Organic polymer, semiconductor hard mask composition containing same, and patterning method using same

Abstract

A hardmask polymer for semiconductor applications is disclosed, which comprises a polymer of specific monomer components, and achieves improved etching resistance, solubility, and mechanical properties. The hardmask polymer is an organic polymer comprising a structure represented by formula 1, where R1 is a hydrocarbon containing one or more benzene rings, and n is an integer of 1 to 10,000. Also disclosed are a hardmask composition for semiconductor applications comprising the organic polymer, and a patterning method using the hardmask composition. JPEG2025511532000039.jpg1998

Description

[Technical field]

[0001] The present invention relates to an organic polymer, a hard mask composition for semiconductor applications containing the organic polymer, and a patterning method using the hard mask composition. More specifically, the present invention relates to an organic polymer comprising a polymer of specific monomer components, which achieves improved etching resistance, solubility, and mechanical properties, a hard mask composition for semiconductor applications containing the organic polymer, and a patterning method using the hard mask composition. [Background technology]

[0002] Efficient lithography techniques are essential to meet the continuing demand for decreasing feature sizes in the semiconductor industry.

[0003] In the lithography process, a light source with a narrower wavelength band is required to form finer photoresist patterns. Conventionally, an i-line light source with a wavelength of 365 nm was used. Later, in order to form finer patterns, lithography technology was developed that uses extreme ultraviolet (EUV, 13.5 nm) light sources emitted from ArF (198 nm) and KrF (248 nm).

[0004] The photoresist becomes gradually thinner as the size of the pattern decreases to prevent the photoresist pattern from collapsing, however, the use of a thin photoresist pattern limits the etch depth of the etching target layer.

[0005] To solve this problem, a layer material with good etching resistance is introduced between the photoresist layer and the etching target layer. This layer material is called a hard mask. In the hard mask process, the hard mask is patterned by etching using the photoresist pattern, and the etching target layer is etched using the hard mask pattern. The hard mask is formed by chemical vapor deposition or spin coating.

[0006] However, chemical vapor deposition has drawbacks such as increased capital costs for equipment, increased processing time, and particle defects. Because of these drawbacks, there are ongoing efforts to develop materials that are amenable to spin coating.

[0007] Many hardmask materials are known in the art, but as mentioned above, they have limited direct application in spin coating. Therefore, there is a need for better materials that simultaneously meet the requirements in terms of etch resistance, solubility, and storage stability.

[0008] [Prior art document] [Patent documents] (Patent Document 1) (0001) Korean Patent No. 10-0874655 (Patent Document 2) (0002) Korean Patent No. 10-1082104 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been made in consideration of the above-mentioned problems, and aims to provide an organic polymer containing a polymer having a specific monomer component, and to provide a hard mask composition for semiconductor applications containing an organic polymer having improved etching resistance, solubility, and mechanical properties, and a patterning method using the hard mask composition. [Means for solving the problem]

[0010] The present invention provides a hardmask polymer for semiconductor applications comprising a structure represented by Formula 1.

[0011] [ka]

[0012] In the formula, R1 is a hydrocarbon containing one or more benzene ring structures, and n is an integer of 1 to 10,000.

[0013] In one embodiment, the hydrocarbon containing a benzene ring structure may have a structure represented by Formula 2 or Formula 3 below.

[0014] [ka]

[0015] Wherein R2 is H, OH or a C1-C5 hydrocarbon.

[0016] [ka]

[0017] wherein R3 and R4 are each independently benzene, naphthalene, or biphenyl, unsubstituted or substituted with OH or a C1-C5 hydrocarbon, provided that R3 and R4 may be linked via a hydrocarbon or ether group to form a ring structure or may each independently be bonded to each other.

[0018] In certain embodiments, the structure of Formula 3 may be represented by one of Formulas 4-8.

[0019] [ka]

[0020] In some embodiments, the hard mask polymer for semiconductor applications can include a structure represented by Formula 9.

