FR2803850A1 - Anti-reflecting coating composition, used in semiconductor devices, comprises anthracenemethyl acrylate derivative polymer and polymer with dimethoxy methyl phenylmethacrylate derivative units - Google Patents

Abstract

An anti-reflecting coating composition, comprises an anthracenemethyl acrylate derivative polymer and a polymer comprising repeating (dimethoxy methyl)phenylmethacrylate derivative units. An anti-reflecting coating composition comprises a polymer of formula (I) or (II) and a polymer comprising repeating units of formula (III). R, R', R'', R''' = H or CH3; R1-R9 = H, OH, methoxycarbonyl, carboxyl, hydroxymethyl or optionally substituted, optionally branched 1-8C (alkoxy)alkyl; x, y, z = 0.01-0.99; m = 1 or 2; n = 2-4; and R0 = CH3 or -CH2CH3. Independent claims are included for; (1) Preparation of the anti-reflecting coating composition comprising dissolving a mixture of a polymer of formula (I) or (II) and a polymer of formula (III) in an organic solvent, followed by the addition of the anthracene derivative; and (2) Application of the anti-reflecting coating composition onto a tablet which is then hardened by heating at 80-300 deg C.

Description

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 ANTI-REFLECTIVE COATING COMPOSITION

PREPARATION METHOD AND BACK PLAN SEMICONDUCTOR DEVICE OF THE INVENTION Field of the Invention
The present invention relates to an antireflective organic coating material which allows the stable formation of ultra-fine patterns suitable for semiconductor devices 64M, 256M, IG, 4G and 16G DRAM. More particularly, the present invention relates to an antireflective organic coating material which contains a chromophore having a high absorption coefficient at wavelengths useful in sub-microlithography. A layer of said anti-reflective material can prevent retro-reflection of light from the lower layers or surface of the semiconductor chip and also eliminate standing waves in the photoresist layer, during a process of sub-microlithography using KrF 248 nm, 193 nm F19 or F2 157 nm laser sources. In addition, the present invention relates to an anti-reflective coating composition comprising such a substance, an antireflective layer obtained from such a composition and their method of preparation.

Description of the prior art
In a sub-microlithography process, one of the most important processes for the fabrication of highly integrated semiconductor devices, stationary waves and wave-reflective streaks inevitably occur because of the optical properties of the layers. lower applied on the waffle and thickness variations of the photosensitive layer applied thereto. In addition, the sub-microlithographic process generally suffers from the problem resulting from the alteration of the CD (critical dimension) by diffracted and reflected light from the lower layers.

 To solve these problems, it has been proposed to have a film, called anti-reflective coating (hereinafter sometimes referred to by the abbreviation "ARC") between the substrate and the photosensitive layer. Generally, ARCs are either organic or inorganic, depending on the substance used, or either "absorbing" or "interfering", depending on their mechanism of action. In microlithographic processes using I-line radiation (wavelength 365 nm), inorganic ARCs, for example TiN or amorphous carbon layers, are employed when one wishes to take advantage of the absorption mechanism, and SiON layers are employed when an interference mechanism is used. ARC SiON

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 may also be suitable for sub-microlithographic processes that use a light source of KrF.

Recently, extensive and intensive studies have been made and are continuing for the application of organic ARCs for this sub-microlithography. In consideration of the current state of development, organic ARCs must meet the following basic requirements to be usable:
First, the peeling of the photoresist layer due to dissolution in the organic ARC solvents should not occur when a lithographic process is used. In this respect, organic ARC substances must be designed so that their cured films have a crosslinked structure without the formation of by-products.

 Second, there must be no migration of chemicals, such as amines or acids, into or from the RCAs. If acids migrate from the ARC, the photosensitive patterns form an overhanging area while the exudation of bases, such as amines, cause a phenomenon of enlargement to the foot.

 Tertio, it will be necessary to achieve faster etching rates in ARC than in the upper photosensitive film, which allows to implement a smooth etching process, the photosensitive film serving as a mask.

 Finally, organic ARCs should be as thin as possible while playing an excellent role in preventing light reflection.

 Despite the diversity of ARC materials, those that are likely to be satisfactorily applied to submicrolithographic processes using ArF light have not yet been discovered. For inorganic ARCs, no substances have yet been reported to control interference at the ArF wavelength, that is, at 193 nm. As a result, extensive research has been undertaken to develop organic substances that behave like superb ARCs. In fact, in most cases of sub-microlithography, the photosensitive layers are not necessarily associated with organic ARCs that prevent the occurrence of standing waves and reflective streaks upon exposure to light and eliminate light. influence of retro-diffraction and reflection of light by the lower layers. Therefore, the development of these ARC substances with strong wavelength absorbing properties is one of the hottest and most urgent challenges in this technical field.

 In U.S. Patent No. 4,910,122 there is disclosed an ARC which is disposed beneath the photosensitive layers to eliminate defects caused by the reflected light.

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The coating disclosed herein can be made thin, smooth and uniform and includes a light-absorbing dye that eliminates most defects caused by reflecting light, resulting in better image definition of photosensitive substances. These types of ARCs, however, suffer from the disadvantage of having complicated formulations, being extremely limited in the choice of materials, and being difficult to apply to photolithography employing far ultraviolet radiation. (DUV).

For example, the ARC of the above reference comprises four colored compounds, including polyamic acid, curcumin, Bixinc and Sudan G orange and two solvents, including cyclohexanone and N-methyl-2-pyrrolidone. . This multi-component system is not easy to formulate and may interfere with the composition of the photoresist layer applied thereto, thereby leading to undesirable results.

 The object of the present invention is therefore to overcome the problems encountered in the prior art and to obtain a new organic compound which can be used as ARC for sub-microlithography using the 193 nm, 193 kr, 248 nm and 193 nm F19 lasers. .

 The present invention further relates to a process for the preparation of an organic compound which prevents diffusion and reflection caused by sub-microlithography light exposure.

 The present invention further relates to an ARC composition, containing such a compound, which prevents diffusion / reflection and also relates to its method of preparation.

 The present invention also relates to an ARC obtained from such a composition and also relates to its method of preparation.

