Aromatic condensation polymer compound of double or triple copolymer and resist underlayer composition

Abstract

This invention provides aromatic condensation polymer compounds of bis or trimeromers having a weight-average molecular weight of 1,500 to 30,000, formed by a condensation reaction between heteroaromatic compounds, cyclopentanone derivatives, and aromatic compounds under acid-catalyzed conditions. Furthermore, this invention provides an antireflective photoresist underlayer composition comprising (i) an aromatic condensation polymer compound of bis or trimeromers or a mixture thereof and (ii) an organic solvent.

Description

Technical Field

[0001] This invention relates to a novel aromatic condensation polymer compound with antireflective properties, useful in lithography processes, and a photoresist underlayer composition. More specifically, this invention relates to an aromatic condensation polymer compound in the form of an aromatic condensation polymer having strong ultraviolet absorption in the ultraviolet wavelength range, and a photoresist underlayer composition comprising this compound. Prior Technology

[0002] With the increasing demand for miniaturization processes in the semiconductor industry, efficient lithography is crucial for achieving ultra-fine precision. In particular, there is a growing demand for new materials for hard masking processes, which are essential in etching.

[0003] Generally, a hard mask layer serves as an intermediate layer, transferring the fine pattern of photoresist to the underlying substrate layer through selective etching processes. Therefore, the hard mask layer needs to possess properties such as chemical resistance, heat resistance, and etching resistance to withstand multiple etching processes. Commonly used hard mask layers are ACLs (amorphous carbon layers) fabricated using chemical vapor deposition (CVD). However, this method has several drawbacks, including high facility investment costs, particle generation during the process, and optical alignment problems due to the opacity of the film, making its use very inconvenient.

[0004] Recently, spin coating, an alternative to CVD processes, has been introduced to form hard masks. Spin coating uses solvent-soluble organic polymer materials to form the hard mask composition. The most important aspect of this process is the formation of an organic polymer coating film that also exhibits etch resistance.

[0005] However, the two properties required for organic hard masking layers, namely solubility and etch resistance, conflict with each other, thus necessitating a hard masking composition that can satisfy both properties simultaneously.

[0006] Materials that satisfy the properties of organic hard masking layers and are introduced into semiconductor lithography processes are disclosed, for example, in Korean Patent Publication Nos. 10-2009-0120827, 10-2008-0107210, and WO 2013100365 A1. These materials are photoresist underlayer materials using copolymers with appropriately high molecular weights synthesized using hydroxypyrene in existing phenolic resin manufacturing methods.

[0007] However, as semiconductor lithography processes become increasingly sophisticated, these photoresist underlayer materials have reached a point where they are less selective in etching compared to traditional inorganic hard masking materials, making it difficult to fully utilize their masking function.

[0008] Therefore, it has become urgent to introduce photoresist underlayer materials that are more suitable for etching processes. Summary of the Invention

[0009] [Unresolved Issues]

[0010] The present invention aims to provide a novel aromatic condensation polymer compound with excellent polymer solubility, high etch selectivity and sufficient multiple etch resistance, as well as a composition containing the polymer.

[0011] Furthermore, the present invention aims to provide a novel aromatic condensation polymer compound that can be used to perform lithography by minimizing the reflectivity between the photoresist and the back layer, and a composition containing the polymer.

[0012] [Technical Solution]

[0013] The novel aromatic condensation polymer compound according to the present invention can be an aromatic condensation polymer compound of a bis or tripolymer synthesized by a condensation reaction between a heteroaromatic compound represented by the following chemical formula A, a cyclopentanone derivative represented by the following chemical formula B, and an aromatic compound, represented by the following chemical formula 1.

[0014] [Chemical Formula A] [Chemical Formula B]

[0015] In chemical formula A, n and m are 0 or 1, and R 1 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0016] In chemical formula B, R2 to R5 are each hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group. For R2 to R5, the substituted or unsubstituted C1 to C10 alkyl group and the substituted or unsubstituted C6 to C20 aryl group may be interconnected to form a hydrocarbon ring and / or an aromatic ring.

[0017] [Chemical Formula 1]

[0018] In Formula 1, n and m are each 0 or 1, and R1 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group. Furthermore, R2 to R5 are each hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group. For R2 to R5, the substituted or unsubstituted C1 to C10 alkyl group and the substituted or unsubstituted C6 to C20 aryl group may be interconnected to form a hydrocarbon ring and / or an aromatic ring.