[0021] [ka]

[0022] In the formula, R5 and R6 are each independently a hydrocarbon containing one or more benzene ring structures, and m and o are each independently an integer of 1 to 10,000.

[0023] In certain embodiments, R5 can have a structure represented by formula 10.

[0024] [ka]

[0025] wherein R7 is H, OH, or a C1-C5 hydrocarbon, and R6 can have the structure represented by formula 11.

[0026] [ka]

[0027] wherein R8 and R9 are each independently benzene, naphthalene, or biphenyl, unsubstituted or substituted with OH or a C1-C5 hydrocarbon, provided that R8 and R9 may be linked via a hydrocarbon or ether group to form a ring structure or may each independently be bonded to each other.

[0028] In certain embodiments, the structure of formula 11 can be represented by one of formulas 12-16.

[0029] [ka]

[0030] In some embodiments, hardmask polymers for semiconductor applications can have a weight average molecular weight of 1,000 to 20,000.

[0031] The present invention also provides a hardmask composition for semiconductor applications comprising the hardmask polymer.

[0032] The hard mask composition may include 100 parts by weight of an organic solvent, 1 to 20 parts by weight of the hard mask polymer for semiconductor applications, 0.1 to 3 parts by weight of a crosslinker, and 0.001 to 0.1 parts by weight of a catalyst.

[0033] In certain embodiments, the organic solvent may be selected from the group consisting of propylene glycol monomethyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), cyclohexanone, butyrolactone, ethyl lactate, N-methylpyrrolidone (NMP), methyl methoxypropionate (MMP), ethyl ethoxypropionate (EEP), dimethylformamide (DMF), and mixtures thereof.

[0034] In certain embodiments, the crosslinker can be a methylated melamine resin, a methylated urea resin, or a glycoluril derivative represented by Formula 17.

[0035] [ka]

[0036] In an embodiment, the catalyst may be pyridinium p-toluenesulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, or an alkyl ester of an organic sulfonic acid.

[0037] The present invention also provides a patterning method using the hard mask composition. Effect of the Invention

[0038] Due to their high etch selectivity and solubility, the organic polymers and hard mask compositions of the present invention can be applied by spin coating, and their use can provide a patterning process with lower cost and defect rates than the use of conventional hard masks formed by chemical vapor deposition.

[0039] Furthermore, due to the presence of divinylbenzene repeat units and aromatic rings in the organic polymer, the hardmask composition may have good etch resistance, high etch selectivity, and high solubility. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0040] A preferred embodiment of the present invention will be described in detail below. In the description of the present invention, detailed descriptions of related technologies will be omitted if it is believed that such descriptions may unnecessarily obscure the essence of the present invention. Throughout this specification, the singular forms "a", "an" and "the" are intended to include the plural forms unless the context clearly indicates otherwise. It should be understood that terms such as "including" or "having" are intended to indicate the presence of features, numbers, steps, operations, components, parts, or combinations thereof disclosed herein, and are not intended to exclude the possibility that one or more other features, numbers, steps, operations, components, parts, or combinations thereof may be present or may be added. Each step of the method described herein may be performed in a different order than that explicitly described. In other words, each step may be performed in the same order as described, substantially simultaneously, or in the reverse order.

[0041] The present disclosure is not limited to the illustrated embodiments, but may be embodied in various different forms. Rather, the disclosed embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope and spirit of the invention to those skilled in the art. In the drawings, dimensions such as width and thickness of elements may be exaggerated for clarity. The drawings are described from the perspective of the viewer. When an element is referred to as being "on" another element, it will be understood that it may be directly on the other element, or that one or more intervening elements may be present therebetween. It will be understood by those skilled in the art that the present invention may be embodied in various different forms without departing from the spirit and scope of the invention as defined by the appended claims. The same reference numbers refer to substantially the same elements throughout the drawings.

[0042] As used herein, the term "and / or" includes both combinations of multiple related disclosed items and any items among multiple related disclosed items. As used herein, "A or B" means "A", "B", or "A and B".

[0043] The present invention relates to hardmask polymers for semiconductor applications that comprise a structure represented by Formula 1.