 The present invention relates to acrylic polymer resins that can be used as ARCs. Preferred polymeric resins contain a chromophore that exhibits strong absorption at wavelengths of 193 nm and 248 nm. A crosslinking mechanism is introduced between the alcohol groups and other functional groups in the polymer resins so that the crosslinking reaction takes place when the polymer resin coatings are "cured by baking" which greatly improves the formation, strength and dissolution properties of ARCs. In particular, optimum crosslinking reaction efficiency and storage stability are achieved by the present invention. The ARC resins of the present invention exhibit superior stability in all hydrocarbon solvents, but are of such high solvent resistance after curing by curing that they do not dissolve at all in any solvent. These advantages make it possible to apply the resins without

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 no problem and the coatings prevent the problems of overhanging zone formation and foot enlargement which can arise when forming images on photosensitive materials. In addition, the coatings made from the acrylic polymers of the present invention have a faster etch rate than the photosensitive films, which improves the etch selection ratio between them.

R1 Y c=o (formule chimique 39) o (ÇH2)m 1 RI R6 Rs R. dans laquelle,
R' est l'hydrogène ou -CH3
R, à R9, qui sont identiques ou différents, représentent chacun un hydrogène, hydroxy, méthoxycarbonyle, carboxyle, hydroxyméthyle, ou un alkyle ou un alcoxyalkyle en C, à C6, linéaires ou ramifiés, substitués ou non substitués ; m est un entier de 1 à 4. The invention relates to a 9-anthracenealkyl acrylate derivative, having the following structural formula 39:

R 1 Y c = o (chemical formula 39) wherein R 1
R 'is hydrogen or -CH3
R 1 to R 9, which are the same or different, each represents hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, or linear or branched, substituted or unsubstituted C 1 -C 6 alkyl or alkoxyalkyl; m is an integer of 1 to 4.

F.4 (ÇH,)nOK R 1 R, + f-<:H 1 -- 9....lhn<cnc .Ikyf acry111c R 7 Z-- 1 1;1-1 R, C-0 (schéma réactionnel 4) Ro Ri It relates to a process for the preparation of 9-anthracene alkylacrylate derivative comprising the reaction of 9-anthracene alkylalcohol with an acryloyl chloride in tetrahydrofuran, as shown in the following reaction scheme 4:

F.4 (HH,) nOK R 1 R, + f - <: H 1 - 9 .... lhn <cnc .Ikyf acry111c R 7 Z-- 1 1; 1-1 R, C-0 (scheme reaction 4) Ro Ri

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 wherein R is hydrogen or -CH; R 1 to R 9, which are the same or different, each represents hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl or linear or branched, substituted or unsubstituted C 1 -C 6 alkyl or alkoxyalkyl and n is an integer of 1 to 4.

c-o 1 JL (formule chimique 40) nc-o

Elle se rapporte à Un procédé de préparation de 4-formylphénylméthacrylate qui comprend la réaction du chlorure de méthacryloyle avec le 4hydroxybenzaldéhyde. It relates to 4-formylphenylmethacrylate, corresponding to the following structural formula 40:

co 1 JL (chemical formula 40) nc-o

It relates to a process for preparing 4-formylphenylmethacrylate which comprises reacting methacryloyl chloride with 4-hydroxybenzaldehyde.

c=O x 9= - (CH)m (CH2)n 1 (formule générale 1) oit RI P,6 R, dans laquelle,
R et R1, identiques ou différents, représentent chacun l'hydrogène ou -CH3;
R1 à R9. identiques ou différents, représentent chacun un hydrogène, hydroxy, méthoxycarbonyle, carboxyle, hydroxyméthyle ou un alkyle ou un alcoxyalkyle en C, à C6, linéaires ou ramifiés, substitués ou non substitués; x et y représentent chacun une fraction molaire dans la fourchette de 0,01 à 0,99 ; et m vaut 1 ou 2 et n est un entier de 2 à 4. It relates to a polymer corresponding to the following general formula I:

c = O x 9 = - (CH) m (CH 2) n 1 (general formula 1) where R 1 P, 6 R, in which,
R and R1, identical or different, each represent hydrogen or -CH3;
R1 to R9. identical or different, each represents a hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl or a linear or branched, substituted or unsubstituted C 1 -C 6 alkyl or alkoxyalkyl; x and y each represents a mole fraction in the range of 0.01 to 0.99; and m is 1 or 2 and n is an integer of 2 to 4.

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 In particular, it relates to a polymer of the general formula 1 above wherein R 1 to R 9 are each hydrogen, R 'is hydrogen; x and y each represent 0.5; and m is 1 and n is 2.3 or 4.

avec un monomère (II) de type hydroxyalkylacrylate en présence d'un initiateur dans un solvant comme représenté par le schéma réactionnel 5 suivant:

(I) (II) (schéma réactionnel 5)

dans lequel R ; R, à R9; et m et n ont les significations indiquées à propos de la formule générale 1 et la fraction molaire de chacun des monomères est dans la fourchette de 0,01 à 0,99, l'initiateur étant choisi dans le groupe consistant en 2,2azobis isobutyronitrile, acétylperoxyde, laurylperoxyde et t-butylperoxyde, le solvant étant choisi dans le groupe consistant en tétrahydrofurane, toluène, benzène, The invention also relates to a process for the preparation of a copolymer (III) which comprises the reaction of a 9-anthracene alkylacrylate monomer (I)

with a hydroxyalkylacrylate monomer (II) in the presence of an initiator in a solvent as represented by the following reaction scheme:

(I) (II) (Reaction Scheme 5)

in which R; R, to R9; and m and n have the meanings indicated for general formula 1 and the mole fraction of each of the monomers is in the range of 0.01 to 0.99, the initiator being selected from the group consisting of 2,2azobis isobutyronitrile acetylperoxide, laurylperoxide and t-butylperoxide, the solvent being selected from the group consisting of tetrahydrofuran, toluene, benzene,

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 methylethyl ketone and dioxane, the reaction being carried out at a temperature of 50 to 90 C.