[0019] In addition, o, p, and q have the following ranges: o / (o+p+q)=0.1~0.5, p / (o+p+q)=0.3~0.6, and q / (o+p+q)=0~0.4.

[0020] Meanwhile, the weight-average molecular weight (Mw) of the aromatic condensation polymer compound (copolymer) represented by chemical formula 1 can be 1,500 to 30,000, and is preferably 2,000 to 15,000.

[0021] Furthermore, the photoresist underlayer composition according to the present invention comprises: (i) the above-mentioned aromatic condensation polymer compound or mixture thereof of the bis or tripolymer according to the present invention; and (ii) an organic solvent.

[0022] [Technical Effects]

[0023] According to the present invention, the aromatic condensation polymer compounds of the bis or trimer copolymers in Formula 1 have a very high carbon content in the polymer compound and also have an oxygen-free structure in the aromatic ring, thus resulting in a very low Ohnishi parameter value for predicted etch resistance. Therefore, when using photoresist underlayer compositions containing aromatic condensation polymer compounds of bis or trimer copolymers, there is a very advantageous effect in terms of etch resistance.

[0024] Furthermore, according to the present invention, the aromatic condensation polymer compound of the dipolymer as shown in Formula 1 or the aromatic condensation polymer compound of the tripomer as shown in Formula 2 has a very high packing density in terms of polymer structure. Therefore, when a photoresist underlayer composition containing the dipolymer or tripomer is used to form a film, the film density increases and the etching resistance becomes very excellent.

[0025] Therefore, according to the present invention, aromatic condensation polymer compounds of bis or tripolymers or photoresist underlayer compositions containing them have the advantage of high etch selectivity compared to conventional organic hard masks and sufficient resistance to multiple etches, thus providing lithography structures with excellent pattern evaluation results.

[0026] In particular, according to the present invention, the aromatic condensation polymer compound of the bi or tripolymer or the photoresist underlayer composition containing it, when forming a thin film, has a practical range of refractive index and absorbance as an antireflective film in the deep ultraviolet region such as ArF (193 nm) and KrF (248 nm), and thus has the advantage of minimizing the reflectivity between the photoresist and the back layer. Simple Explanation of the Diagram

[0027] none Implementation

[0028] The terminology used herein will be fully understood by those skilled in the art, and the following definitions are set forth for the purpose of explaining the invention.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as understood by one of ordinary skill in the art. The representative methods, apparatuses, and materials described herein, as well as any equivalent or similar methods, apparatuses, and materials, may be used in the practice or testing of this invention.

[0030] Furthermore, unless otherwise stated, all figures indicating amounts of components, reaction conditions, etc., in this specification and the claims should in all cases be understood to be modified by the word "approximately". Therefore, unless stated to the contrary, the numerical parameters listed in this specification and the claims are approximate values ​​and may vary according to the desired properties sought in the invention. As used herein, when referring to values ​​or amounts of mass, weight, time, volume, concentration, or percentage, the word "approximately" is intended to include certain variations from the specified value or amount, and these variations are included when it is appropriate to perform the disclosed methods.

[0031] The present invention will now be described in detail.

[0032] Although the invention will be described in detail below by way of specific embodiments, the invention may be modified in various ways and may have various forms.

[0033] It should be understood that the present invention is not limited to the specific embodiments described below, but includes all modifications, equivalents or alternatives within the spirit and technical scope of the present invention.

[0034] This invention relates to a novel aromatic condensation polymer compound and a photoresist underlayer composition.

[0035] The novel aromatic condensation polymer compound according to the present invention may be an aromatic condensation polymer compound of a bis or tripolymer represented by the following chemical formula 1, synthesized by a condensation reaction between a heteroaromatic compound represented by the following chemical formula A, a cyclopentanone derivative represented by the following chemical formula B, and an aromatic compound.

[0036] [Chemical Formula A] [Chemical Formula B]

[0037] In chemical formula A, n and m are 0 or 1, and R 1 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0038] In formula B, R2 to R5 are each hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group. For R2 to R5, the substituted or unsubstituted C1 to C10 alkyl group and the substituted or unsubstituted C6 to C20 aryl group may be interconnected to form a hydrocarbon ring and / or an aromatic ring.

