Novel aromatic condensation polymer compound and resist underlayer film composition

Abstract

The present invention provides an aromatic condensation biopolymer or terpolymer compound having a weight average molecular weight of 1,500 to 30,000 and formed by a condensation reaction with a heteroaromatic compound, a cyclopentanone derivative, and an aromatic compound under an acid catalyst condition. Also provided is an antireflective resist underlayer film composition comprising: (i) the aromatic condensation biopolymer or terpolymer compound or a polymer compound blend comprising same; and (ii) an organic solvent.

Description

Novel aromatic condensation polymer compound and resist underlayer film composition

[0001] The present invention relates to a novel aromatic condensation polymer compound and a resist underlayer film composition having antireflection film properties useful for a lithographic process, and more particularly, to an aromatic condensation polymer compound formed in the form of an aromatic condensation polymer having strong ultraviolet absorption in the ultraviolet wavelength region, and a resist underlayer film composition characterized by including the same.

[0002] As the semiconductor industry increasingly demands miniaturization, effective lithographic processes are essential to realize these ultra-fine technologies. In particular, demand for new materials for the hardmask process, which is crucial for the etching process, is increasing.

[0003]

[0004] In general, the hardmask film acts as an intermediate film that transfers the fine pattern of the photoresist to the lower substrate layer through a selective etching process. Therefore, the hardmask layer is required to have characteristics such as chemical resistance, heat resistance, and etching resistance to withstand multiple etching processes. The hardmask film used in the past was an amorphous carbon layer (ACL) film made by the chemical vapor deposition (CVD) method. However, this had many disadvantages such as high unit cost of equipment investment, particles generated during the process, and photoalign problems due to the opacity of the film, making it very inconvenient to use.

[0005]

[0006] Recently, a spin-on coating method has been introduced, forming a hardmask instead of the chemical vapor deposition method. This method uses an organic polymer material that is soluble in a solvent to form a hardmask composition. The most important characteristic of this method is that it must form an organic polymer coating film that also possesses etching resistance.

[0007] However, the two properties required for such an organic hardmask layer, namely solubility and etching resistance, are in conflict with each other, and a hardmask composition that can satisfy both of these properties is needed.

[0008]

[0009] Materials that satisfy the characteristics of these organic hardmask materials and are introduced into semiconductor lithographic processes have recently been introduced (Domestic Patent Publication No. 10-2009-0120827, Domestic Patent Publication No. 10-2008-0107210, WO 2013100365 A1, etc.). These materials were resist underlayer film materials using copolymers with appropriate high molecular weights synthesized using conventional phenol resin manufacturing methods using hydroxypyrene.

[0010]

[0011] However, as semiconductor lithographic processes have become increasingly refined, it has become difficult for these resist underlayer materials to sufficiently perform their role as masks due to insufficient etching selectivity in the etching process compared to conventional inorganic hard mask materials.

[0012]

[0013] Therefore, the introduction of a resist underlayer material more optimized for the etching process has become urgently needed.

[0014] The present invention aims to provide a novel aromatic condensation polymer having excellent polymer solubility, high etching selectivity, and sufficient resistance to multi-etching, and a composition containing the same.

[0015]

[0016] In addition, the present invention aims to provide a novel aromatic condensation polymer and a composition comprising the same, which can be used to perform lithographic techniques by minimizing reflectivity between a resist and a backside layer.

[0017] The novel aromatic condensation polymer compound according to the present invention may be an aromatic condensation polymer compound of a heteroaromatic compound represented by the following chemical formula a, a cyclopentanone derivative represented by the following chemical formula b, and a double or upper copolymer represented by the following chemical formula 1 synthesized by a condensation reaction with an aromatic compound.

[0018]

[0019] <Chemical formula a> <Chemical formula b>

[0020] In the above <chemical formula a>, n and m are 0 or 1, respectively,

[0021] R1 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

[0022] In the above <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, and the substituted or unsubstituted C1 to C10 alkyl group and the substituted or unsubstituted C6 to C20 aryl group of R2 to R5 can be connected to each other to form a hydrocarbon ring and / or an aromatic ring.

[0023]

[0024] <Chemical Formula 1>

[0025] In the above <Chemical Formula 1>

[0026] n and m are 0 or 1, respectively,

[0027] R1 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

[0028] 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 of R2 to R5 can be connected to each other to form a hydrocarbon ring and / or an aromatic ring.

