KR102510788B1 - A composition of anti-reflective hardmask - Google Patents

Abstract

An antireflection hard mask composition comprising an organic polymer having a hydroxyl group in a backbone or a side chain and a polymer in which a metal or metalloid is partially substituted for the hydroxyl group is provided.

Description

Hard mask composition for antireflection {A COMPOSITION OF ANTI-REFLECTIVE HARDMASK}

The present invention relates to a hard mask composition having antireflection film properties useful for a lithographic process, which exhibits strong absorption in the ultraviolet wavelength region and is relatively transparent in the visible light region, and has an aromatic ring containing an organometal in the form of a polymer. It relates to an (aromatic ring) polymer and a hard mask composition comprising the same.

As miniaturization processes are increasingly required in the semiconductor industry, an effective lithographic process is essential to realize these ultra-fine technologies. In particular, the demand for new materials for the hard mask process, which is very essential in the etching process, is increasing.

In general, a hard mask film serves as an intermediate film that transfers a fine pattern of photoresist to a lower substrate layer through a selective etching process. Therefore, the hard mask layer requires chemical resistance, heat resistance, and etching resistance to withstand multiple etching processes. The existing hard mask film used an ACL (amorphous carbon layer) film made by the chemical vapor deposition (CVD) method, but the disadvantages of this are the high unit cost of equipment investment and the particles generated during the process, and the film quality is opaque. There were many inconveniences in use due to photo misalignment problems caused by .

Recently, a spin-on hardmask formed by a spin-on coating method has been introduced instead of such a chemical vapor deposition method. In the spin-on coating method, a hard mask composition is formed using an organic polymer material having solubility in a solvent. At this time, the most important characteristic is that an organic polymer coating film having etching resistance should be formed.

However, since solubility and etching resistance, which are two characteristics required for such an organic hard mask layer, are in a conflicting relationship with each other, a hard mask composition capable of satisfying both of them was required. Materials introduced into the semiconductor lithography process while satisfying the characteristics of these organic hard mask materials have recently been introduced (Patent Publication 10-2009-0120827, Patent Publication 10-2008-0107210, Patent WO 2013100365 A1). They were hard mask materials using a copolymer having an appropriate high molecular weight synthesized by a conventional phenol resin manufacturing method using hydroxypyrene.

However, as the recent semiconductor lithographic process undergoes further miniaturization, in the case of organic hard mask materials, it is difficult to sufficiently perform the mask role due to the lack of etching selectivity in the etching process compared to conventional inorganic hard mask materials. it has reached

In addition, as the thickness of the organic hard mask film gradually increases, it appears opaque in a photo alignment process using a wavelength of 633 nm, so increasing the thickness is limited.

Therefore, it is urgently needed to introduce a hard mask material that is more transparent in the 633 nm region than conventional hard mask materials and can exhibit a higher selectivity in an etching process.

An object of the present invention is to provide an organometallic hardmask polymer having excellent polymer solubility and a composition including the same.

An object of the present invention is to provide an organometallic hardmask polymer having high etching selectivity and sufficient resistance to multiple etching, and a composition including the same.

An object of the present invention is to provide an organometallic hardmask polymer capable of minimizing reflectivity between a resist and a back layer and a composition including the same.

A hard mask composition according to embodiments of the present invention includes a high molecular weight polymer including, as a monomer, an organic molecule having a hydroxyl group on a backbone or a side chain, and partially substituting a metal or metalloid for the hydroxyl group.

A hard mask composition according to embodiments of the present invention

(a) an organometallic aromatic polymer represented by Formula 1 or a polymer blend including the same; and

(b) contains an organic solvent.

[Formula 1]

In the above formula, R1 _, R2, and R3 is any one selected from the group consisting of C1~C10 alkyl, C1~C10 alkoxy, C2~C10 alkenyl, and C6~C20 aryl groups,

R1 _, R2, and R3 is each may be the same or different,

M is a metal or metalloid of Group 14, 13, 10, or 4;

R4 and R5 are any one selected from hydrogen (H), C1~C10 alkyl, C2~C10 alkenyl, and C6~C40 aryl groups, and R4 and R5 are may be the same as or different from each other, A is a C6~C40 aryl group, may be unsubstituted or substituted with a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, or a hydroxyl group, and an ether bond, a ketone bond, or an ester bond May contain or contain,

m/(m+n)= 0.1 to 0.9,

The weight average molecular weight (Mw) of the polymer is 1,000 to 30,000.

