2: 2-Naphthaldehyde D: Benzyl alcohol E: 1,4-Benzenedimethanol Preparation Example 1 Approximately 10 parts by weight of 9,9-bis(4-hydroxyphenyl)fluorene, approximately 3.74 parts by weight of 1-hydroxypyrene, approximately 2.7 parts by weight of benzaldehyde, approximately 8.5 parts by weight of toluene, and approximately 25 parts by weight of tetrahydronaphthalene were added to a flask and stirred thoroughly at approximately 120°C. Then, approximately 0.27 parts by weight of p-Toluenesulfonic monohydrate was added to the flask, and the reaction was carried out at approximately 120°C for approximately 5 hours. The reactants were neutralized with pyridine and purified with approximately 1 wt% aqueous hydrochloric acid and distilled water. The purified reactants were then extracted with heptane to obtain an aromatic ring-containing polymer.

[0204] Preparation Examples 2 to 10 As shown in Table 1 below, the monomer content changed. The remaining processes were carried out in the same manner as in Preparation Example 1.

[0205] [Table 1]

[0206] Example 1 About 70 parts by weight of the polymer obtained in Preparation Example 1 were uniformly mixed with about 30 parts by weight of propylene glycol monomethyl ether acetate to prepare a polymer composition for preparing a hard mask.

[0207] Examples 2 to 8 and Comparative Examples 1 and 2 As shown in Table 2 below, the contents of polymers and organic solvents changed.

[0208] [Table 2]

[0209] Evaluation example Evaluation Example 1. Solubility At room temperature, the polymer prepared in the preparation example was continuously added to propylene glycol monomethyl ether acetate (PGMEA) and stirred. The solid content at which the polymer precipitates is derived from the solubility.

[0210] Evaluation Example 2. Weight-average molecular weight The weight-average molecular weight of the polymers prepared in the preparation examples was determined using the gel permeation chromatography (GPC, Waters E2695 separations module W / SHC (blue)). The polymers were dissolved in tetrahydrofuran (THF) and the weight-average molecular weight was determined based on polystyrene conversion.

[0211] Evaluation Example 3. Coating Thickness With a 30-inch silicon wafer rotating at approximately 1000 rpm, the polymer compositions of the examples and comparative examples were coated onto the upper surface of the wafer using the material coating track equipment (TEL-MARK 8 / 8-inch wafer from Tokyo Electron), and then baked at 400°C. The thickness of the hard mask formed on the silicon wafer was measured using a VM-120 from DNS Corporation of Japan as the coating thickness.

[0212] Evaluation Example 4. Fill Depth Using the same method as in Evaluation Example 3, the hard mask was coated with a polymer composition onto a patterned silicon wafer with an L / S depth of 4000 angstroms and a CD size of 40 nm, and after baking, the fill depth in the pattern was measured.

[0213] Evaluation Example 5. Etching Rate The substrate formed by the hard mask is mounted in a dry etching apparatus, and the hard mask is etched with etching gas. A silicon wafer including an amorphous carbon layer is etched under the same conditions. The etching rates are compared relative to the etching rate of 100% of the amorphous carbon layer.

[0214] The etching rate was determined according to the standards of the National Institute for Nanoscience and Technology (NINS) using NINS's dry etch equipment (Oxford, ICP380).

[0215] As shown in Table 3 below, the weight-average molecular weight and solubility of the polymers prepared in the preparation examples are derived.

[0216] [Table 3]

[0217] As shown in Table 4 below, the coating thickness, filling depth, and etching rate of the polymer compositions prepared in the Examples and Comparative Examples are derived.

[0218] [Table 4]

[0219] As shown in Tables 3 and 4, the polymer compositions of the embodiments have improved coatability and etching speed.

Claims

1. A polymer composition for preparing a hard mask, characterized in that, It comprises a polymer containing repeating units 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 chemical formula 1, R1 is selected from the group consisting of chemical formula 2 or chemical formula 3; R2 or R3 is independently selected from the group consisting of chemical formulas 4 to 6; R4 and R5 are independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups with 1 to 7 carbon atoms, substituted or unsubstituted aryl groups with 5 to 12 carbon atoms, or aldehyde groups with 1 to 7 carbon atoms; n is a natural number from 1 to 30; and m is a natural number from 1 to 30. In chemical formulas 2, 3, 4, 5, and 6, R6, R7, R8, R9, R10, R11, R12, or R13 are independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 7 carbon atoms, substituted or unsubstituted aryl groups having 5 to 12 carbon atoms, or aldehyde groups having 1 to 7 carbon atoms.

2. The polymer composition for preparing a hard mask according to claim 1, characterized in that, The polymer has a weight-average molecular weight of 3250 g / mol to 4200 g / mol.

3. The polymer composition for preparing a hard mask according to claim 1, characterized in that, R4, R6, R7 and R9 are hydroxyl groups, and R11, R12 and R13 are hydrogen.

4. The polymer composition for preparing a hard mask according to claim 3, characterized in that, R5, R8, or R10 are substituted or unsubstituted benzyl groups.

5. The polymer composition for preparing a hard mask according to claim 1, characterized in that, The polymer has a solubility of more than 30 wt% relative to propylene glycol monomethyl ether acetate.