[0039] [Chemical Formula 1]

[0040] In Formula 1, n and m are each 0 or 1, and R1 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group. Furthermore, R2 to R5 are each hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group. For R2 to R5, the substituted or unsubstituted C1 to C10 alkyl group and the substituted or unsubstituted C6 to C20 aryl group may be interconnected to form a hydrocarbon ring and / or an aromatic ring.

[0041] In addition, o, p, and q have the following ranges: o / (o+p+q)=0.1~0.5, p / (o+p+q)=0.3~0.6, and q / (o+p+q)=0~0.4.

[0042] Meanwhile, the weight-average molecular weight (Mw) of the aromatic condensation polymer compound (copolymer) represented by chemical formula 1 can be 1,500 to 30,000, and is preferably 2,000 to 15,000.

[0043] The heteroaromatic compound represented by chemical formula A that constitutes an aromatic condensation polymer compound represented by chemical formula 1 (bi or tripolymer) is preferably a heteroaromatic compound represented by chemical formula A-1.

[0044] [Chemical Formula A-1]

[0045] In chemical formula A-1, n and m are both 0 or 1, and R 1 is hydrogen, phenyl, naphthyl, phenanthryl or pyrene.

[0046] Furthermore, the cyclopentanone derivative represented by chemical formula B is preferably any one of the compounds represented by the following chemical formulas B-1 to B-10.

[0047] [Chemical Formula B-1] [Chemical Formula B-2] [Chemical Formula B-3] [Chemical Formula B-4] [Chemical Formula B-5] [Chemical Formula B-6] [Chemical Formula B-7] [Chemical Formula B-8] [Chemical Formula B-9] [Chemical Formula B-10]

[0048] The synthesis of aromatic condensation polymer compounds of bis or trimer copolymers represented by Chemical Formula 1 is carried out by a condensation reaction of the heteroaromatic compound represented by Chemical Formula A, the cyclopentanone derivative represented by Chemical Formula B, and the aromatic compound under acid catalytic conditions. In particular, polymerization can be carried out at a reaction temperature of 100 to 130°C and a reaction time of 10 to 20 hours to obtain the above-mentioned weight-average molecular weight (Mw).

[0049] The acid catalyst can be a commonly used strong acid, such as sulfuric acid, nitric acid, hydrochloric acid, or p-toluenesulfonic acid, and if necessary, an acid with relatively weak acid properties, such as methanesulfonic acid or phosphoric acid, can be used. Preferred acid catalysts are sulfuric acid, p-toluenesulfonic acid, or methanesulfonic acid.

[0050] The concentration of the acid catalyst can be 1 to 20 mol% based on the total monomer concentration used, preferably 3 to 10 mol%.

[0051] Meanwhile, aromatic condensation polymer compounds of bis or tripolymers represented by chemical formula 1 may have, for example, the forms of the following chemical formulas 1-1 to 1-39.

[0052] [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formulas 1-5] [Chemical Formulas 1-6] [Chemical Formulas 1-7] [Chemical Formulas 1-8] [Chemical Formulas 1-9] [Chemical Formulas 1-10] [Chemical Formula 1-11] [Chemical Formula 1-12] [Chemical Formula 1-13] [Chemical Formula 1-14] [Chemical Formula 1-15] [Chemical Formula 1-16] [Chemical Formula 1-17] [Chemical Formula 1-18] [Chemical Formula 1-19] [Chemical Formula 1-20] [Chemical Formula 1-21] [Chemical Formula 1-22] [Chemical Formula 1-23] [Chemical Formula 1-24] [Chemical Formula 1-25] [Chemical Formula 1-26] [Chemical Formula 1-27] [Chemical Formula 1-28] [Chemical Formula 1-29] [Chemical Formulas 1-30] [Chemical Formula 1-31] [Chemical Formula 1-32] [Chemical Formula 1-33] [Chemical Formula 1-34] [Chemical Formula 1-35] [Chemical Formula 1-36] [Chemical Formula 1-37] [Chemical Formula 1-38] [Chemical Formula 1-39]

[0053] In formulas 1-11 to 1-39, R2 to R5 are each hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group. For R2 to R5, the substituted or unsubstituted C1 to C10 alkyl group and the substituted or unsubstituted C6 to C20 aryl group may be interconnected to form a hydrocarbon ring and / or an aromatic ring. The hydrocarbon ring and the aromatic ring may preferably be cyclopentyl, 2-hydroxyfluorenone, or fluorenone.