In the hard mask composition based on the organometallic aromatic polymer according to embodiments of the present invention, a stable polymer can be prepared by reacting a metal or metalloid compound with an existing novolak-based polymer.

The hard mask composition based on the organometallic polymer according to embodiments of the present invention has a very excellent role as an etch barrier by a metal or metalloid component, so that the entire hard mask thin film has excellent etching resistance. Therefore, it is possible to provide a lithographic structure having excellent pattern evaluation results due to sufficient resistance to multiple etching due to a high etching selectivity compared to conventional organic hard masks.

The hard mask composition based on organometallic aromatic polymer according to embodiments of the present invention 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 forming a resist. It is possible to minimize the reflectivity between the back layer and the back layer.

In addition, by providing a more transparent film quality in the photo alignment process, it is suitable for realizing a relatively high thickness organic hard mask process.

An antireflection hard mask composition according to embodiments includes a high molecular weight polymer including an organic molecule having a hydroxyl group on a backbone or a side chain as a monomer and partially substituting a metal or metalloid for the hydroxyl group.

The metal or metalloid may be selected from metals or metalloids capable of exhibiting excellent selectivity in an etching process. The metal or metalloid may be a Group 14, 13, 10, or 4 metal or metalloid.

In the case of a group 14 metalloid, it may be silicon (Si) or germanium (Ge), but is not limited thereto.

In the case of a Group 14 metal, it may be tin (Sn), but is not limited thereto.

In the case of group 13 metalloid (B), it may be boron (B), but is not limited thereto.

In the case of a Group 13 metal, it may be aluminum (Al), but is not limited thereto.

In the case of a Group 10 metal, it may be nickel (Ni), but is not limited thereto.

In the case of a Group 4 metal, it may be titanium (Ti), but is not limited thereto.

Higher polymers in which metalloid atoms are partially substituted may be more preferred for antireflective hardmask compositions. In the case of a metal, a very good selectivity is exhibited during an etching process, but conversely, a problem of contamination by particles of a metal component may occur. Therefore, a metalloid component may be more preferable as it is free from contamination problems of the particles. In addition, among metalloid components, a material that can be easily removed under halogen (Cl 2 , CFx)-based etching gas conditions in an ashing process after an etching process may be more preferable. Thus, the metalloid may be group 14 germanium or the like.

The organic molecule having a hydroxyl group in the backbone or side chain may be 1-naphthol, 1-pyrenol or 9,9-bishydroxyphenylfluorene.

According to embodiments, the antireflection hard mask composition may include a polymer composed of an organometallic aromatic compound represented by the following Chemical Formula 1 or a polymer blend including the same, and (b) an organic solvent.

[Formula 1]

In the above formula, R1 _, R2, and R3 is any one selected from the group consisting of C1~C10 alkyl, C1~C10 alkoxy, C2~C10 alkenyl, and C6~C20 aryl groups,

R1 _, R2, and R3 is each may be the same or different,

M is a metal or metalloid of Group 14, 13, 10, or 4;

R4 and R5 are any one selected from hydrogen (H), C1~C10 alkyl, C2~C10 alkenyl, and C6~C40 aryl groups, and R4 and R5 are may be the same as or different from each other, A is a C6~C40 aryl group, may be unsubstituted or substituted with a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, or a hydroxyl group, and an ether bond, a ketone bond, or an ester bond may or may not include,

m/(m+n)= 0.1 to 0.9,

The weight average molecular weight (Mw) of the polymer is 1,000 to 30,000.

The weight average molecular weight (Mw) of the polymer may be 2,000 to 10,000.

M may be a Group 14 metalloid. M may be a Group 14 metal.

R1, R2, and R3 may be any one selected from the group consisting of a C1~C10 alkyl group or a C6~C20 aryl group.

R4 and R5 may each be any one selected from the group consisting of hydrogen, phenyl(?), bismethylbenzene, biphenyl, and phenoxyphenyl.

A may be naphthalene, pyrene or hydroxyphenylfluorene.

In order to prepare an antireflection hard mask composition, the above (a) organometallic polymer is preferably used in an amount of 1 to 30% by weight based on 100 parts by weight of (b) the organic solvent used. When the organometallic polymer is used in an amount of less than 1 part by weight or more than 30 parts by weight, the desired coating thickness is less than or exceeds, making it difficult to accurately match the coating thickness.

And, the organic solvent is not particularly limited as long as it has sufficient solubility for the organometallic aromatic ring-containing polymer, and examples thereof include propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, ethyl lactate, and the like. can be heard

In addition, the antireflective hard mask composition of the present invention may further include (c) a crosslinking agent component and (d) an acid catalyst.