[0029] The above o, p, and q have ranges of o / (o+p+q)=0.1~0.5, p / (o+p+q)=0.3~0.6, and q / (o+p+q)=0~0.4.

[0030]

[0031] Meanwhile, the weight average molecular weight (Mw) of the aromatic condensation polymer compound (copolymer) represented by the above chemical formula 1 may be 1,500 to 30,000, and preferably 2,000 to 15,000.

[0032]

[0033] In addition, the resist underlayer film composition of the present invention,

[0034] i) an aromatic condensation polymer compound of the double or triple copolymer of the present invention or a mixture thereof; and

[0035] ii) A resist underlayer film composition comprising an organic solvent.

[0036] The aromatic condensation polymer compound of the double or triple copolymer of the chemical formula 1 according to the present invention has a very high carbon content in the polymer compound, and also has a structure in which no oxygen is included in the aromatic ring, so that the Ohnishi Parameter value for predicting etch resistance is very low, and thus, when a resist underlayer film composition including the aromatic condensation polymer compound of the double or triple copolymer is used, there is a very advantageous advantage in etch resistance.

[0037]

[0038] In addition, the aromatic condensation polymer compound of the double copolymer of the chemical formula 1 according to the present invention, or the aromatic condensation polymer compound of the triple copolymer of the chemical formula 2, has a very high packing density in terms of polymer structure, so that when a thin film is formed using a resist underlayer film composition including the aromatic condensation polymer compound of the double or triple copolymer, the film density increases and the etching resistance is very excellent.

[0039]

[0040] Therefore, the resist underlayer film composition comprising the aromatic condensation polymer compound of the double or upper copolymer of the present invention, or a mixture thereof, has an advantage in that it has a high etching selectivity compared to a conventional organic hard mask, has sufficient resistance to multiple etching, and thus can provide a lithographic structure having excellent pattern evaluation results.

[0041]

[0042] In particular, the resist underlayer film composition comprising the aromatic condensation polymer compound of the double or upper copolymer of the present invention or a mixture thereof has a refractive index and absorbance in a useful range as an antireflection film in the deep UV region such as ArF (193 nm) and KrF (248 nm) when forming a film, thereby having the advantage of minimizing reflectivity between the resist and the back layer.

[0043] Although the following terms are believed to be well understood by those skilled in the art, the following definitions are provided to facilitate explanation of the presently disclosed subject matter.

[0044]

[0045] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the presently disclosed subject matter belongs. Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the presently disclosed subject matter, representative methods, devices, and materials are described.

[0046]

[0047] Additionally, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in this specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the presently disclosed subject matter. As used herein, the term "about" when referring to a value or amount of mass, weight, time, volume, concentration, or percentage is intended to encompass variations of up to ±1 wt.% from the stated amount, as long as such variations are suitable to perform the disclosed method.

[0048]

[0049] Since the present invention can be modified in various ways and can take many forms, specific embodiments are illustrated and described in detail in the text.

[0050]

[0051] However, this is not intended to limit the present invention to a specific disclosure form, but should be understood to include all modifications, equivalents, or substitutes included in the spirit and technical scope of the present invention.

[0052]

[0053] The present invention is described in more detail below.

[0054]

[0055] The present invention relates to a novel aromatic condensation polymer compound and a resist underlayer film composition.

[0056]

[0057] The novel aromatic condensation polymer compound of the present invention is

[0058] It may be an aromatic condensation polymer compound of a heteroaromatic compound represented by the following chemical formula a, a cyclopentanone derivative represented by the following chemical formula b, and a double or upper copolymer represented by the following chemical formula 1 synthesized by a condensation reaction with an aromatic compound.

[0059]

[0060] <Chemical formula a> <Chemical formula b>

[0061] In the above <chemical formula a>, n and m are 0 or 1, respectively,

[0062] R1 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

[0063] In the above <chemical formula b>

[0064] 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 of R2 to R5 can be connected to each other to form a hydrocarbon ring and / or an aromatic ring.

[0065]

[0066] <Chemical Formula 1>

[0067]

[0068] In the above <Chemical Formula 1>

[0069] n and m are 0 or 1, respectively,

[0070] R1 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

[0071] 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 of R2 to R5 can be connected to each other to form a hydrocarbon ring and / or an aromatic ring.