[0054] In chemical formulas 1-1 to 1-10, n can be 10 to 100.

[0055] In chemical formulas 1-11 to 1-39, o, p, and q have the following ranges: o / (o+p+q) = 0.1~0.5, p / (o+p+q) = 0.3~0.6, and q / (o+p+q) = 0~0.4.

[0056] More preferably, the aromatic condensation polymer compound of the di or tripolymer represented by chemical formula 1 may have, for example, the form of chemical formulas 2-1 to 2-14.

[0057] [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] [Chemical Formula 2-4] [Chemical Formula 2-5] [Chemical Formula 2-6] [Chemical Formula 2-7] [Chemical Formula 2-8] [Chemical Formula 2-9] [Chemical Formula 2-10] [Chemical Formula 2-11] [Chemical Formula 2-12] [Chemical Formula 2-13] [Chemical Formula 2-14]

[0058] In addition, the above polymers can be mixed with phenolic resins or aromatic C6 to C20 phenolic polymers with hydroxyl groups to improve the solubility, coating properties or curing properties of the overall photoresist underlayer composition.

[0059] Furthermore, the photoresist underlayer composition according to the present invention comprises: (i) the above-mentioned aromatic condensation polymer compound or mixture of such polymer compounds of the bis or tripolymer according to the present invention; and (ii) an organic solvent.

[0060] In the photoresist underlayer composition, based on 100 parts by weight of the total composition, (i) the amount of aromatic condensation polymer compound of bis or tripolymer, or a mixture of such polymer compounds, may be 1 to 30 parts by weight. If the amount of (i) used is less than 1 part by weight or more than 30 parts by weight, the coating thickness will become less than or greater than the target coating thickness, making it difficult to achieve a precise coating thickness.

[0061] There are no particular limitations on the organic solvents, as long as they have sufficient solubility for the above-mentioned aromatic ring-containing polymers. For example, they can be propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, ethyl lactate, etc.

[0062] Furthermore, the photoresist lower layer composition according to the present invention may further include (iii) a crosslinking agent and (iv) an acid catalyst.

[0063] (iii) The crosslinking agent is preferably capable of crosslinking the repeating units of the polymer by heating in the catalytic reaction of the generated acid, and (iv) the acid catalyst is preferably a thermally activated acid catalyst.

[0064] There are no particular restrictions on the crosslinking agents (iii) used in the photoresist underlayer composition, as long as they are crosslinking agents that can react with aromatic ring polymers in a manner that can be catalyzed by the generated acid.

[0065] Examples of crosslinking agents may include melamine-based, substituted urea-based, or polymers thereof. Preferably, the crosslinking agent has at least two substituents that form crosslinks, and is a compound such as methoxymethylated oxalurone, butoxymethylated oxalurone, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea.

[0066] Furthermore, crosslinking agents with high heat resistance can be used as crosslinking agents, and compounds containing crosslinking substituents with aromatic rings in their molecules are preferably used. Examples of such compounds include compounds having the following structural formula.

[0067] As the (iv) acid catalyst used in the photoresist lower layer composition of the present invention, organic acids such as p-toluenesulfonic acid monohydrate can be used, and TAG (thermal acid generator) compounds that ensure storage stability can also be used as catalysts. TAG is an acid generator compound that releases acid during heat treatment; for example, pyridinium p-toluenesulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, alkyl esters of organic sulfonic acids, etc., are preferably used.

[0068] When the photoresist underlayer composition according to the invention further comprises (iii) a crosslinking agent and (iv) an acid catalyst, the total 100% by weight of the photoresist underlayer composition according to the invention may comprise: (i) 1 to 30% by weight (more preferably 3 to 15% by weight) of an aromatic condensation polymer compound of a di or tripolymer or a mixture of such polymer compounds, (iii) 0.1 to 5% by weight (more preferably 0.1 to 3% by weight) of a crosslinking agent, (iv) 0.001 to 0.05% by weight (more preferably 0.001 to 0.03% by weight) of an acid catalyst, and (ii) an organic solvent as the remainder, preferably containing 75 to 98% by weight of an organic solvent.