The (c) crosslinking agent component used in the hard mask composition of the present invention is preferably capable of crosslinking the repeating units of the polymer by heating in a reaction catalyzed by the generated acid, and the (d) acid catalyst is heat It is preferably an acid catalyst that is activated.

The cross-linking agent component (c) used in the hard mask composition of the present invention is specifically limited as long as it is a cross-linking agent that can react with a reactive group (eg, a hydroxyl group) of an aromatic ring-containing polymer in a manner that can be catalyzed by the resulting acid. It doesn't work. As specific examples of this, etherified amino resins such as methylated or butylated melamine resins (specific examples are N-methoxymethyl-melamine resins or N-butoxymethyl-melamine resins) and methylated butylated or butylated urea resin (specifically, Cymel U-65 Resin or UFR 80 Resin), a glycoluril compound (specifically, Powderlink 1174), or a bisepoxy compound (specifically, 2 ,6-bis(hydroxymethyl)-p-cresol compound) and the like.

As the (d) acid catalyst used in the hard mask composition of the present invention, an organic acid such as p-toluenesulfonic acid monohydrate may be used, and TAG (Thermal Acid Generator) with storage stability A compound of the system can also be used as a catalyst. TAG is an acid generator compound designed to release acid upon heat treatment, for example, pyridinium P-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, Preference is given to using benzoin tosylate, 2-nitrobenzyl tosylate and alkyl esters of organic sulfonic acids and the like.

When the final hardmask composition further comprises (c) a crosslinking agent component and (d) an acid catalyst, the hardmask composition of the present invention is (a) a polymer composed of an organometallic aromatic compound having strong absorption characteristics in the ultraviolet region, or 1 to 30% by weight of a polymer mixture including the same, (c) 0.1 to 5% by weight of a crosslinking agent component, (d) 0.001 to 0.05% by weight of an acid catalyst, and (b) the remaining amount of the organic solvent. . Here, when the amount of the polymer composed of the organometallic aromatic compound or a polymer blend containing the same is less than 1% by weight or more than 30% by weight, the desired coating thickness is less than or exceeds the desired coating thickness, making it difficult to accurately match the coating thickness. A polymer composed of an organometallic aromatic compound or a polymer mixture containing the same may be used in an amount of 3% to 15% by weight.

In addition, when the amount of the crosslinking agent component is less than 0.1% by weight, crosslinking properties may not appear, and when it exceeds 5% by weight, the optical properties of the coating film may be changed due to excessive input. The crosslinking agent component may be used in an amount of 0.1 to 3% by weight.

In addition, when the acid catalyst is less than 0.001% by weight, crosslinking properties may not be well displayed, and when it exceeds 0.05% by weight, storage stability may be affected due to an increase in acidity due to excessive input. The acid catalyst may be used in an amount of 0.001 to 0.03% by weight.

And the organic solvent may be used in an amount of 75 to 98% by weight.

Hereinafter, the present invention will be described in more detail through examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Preparation Example 1)

In a round flask, 14.5 g (100 mmol) of 1-naphthol and 3.3 g (110 mmol) of paraformaldehyde were dissolved in 45 g (monomer 2.5 times) of propylene glycol monomethyl ether acetate (PGMEA), followed by temperature Heat it to about 60 degrees and melt it cleanly for about 15 minutes.

A catalytic amount (2-5 mol%) of concentrated sulfuric acid is added thereto, followed by polymerization for about 4-10 hours depending on the temperature while maintaining the reaction temperature at 100-130 degrees.

After polymerization, the reactants were dropped into an excess of methanol/water (7:3) co-solvent and neutralized with triethylamine (TEA).

After dissolving the precipitate in an appropriate amount of THF solvent, add an appropriate amount of pyridine to dissolve it cleanly, and then partially substitute triphenylgermanium chloride in an amount of 20 to 80 mol% compared to 1-naphthol After adding slowly in an amount of, the reaction temperature is reacted at 60 degrees for about 4 hours.

After the reaction is over, the precipitate produced after dropping the reactant into an excess of water is caught and dissolved again in an appropriate amount of THF solvent, and then reprecipitated using an excess of methanol. The resulting precipitate was filtered and dried in a vacuum oven at 50 degrees for about 20 hours, and then a polymer having a weight average molecular weight (Mw) of 4,100 could be obtained.