[0072] The above o, p, and q have ranges of o / (o+p+q)=0.1~0.5, p / (o+p+q)=0.3~0.6, and q / (o+p+q)=0~0.4.

[0073]

[0074] Meanwhile, the weight average molecular weight (Mw) of the aromatic condensation polymer compound (copolymer) represented by the above chemical formula 1 may be 1,500 to 30,000, and preferably 2,000 to 15,000.

[0075]

[0076] The heteroaromatic compound represented by the above chemical formula a, which constitutes the aromatic condensation polymer compound of the double or upper copolymer represented by the above chemical formula 1, may preferably be a heteroaromatic compound represented by the following chemical formula a-1,

[0077]

[0078] <Chemical formula a-1>

[0079] In the above chemical formula a-1, n and m are each 0 or 1, and R1 is hydrogen, phenyl, naphthyl, phenanthryl, or pyrenyl group.

[0080]

[0081] In addition, the cyclopentanone derivative represented by the above chemical formula b may preferably be any one of the compounds represented by the following chemical formulas b-1 to b-10.

[0082]

[0083]

[0084] <Chemical Formula B-1> <Chemical Formula B-2> <Chemical Formula B-3>

[0085]

[0086] <Chemical Formula B-4> <Chemical Formula B-5> <Chemical Formula B-6>

[0087]

[0088] <Chemical Formula B-7> <Chemical Formula B-8>

[0089]

[0090] <Chemical Formula B-9> <Chemical Formula B-10>

[0091]

[0092] The synthesis of the aromatic condensation polymer compound of the double or upper copolymer represented by the above chemical formula 1 is obtained by a condensation reaction with a heteroaromatic compound represented by the above chemical formula a, a cyclopentanone derivative, and an aromatic compound under acid catalyst conditions, and in particular, the above weight average molecular weight (Mw) can be obtained by polymerization at a reaction temperature of 100 to 130°C and a reaction time of 10 to 20 hours.

[0093]

[0094] The above acid catalyst may be a strong acid such as sulfuric acid, nitric acid, hydrochloric acid, or paratoluene sulfonic acid, which are commonly used, and, if necessary, an acid with relatively weak acid properties such as methanesulfonic acid or phosphoric acid may be used. Preferred acid catalysts may be sulfuric acid, paratoluenesulfonic acid, or methanesulfonic acid.

[0095] The concentration of the acid catalyst can be used at a concentration of 1 to 20 mol%, preferably 3 to 10 mol%, based on the total monomer concentration used.

[0096]

[0097] Meanwhile, the aromatic condensation polymer compound of the double or upper copolymer represented by the preferred chemical formula 1 may have, for example, the form of the chemical formulas 1-1 to 1-39 below.

[0098] <Chemical Formula 1-1> <Chemical Formula 1-2>

[0099]

[0100]

[0101] <Chemical Formula 1-3> <Chemical Formula 1-4>

[0102]

[0103]

[0104] <Chemical Formula 1-5> <Chemical Formula 1-6>

[0105]

[0106]

[0107] <화학식 1-7> <화학식 1-8>

[0108]

[0109]

[0110] <화학식 1-9> <화학식 1-10>

[0111]

[0112]

[0113] <화학식 -11>

[0114]

[0115]

[0116] <화학식 1-12>

[0117]

[0118]

[0119] <화학식 1-13>

[0120]

[0121]

[0122] <화학식 1-14>

[0123]

[0124]

[0125] <화학식 1-15>

[0126]

[0127]

[0128] <화학식 1-16>

[0129]

[0130]

[0131] <화학식 1-17>

[0132]

[0133]

[0134] <화학식 1-18>

[0135]

[0136]

[0137] <화학식 1-19>

[0138]

[0139]

[0140] <화학식 1-20>

[0141]

[0142]

[0143] <화학식 1-21>

[0144]

[0145]

[0146] <화학식 1-22>

[0147]

[0148]

[0149] <화학식 1-23>

[0150]

[0151]

[0152] <화학식 1-24>

[0153]

[0154]

[0155] <화학식 1-25>

[0156]

[0157]

[0158] <화학식 1-26>

[0159]

[0160]

[0161] <화학식 1-27>

[0162]

[0163]