Ru R C 1 x C 1 z C 1 -y ,LH "' ? (Çll2>m R j. j..1. 011 (formule générale II) R7 N" 1 T R R5 R4 10 dans laquelle R, R' et R", qui sont identiques ou différents, sont chacun des hydrogènes ou -CH,;
R, à R9, qui sont identiques ou différents, représentent chacun un hydrogène, hydroxy, méthoxycarbonyle, carboxyle, hydroxyméthyle ou un alkyle ou un alcoxyalkyle en C, à C6, linéaires ou ramifiés, substitués ou non substitués; x, y et z représentent chacun une fraction molaire dans la fourchette de 0,01 à 0,99; et m vaut 1 ou 2 et n est un entier de 2 à 4. It relates to a polymer corresponding to the general formula (II):

Wherein R, R 'and R ", wherein R, R' and R", wherein R, R 'and R "are as follows: are identical or different, are each hydrogens or -CH;
R 1 to R 9, which are the same or different, each represents hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl or linear or branched, substituted or unsubstituted C 1 -C 6 alkyl or alkoxyalkyl; x, y and z each represents a mole fraction in the range of 0.01 to 0.99; and m is 1 or 2 and n is an integer of 2 to 4.

 It also relates to a polymer of the general formula II above wherein R 1 -R 9 each represent hydrogen; R1 is hydrogen; y and z are 0.3.0.5 and 0.2, respectively, and m is 1 and n is 2.3 or 4.

 It also relates to a polymer of formula II above wherein R 1 -R 9 are each hydrogen, R 1 is -CH 2; x, y and z are 0.3.0.5 and 0.2, respectively; and m is 1 and n is 2, 3 or 4.

 The invention relates to a process for the preparation of a copolymer (IV) which comprises the reaction of a monomer (I) of the 9-anthracene alkylacrylate type, a monomer of the hydroxyalkylacrylate (II) type and methylmethacrylate (III) together in the presence of an initiator in a solvent as shown in the following reaction scheme 6:

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Ri f Rrt Iii CI -<:Hl C-CH 1 C-Cil, CI =0 C-O 1 + b=o 1 OCHs Pl c (CHI) 1 1 R OH R7 (III) R6 Rs R. (II) (1) (schéma réactionnel 6) RI RU R C=O c-o C-0 1 JY OCH) (Cfi,)m (CHI)n 1 OH poli R / / Rs (rv) R6 R, R. où, R, R' et R"'; R, à R,,; et m et n ont les significations indiquées à propos de la formule générale II et la fraction molaire de chaque monomère est dans la fourchette de 0,01 à 0,99, l'initiateur étant choisi dans le groupe consistant en 2,2-azobisisobutyronitrile, acétylperoxyde, laurylperoxyde et t-butylperoxyde, le solvant étant choisi dans le groupe consistant en tétrahydrofurane, toluène, benzène, méthyl éthyl cétone et dioxane, la réaction étant effectuée à une température de 50 à 90 C.

## STR2 ## wherein R 1 is CH 2 R 6 R 7 (III) R 6 ) (Reaction Scheme 6) RI RU RC = OcoC-O 1 JY OCH) (Cfi) m (CHI) n 1 OH polished R / / Rs (rv) R6 R, R, where R, R 'and R 1 to R 2, and m and n have the meanings indicated for the general formula II and the mole fraction of each monomer is in the range of 0.01 to 0.99, the initiator being selected from the group consisting of 2,2-azobisisobutyronitrile, acetylperoxide, laurylperoxide and t-butylperoxide, the solvent being selected from the group consisting of tetrahydrofuran, toluene, benzene, methyl ethyl ketone and dioxane, the reaction being carried out at a temperature of 50 at 90 C.

R"' r - -4%. (formule générale III) The invention relates to a polymer comprising repeating units of the following general formula III:

R "-4% (general formula III)

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dans laquelle R"1 est hydrogène ou -CH, et Ri est -CH, ou -CH1CI-I,.

wherein R "1 is hydrogen or -CH, and R1 is -CH, or -CH1CI-I ,.

 It relates to a process for preparing a copolymer which comprises polymerizing formylphenylmethacrylate to form a polymer and then reacting said polymer with methanol or ethanol.

 The invention further relates to an antireflective coating composition comprising a polymer of formula I, II or III, an antireflective coating composition further comprising an anthracene derivative.

1,2,10-anthracènetriol, acide anthraflavique, 9-anthraldéhyde oxime, 9anthraldéhyde, 2-amino-7-méthyl-5-oxo-H-[ I ]-benzopyrano [2,3-b]pyridine-3- carbonitrile, 1-aminoanthraquinone, acide anthraquinone-2 carboxylique, 1,5dihydroxyanthraquinone, anthrone, 9-anthryl-trifluorométhyl cétone, dérivés de 9alkylanthracène représentés par la formule développée suivante 16, les dérivés de 9carboxyl anthracène répondant à la formule développée suivante 17, les dérivés de 1carboxyl anthracène répondant à la formule développée suivante 18, et leurs combinaisons :

(formule chimique 16) (formule chimique 17) (formule chimique 18)

où R11, R,,, Rl3, RI4 et RI5 qui sont identiques ou différents, représentent chacun -H-, OH, -CH3, -CH10H, -(CH2)pCH3. p étant un entier de 1 à 3, ou un alkyle ou alcoxyalkyle substitués ou non substitués, linéaires ou ramifiés, contenant de 1 à 5 atomes de carbone. It also relates to an anti-reflective coating composition as above further comprising an anthracene derivative, wherein the anthracene derivative is selected from the group consisting of anthracene, 9-anthracene methanol, 9-anthracene carbonitrile 9-anthracene carboxylic acid, dithranol,

1,2,10-anthracenetriol, anthraflavic acid, 9-anthraldehyde oxime, 9anthraldehyde, 2-amino-7-methyl-5-oxo-H- [1] benzopyrano [2,3-b] pyridine-3-carbonitrile, 1-aminoanthraquinone, 2-anthraquinone carboxylic acid, 1,5dihydroxyanthraquinone, anthrone, 9-anthryl-trifluoromethyl ketone, 9-alkylanthracene derivatives represented by the following structural formula 16, 9-carboxy-anthracene derivatives having the following structural formula 17, 1carboxyl anthracene having the following structural formula 18, and combinations thereof:

(chemical formula 16) (chemical formula 17) (chemical formula 18)

wherein R11, R1, R13, R14 and R15 which are the same or different, each represents -H-, OH, -CH3, -CH10H, - (CH2) pCH3. p being an integer of 1 to 3, or a substituted or unsubstituted, linear or branched alkyl or alkoxyalkyl containing from 1 to 5 carbon atoms.