Preparation Example 2)

After dissolving 14.5 g (100 mmol) of 1-naphthol and 12 g (110 mmol) of benzaldehyde in 66 g of PGMEA solvent, a polymer was synthesized in the same manner as in Preparation Example 1.

In the presence of pyridine, a polymer partially substituted with a germanium (Ge) element was finally synthesized using an appropriate amount of triphenylgermanium chloride.

After polymer purification, a polymer having a weight average molecular weight (Mw) of 3,500 could be obtained.

Preparation Example 3)

After dissolving 22g (100mmol) of 1-pyrenol and 3.3g (110mmol) of paraformaldehyde in 65g of PGMEA solvent, synthesizing a polymer in the same manner as in Preparation Example 1, triphenylgermanium chloride The final polymer was synthesized by partial substitution. After polymer purification, a polymer having a weight average molecular weight (Mw) of 3,700 could be obtained.

Preparation Example 4)

After dissolving 22g (100mmol) of 1-pyrenol and 18.3g (110mmol) of 1,4-bis(methoxymethyl)benzene in PGMEA solvent, polymer After synthesizing, the final polymer was synthesized by partial substitution of triphenylgermanium chloride. After polymer purification, a polymer having a weight average molecular weight (Mw) of 3,600 could be obtained.

Preparation Example 5)

After dissolving 35 g (100 mmol) of 9,9-bishydroxyphenylfluorene {9,9-Bis (4-hydroxyphenyl) fluorene} and 13 g (120 mmol) of benzaldehyde in a PGMEA solvent, the polymer was prepared in the same manner as in Preparation Example 1. After synthesis, triphenylgermanium chloride was partially substituted to synthesize the final polymer. After polymer purification, a polymer having a weight average molecular weight (Mw) of 4,100 could be obtained.

Preparation Example 6)

After dissolving 18g (50mmol) of 9,9-bishydroxyphenylfluorene and 11g (60mmol) of biphenylaldehyde in PGMEA solvent, synthesizing a polymer in the same manner as in Preparation Example 1, triphenylgermanium The final polymer was synthesized by partial substitution of chloride. After polymer purification, a polymer having a weight average molecular weight (Mw) of 3,900 could be obtained.

Preparation Example 7)

After dissolving 18 g (50 mmol) of 9,9-bishydroxyphenylfluorene and 12 g (60 mmol) of 4-phenoxybenzaldehyde in PGMEA solvent, the polymer was synthesized in the same manner as in Preparation Example 1, A final polymer was synthesized by partial substitution of triphenylgermanium chloride. After polymer purification, a polymer having a weight average molecular weight (Mw) of 4,300 could be obtained.

Preparation Example 8)

After dissolving 22g (100mmol) of 1-pyrenol and 3.3g (110mmol) of paraformaldehyde in a PGMEA solvent, a polymer was synthesized in the same manner as in Preparation Example 1, and then partially substituted with triphenyltin chloride. The final polymer was synthesized. After polymer purification, a polymer having a weight average molecular weight (Mw) of 3,900 could be obtained.

Preparation Example 9)

After dissolving 36g (100mmol) of 9,9-bishydroxyphenylfluorene and 13g (120mmol) of benzaldehyde in a PGMEA solvent, synthesizing a polymer in the same manner as in Preparation Example 1, trimethyltin chloride (Trimethyltin chloride) The final polymer was synthesized by partial substitution.

After polymer purification, a polymer having a weight average molecular weight (Mw) of 3,300 could be obtained.

Preparation Example 10)

After dissolving 36g (100mmol) of 9,9-bishydroxyphenylfluorene and 13g (120mmol) of benzaldehyde in PGMEA solvent, synthesizing a polymer in the same manner as in Preparation Example 1, chlorotriethoxysilane The final polymer was synthesized by partial substitution.

After polymer purification, a polymer having a weight average molecular weight (Mw) of 3,500 could be obtained.

Comparative Preparation Example) Synthesis of Phenol Novolac Derivative Polymer

35 g (100 mmol) of 9,9-bishydroxyphenylfluorene (BPF) and 12.7 g (120 mmol) of benzaldehyde were dissolved in 115 g of PGMEA, and then 1 g of concentrated sulfuric acid was added thereto.

After reacting at a reaction temperature of 120 degrees for about 10 hours, the reactants were precipitated by dropping them into an excess of methanol/water (7/3) co-solvent, and then neutralized using triethylamine.