[0164] <화학식 1-28>

[0165]

[0166]

[0167] <화학식 1-29>

[0168]

[0169]

[0170] <화학식 1-30>

[0171]

[0172]

[0173] <화학식 1-31>

[0174]

[0175]

[0176] <화학식 1-32>

[0177]

[0178]

[0179] <화학식 1-33>

[0180]

[0181]

[0182] <화학식 1-34>

[0183]

[0184]

[0185] <화학식 1-35>

[0186]

[0187]

[0188] <화학식 1-36>

[0189]

[0190]

[0191] <화학식 1-37>

[0192]

[0193]

[0194] <Chemical Formula 1-38>

[0195]

[0196]

[0197] <Chemical Formula 1-39>

[0198]

[0199]

[0200] In the above <Chemical Formula 1-11> to <Chemical Formula 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 of R2 to R5 may be connected to each other to form a hydrocarbon ring and / or an aromatic ring, and the hydrocarbon ring and the aromatic ring may preferably be a cyclopentyl group, a 2-hydroxy flurenone group, or a flurenone group.

[0201] In the above <Chemical Formula 1-1> to <Chemical Formula 1-10>, n can be 10 to 100,

[0202] In the above <Chemical Formula 1-11> to <Chemical Formula 1-39>, o, p, and q have a range of o / (o+p+q)=0.1~0.5, p / (o+p+q)=0.3~0.6, and q / (o+p+q)=0~0.4.

[0203]

[0204] The aromatic condensation polymer compound of the double or upper copolymer represented by the more preferable chemical formula 1 may have, for example, the form of the chemical formulas 2-1 to 2-14 below.

[0205]

[0206] <Chemical Formula 2-1> <Chemical Formula 2-2>

[0207]

[0208]

[0209] <화학식 2-3> <화학식 2-4>

[0210]

[0211] <화학식 2-5>

[0212]

[0213]

[0214] <화학식 2-6>

[0215]

[0216]

[0217] <화학식 2-7>

[0218]

[0219]

[0220] <화학식 2-8>

[0221]

[0222]

[0223] <화학식 2-9>

[0224]

[0225]

[0226] <화학식 2-10>

[0227]

[0228]

[0229] <화학식 2-11>

[0230]

[0231]

[0232] <화학식 2-12>

[0233]

[0234]

[0235] <화학식 2-13>

[0236]

[0237]

[0238] <Chemical Formula 2-14>

[0239]

[0240]

[0241] In addition, the above polymers may be mixed with novolac resins or aromatic C6 to C20 novolac polymerization polymers having hydroxyl groups to improve the dissolution properties and coating properties or curing properties of the entire resist underlayer film composition.

[0242]

[0243] In addition, the resist underlayer film composition of the present invention is a resist underlayer film composition comprising: i) an aromatic condensation polymer compound of the double or triple copolymer of the present invention or a blend of these polymer compounds; and ii) an organic solvent.

[0244]

[0245] Among the resist underlayer film compositions, (i) the aromatic condensation polymer compound of the double or triple copolymer of the present invention or a blend of these polymer compounds may be used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the total composition. If the amount of (i) used is less than 1 part by weight or more than 30 parts by weight, the desired coating thickness may be lowered or exceeded, making it difficult to achieve an accurate coating thickness.

[0246]

[0247] The above organic solvent is not particularly limited as long as it is an organic solvent having sufficient solubility for the above aromatic ring-containing polymer, and may be, for example, propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, ethyl lactate, etc.

[0248]

[0249] In addition, the resist underlayer film composition of the present invention may further comprise (iii) a cross-linking agent component and (iv) an acid catalyst.

[0250] The above (iii) crosslinking agent component is preferably capable of crosslinking repeating units of the polymer by heating in a catalytic reaction by the generated acid, and the above (iv) acid catalyst is preferably a heat-activated acid catalyst.

[0251]

[0252] The crosslinking agent component (iii) used in the resist underlayer film composition of the present invention is not particularly limited as long as it is a crosslinking agent that can react with an aromatic ring-containing polymer in a manner that can act as a catalyst by the generated acid.