6. The polymer composition for preparing a hard mask according to claim 1, characterized in that, The coating thickness exceeds 15,000 angstroms.

7. The polymer composition for preparing a hard mask according to claim 6, characterized in that, The filling depth exceeds 300nm.

8. The polymer composition for preparing a hard mask according to claim 7, characterized in that, The coating thickness-weighted fill depth exceeds 0.45 μm. 2 , The coating thickness weighted filling depth is the product of the coating thickness and the filling depth.

9. The polymer composition for preparing a hard mask according to claim 1, characterized in that, It contains repeating units represented by the following chemical formula 7. [Chemical Formula 7] In the chemical formula 7, n is a natural number from 1 to 30, and m is a natural number from 1 to 30.

10. The polymer composition for preparing a hard mask according to claim 1, characterized in that, It contains repeating units represented by the following chemical formula 8. [Chemical Formula 8] In the chemical formula 8, n is a natural number from 1 to 30, and m is a natural number from 1 to 30.

11. The polymer composition for preparing a hard mask according to claim 1, characterized in that, It contains repeating units represented by the following chemical formula 9. [Chemical Formula 9] In the chemical formula 9, n is a natural number from 1 to 30, and m is a natural number from 1 to 30.

12. The polymer composition for preparing a hard mask according to claim 1, characterized in that, It contains repeating units represented by the following chemical formula 10. [Chemical Formula 10] In the chemical formula 10, n is a natural number from 1 to 30, and m is a natural number from 1 to 30.

13. The polymer composition for preparing a hard mask according to claim 1, characterized in that, It contains repeating units represented by the following chemical formula 11. [Chemical Formula 11] In the chemical formula 11, n is a natural number from 1 to 30, and m is a natural number from 1 to 30.

14. The polymer composition for preparing a hard mask according to claim 1, characterized in that, It contains repeating units represented by the following chemical formula 12. [Chemical Formula 12] In the chemical formula 12, n is a natural number from 1 to 30, and m is a natural number from 1 to 30.

15. The polymer composition for preparing a hard mask according to claim 1, characterized in that, It contains repeating units represented by the following chemical formula 13. [Chemical Formula 13] In the chemical formula 13, n is a natural number from 1 to 30, and m is a natural number from 1 to 30.

16. The polymer composition for preparing a hard mask according to claim 1, characterized in that, It contains repeating units represented by the following chemical formula 14. [Chemical Formula 14] In the chemical formula 14, n is a natural number from 1 to 30, and m is a natural number from 1 to 30.

17. The polymer composition for preparing a hard mask according to claim 1, characterized in that, The polymer composition also contains a solvent.

18. A method for preparing a polymer composition for fabricating a hard mask, characterized in that, The preparation method includes the following steps: Prepare at least one monomer selected from the group consisting of pyrene compounds, fluorene compounds, benzene compounds, naphthalene compounds, or phenolic compounds; and Polymerize the monomers, The polymer composition comprises a polymer containing repeating units 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 chemical formula 1, R1 is selected from the group consisting of chemical formula 2 or chemical formula 3; R2 or R3 is independently selected from the group consisting of chemical formulas 4 to 6; R4 and R5 are independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups with 1 to 7 carbon atoms, substituted or unsubstituted aryl groups with 5 to 12 carbon atoms, or aldehyde groups with 1 to 7 carbon atoms; n is a natural number from 1 to 30; and m is a natural number from 1 to 30. In chemical formulas 2, 3, 4, 5, and 6, R6, R7, R8, R9, R10, R11, R12, or R13 are independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 7 carbon atoms, substituted or unsubstituted aryl groups having 5 to 12 carbon atoms, or aldehyde groups having 1 to 7 carbon atoms.

19. The method for preparing the polymer composition for preparing a hard mask according to claim 18, characterized in that, The monomer is polymerized at a temperature of 90°C to 140°C for 3 to 8 hours.

20. A method for manufacturing a semiconductor device, characterized in that, The manufacturing method includes the following steps: Prepare a semiconductor substrate, including the etched target layer; A hard mask is formed on the semiconductor substrate; Patterning the hard mask; and The etched object layer is patterned. The steps for forming the hard mask include the following: A polymer composition is coated onto the etched object layer to form a polymer composition layer; and Curing the polymer composition, The polymer composition comprises a polymer containing repeating units 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 chemical formula 1, R1 is selected from the group consisting of chemical formula 2 or chemical formula 3; R2 or R3 is independently selected from the group consisting of chemical formulas 4 to 6; R4 and R5 are independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups with 1 to 7 carbon atoms, substituted or unsubstituted aryl groups with 5 to 12 carbon atoms, or aldehyde groups with 1 to 7 carbon atoms; n is a natural number from 1 to 30; and m is a natural number from 1 to 30. In chemical formulas 2, 3, 4, 5, and 6, R6, R7, R8, R9, R10, R11, R12, or R13 are independently selected from the group consisting of hydrogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 7 carbon atoms, substituted or unsubstituted aryl groups having 5 to 12 carbon atoms, or aldehyde groups having 1 to 7 carbon atoms.

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