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 Still another object of the invention is a method of preparing an anti-reflective coating composition which comprises dissolving a polymer according to formulas I, II or III in an organic solvent and then adding to the solution of an additive derived from an anthracene selected from the group as defined above, the additive anthracene derivative being used in a proportion of 0.1 to 30% by weight, the organic solvent being selected from the group consisting of ethyl ethoxypropionate, methyl 3-ethoxypropionate, cyclohexanone and propylene glycol methyl ether acetate.

anti-réfléchissant comprenant un polymère répondant à l'une ou l'autre des formules I, II et un polymère répondant à la formule III, comprenant en outre un dérivé d'anthracène, le dérivé d'anthracène étant choisi dans le groupe défini ci-dessus. The present invention further relates to a coating composition

anti-reflective composition comprising a polymer corresponding to either one of Formulas I, II and a polymer of Formula III, further comprising an anthracene derivative, the anthracene derivative being selected from the group defined herein -above.

éthoxypropionate, c5clohexanone et propylèneglycolméthyl éther acétate. The invention further relates to a preparation of an anti-reflective coating composition which comprises dissolving a mixture of a polymer of formula 1 or formula II, and a polymer having the formula III, in an organic solvent, and then adding thereto an additive derived from anthracene, selected from the group defined above, the anthracene derivative additive being used in a proportion of 0.1 to 30% by weight, the organic solvent being selected from the group consisting of ethyl 3-ethoxypropionate, methyl 3-

ethoxypropionate, cyclohexanone and propylene glycol methyl ether acetate.

 The present invention further relates to a method of forming an antireflective coating in which antireflection coating compositions such as above are applied to a wafer and subjecting the wafer to a curing by baking. 300 C.

 The present invention also relates to a semiconductor device manufactured using anti-reflective coatings as above.

R1 C-0 C-o 1 (CH))m (CH:)ci (CH2)- (CHI)N 1 R. , \ R7 OH (formule générale I) Ro R, R4 The ARC resins of the present invention are selected from the group consisting of acrylic polymers represented by the following general formulas I, II and III:

R 1 C-O Co 1 (CH)) m (CH 2) n (CH 2) - (CH 1) N 1 R 1, R 7 OH (general formula I) Ro R, R 4

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, z~~ bzz~-~- - x ; -0 J = r - ' (f"3)n (formule générale 11) R. ott L RI Ra c-o (formule générale III) dans lesquelles,
R, R', R" et R"' sont, indépendamment des hydrogènes ou des groupes méthyles; Ro est un groupe méthyle ou un groupe éthy le;
R, à R9, qui sont identiques ou différents, représentent chacun un hydrogène, hydroxy, méthoxycarbonyle, carboxyle, hydroxyméthyle ou un alkyle ou un alcoxyalkyle linéaires ou ramifiés, substitués ou non-substitués en C,-C,; x, y et z sont chacun une fraction molaire dans la fourchette de 0,01 à 0,99; et m et n sont, indépendamment un entier de I à 4.

, z ~~ bzz ~ - ~ - - x; ## STR5 ## in which,
R, R ', R "and R"' are, independently of hydrogens or methyl groups; Ro is a methyl group or an ethyl group;
R 1 to R 9, which are the same or different, each represents hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl or a linear or branched, substituted or unsubstituted C 1 -C 4 alkyl or alkoxyalkyl; x, y and z are each a mole fraction in the range of 0.01 to 0.99; and m and n are independently an integer of I to 4.

In a preferred compound of formula I, m is 1 or 2 and n is an integer of 1 to 4. In a preferred compound of formula II, m is 1 or 2 and n is an integer of 2 to 4.

 The polymers of the present invention are designed to provide an absorbance greater than 193 nm and 248 nm wavelengths. To achieve this result, a chromophore substitute capable of absorbing light at 193 nm wavelengths and 248 nm on the polymer backbone is grafted.

 The polymer of general formula I, as illustrated in the reaction scheme according to I, can be obtained by polymerizing monomers of 9anthaenemethyl acrylate type and monomers (II) of the hydroxyalkyl acrylate type in the presence of an initiator in a solvent. Each of the monomers has a mole fraction of between 0.01 and 0.99.

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r 1 C-0 ' (schéma rcactionncl I) o on 1 c-o C-0 C-0 1 (CH <CH,)n Pl '4 où R, R', R, à R9, x, y, m et n sont chacun comme définis ci-dessus.

## STR1 ## where R, R ', R, to R9, x, y, m and n are each as defined above.

C-CH, Ç-#. Ç-Oi, t c-o ! c-o f OCH, (CHl)w "r"''" YT"r"''' R / / R, , (schéma réactionnel 2) co (ii) (ni) The polymers of the general formula II can be prepared in the same manner as the polymers of the general formula I, using monomers (I) of the 9-anthracenemethyl acrylate type, monomers (II) of the hydroxyalkyl acrylate type, monomers (III) methyl methacrylate in a fraction. molar from 0.01 to 0.99 for each of the monomers as illustrated in the following reaction scheme 2:

C-CH, C- #. That's it! ## STR1 ## where R (Reaction Scheme 2) co (ii) (nl)

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ou K, K , k , k, a J'9' x, y, z, m ei n ont cnacun la Oelll1lUOn aonnee ci-aessus.

or K, K, k, k, a I9 'x, y, z, m, n have the above mentioned Oelll1lUOn.

(schéma réactionnel 3) où R"' et R0 sont tels que définis ci-dessus. The preparation of the polymer of general formula III) is illustrated by Reaction Scheme 3. As shown, first, methacryloyl chloride (IV) is reacted with 4-hydroxy-benzaldehyde (V) to obtain 4-formylphenylmethacrylate (VI) which is then polymerized in the presence of an initiator in a solvent, followed by the substitution of 4-formylphenyl groups with methanol or ethanol:

(Reaction Scheme 3) where R "'and R0 are as defined above.