[0044] [ka]

[0045] In the formula, R1 is a hydrocarbon containing one or more benzene ring structures, and n is an integer of 1 to 10,000.

[0046] The hardmask polymer includes as a monomer a copolymer of divinylbenzene and a hydrocarbon containing a benzene ring structure, as shown in Formula 1.

[0047] The hydrocarbon containing a benzene ring structure may have a structure represented by formula 2 or 3.

[0048] [ka]

[0049] Wherein R2 is H, OH or a C1-C5 hydrocarbon.

[0050] [ka]

[0051] wherein R3 and R4 are each independently benzene, naphthalene, or biphenyl, unsubstituted or substituted with OH or a C1-C5 hydrocarbon, provided that R3 and R4 may be linked via a hydrocarbon or ether group to form a ring structure or may each independently be bonded to each other.

[0052] The hydrocarbon containing a benzene ring structure may be a substituted or unsubstituted fluorene derivative, or a substituted or unsubstituted pyrene derivative.

[0053] Specifically, the structure of formula 3 may be represented by any one of formulas 4 to 8 below.

[0054] [ka]

[0055] As mentioned above, the hydrocarbon containing a benzene ring structure may be a substituted or unsubstituted fluorene derivative or a substituted or unsubstituted pyrene derivative. The polycyclic structure may be substituted with one or several atoms to form the monomer.

[0056] The term "substituted" in the phrase "substituted or unsubstituted" used herein means that one or more hydrogen atoms in a hydrocarbon are each independently replaced with the same or different substituents.

[0057] Suitable substituents include -F, -Cl, -Br, -CN, -NO2, -OH; C1-C2 which are unsubstituted or substituted with -F, -Cl, -Br, -CN, -NO2, or -OH. 20 Alkyl groups; C1-C unsubstituted or substituted with -F, -Cl, -Br, -CN, -NO2, or -OH. 20 Alkoxy groups; unsubstituted or C1-C 20 Alkyl groups, C1-C 20 C6-C substituted with alkoxy groups, -F, -Cl, -Br, -CN, -NO2, or -OH 30 Aryl groups; unsubstituted or C1-C 20 Alkyl groups, C1-C 20 C6-C substituted with alkoxy groups, -F, -Cl, -Br, -CN, -NO2, or -OH 30 Heteroaryl groups; unsubstituted or C1-C 20 Alkyl groups, C1-C 20 C5-C substituted with alkoxy groups, -F, -Cl, -Br, -CN, -NO2, or -OH 20 Cycloalkyl groups; unsubstituted or C1-C 20 Alkyl groups, C1-C 20 C5-C substituted with alkoxy groups, -F, -Cl, -Br, -CN, -NO2, or -OH 30 heterocycloalkyl group; and a group represented by -N(G1)(G2), wherein G1 and G2 are each independently hydrogen, C1-C 10 Alkyl groups, unsubstituted or C1-C 20 Substituted with alkyl groups, C1-C 20 Alkyl group or C6-C 30 aryl groups).

[0058] As used herein, the term "alkyl" includes straight chain, branched chain, cyclic hydrocarbon radicals, and combinations thereof. The term may optionally include one or more double bonds, triple bonds, or combinations thereof within the chain. Thus, "alkyl" is intended to include alkenyl and alkynyl.

[0059] The term "heteroalkyl," by itself or in combination with other terms, means, unless otherwise stated, a stable linear, branched, cyclic hydrocarbon radical or combination thereof, which consists of one or more carbon atoms and one or more heteroatoms selected from the group consisting of O, N, P, Si, and S, wherein the nitrogen, phosphorus, and sulfur atoms may optionally be oxidized and the nitrogen heteroatom may optionally be quaternized.

[0060] The terms "cycloalkyl" and "heterocycloalkyl", alone or in combination with other terms, represent, unless otherwise stated, cyclic versions of "alkyl" and "heteroalkyl", respectively.