The precipitate was dissolved in an appropriate amount of THF, then re-precipitated in an excess of methanol/water (9/1) co-solvent, and then the precipitate was hung and dried in an oven to obtain a polymer having a weight average molecular weight of 3,300.

Preparation of anti-reflection hard mask composition

0.9 g of each of the polymers prepared in Preparation Examples 1 to 10 and Comparative Preparation Example was weighed, and 0.1 g of a glycoluril compound crosslinking agent (Powderlink 1174) and pyridinium P-toluene sulfonate 　 1 mg were added to propylene glycol monomethyl After dissolving in 9g of ether acetate (PGMEA), it was filtered to make a composition solution consisting of the polymer of Preparation Examples 1 to 10 and a composition solution consisting of the polymer of Comparative Preparation Example, respectively.

Measurement of refractive index and extinction coefficient of hardmask composition

The hard mask composition solutions made of the polymers of Preparation Examples 1 to 10 and the hard mask composition solutions made of the polymers of Comparative Preparation Examples were each spin-coated on a silicon wafer and baked at 240° C. for 60 seconds to form a film with a thickness of 3000 Å. The refractive index n and extinction coefficient k were respectively obtained for . The device used was an ellipsometer (J. A. Woollam), and the measurement results are shown in Table 1.

As a result of the evaluation, it was confirmed that there was a refractive index and absorbance usable as an antireflection film at ArF (193 nm) and KrF (248 nm) wavelengths. In general, the polymer synthesized in Comparative Preparation Example shows a relatively high transmittance in the 633 nm region, but it can be seen that the hard mask composition according to the Preparation Examples of the present invention shows a relatively low absorption rate compared to the polymer of Comparative Preparation Example. It can be seen that it can be used as a highly transparent antireflection film in the region.

sample type Optical properties (193nm) Optical properties (248nm) Refractive index (n) Extinction coefficient (k) Refractive index (n) Extinction coefficient (k) Preparation Example 1 1.50 0.40 1.67 0.23 Preparation Example 2 1.50 0.55 1.71 0.33 Preparation Example 3 1.49 0.64 1.70 0.46 Production Example 4 1.52 0.65 1.73 0.45 Preparation Example 5 1.54 0.50 1.72 0.22 Preparation Example 6 1.53 0.51 1.72 0.23 Preparation Example 7 1.52 0.49 1.73 0.21 Preparation Example 8 1.52 0.65 1.73 0.43 Preparation Example 9 1.53 0.43 1.71 0.22 Preparation Example 10 1.55 0.41 1.73 0.21 Comparative Manufacturing Example 1.48 0.68 1.95 0.35

Lithographic Evaluation of Antireflective Hardmask Compositions

Hardmask compositions were formed using the polymers of Preparation Examples 1, 3, 5, and 7 and the polymers of Comparative Preparation Example in the same manner as the hardmask composition formation method described above.

Then, the hard mask composition was spin-coated on each aluminum-coated silicon wafer and baked at 400° C. for 90 seconds to form an antireflection hard mask film having a thickness of 3000 Å.

KrF photoresist was coated on each formed antireflection hard mask film, baked at 110 ° C for 60 seconds, exposed using ASML (XT: 1400, NA 0.93) exposure equipment, and then TMAH (tetramethyl ammonium hydroxide) 2.38 Each was developed for 60 seconds with a wt % aqueous solution. Then, as a result of examining each 90 nm line and space pattern using V-SEM, the results shown in Table 2 were obtained. The EL (expose latitude) margin according to the change in the exposure amount and the DoF (depth of focus) margin according to the change in the distance from the light source were considered and recorded in Table 2. As a result of the pattern evaluation, good results were confirmed in terms of profile or margin, and it was found that the EL margin and DoF margin required in the lithographic pattern evaluation were satisfied.

sample type pattern characteristics EL margin
(ΔmJ/energy mJ) DoF margin
(μm) pattern shape Preparation Example 1 0.3 0.4 cubic Preparation Example 3 0.3 0.3 cubic Preparation Example 5 0.4 0.3 cubic Preparation Example 7 0.3 0.4 cubic Comparative Manufacturing Example 0.2 0.2 undercut