 To initiate the polymerization reaction into the polymers of general formulas I, II and III, customary initiators may be used, giving preference to 2,2-azobisisobutyronitrile (AIBN), acetylperoxide, laurylperoxide and t-butylperoxide. It is also possible to use current solvents for the polymerization. Preferably, the solvent is selected from the group consisting of tetrahydrofuran, toluene, benzene, methyl ethyl ketone and dioxane.

 Preferably, the polymers of general formulas 1 and II are polymerized at 50-90.degree.

Pl (CH2)noH , :5 1 R, + fE(;Hz 1 #- 9-anthr ccne IlkyllCrylate IR% , C-0 R, RI R, (schéma réactionnel The 9-anthracene alkyl acrylate monomers (I) used to prepare the polymers of the general formulas I and II are novel compounds which can be prepared by the reaction of a 9-anthracene alcohol with chlorine-type compounds. acryloyl in a solvent as illustrated in Reaction Scheme 4:

## STR5 ## wherein R 1, R 1 + R (R) + R (R) + R (R) + R (R) + R (R)

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 The above reactions are commercially available or can be prepared using known preparation methods.

 The present invention also relates to an ARC composition which is based on a polymer blend comprising the polymer of general formula or II and the polymer of general formula III, in combination with at least one additive selected from the group consisting of anthracene derivatives shown in Table I below.

TABLE 1

<Tb>
<tb> CH2OH <SEP> CN
<tb>#<SEP>#<SEP>#
<Tb>

CCO w w w Ww w 1 .; ,mihr:tccm <)-aIlIIH..dllIl1lh()Il,,1 ()-,lIlIhr,'(Il(;1I hOllil' ik Formule chimique) Formule chimiquc 2 ormule chimique

CCO www Ww w 1. , mihr: tccm <) - aIlIIH..dllIl1lh () Il ,, 1 () -, lIlIhr, '(Il (; 1I hilll' ik Chemical formula) Chemical formula 2 chemical ormule

<Tb>
<tb> OH <SEP> OH
<tb> OH <SEP> 1 <SEP> on <SEP>
<Tb>

CoQ i i OH :t...!th.." (J-;I1\111I(h.(nL'LlIh\)\\ liqUL'-' clUhi:uurl 1 Il!-,IIHllI,IU':lldliof Formulc chimiquc --1 Formule chimiquc 5 cliiiiiiqtle 6 0 Il NOII Oli cil M)Y H 110 I / / / 1 \ \ \ 0 .IL'H.Je... ,lIltI1l,lu..'lh. Il.1\ !tllh.." 'J...1111111,dd0], dL' (1\ lm... 1}-.IJIIIII,lldL'!l\dl.: Formule chimique 7 Formule chimique Formulc chimique 9 .N p Nll1 H3C 0 Nil, \ 1 \ cpH 0 N NI, 2 0 2-;uni)i<-7-)ncU)\ï-5-t\c-))- hcn/cp\r:H)a!2..h]-p)ridinc-3earhollllrile 1 -kiiiiiiioziiiilitaqtiiiloiie acidc a Ihraqmnonc-2-cnrhoyliyuc Formuleclilmique 10 Formule chimique 1 Formule chimique 12

## EQU1 ## Chemical formula Chemical formula: ## STR2 ## wherein: ## STR2 ## wherein: ## STR1 ## wherein: ## STR2 ## wherein: ## STR2 ## 1111111, dd0], (1 \ lm ... 1} -. IJIIIII, lldL '! l \ dl .: Chemical formula 7 Chemical formula Chemical formula 9 .N p Nll1 H3C ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## .h] -p) ridinc-3earhollllrile 1 -kiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii

<Desc / Clms Page number 15>

<Tb>
<Tb>
<tb> OH <SEP>###
<Tb>

1 ':;;-dIl1 dl Il'::- ,mlh, d(jIII IH)fh.' aiiihumc ''-.uuh)-)nnuro!))0h\ch)!ic

1 ': ;; - dIl1 dl Il' :: -, mlh, d (jIII IH) fh. '("uuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuu)

<Tb>
<tb> Formula <SEP> Chemical <SEP> 13 <SEP> Formula <SEP> Chemical <SEP> 14 <SEP> Formula <SEP> Chemical <SEP> 15
<Tb>

R I" RI, 1 RIS 1 dcrcdc-j!\!.mh!.c!)c doiivosdc 9-caihowl .inilir.iccnc t'cmcsdc)-L.t!ho\\!ant))raccnc

RI "RI, 1 RIS 1 dcrcdc-j! \ !. mh! .C!) C doiivosdc 9-caihowl .inilir.iccnc tlccdc) -Lt! Ho \\ ant))

<Tb>
<tb> Formula <SEP> Chemical <SEP> 16 <SEP> Formula <SEP> Chemical <SEP> 17 <SEP> Formula <SEP> Chemical <SEP> 18
<Tb>

In Table 1, R 11, R 12, R 13, R 14, and R 11, independently, are hydrogen, hydroxy, hydroxymethyl, or linear or branched, substituted or unsubstituted C 1 -C 5 alkyl or alkoxyalkyl.

 ARC compositions according to the present invention can be obtained by dissolving a polymer of formula 1 or II and a polymer of general formula III in a solvent to form a solution; (ii) optionally adding a compound selected from Table 1 to said solution, from 0.1 to 30% by weight and (iii) filtering the solution.

 The usual organic solvents can be used to prepare the composition, but with preference for ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, cyclohexanone and propylene methyl ether acetate. The solvent is preferably used in a proportion of from 200 to 5000% by weight, expressed with respect to the total weight of the ARC resin polymers used.

 In another aspect of the present invention, an ARC is formed from the coating composition described above. After filtration, this coating composition can be applied to a wafer in a conventional manner and then cured by baking (i.e. heated to 100-300 ° C for 10-1000 seconds) to form an ARC. reticle. Quality semiconductor devices can be made using ARCs of the present invention because this ARC crosslinked structure exhibits optically stable light exposure conditions when forming an image in the photosensitive layer.