[0069] In the above composition, if (i) the polymer is less than 1% by weight or more than 30% by weight, the coating thickness will be less than or more than the target coating thickness, making it difficult to achieve a precise coating thickness.

[0070] Furthermore, if the crosslinking agent is less than 0.1% by weight, crosslinking properties may not appear, while if it exceeds 5% by weight, the optical properties of the coated film may change due to excessive addition.

[0071] Furthermore, if the acid catalyst is less than 0.001% by weight, the crosslinking properties may not appear well, while if it exceeds 0.05% by weight, the acidity may increase due to excessive addition, which may affect storage stability.

[0072] The present invention will be described in more detail below through embodiments, but the following embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0073] [Example 1] [Chemical Formula 2-1]

[0074] In a 250 mL round-bottom flask, 17.6 g (60 mmol) of naphthylcarbazole and 6 g (72 mmol) of cyclopentanone were dissolved in 60 g of γ-butyrolactone (GBL), followed by the addition of 1.6 g of p-toluenesulfonic acid (PTSA). Polymerization was then carried out at 120 °C for 20 hours.

[0075] After polymerization, the reactants were precipitated in excess methanol / water (8:2) solvent and then neutralized with triethylamine. The resulting precipitate was washed with excess methanol for about 1 hour, then filtered and dried in a vacuum oven at 65°C for 24 hours to obtain 17 g (75% yield) of the desired polymer of formula 2-1.

[0076] The polymer of chemical formula 2-1 has a weight-average molecular weight (Mw) of 4,600 and a polydispersity (Mw / Mn) of 1.85.

[0077] [Example 2] [Chemical Formula 2-2]

[0078] 7 g (60 mmol) of indole and 6.6 g (60 mmol) of 2-norborneone were synthesized in the same manner as in Example 1 to obtain 10 g (74% yield) of the desired polymer of formula 2-2. The synthesized polymer of formula 2-2 had a weight-average molecular weight (Mw) of 4,300 and a polydispersity (Mw / Mn) of 1.89.

[0079] [Example 3] [Chemical Formula 2-3]

[0080] 8.8 g (30 mmol) of naphthylcarbazole and 7.2 g (40 mmol) of fluorenone were synthesized in the same manner as in Example 1 to obtain 7 g (49% yield) of the desired polymer of formula 2-3. The synthesized polymer of formula 2-3 had a weight-average molecular weight (Mw) of 3,700 and a polydispersity (Mw / Mn) of 1.88.

[0081] [Example 4] [Chemical Formula 2-4]

[0082] 6.7 g (40 mmol) of carbazole and 7.8 g (40 mmol) of 2-hydroxy-9-fluorenone were synthesized in the same manner as in Example 1 to obtain 10 g (69% yield) of the desired polymer of formula 2-4. The synthesized polymer of formula 2-4 had a weight-average molecular weight (Mw) of 3,300 and a polydispersity (Mw / Mn) of 1.89.

[0083] [Example 5] [Chemical Formula 2-5]

[0084] 14.7 g (50 mmol) of carbazole, 9.3 g (110 mmol) of cyclopentanone, and 7.2 g (50 mmol) of 1-naphthol were synthesized in the same manner as in Example 1 to obtain 19 g (63% yield) of the desired polymer of formula 2-5. The synthesized polymer of formula 2-5 had a weight-average molecular weight (Mw) of 3,900 and a polydispersity (Mw / Mn) of 1.88.

[0085] [Example 6] [Chemical Formula 2-6]

[0086] 14.6 g (60 mmol) of phenylcarbazole, 9.3 g (110 mmol) of cyclopentanone, and 8.7 g (40 mmol) of 1-pyrene were synthesized in the same manner as in Example 1 to obtain 26 g (82% yield) of the desired polymer of formula 2-6. The synthesized polymer of formula 2-6 had a weight-average molecular weight (Mw) of 3,800 and a polydispersity (Mw / Mn) of 1.85.