Etching Characteristics Evaluation of Antireflective Hard Mask Compositions

An anti-reflection hard mask film made of a hard mask composition including the polymers of Preparation Examples 3, 5, and 6 and the polymer of Comparative Preparation Example was formed on the wafer on which the silicon nitride film was formed, an SiON anti-reflection film was formed thereon, and a KrF The photoresist was coated, baked at 110 ° C for 60 seconds, exposed using exposure equipment from ASML (XT: 1400, NA 0.93), and then developed for 60 seconds with a 2.38 wt% aqueous solution of TMAH (tetramethyl ammonium hydroxide). Subsequently, the patterned PR is used as a mask and the lower SiON anti-reflection film (BARC) is dry etched using a CHF ₃ /CF ₄ mixed gas, and then the SiON anti-reflection film is used as a mask to reflect the O ₂ /N ₂ mixed gas The hard mask was formed by etching the prevention hard mask film. Thereafter, the silicon nitride (SiN) film is dry etched using the hard mask as a mask with the CHF ₃ /CF ₄ mixed gas, and then O ₂ ashing and wet strip process for the remaining hard mask and organic materials proceeded.

Immediately after hard mask etching and silicon nitride etching, cross-sections of each specimen were examined with V-SEM, and the results are listed in Table 3. As a result of the etching evaluation, the pattern shapes after hard mask etching and silicon nitride etching did not show bowing in each case and were all good, so that the etching process of the silicon nitride film was well performed due to sufficient resistance to the etching process. confirmed that

Sample Pattern shape (after hard mask etch) Pattern shape (after SiN etching) Preparation Example 3 vertical shape vertical shape Preparation Example 5 vertical shape vertical shape Preparation Example 6 vertical shape vertical shape Comparative Manufacturing Example slightly bowing Boeing shape

Claims (14)

It includes an organic polymer having a hydroxyl group in a backbone or a side chain, and a polymer in which a metal or metalloid is partially substituted for the hydroxyl group,
The metal or metalloid is Ge, Sn, Group 13, Group 10, or Group 4 metal or metalloid, characterized in that, the antireflection hard mask composition. delete According to claim 1,
Wherein the metal or metalloid is Ge or Sn. According to claim 1,
The anti-reflection hard mask composition of claim 1 , wherein the organic polymer having a hydroxyl group in the backbone or side chain includes 1-naphthol, 1-pyrenol, or 9,9-bishydroxyphenylfluorene. (a) a polymer composed of an organometallic aromatic compound represented by Formula 1 or a polymer blend including the same; and
(b) organic solvents;
Anti-reflection hard mask composition comprising a.
[Formula 1]

In the above formula, R1 _, R2, and R3 is any one selected from the group consisting of C1~C10 alkyl, C1~C10 alkoxy, C2~C10 alkenyl, and C6~C20 aryl groups,
R1 _, R2, and R3 is each may be the same or different,
M is Ge, Sn, a metal or metalloid of Group 13, 10, or 4;
R4 and R5 are any one selected from hydrogen (H), C1~C10 alkyl, C2~C10 alkenyl, and C6~C40 aryl groups, and R4 and R5 are may be the same as or different from each other, A is an aryl group of C6~C40, and may be unsubstituted or substituted with a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, or a hydroxyl group, and an ether bond, a ketone bond, or an ester bond may or may not include,
m/(m+n)= 0.1 to 0.9,
The weight average molecular weight (Mw) of the polymer is 1,000 to 30,000. According to claim 5,
The M is Ge or Sn anti-reflection hard mask composition. delete According to claim 5,
Wherein R1, R2, and R3 are any one selected from the group consisting of C1-C10 alkyl and C6-C20 aryl groups, respectively. According to claim 5,
wherein R4 and R5 are each selected from the group consisting of hydrogen, phenyl, bismethylbenzene, biphenyl, and phenoxyphenyl. According to claim 5,
Wherein A is naphthalene, pyrene or hydroxyphenylfluorene antireflective hard mask composition. The method of any one of claims 5, 6, 8 to 10,
The hard mask composition further comprises a crosslinker and an acid catalyst component. According to claim 11,
The hard mask composition,
(a) 1 to 30% by weight of a polymer composed of the organometallic aromatic compound represented by Formula 1 or a polymer mixture containing the polymer or a polymer blend containing the same;
(b) 0.1 to 5% by weight of the crosslinking agent component;
(c) 0.001 to 0.05% by weight of the acid catalyst; and
(d) An antireflective hard mask composition comprising a residual amount of the organic solvent. According to claim 11,
The crosslinking agent is any one selected from the group consisting of a melamine resin, an amino resin, a glycoluril compound, and a bis-epoxy compound. According to claim 11,
The acid catalyst is p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzo An antireflective hardmask composition selected from the group consisting of phosphorus tosylate, 2-nitrobenzyl tosylate and alkyl esters of organic sulfonic acids.