 ARCs of the present invention have been found to exhibit high performance in submicrolithographic processes when used as

<Desc / Clms Page number 16>

 light sources of KrF lasers at 248 nm, ArF at 193 nm and F at 157 nm. The same goes for E-beams at 157 nm, EUV beams (far ultraviolet) and ion beams as light sources.

 The invention will be better understood in the light of the following examples which are given for illustrative purposes but should not be considered as limiting the present invention.

ANTHRACENEMETI IYLACRYLATE-(2-HYDROXYETI IYLACRYEATE)] Synthèse du 9-aiitliracèiieméthylacrylate
On dissout 0,5 mole de 9-anthracène-méthanol et 0,5 mole de pyridine dans du tétrahydrofurane puis on ajoute 0,5 mole de chlorure d'acryloyle. Au terme de la réaction, on filtre le produit et on extrait à l'acétate d'éthyle. On lave l'extrait à plusieurs reprises à l'eau distillée et on sèche par distillation sous vide pour obtenir le 9-anthracénylméthylacrylate, représenté par la formule développée suivante. Example I
SYNTHESIS OF BINARY COPOLYMER OF POLY- [9-

ANTHRACENEMETI IYLACRYLATE- (2-HYDROXYETI IYLACRYEATE)] Synthesis of 9-Allylacetylmethylacrylate
0.5 mole of 9-anthracene-methanol and 0.5 mole of pyridine are dissolved in tetrahydrofuran and then 0.5 mole of acryloyl chloride is added. At the end of the reaction, the product is filtered and extracted with ethyl acetate. The extract was washed several times with distilled water and dried by distillation in vacuo to give 9-anthracenylmethylacrylate, represented by the following structural formula.

c=o 0 Cil, (formule chimique! 19) (formule chimique

Synthèse d'un copolymère binaire de pply- [9-anthracèneméthylacrlate- 2-h d éthylacrylate)]
Dans un ballon à fond rond de 500 ml, on introduit 0,5 mole de 9-anthracèneméthylacrylate et 0,5 mole de 2-hydroxyéthylacrylate. On ajoute ce mélange à 300 g de tétrahydrofurane (THF) préparé séparément sous agitation. Ensuite en présence de 0,1-3 g de 2,2-azobisisobutyronitile (AIBN), on soumet le mélange réactionnel à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans l'éther éthylique ou l'hexane normal, on filtre le précipité et on le sèche pour obtenir le copolymère de poly- [9- anthracèneméthylacrylate-(2-hydroxyéthylacrylate)], un polymère selon la présente invention, répondant à la formule développée 20 suivante, selon un rendement de 83%. Yield 84%.

c = o 0 Cil, (chemical formula! 19) (chemical formula

Synthesis of a binary copolymer of pply- [9-anthracenemethylacrylate-2-hd ethylacrylate]]
500 ml of a round-bottomed flask are charged with 0.5 moles of 9-anthracenemethylacrylate and 0.5 moles of 2-hydroxyethylacrylate. This mixture is added to 300 g of tetrahydrofuran (THF) prepared separately with stirring. Then in the presence of 0.1-3 g of 2,2-azobisisobutyronitile (AIBN), the reaction mixture is subjected to polymerization at 60-75 C for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane, the precipitate is filtered off and dried to obtain the copolymer of poly- [9-anthracenemethylacrylate- (2-hydroxyethylacrylate)], a polymer according to the present invention, having the following structural formula, in a yield of 83%.

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METHYLACRYLA TE-(3-HYDROXYPROPYLACRYLA TE)l
Dans un ballon à fond rond de 500 ml, on introduit 0,5 mole du 9anthracénylméthylacrylate synthétisé dans l'exemple 1, et 0,5 mole de 3hydroxypropylacrylate. On ajoute ce mélange à 300 g de TI-IF préparé séparément sous agitation. Ensuite, en présence de 0,1-3 g d'AIBN, on soumet le mélange réactionnel à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans l'éther éthylique ou l'hexane normal et on filtre le précipité et le sèche pour obtenir un copolymère

poly [9-anthracén}lméthylacrylate-(3-hydro:5-propylacrylate)], un polymère selon la présente invention, répondant à la formule chimique suivante21. Rendement de 82%.

co Jos f=() 05 (formule chimique 21 ) Cil (CHj), oCo' C - <> 1 1 (chemical formula 20) in (Cil,), 1 oeo 'uit Example II
SYNTHESIS OF BINARY COPOLYMER OF POLY- [9-ANTHRACENYL-

METHYLACRYLA TE- (3-HYDROXYPROPYLACRYLA TE) l
500 ml of a round-bottomed flask were charged with 0.5 mol of the 9-anthracenylmethylacrylate synthesized in Example 1 and 0.5 mol of 3-hydroxypropylacrylate. This mixture is added to 300 g of separately prepared TI-IF with stirring. Then, in the presence of 0.1-3 g of AIBN, the reaction mixture is subjected to polymerization at 60-75 ° C. for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane and the precipitate is filtered and dried to obtain a copolymer

poly [9-anthracen] 1-methylacrylate- (3-hydro: 5-propylacrylate)], a polymer according to the present invention, having the following chemical formula21. Yield 82%.

co Jos f = () 05 (chemical formula 21) Cil (CHj), oCo '

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SYNTHESE DU COPOLYMERE POLY-[9-ANTHRACENEMETHYLACRYLA TE-(4-IIYDROXYBUTYLACRYLA TE)] Dans un ballon de 500 ml à fond rond, on introduit 0,5 mole de 9anthracèneméthytacrytate et 0,5 mole de 4-hydro\ybuty)acry)ate. On ajoute ce mélange à 300 g de THF préparé à part sous agitation. Ensuite, en présence de 0,1- 3 g d'AIBN, on soumet le mélange réactionnel à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans l'éther éthylique ou l'hexane normal et on filtre le précipité

et le sèche pour obtenir un copolymère poly- [9-anthracèneméthylacryIate-(4hydroxybutylacrylate)]. un polymère selon la présente invention, répondant à la formule chimique développée suivante 22. Rendement 81%.