[0087] [Example 7] [Chemical Formula 2-7]

[0088] 17.6 g (60 mmol) of naphthylcarbazole, 19.8 g (110 mmol) of 9-fluorenone, and 8.7 g (40 mmol) of 1-pyrene were synthesized in the same manner as in Example 1 to obtain 35 g (79% yield) of the desired polymer of formula 2-7. The synthesized polymer of formula 2-7 had a weight-average molecular weight (Mw) of 3,900 and a polydispersity (Mw / Mn) of 1.88.

[0089] [Example 8] [Chemical Formula 2-8]

[0090] 17.6 g (60 mmol) of naphthylcarbazole, 19.8 g (110 mmol) of 9-fluorenone, and 8.1 g (40 mmol) of 1-pyrene were synthesized in the same manner as in Example 1 to obtain 32 g (73% yield) of the desired polymer of formula 2-8. The synthesized polymer of formula 2-8 had a weight-average molecular weight (Mw) of 3,500 and a polydispersity (Mw / Mn) of 1.95.

[0091] [Example 9] [Chemical Formula 2-9]

[0092] 7 g (60 mmol) of indole, 9.3 g (110 mmol) of cyclopentanone, and 8.7 g (40 mmol) of 1-pyrene were synthesized in the same manner as in Example 1 to obtain 18 g (75% yield) of the desired polymer of formula 2-9. The synthesized polymer of formula 2-9 had a weight-average molecular weight (Mw) of 4,500 and a polydispersity (Mw / Mn) of 1.93.

[0093] [Example 10] [Chemical Formula 2-10]

[0094] 10 g (60 mmol) of carbazole, 9.3 g (110 mmol) of cyclopentanone, and 8.7 g (40 mmol) of 1-pyrene were synthesized in the same manner as in Example 1 to obtain 20 g (74% yield) of the desired polymer of formula 2-10. The synthesized polymer of formula 2-10 had a weight-average molecular weight (Mw) of 4,300 and a polydispersity (Mw / Mn) of 1.91.

[0095] [Example 11] [Chemical Formula 2-11]

[0096] 7 g (60 mmol) of indole, 18 g (100 mmol) of 9-fluorenone, and 8.8 g (40 mmol) of phenyl-1-naphthylamine were synthesized in the same manner as in Example 1 to obtain 27 g (80% yield) of the desired polymer of formula 2-11. The synthesized polymer of formula 2-11 had a weight-average molecular weight (Mw) of 5,300 and a polydispersity (Mw / Mn) of 1.90.

[0097] [Example 12] [Chemical Formula 2-12]

[0098] 7 g (60 mmol) of indole, 18 g (100 mmol) of 9-fluorenone, and 11.4 g (40 mmol) of bis-2-naphthol were synthesized in the same manner as in Example 1 to obtain 28 g (77% yield) of the desired polymer of formula 2-12. The synthesized polymer of formula 2-12 had a weight-average molecular weight (Mw) of 5,100 and a polydispersity (Mw / Mn) of 1.93.

[0099] [Example 13] [Chemical Formula 2-13]

[0100] 17.6 g (60 mmol) of naphthylcarbazole, 18 g (100 mmol) of 9-fluorenone, and 4.7 g (40 mmol) of indole were synthesized in the same manner as in Example 1 to obtain 30 g (74% yield) of the desired polymer of formula 2-13. The synthesized polymer of formula 2-13 had a weight-average molecular weight (Mw) of 5,500 and a polydispersity (Mw / Mn) of 1.91.

[0101] [Example 14] [Chemical Formula 2-14]

[0102] 10 g (60 mmol) of carbazole, 18 g (100 mmol) of 9-fluorenone, and 4.7 g (40 mmol) of indole were synthesized in the same manner as in Example 1 to obtain 26 g (80% yield) of the desired polymer of formula 2-14. The synthesized polymer of formula 2-14 had a weight-average molecular weight (Mw) of 6,500 and a polydispersity (Mw / Mn) of 1.97.

[0103] [Comparative Example] Synthesis of Phenolic Polymers

[0104] 35 g (100 mmol) of 9,9-dihydroxyphenylfluorene and 11.7 g (110 mmol) of benzaldehyde were dissolved in 109 g of PGMEA, and then 1 g of concentrated sulfuric acid was added. After polymerization was carried out in the same manner as in Example 1, the polymer was purified and dried in a vacuum oven. The phenolic polymer of the comparative example has a weight-average molecular weight (Mw) of 3,300.