[0253] Examples of the crosslinking agent include melamine-based, substituted urea-based, or polymer-based thereof. Preferably, the crosslinking agent has at least two crosslinking-forming substituents, and is a compound such as methoxymethyl glycoluril, butoxymethyl glycoluril, methoxymethyl melamine, butoxymethyl melamine, methoxymethyl benzoguanamine, butoxymethyl benzoguanamine, methoxymethyl urea, butoxymethyl urea, or methoxymethyl thiourea.

[0254] In addition, a crosslinking agent with high heat resistance can be used as the crosslinking agent, and a compound containing a crosslinking-forming substituent having an aromatic ring in the molecule can be preferably used. Examples of these compounds include compounds having the following structural formula.

[0255]

[0256]

[0257]

[0258]

[0259] As the acid catalyst (iv) used in the resist underlayer film composition of the present invention, an organic acid such as p-toluenesulfonic acid monohydrate can be used, and a TAG (Thermal Acid Generator) compound that ensures storage stability can also be used as a catalyst. TAG is an acid generator compound that is designed to release acid during heat treatment, and for example, it is preferable to use pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.

[0260]

[0261] In the case where the resist underlayer film composition of the present invention further comprises (iii) a crosslinking agent component and (iv) an acid catalyst, the resist underlayer film composition of the present invention

[0262] (i) 1 to 30 wt%, more preferably 3 to 15 wt%, of an aromatic condensation polymer compound of a double or triple copolymer or a blend of these polymer compounds,

[0263] (iii) 0.1 to 5 wt% of crosslinking agent component, more preferably 0.1 to 3 wt%,

[0264] (iv) 0.001 to 0.05 wt%, more preferably 0.001 to 0.03 wt%, of an acid catalyst, and

[0265] (ii) It can be made up of 100 wt% of the total by using an organic solvent as the remaining component, and it is preferable to contain 75 to 98 wt% of the organic solvent.

[0266]

[0267] If the polymer (i) in the above composition is less than 1 wt% or more than 30 wt%, the desired coating thickness is lowered or exceeded, making it difficult to achieve an accurate coating thickness.

[0268]

[0269] In addition, if the crosslinking agent component is less than 0.1 wt%, crosslinking properties may not be exhibited, and if it exceeds 5 wt%, the optical properties of the coating film may change due to excessive addition.

[0270] In addition, if the acid catalyst is less than 0.001 wt%, crosslinking characteristics may not be well exhibited, and if it exceeds 0.05 wt%, storage stability may be affected due to an increase in acidity caused by excessive addition.

[0271]

[0272] Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for the purpose of explanation only and are not intended to limit the scope of the present invention.

[0273] (Example 3-1)

[0274]

[0275] <Chemical Formula 2-1>

[0276] In a 250 mL round flask, 17.6 g (60 mmol) of naphthylcarbazole and 6 g (72 mmol) of cyclopentanone were dissolved in 60 g of gamma-butyrolactone (GBL), and then 1.6 g of para-toluenesulfonic acid (PTSA) was added, followed by polymerization at 120 degrees for 20 hours.

[0277] After polymerization, the reactant was precipitated in an excess of methanol / water (8:2) and then neutralized with triethylamine. The resulting precipitate was filtered and washed with an excess of methanol for about 1 hour. The precipitate was then filtered and dried in a vacuum oven at 65°C for 24 hours to obtain 17 g (yield: 75%) of the desired polymer of chemical formula 2-1.

[0278] The polymer of the above chemical formula 2-1 had a weight average molecular weight (Mw) of 4,600 and a polydispersity (Mw / Mn) of 1.85.

[0279]

[0280] (Example 3-2)

[0281]

[0282] <Chemical Formula 2-2>

[0283] Indole 7g (60mmol) and 2-norbornanone 6.6g (60mmol) were synthesized in the same manner as in Example 1 to obtain 10g (yield 74%) of the desired polymer of chemical formula 2-2.

[0284] The synthesized polymer of the above chemical formula 2-2 had a weight average molecular weight (Mw) of 4,300 and a polydispersity (Mw / Mn) of 1.89.

[0285]

[0286] (Example 3-3)

[0287]

[0288] <Chemical Formula 2-3>

[0289] 8.8 g (30 mmol) of naphthylcarbazole and 7.2 g (40 mmol) of flurenone were synthesized in the same manner as in Example 1 to obtain 7 g (49% yield) of the desired polymer of Chemical Formula 2-3. The synthesized polymer of Chemical Formula 2-3 had a weight average molecular weight (Mw) of 3,700 and a polydispersity index (Mw / Mn) of 1.88.