[0061] The term "aryl" means, unless otherwise specified, a polyvalent unsaturated aromatic hydrocarbon substituent which may be a single ring or multiple rings (1-3 rings) fused or covalently linked together. The term "heteroaryl" refers to an aryl group (or ring) containing (each individual ring, if multiple rings) 1-4 heteroatoms selected from N, O, and S, where the nitrogen and sulfur atoms are optionally oxidized and the nitrogen atom is optionally quaternized. Heteroaryl groups may be attached to the remainder of the molecule through a carbon or heteroatom.

[0062] Aryl includes 4-7 membered, preferably 5 or 6 membered, single or fused rings. Aryl is also intended to include structures in which one or more aryl groups are linked via chemical bonds. Specific examples of suitable aryl groups include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, and fluoranthenyl.

[0063] Heteroaryl includes 5- or 6-membered monocyclic heteroaryls and polycyclic heteroaryls fused to one or more benzene rings, which may be partially saturated. Heteroaryl is also intended to include structures in which one or more heteroaryl groups are linked via chemical bonds. Heteroaryl groups include divalent aryl groups in which heteroatoms in the ring are oxidized or quaternized to form N-oxides or quaternary salts. Examples of suitable heteroaryl groups include: monocyclic heteroaryl groups, such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, and pyridazinyl; polycyclic heteroaryl groups, such as benzofuranyl, benzothiophenyl, isobenzofuranyl, benzo ... Examples include, but are not limited to, midazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, and benzodioxolyl; their corresponding N-oxides (e.g., pyridyl N-oxide and quinolyl N-oxide); and quaternary salts thereof.

[0064] Substituted or unsubstituted fluorene derivatives or substituted or unsubstituted pyrene derivatives can be attached to divinylbenzene to form a polymer, as shown in Formula 1.

[0065] As an example, polymerization with a compound having the structure of Formula 2 above (1-hydroxypyrene) gives a structure represented by Formula 18.

[0066] [ka]

[0067] In the formula, n is an integer of 1 to 10,000.

[0068] Polymerization with 9,9-bis(4-hydroxyphenyl)fluorene having the structure of Formula 4 and with 9,9-bis(6-hydroxy-2-naphthyl)fluorene having the structure of Formula 5 can provide structures represented by Formulas 19 and 20, respectively.

[0069] [ka]

[0070] In the formula, n is an integer of 1 to 10,000;

[0071] [ka]

[0072] In the formula, n is an integer of 1 to 10,000;

[0073] Each of these polymers has -OH groups attached to some of the benzene ring structures, allowing functional groups to be added by forming ester bonds (through a dehydration-condensation reaction). These functional groups can not only change the solubility of the resulting polymer, but also the physical properties of the desired hardmask.

[0074] Although the hard mask polymer for semiconductor applications only has the structure of Formula 1, it may be a combination of two or more polymer structures to achieve improved physical properties. For example, the hard mask polymer for semiconductor applications may include a structure represented by the following Formula 9:

[0075] [ka]

[0076] In the formula, R5 and R6 are each independently a substituted or unsubstituted fluorene or a substituted or unsubstituted pyrene, and m and o are each independently an integer of 1 to 10,000.

[0077] The structure of formula 9 may be a copolymer containing two or more types of structures that can be represented by formula 1.

[0078] Specifically, the hard mask polymer may be a copolymer of a pyrene derivative as R5 and a fluorene derivative as R6, which are represented by Formulas 10 and 11, respectively.

[0079] [ka]

[0080] In the formula, R7 is H, OH or a C1-C5 hydrocarbon.

[0081] [ka]

[0082] wherein R8 and R9 are each independently benzene, naphthalene, or biphenyl, unsubstituted or substituted with OH or a C1-C5 hydrocarbon, provided that R8 and R9 may be linked via a hydrocarbon or ether group to form a ring structure or may each independently be bonded to each other.

[0083] Specifically, the fluorene derivative having the structure of formula 11 may be represented by any one of formulas 12 to 16.