[0105] <Fabrication of Photoresist Underlayer>

[0106] 1 g of polymer and 300 ppm of surfactant prepared in Examples 1, 2, 3, 7, 11, 12, 13 and 14 and the comparative examples were completely dissolved in 7 g of propylene glycol monomethyl ether acetate (PGMEA) and 2 g of cyclohexanone, and filtered using a 0.1 μm membrane filter to prepare the photoresist lower layer composition of Examples 1, 2, 3, 7, 11, 12, 13 and 14 and the comparative examples, respectively.

[0107] Examples 1, 2, 3, 7, 11, 12, 13, and 14, as well as the comparative examples, were each spin-coated onto a silicon wafer and baked at 240 degrees Celsius for 60 seconds to form a thin film with a thickness of 3000 Å. The refractive index n and extinction coefficient k of the formed films were measured. An ellipsometry (JA Woollam) was used, and the measurement results are shown in Table 1 below.

[0108] [Table 1] Photoresist lower layer composition Optical properties (193 nanometers) Optical properties (248 nanometers) Refractive index (n) Extinction coefficient (k) Refractive index (n) Extinction coefficient (k) Example 1 1.53 0.51 1.71 0.51 Example 2 1.55 0.48 1.70 0.54 Example 3 1.52 0.61 1.73 0.57 Example 7 1.51 0.63 1.72 0.55 Example 11 1.53 0.58 1.72 0.54 Example 12 1.55 0.66 1.74 0.59 Example 13 1.54 0.61 1.72 0.54 Example 14 1.53 0.61 1.71 0.53 Comparison Examples 1.48 0.68 1.95 0.35

[0109] Based on the evaluation results, as shown in Table 1 above, it is confirmed that the photoresist lower layer composition of the present invention has a refractive index and absorbance that can be used as an anti-reflective film for ArF (193 nm) and KrF (248 nm) wavelengths.

[0110] Meanwhile, the refractive index range of materials commonly used as semiconductor antireflective films is approximately 1.4 to 1.8. The extinction coefficient is important; higher absorbance is better, but generally, if the k-value is 0.3 or higher, it is suitable for use as an antireflective film. Therefore, it can be seen that the hard mask composition of the present invention can be used as an antireflective film.

[0111] <Etching Properties Evaluation of Anti-reflective Hard Mask Components>

[0112] Examples 1, 4, 6, 7, 10, 11, 12 and 14, and the comparative examples, were formed by heat-treating the photoresist underlayer composition (10 wt%) at 400 degrees Celsius for 120 seconds to form thin films. Then, they were dry-etched for 60 seconds using a N₂ / O₂ mixed gas (50 mT / 300 W / 10 O₂ / 50 N₂ conditions) and a CFx gas (100 mT / 600 W / 42 CF₄ / 600 Ar / 15 O₂ conditions), respectively, and the film thickness was measured before and after etching.

[0113] The change in film thickness was divided by the etching time to calculate each etching rate ( / s). The results are shown in Table 2 below.

[0114] [Table 2] Photoresist lower layer composition N₂ / O₂ etching ( / s) CFx Etching ( / s) Example 1 35.8 28.7 Example 4 35.5 27.9 Example 6 35.6 29.3 Example 7 34.8 23.5 Example 10 35.7 29.1 Example 11 32.5 21.1 Example 12 34.5 24.5 Example 14 32.1 20.9 Comparison Examples 36.2 30.5

[0115] As shown in Table 2 above, it can be seen that the photoresist lower layer composition of the present invention is superior to or equivalent to the comparative examples in terms of N₂ / O₂ etching ( / s), and is significantly superior to the comparative examples in terms of CFx etching ( / s), which is most widely used in semiconductor manufacturing. []