[0290]

[0291] (Example 3-4)

[0292]

[0293] <Chemical Formula 2-4>

[0294] 6.7 g (40 mmol) of carbazole and 7.8 g (40 mmol) of 2-hydroxy-9-flurenone were synthesized in the same manner as in Example 1 to obtain 10 g (69% yield) of the desired polymer of Chemical Formula 2-4. The synthesized polymer of Chemical Formula 2-4 had a weight average molecular weight (Mw) of 3,300 and a polydispersity index (Mw / Mn) of 1.89.

[0295] (Example 3-5)

[0296]

[0297] <Chemical Formula 2-5>

[0298] 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 Chemical Formula 2-5. The synthesized polymer of Chemical Formula 2-5 had a weight average molecular weight (Mw) of 3,900 and a polydispersity index (Mw / Mn) of 1.88.

[0299]

[0300] (Example 3-6)

[0301]

[0302] <Chemical Formula 2-6>

[0303] 14.6 g (60 mmol) of phenylcarbazole, 9.3 g (110 mmol) of cyclopentanone, and 8.7 g (40 mmol) of 1-pyrenol were synthesized in the same manner as in Example 1 to obtain 26 g (82% yield) of the desired polymer of Chemical Formula 2-6. The synthesized polymer of Chemical Formula 2-6 had a weight average molecular weight (Mw) of 3,800 and a polydispersity index (Mw / Mn) of 1.85.

[0304]

[0305] (Example 3-7)

[0306]

[0307] <Chemical Formula 2-7>

[0308] 17.6 g (60 mmol) of naphthylcarbazole, 19.8 g (110 mmol) of 9-flurenone, and 8.7 g (40 mmol) of 1-pyrenol were synthesized in the same manner as in Example 1 to obtain 35 g (79% yield) of the desired polymer of Chemical Formula 2-7. The synthesized polymer of Chemical Formula 2-7 had a weight average molecular weight (Mw) of 3,900 and a polydispersity index (Mw / Mn) of 1.88.

[0309]

[0310] (Example 3-8)

[0311]

[0312] <Chemical Formula 2-8>

[0313] 17.6 g (60 mmol) of naphthylcarbazole, 19.8 g (110 mmol) of 9-flurenone, 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 Chemical Formula 2-8. The synthesized polymer of Chemical Formula 2-8 had a weight average molecular weight (Mw) of 3,500 and a polydispersity index (Mw / Mn) of 1.95.

[0314]

[0315] (Example 3-9)

[0316]

[0317] <Chemical Formula 2-9>

[0318] 7 g (60 mmol) of indole, 9.3 g (110 mmol) of cyclopentanone, and 8.7 g (40 mmol) of 1-pyrenol were synthesized in the same manner as in Example 1 to obtain 18 g (75% yield) of the desired polymer of Chemical Formula 2-10. The synthesized polymer of Chemical Formula 2-9 had a weight average molecular weight (Mw) of 4,500 and a polydispersity index (Mw / Mn) of 1.93.

[0319]

[0320] (Example 3-10)

[0321]

[0322] <Chemical Formula 2-10>

[0323] 10 g (60 mmol) of carbazole, 9.3 g (110 mmol) of cyclopentanone, and 8.7 g (40 mmol) of 1-pyrenol were synthesized in the same manner as in Example 1 to obtain 20 g (74% yield) of the desired polymer of Chemical Formula 2-10. The synthesized polymer of Chemical Formula 2-10 had a weight average molecular weight (Mw) of 4,300 and a polydispersity index (Mw / Mn) of 1.91.

[0324]

[0325] (Example 3-11)

[0326]

[0327] <Chemical Formula 2-11>

[0328] Indole 7g (60mmol), 9-flurenone 18g (100mmol), and phenyl-1-naphthylamine 8.8g (40mmol) were synthesized in the same manner as in Example 1 to obtain 27g (80% yield) of the desired polymer of Chemical Formula 2-11. The synthesized polymer of Chemical Formula 2-11 had a weight average molecular weight (Mw) of 5,300 and a polydispersity index (Mw / Mn) of 1.90.