[0084] [ka]

[0085] For example, when R3 is a structure of formula 10 and R4 is a structure of formula 13, the polymer can have a structure represented by formula 21:

[0086] [ka]

[0087] In the formula, m and o are integers from 1 to 10,000.

[0088] The hard mask polymer for semiconductor applications may have a structure of formula 1 or formula 9. Alternatively, a mixture of a compound having the structure of formula 1 and a compound having the structure of formula 9 may be used to control and improve physical properties. In this case, the mixing weight ratio of the compound having the structure of formula 1 and the compound having the structure of formula 9 may be in the range of 1:2 to 2:1. Within this range, the hard mask compound of the present invention has high etching resistance and can be easily dissolved in a solvent. However, outside this range, the hard mask compound may have poor etching resistance, low solubility in a solvent, or low refractive index and extinction coefficient, making it difficult to use for forming a hard mask for semiconductor applications.

[0089] The hard mask polymer may have a weight average molecular weight of 1,000 to 20,000. The length of the polymer may vary depending on the polymerization time and reaction temperature. The weight average molecular weight of the hard mask polymer may range from 1,000 to 20,000, preferably 3,000 to 7,000, more preferably 4,000 to 6,000. If the weight average molecular weight of the hard mask polymer is less than the lower limit, the polymerization may be incomplete and the etching resistance may be reduced. On the other hand, if the weight average molecular weight of the hard mask polymer exceeds the upper limit, the solubility of the hard mask polymer in the solvent may be reduced, making it difficult to use for spin coating.

[0090] The present invention also provides a hardmask composition for semiconductor applications comprising the hardmask polymer.

[0091] The hard mask polymer can be used to prepare a hard mask composition for semiconductor applications. Conventional hard masks for semiconductor applications require high etch resistance, so many of them are formed by chemical vapor deposition (CVD). However, chemical vapor deposition involves a lot of costs because the processing conditions are cumbersome and difficult to achieve.

[0092] To overcome this drawback, hard mask compositions for semiconductor applications that can be applied by spin coating have been developed, but such compositions are difficult to develop because they are required to have strong etching resistance.

[0093] Specifically, in order to increase the etching resistance of hard masks for semiconductor applications, it is necessary to use polymers with high carbon content.However, polymers with high carbon content tend to form network structures or solid phases due to the attractive forces between polymer molecules, and have the disadvantage of low solubility in solvents.In contrast, the polymers of the present invention can be used to provide hard mask compositions for semiconductor applications that can be applied by spin coating due to their high carbon content and high solubility in solvents.

[0094] The hard mask composition for semiconductor applications may include 100 parts by weight of an organic solvent, 1 to 20 parts by weight of a hard mask polymer for semiconductor applications, 0.1 to 3 parts by weight of a crosslinker, and 0.001 to 0.1 parts by weight of a catalyst.

[0095] The organic solvent is used to dissolve the hard mask polymer present in the composition. As described above, the organic solvent is preferably used in a weight ratio of 5 to 100:1 relative to the polymer. If the amount of the organic solvent used is less than 5 times the amount of the polymer, the viscosity of the composition may increase, making it difficult to use the composition for spin coating. On the other hand, if the amount of the organic solvent used is more than 100 times the amount of the polymer, the thickness of the resulting semiconductor hard mask is excessively reduced, and the hard mask cannot perform its function.

[0096] The organic solvent is preferably selected from the group consisting of propylene glycol monomethyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), cyclohexanone, butyrolactone, ethyl lactate, N-methylpyrrolidone (NMP), methyl methoxypropionate (MMP), ethyl ethoxypropionate (EEP), dimethylformamide (DMF), and mixtures thereof. The organic solvent is most preferably propylene glycol methyl ether acetate (PGMEA).

[0097] The crosslinking agent is a component that crosslinks the polymer dissolved in the organic solvent. The crosslinking agent can be used in an amount of 0.1 to 3 parts by weight per 100 parts by weight of the organic solvent. If the amount of the crosslinking agent used is less than 0.1 parts by weight, crosslinking does not occur during spin coating, and the etching resistance of the resulting semiconductor hard mask is poor. If the amount of the crosslinking agent used is more than 3 parts by weight, the hard mask polymer is crosslinked before spin coating, making it difficult to use the composition for spin coating. Excess crosslinking agent acts as an impurity during the formation of the semiconductor hard mask, resulting in poor etching resistance of the hard mask.