[0116] none

Claims

1. An aromatic condensation polymer compound of the terpolymer, represented by the following chemical formula 1, synthesized by a condensation reaction between a heteroaromatic compound represented by the following chemical formula A, a cyclopentanone derivative represented by the following chemical formula B, and an aromatic compound, wherein, [Chemical Formula A] [Chemical Formula B] In Formula A, n and m are each 0 or 1, and R1 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group. In Formula B, R2 to R5 are each hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, and for R2 to R5, the substituted or unsubstituted C1 to C10 alkyl group and the substituted or unsubstituted C6 to C20 aryl group may be interconnected to form a hydrocarbon ring and / or an aromatic ring. [Formula 1] In Formula 1, n and m are each 0 or 1, and R1 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group. R2 to R5 are each hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, and for R2 to R5, the substituted or unsubstituted C1 to C10 alkyl group and the substituted or unsubstituted C6 to C20 aryl group may be interconnected to form a hydrocarbon ring and / or an aromatic ring, wherein Ar is naphthol, pyrene, pyrene, bis-2-naphthol, phenyl-1-naphthylamine, or indole, wherein o, p, and q have the following ranges: o / (o+p+q) = 0.1 to 0.5, p / (o+p+q) = 0.3 to 0.6, and q / (o+p+q) = greater than 0 to 0.4, and wherein q is not 0.

2. The aromatic condensation polymer compound of the trimer as claimed in claim 1, wherein the weight-average molecular weight (Mw) of the aromatic condensation polymer compound represented by formula 1 is 1,500 to 30,000.

3. The aromatic condensation polymer compound of the terpolymer as claimed in claim 1, wherein the aromatic condensation polymer compound of the terpolymer represented by Formula 1 is any one of the following Formulas 1-11 to 1-39: [Formula 1-11] [Formula 1-12] [Formula 1-13] [Formula 1-14] [Formula 1-15] [Formula 1-16] [Formula 1-17] [Formula 1-18] [Formula 1-19] [Formula 1-20] [Formula 1-21] [Formula 1-22] [Formula 1-23] [Formula 1-24] [Formula 1-25] [Formula 1-26] [Formula 1-27] [Formula 1-28] [Formula 1-29] [Formula 1-30] [Formula 1-31] ​​[Formula 1-32] [Formula 1-33] [Formula 1-34] [Chemical Formula 1-35] [Chemical Formula 1-36] [Chemical Formula 1-37] [Chemical Formula 1-38] [Chemical Formula 1-39] Wherein, In formulas 1-11 to 1-39, R2 to R5 are each hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, and the substituted or unsubstituted C1 to C10 alkyl group and the substituted or unsubstituted C6 to C20 aryl group may be linked together to form a ring, and wherein, in formulas 1-11 to 1-39, o, p, and q have the following ranges: o / (o+p+q) = 0.1 to 0.5, p / (o+p+q) = 0.3 to 0.6, and q / (o+p+q) = greater than 0 to 0.4, wherein q is not 0.

4. The aromatic condensation polymer compound of the terpolymer as claimed in claim 1, wherein the aromatic condensation polymer compound of the terpolymer is any one of the following chemical formulas 2-5 to 2-14, [Chemical Formula 2-5] [Chemical Formula 2-6] [Chemical Formula 2-7] [Chemical Formula 2-8] [Chemical Formula 2-9] [Chemical Formula 2-10] [Chemical Formula 2-11] [Chemical Formula 2-12] [Chemical Formula 2-13] [Chemical Formula 2-14] wherein, In chemical formulas 2-5 to 2-14, o, p, and q have the following ranges: o / (o+p+q) = 0.1 to 0.5, p / (o+p+q) = 0.3 to 0.6, and q / (o+p+q) = greater than 0 to 0.4, where q is not 0.

5. A photoresist underlayer composition, comprising: (i) an aromatic condensation polymer compound of a tripolymer as claimed in any one of claims 1 to 4, or a mixture of said polymer compounds; And (ii) organic solvents.

6. The photoresist underlayer composition as claimed in claim 5, wherein, based on 100 parts by weight of the entire photoresist underlayer composition, (i) the content of the aromatic condensation polymer compound of the trimer or a mixture of the polymer compounds is 1 to 30 parts by weight.

7. The photoresist underlayer composition as described in claim 5, further comprising: (iii) Crosslinking agents and (iv) acid catalysts.

8. The photoresist underlayer composition as claimed in claim 7, wherein the photoresist underlayer composition comprises 100% by weight and includes: (i) 1 to 30% by weight of the aromatic condensation polymer compound of the trimer or a mixture of the polymer compounds; (iii) 0.1 to 5% by weight of the crosslinking agent; (iv) 0.001 to 0.05% by weight of the acid catalyst; and (ii) the organic solvent as the remainder.