[0329]

[0330] (Example 3-12)

[0331]

[0332] <Chemical Formula 2-12>

[0333] Indole 7g (60mmol), 9-flurenone 18g (100mmol), and bi-2-naphthol 11.4g (40mmol) were synthesized in the same manner as in Example 1 to obtain 28g (77% yield) of the desired polymer of Chemical Formula 2-12. The synthesized polymer of Chemical Formula 2-12 had a weight average molecular weight (Mw) of 5,100 and a polydispersity index (Mw / Mn) of 1.93.

[0334]

[0335] (Example 3-13)

[0336]

[0337] <Chemical Formula 2-13>

[0338] 17.6 g (60 mmol) of naphthylcarbazole, 18 g (100 mmol) of 9-flurenone, 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 Chemical Formula 2-13. The synthesized polymer of Chemical Formula 2-13 had a weight average molecular weight (Mw) of 5,500 and a polydispersity index (Mw / Mn) of 1.91.

[0339]

[0340] (Example 3-14)

[0341]

[0342] <Chemical Formula 2-14>

[0343] 10 g (60 mmol) of carbazole, 18 g (100 mmol) of 9-flurenone, 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 Chemical Formula 2-14. The synthesized polymer of Chemical Formula 2-14 had a weight average molecular weight (Mw) of 6,500 and a polydispersity index (Mw / Mn) of 1.97.

[0344]

[0345] (Comparative Example) Synthesis of Phenolic Polymer

[0346]

[0347]

[0348] 35 g (100 mmol) of 9,9-bishydroxyphenylfluorene 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 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 was able to obtain a polymer having a weight average molecular weight (Mw) of 3,300.

[0349]

[0350] <Manufacturing of a resist underlayer composition>

[0351] In Examples 3-1, 3-2, 3-3, 3-7, 3-11, 3-12, 3-13, and 3-14, and in Comparative Examples, 1 g of the polymer and 300 ppm of the surfactant were completely dissolved in 7 g of propylene glycol monomethyl ether acetate (PGMEA) and 2 g of cyclohexanone, and then filtered using a 0.1 um membrane filter to prepare resist underlayer film composition solutions of Examples 3-1, 3-2, 3-3, 3-7, 3-11, 3-12, 3-13, and 3-14, and resist underlayer film composition solutions of Comparative Examples, respectively.

[0352] The resist underlayer film composition solutions of Examples 3-1, 3-2, 3-3, 3-7, 3-11, 3-12, 3-13, and 3-14, and the resist underlayer film composition solution of the comparative example were spin-coated on a silicon wafer and baked at 240°C for 60 seconds to form a film having a thickness of 3000 Å. The refractive index n and extinction coefficient k of the formed films were each determined. The equipment used was an Ellipsometer (JA Woollam), and the measurement results are shown in Table 1.

[0353]

[0354] As a result of the evaluation, as shown in Table 1 above, it was confirmed that the resist underlayer film composition of the present invention has a refractive index and absorbance that can be used as an antireflection film at ArF (193 nm) and KrF (248 nm) wavelengths.

[0355] Meanwhile, the refractive index range of materials typically used as semiconductor anti-reflection films is approximately 1.4 to 1.8, and what is important is the absorption coefficient, and the higher the absorption, the better, but since there is no problem in using it as an anti-reflection film if the k value is typically 0.3 or higher, it can be seen that the hard mask composition of the present invention can be used as an anti-reflection film.

[0356]

[0357] <Evaluation of etching characteristics for antireflection hard mask compositions>

[0358] The resist underlayer film composition solutions of Examples 3-1, 3-4, 3-6, 3-7, 3-10, 3-11, 3-12, and 3-14, and the resist underlayer film composition solution (10 wt%) of the comparative example were heat-treated at a temperature of 400°C for 120 seconds to form a thin film, and then dry-etched for 60 seconds using N2 / O2 mixed gas (50 mT / 300 W / 10 O2 / 50 N2 conditions) and CFx gas (100 mT / 600 W / 42 CF4 / 600 Ar / 15 O2 conditions), respectively, and the thickness of the thin film was measured before and after etching.

[0359] The etch rate ( / s) for each film was calculated by dividing the change in film thickness by the etching time. The results are shown in Table 2 below.