[0098] The crosslinker can be a methylated melamine resin, a methylated urea resin, or a glycoluril derivative represented by formula 17.

[0099] [ka]

[0100] The catalyst is used to promote the crosslinking reaction of the polymer by the crosslinking agent. The amount of the catalyst used is 0.001 to 0.1 parts by weight per 100 parts by weight of the organic solvent. If the amount of the catalyst is less than 0.001 parts by weight, the rate of the crosslinking reaction is slow, making it difficult to form a hard mask at the desired time. On the other hand, if the amount of the catalyst is more than 0.1 parts by weight, the curing speed of the hard mask composition increases, making it difficult to form a hard mask by spin coating.

[0101] The catalyst can be pyridinium p-toluenesulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate or an alkyl ester of an organic sulfonic acid.

[0102] The present invention further provides a patterning method using the hard mask composition. As described above, the hard mask polymer of the present invention can be used to form a hard mask having good etching resistance and can be easily dissolved in a solvent. Therefore, the hard mask composition of the present invention can be used in a semiconductor patterning process, particularly in spin coating.

[0103] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings so that those skilled in the art can easily carry out the present invention. In the description of the present invention, detailed descriptions of related known functions or structures are omitted if it is considered that they may unnecessarily obscure the essence of the present invention. Certain features shown in the drawings have been enlarged, reduced, or simplified to facilitate explanation, and the drawings and their elements are not necessarily in proportion. However, those skilled in the art will easily understand such details. EXAMPLES

[0104] [Example 1] 20 g of 1-hydroxypyrene (Formula 2), 11 g of 1,4-divinylbenzene, and 150 g of propylene glycol monomethyl ether acetate (PGMEA) were placed in a reactor. The inside of the reactor was maintained under a nitrogen atmosphere. Then, 0.5 g of triflic acid was added. The mixture was heated to 140° C. and refluxed for 6 hours. After the reaction was completed, the reaction mixture was slowly dripped into 1500 g of methanol to precipitate the polymer. The precipitated polymer was collected and dried under vacuum.

[0105] [Example 2] The procedure of Example 1 was repeated, except that 21 g of 1,6-dihydroxypyrene (Formula 2) was used instead of 1-hydroxypyrene.

[0106] [Example 3] The procedure of Example 1 was repeated, except that 32 g of 9,9-bis(4-hydroxyphenyl)fluorene (Formula 3) was used instead of 1-hydroxypyrene.

[0107] [Example 4]

[0108] The procedure of Example 1 was repeated, except that 40 g of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (Formula 4) was used instead of 1-hydroxypyrene.

[0109] [Example 5]

[0110] The procedure of Example 1 was repeated, except that 10 g of 1-hydroxypyrene and 20 g of 9,9-bis(6-hydroxy-2-naphthyl)fluorene were used instead of 1-hydroxypyrene.

[0111] [Comparative Example 1] 70g of PGMEA was added to 20g of 9,9-bis(4-hydroxyphenyl)fluorene and 9.5g of 1,4-bismethoxymethylbenzene. 0.16g of diethyl sulfate was added to the mixture. The subsequent procedure was the same as in Example 1 to synthesize the polymer.

[0112] [Experimental Example 1] Experiments were carried out to confirm the structures of the high molecular weight polymers prepared in Examples 1-5. The hydroxypyrene compounds, dihydroxypyrene compounds and other compounds used in Examples 1 to 5 had multiple benzene ring structures, so no characteristic peaks were observed even by NMR or FT-IR spectroscopy, which are commonly used to analyze the molecular morphology. Therefore, the weight average molecular weight of the polymer was measured by gel permeation chromatography (GPC). The results are shown in Table 1.