Example III

SYNTHESIS OF THE POLY- [9-ANTHRACENEMETHYLACRYLA TE- (4-IIYDROXYBUTYLACRYLA TE) COPOLYMER) 0.5 ml of 9-anthracenemethylacrylate and 0.5 mol of 4-hydroxybutycarbon were introduced into a 500 ml round bottom flask). ate. This mixture is added to 300 g of THF prepared separately with stirring. Then, in the presence of 0.1-3 g of AIBN, the reaction mixture is subjected to polymerization at 60-75 ° C. for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane and the precipitate is filtered off.

and dried to obtain a poly- [9-anthracenemethylacrylate- (4hydroxybutylacrylate)] copolymer. a polymer according to the present invention, corresponding to the following chemical formula 22. Yield 81%.

Synthèse du 9-antliracèneméthylméthacrylate
On dissout 0,5 mole de 9-anthracèneméthanol et 0,5 mole de pyridine dans du THF et ensuite on ajoute 0,5 mole de chlorure de méthacryloyle. Au terme de la réaction, on filtre le produit et on l'extrait à l'acétate d'éthyle. On lave l'extrait à de nombreuses reprises à l'eau distillée et on sèche par distillation sous vide pour obtenir le 9-anthracèneméthylméthacrylate, répondant à la formule chimique développée 23. Rendement 83%. 00 os 9 "os Y? C = O 1 c";"7 (chemical formula 22) Example IV
SYNTHESIS OF BINARY COPOLYMER POLY- [9-ANTHRACENEMETHYLMETHACRYLATE- (2-HYDROXYETHYLACRYLATE)]

Synthesis of 9-antirhrenemethylmethacrylate
0.5 moles of 9-anthracenemethanol and 0.5 moles of pyridine are dissolved in THF and then 0.5 moles of methacryloyl chloride are added. At the end of the reaction, the product is filtered off and extracted with ethyl acetate. The extract is washed several times with distilled water and dried by distillation in vacuo to give 9-anthracenemethyl methacrylate, corresponding to the chemical formula developed. Yield 83%.

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rC-0 1 î Cli, \ / (formule chimique 2'c)

Synthèse du copolymère binaire de poil' [9-anthracèneméthylméthacrvlatc-(2lià,droxyétli,1,icrà,late)]
Dans un ballon à fond rond de 500 ml, on introduit 0,5 mole de 9- anthracèneméthylméthacrylate et 0,5 mole de 2-hydroxyéthylacrylate. On ajoute ce mélange à 300 g de THF préparé à part sous agitation. Ensuite, en présence de AIBN, on soumet la réaction à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans l'éther éthylique ou l'hexane normal et on filtre le précipité et sèche pour obtenir un

1)Ol' 9-allthl'aCèl1e111Ct11-Iméthacrylate-(2-hydl'O\'eth}'lacl-'lalc], une résine selon la présente invention répondant à la formule développée 24 suivante, selon un rendement de 79 %.

rC-0 1 Cli, \ / (chemical formula 2'c)

Synthesis of the binary hair copolymer [9-anthracenemethylmethacrylate (2Ha, droxyethyl, 1, microlate)]
500 ml of a round bottom flask are charged with 0.5 moles of 9-anthracenemethylmethacrylate and 0.5 moles of 2-hydroxyethylacrylate. This mixture is added to 300 g of THF prepared separately with stirring. Then, in the presence of AIBN, the reaction is subjected to polymerization at 60-75 C for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane and the precipitate is filtered off and dried to obtain a

1) [alpha] 9-allyl [allyl] [11] -tethacrylate- (2-hydyloxy) -alkyl], a resin according to the present invention having the following structural formula 24, in a yield of 79%.

ANTHRACENEMETI IYLMETHACRYLATE-(3-I IYDROXYPROPYLACRYLATE)]
Dans un ballon de 500 ml à fond rond, on introduit 0,5 mole de 9anthracèneméthylméthacrylate synthétisé dans l'Exemple IV et 0,5 mole de 3- hydroxypropylacrylate. On ajoute ce mélange à 300 g de THF préparé à part sous agitation Ensuite, en présence de 0,1-3 g d'AIBN, on soumet le mélange réactionnel à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans l'éther éthylique ou l'hexane normal, on filtre le précipité et le sèche pour obtenir un copolymère poly- Clly C = 0 Jos C = O 10 (chemical formula 24) OO:) CII1 ([1) Example V
SYNTHESIS OF BINARY COPOLYMER OF POLY- [9-

ANTHRACENEMETI IYLMETHACRYLATE- (3-IYDROXYPROPYLACRYLATE)]
500 ml round-bottom flask was charged with 0.5 mole of 9-anthracenemethyl methacrylate synthesized in Example IV and 0.5 mole of 3-hydroxypropyl acrylate. This mixture is added to 300 g of THF prepared separately with stirring. Next, in the presence of 0.1-3 g of AIBN, the reaction mixture is subjected to polymerization at 60-75 ° C. for 5-20 hours under a vacuum. 'nitrogen. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane, the precipitate is filtered off and dried to obtain a poly (methylene chloride) copolymer.

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9-anthracèneméth}lméthaerylate-(2-hydroxypropylacrylate), un polymère selon la présente invention, répondant à la formule chimique développée suivante 25. Rendement 81%

cil, -#- C-0 Jas C=0 . 0 o c=O 1 (formule chimique y ci (Cil,), 1 1 (foriiiiiie ciiiiiilqtje 1 en; oit Y'" Exemple VI
SYNTHESE DU COPOLYMERE BINAIRE DE POLY-[9-

ANTHRACENEMETHYLMETHACRYLATE-(4-IIYDROXYBUTHYLACRYLATE)]
Dans un ballon de 500 ml à fond rond, on introduit 0,5 mole de 9- anthracèneméthylacrylate synthétisé dans l'Exemple IV et 0,5 mole de 4-

hydroxybutylacrylate. On ajoute ce mélange à 300 g de TIIF préparé séparément sous agitation. Ensuite, en présence de 0,1-3 g de AIBN, on soumet la réaction à une polymérisation à 60-75 C pendant 5 à 20 heures sous atmosphère d'azote. Au terme de cette réaction, on précipite la solution dans l'éther éthylique ou l'hexane normal et on filtre le précipité, et on le sèche pour obtenir un copolymère de poly [9-

anthracèneméthylméthacrylate-( 4-hydroxybutylacrylate)]. un polymère selon la présente invention, répondant à la formule chimique développée suivante 26, selon un rendement de 81 %.