[0360]

[0361] As shown in Table 2 above, the resist underlayer film composition of the present invention is superior to or equivalent to the comparative example in N2 / O2 etch( / s), and in particular, it can be seen that it is superior to the comparative example in the case of CFx etch( / s), which is most widely used in semiconductor manufacturing.

[0362] The present invention relates to an aromatic condensation polymer compound in the form of an aromatic condensation polymer having strong ultraviolet absorption in the ultraviolet wavelength region and a resist underlayer film composition characterized by including the same, which is very useful in a hard mask process that is very essential in an etching process and thus has industrial applicability.

Claims

1. An aromatic condensation polymer compound of a double or upper copolymer characterized by being synthesized by a condensation reaction with 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. <Chemical formula a> <Chemical formula b> In the above <chemical formula a>, n and m are each 0 or 1, R1 is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, In the above <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, and the substituted or unsubstituted C1 to C10 alkyl group and the substituted or unsubstituted C6 to C20 aryl group of R2 to R5 can be connected to each other to form a hydrocarbon ring and / or an aromatic ring. <Chemical Formula 1> n and m are 0 or 1, respectively, 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 the substituted or unsubstituted C1 to C10 alkyl group and the substituted or unsubstituted C6 to C20 aryl group of R2 to R5 can be connected to each other to form a hydrocarbon ring and / or an aromatic ring. The above o, p, and q have ranges of o / (o+p+q)=0.1~0.5, p / (o+p+q)=0.3~0.6, and q / (o+p+q)=0~0.

4.

2. In paragraph 1, An aromatic condensation polymer compound (copolymer) of a double or upper copolymer, characterized in that the weight average molecular weight (Mw) of the aromatic condensation polymer compound (copolymer) represented by the above chemical formula 1 is 1,500 to 30,000.

3. In paragraph 1, An aromatic condensation polymer compound of a double or super copolymer represented by the above chemical formula 1, characterized in that it is one of the following chemical formulas 1-1 to 1-39. <Chemical Formula 1-1> <Chemical Formula 1-2> <Chemical Formula 1-3> <Chemical Formula 1-4> <Chemical Formula 1-5> <Chemical Formula 1-6> <Chemical Formula 1-7> <Chemical Formula 1-8> <Chemical Formula 1-9> <Chemical Formula 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 Formula 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> In the above <Chemical Formula 1-11> to <Chemical Formula 1-39>, R2 to R5 are each hydrogen, a C1 to C10 alkyl group, or a C4 to C20 aryl group, and the C1 to C10 alkyl groups and the C4 to C20 aryl groups can be connected to each other to form a ring. In the above <Chemical Formula 1-1> to <Chemical Formula 1-10>, n can be 10 to 100, In the above <Chemical Formula 1-11> to <Chemical Formula 1-39>, o, p, and q have a range of o / (o+p+q)=0.1~0.5, p / (o+p+q)=0.3~0.6, and q / (o+p+q)=0~0.

4.

4. In paragraph 1, An aromatic condensation polymer compound of a double or super copolymer represented by the above chemical formula 1, characterized in that it is one of the following chemical formulas 2-1 to 2-14. <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> In the above <Chemical Formula 2-1> to <Chemical Formula 2-4>, n can be 10 to 100, In the above <Chemical Formula 2-5> to <Chemical Formula 2-14>, o, p, and q have a range of o / (o+p+q)=0.1~0.5, p / (o+p+q)=0.3~0.6, and q / (o+p+q)=0~0.

4. 5.(i) Aromatic condensation polymer compound of double or triple copolymer according to any one of claims 1 to 4 or a blend of these polymer compounds; and ii) A resist underlayer film composition characterized by comprising an organic solvent; 6. In paragraph 5, A resist underlayer film composition, characterized in that the (i) aromatic condensation polymer compound of the double or triple copolymer or a blend of these polymer compounds is contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the entire resist underlayer film composition.

7. In paragraph 5, (iii) A resist underlayer film composition characterized by further comprising a cross-linking agent component and (iv) an acid catalyst.

8. In paragraph 7, (i) 1 to 30 wt% of an aromatic condensation polymer compound of a double or triple copolymer or a blend of these polymer compounds; (iii) 0.1 to 5 wt% of crosslinking agent component; (iv) 0.001 to 0.05 wt% of acid catalyst; and (ii) A resist underlayer film composition characterized in that it comprises 100% by weight of the total using an organic solvent as the remaining component.

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