[0113] [Table 1]

[0114] As can be seen from the results in Table 1, the average molecular weights of the polymers of Examples 1-5 were greater than 4000, demonstrating that the method of the present invention is suitable for preparing high molecular weight polymers. Furthermore, the molecular weights of the polymers of Examples 1-5 were suitable for use of the polymers in forming hard masks for semiconductor applications. The same results were obtained with the polymer of Comparative Example 1, which is an isomer having the same atomic composition but different molecular shape.

[0115] [Examples 6 to 12] An experiment was conducted to compare the performance of hard masks formed using the polymers of Examples 1-5 and Comparative Example 1. Hard mask compositions for semiconductor applications were prepared by dissolving each of the polymers of Examples 1 to 5 and Comparative Example 1 in PGMEA as a solvent. The polymers and other components of the compositions and their amounts (g) are shown in Table 2.

[0116] [Table 2]

[0117] PGMEA was used as the solvent, the glycoluril derivative of formula 15 was used as the crosslinker, and pyridinium p-toluenesulfonate was used as the catalyst.

[0118] [Experimental Example 2] Each of the hard mask compositions prepared in Examples 6 to 12 was coated on a silicon wafer by spin coating, and the coating composition was then heated at 240° C. for 1 minute, followed by heating on a hot plate at 400° C. for 1 minute to form a hard mask.

[0119] The refractive index n and extinction coefficient k were measured for the hard masks formed using the compositions of Examples 6 to 12. The results are shown in Table 3. In this experiment, an ellipsometer and a light source with a wavelength of 193 nm were used.

[0120] [Table 3]

[0121] As can be seen from the results in Table 3, the compositions of Examples 6 to 10, which contained the polymers of Examples 1 to 5, respectively, had refractive indices and extinction coefficients suitable for use in hard masks for semiconductor applications. It was also confirmed that a hard mask can be formed using the composition of Example 11, which contained a mixture of the polymers of Examples 1 and 5. However, it was confirmed that the hard mask formed using the composition of Example 12, which was prepared using 1,4-bismethoxymethylbenzene instead of divinylbenzene, performed poorly due to its high extinction coefficient.

[0122] The hard masks formed using the compositions of Examples 6 to 12 were evaluated for dry etching resistance. Hard masks formed using the compositions of Examples 6-12 were dry etched for 10 seconds using CF4 in a dry etching apparatus. The dry etch rate was defined as (film thickness before dry etch-film thickness after dry etch) / time. The dry etch performance was defined as the dry etch rate of each of the compositions of Examples 6-11 / the dry etch rate of the composition of Example 12. The calculation results are shown in Table 4.

[0123] [Table 4]

[0124] As can be seen from the results in Table 4, the use of the polymers of Examples 1-5 results in a decrease in the etch rate compared to the use of the polymer of Comparative Example 1, indicating the improved etch resistance of the polymers of Examples 1-5 during dry etching. In conclusion, the hard mask polymers of the present invention and the compositions of the present invention prepared using the polymers have high etch resistance.

[0125] [Examples 13 to 23] An experiment was conducted to determine the effect of the amounts of the components in the preparation of the compositions, using the polymer of Example 1 and mixing the components in the amounts (g) shown in Table 5.

[0126] [Table 5]

[0127] Experimental Example 3 The procedure of Experimental Example 2 was repeated, except that the compositions of Examples 13 to 23 were used to determine whether they were suitable for use in forming a hard mask. The results are shown in Table 6.

[0128] [Table 6]

[0129] As can be seen from the results in Table 6, the hard mask formed using the composition of Example 15, which was prepared under the same conditions as Example 6, had suitable physical properties. The hard mask formed using the composition of Example 13, which contained too little polymer, did not remain after etching, and its etch rate and performance could not be measured. This is because the mask layer thickness was too small due to the small amount of polymer present. In contrast, spin coating of the composition of Example 17, which contained too much polymer, was unsuccessful due to the relatively small amount of solvent, making it impossible to proceed with the experiment.

[0130] It was found that the use of the composition of Example 18, which contains an excessively small amount of crosslinking agent, caused inferior etching performance compared to the use of the composition containing the polymer of Comparative Example 1, which is commonly used in the art. On the other hand, the composition of Example 20, which contains an excessively large amount of crosslinking agent, had a high extinction coefficient and was difficult to use for forming a hard mask.

[0131] The composition of Example 21, which used too little catalyst, was not completely cured before the completion of spin coating, and was unable to form a hard mask. The composition of Example 21, which used too much catalyst, was cured before the completion of spin coating, and it was difficult to form a hard mask.

[0132] Although details of the present invention have been described in detail, it will be apparent to those skilled in the art that such details are merely preferred embodiments and are not intended to limit the scope of the invention, therefore, the true scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A hard mask polymer for semiconductor applications comprising a structure represented by Formula 1: 【Chemistry 1】 In the formula, R １ is a hydrocarbon containing one or more benzene ring structures, and n is an integer from 1 to 10,000.

2. The hard mask polymer of claim 1 , wherein the hydrocarbon having a benzene ring structure has a structure represented by Formula 2 or Formula 3: 【Chemistry 2】 In the formula, R ２ is H, OH or C １ -C ５ It is a hydrocarbon; 【Chemistry 3】 In the formula, R ３ and R ４ are each independently unsubstituted or OH or C １ -C ５ benzene, naphthalene or biphenyl, substituted with a hydrocarbon, where R ３ and R ４ may be linked via a hydrocarbon or ether group to form a ring structure, or may each independently be bonded to each other.

3. The hard mask polymer of claim 2, wherein the structure of formula 3 is represented by any one of formulas 4 to 8. 【Chemistry 4】

4. 2. The hard masking polymer of claim 1, wherein the hard mask polymer comprises a structure represented by Formula 9: 【Chemistry 5】 In the formula, R ５ and R ６ are each independently a hydrocarbon containing a benzene ring structure, and m and o are each independently an integer of 1 to 10,000.

5. R ５ 5. The hardmask polymer of claim 4, wherein the hardmask polymer has a structure represented by formula 10: 【Chemistry 6】 In the formula, R ７ is H, OH or C １ -C ５ is a hydrocarbon, R ６ has a structure represented by formula 11: 【Chemistry 7】 In the formula, R ８ and R ９ are each independently unsubstituted or OH or C １ -C ５ benzene, naphthalene or biphenyl, substituted with a hydrocarbon, where R ８ and R ９ may be linked via a hydrocarbon or ether group to form a ring structure, or may each independently be bonded to each other.

6. The hard mask polymer of claim 5, wherein the structure of formula 11 is represented by any one of formulas 12 to 16: 【Chemistry 8】

7. 2. The hardmask polymer of claim 1, wherein the hardmask polymer has a weight average molecular weight of 1,000 to 20,000.

8. A hardmask composition for semiconductor applications comprising the hardmask polymer of any one of claims 1 to 7.

9. 9. The hardmask composition of claim 8, wherein the hardmask composition comprises 100 parts by weight of an organic solvent, 1 to 20 parts by weight of the hardmask polymer, 0.1 to 3 parts by weight of a crosslinker, and 0.001 to 0.1 parts by weight of a catalyst.

10. 10. The hardmask composition of claim 9, wherein the organic solvent is selected from the group consisting of propylene glycol monomethyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), cyclohexanone, butyrolactone, ethyl lactate, N-methylpyrrolidone (NMP), methyl methoxypropionate (MMP), ethyl ethoxypropionate (EEP), dimethylformamide (DMF), and mixtures thereof.

11. 10. The hardmask composition of claim 9, wherein the crosslinker is a methylated melamine resin, a methylated urea resin, or a glycoluril derivative represented by Formula 17. 【Chemistry 9】

12. 10. The hardmask composition of claim 9, wherein the catalyst is pyridinium p-toluenesulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, or an alkyl ester of an organic sulfonic acid.

13. A patterning method using the hard mask composition of claim 8.

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