9-anthracenemethicylmethaerylate- (2-hydroxypropylacrylate), a polymer according to the present invention, having the following chemical structural formula 25. Yield 81%

cil, - # - C-0 Jas C = 0. 0 o = O 1 (chemical formula y ci (Cil,), 1 1 (Example 1)
SYNTHESIS OF BINARY COPOLYMER OF POLY- [9-

ANTHRACENEMETHYLMETHACRYLATE- (4-IIYDROXYBUTHYLACRYLATE)]
500 ml of round-bottomed flask was charged with 0.5 mole of 9-anthracenemethylacrylate synthesized in Example IV and 0.5 mole of 4-

hydroxybutyl acrylate. This mixture is added to 300 g of separately prepared TIIF with stirring. Then, in the presence of 0.1-3 g of AIBN, the reaction is subjected to polymerization at 60-75 C for 5 to 20 hours under a nitrogen atmosphere. At the end of this reaction, the solution is precipitated in normal ethyl ether or hexane and the precipitate is filtered off and dried to obtain a poly [9-] copolymer.

anthracenemethylmethacrylate- (4-hydroxybutylacrylate)]. a polymer according to the present invention, corresponding to the following chemical formula 26, in a yield of 81%.

C-0 Jos CoQ 1 J 05 CH, <'' <f01'171UIt; CI11I111C11e -L 5. "(chemical formula 26) #

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antluacèneméthylaciyIate-(2-hydroxyéthylacrylate)-méthylméthacrylate], un polymère selon la présente invention, répondant à la formule chimique développée 27. Rendement de 80%.

Example VII
SYNTHESIS OF TERNARY COPOLYMER OF POLY- [9-ANTHRACENE-METHYLACRYLATE- (2-HYDROXYETHYLACRYLATE) -METHYL-METHACRYLATE]
500 ml of a round-bottomed flask are charged with 0.3 mol of 9-anthracenemethyl acrylate, 0.5 mol of 2-hydroxyethyl acrylate and 0.2 mol of methyl methacrylate. This mixture is then added to 300 g of separately prepared THF with stirring. in the presence of 0.1-3 g of AIBN, the reaction mixture is subjected to polymerization at 60-75 ° C. for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane and the precipitate is filtered off and dried to obtain a poly- [9-] copolymer.

antluacenomethyl-ethyl-ethyl- (2-hydroxyethylacrylate) -methylmethacrylate], a polymer according to the present invention, having the chemical structural formula 27. Yield of 80%.

METHYLACRYLA TE-(3-HYDROXYPROPYLACRYLA TE)-METI IYL- METHACRYLATE]
Dans un ballon de 500 ml à fond rond, on introduit 0,3 mole de 9anthracèneméthylacrylate, 0,5 mole de 3-hydroxpropylacrylate et 0,2 mole de méthylméthacrylate On ajoute ce mélange à 300 g de THF préparé séparément sous agitation, ensuite, en présence de 0,1-3 g d'AIBN, on soumet le mélange réactionnel à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans )'éther éthylique ou l'hexane normal, et on filtre le précipité et on le sèche pour obtenir un copolymère poly-[9-

anthracèneméthylacrylate-(3-hydroxypropylacrylate)-méthylméthacylate], un polymère selon la présente invention, répondant à la formule chimique développée 28, selon un rendement de 82%. C = O .03 C = O 1 .O 2 O -OS OCH, 1 (Cl 2) 1 # (Ch,), C11, on (Chemical Formula 27) Example VIII
SYNTHESIS OF TERNARY COPOLYMER OF POLY- [9-ANTHRACENE-

METHYLACRYLA TE- (3-HYDROXYPROPYLACRYLA TE) -METI IYL-METHACRYLATE]
500 ml of a round-bottomed flask are charged with 0.3 mol of 9-anthracenemethyl acrylate, 0.5 mol of 3-hydroxpropyl acrylate and 0.2 mol of methyl methacrylate. This mixture is then added to 300 g of separately prepared THF with stirring, followed by in the presence of 0.1-3 g of AIBN, the reaction mixture is subjected to polymerization at 60-75 ° C. for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane, and the precipitate is filtered off and dried to obtain a poly- [9-] copolymer.

anthracenemethylacrylate- (3-hydroxypropylacrylate) -methylmethacrylate], a polymer according to the present invention, having the chemical structural formula 28, in a yield of 82%.

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H) --1-1------ (formule chimique 28) C-0 .C-0 T-c c-c 1 J 1 ? OCII) 1 Cil, loi Exemple IX

SYNTHESE DU COPOLYMERE TERNAIRE DE POI~'-[9-'1NTHRACENE- 11rT11'1~ACRYI.ATr-(4-I IYDROX1'E3UTYLACR1'I.ATI:)-MhTIIl'l.- METHACRYLATE]
Dans un ballon de 500 ml à fond rond, on introduit 0,5 mole de 9-

anthracèncméthylacr) late, 0,5 mole de 4-hydrovy butylacry late et 0,2 mole de méthylméthacrylate. On ajoute ce mélange à 300 g de tétrahydrofurane (THF) préparé séparément sous agitation. Ensuite, en présence de 0,1-3 g d'AIBN, on soumet le mélange réactionnel à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans l'éther éthylique ou l'hexane normal, et on filtre le précipité et le sèche pour obtenir

un copolymère poly-[9-anthracèneméthylacrylate-(4-hydroxybut)Iacrylate)méthylméthacrylate], un polymère selon la présente invention, répondant à la formule chimique développée suivante 29. Rendement 81%.

co 1 - 0 C-0 1 J02 c 1 -o - 05 ' 0 (formule chimique 29) cil, (Cili) 1 OH Exemple X
SYNTHESE DU COPOLYMERE TERNAIRE DE POLY-[9-ANTHRACENE- METHYLMETHACRYLATE-(2-HYDROXYETHYLACRYLATE)-METHYL- METHACRYLATE]
Dans un ballon de 500 ml à fond rond, on introduit 0,3 mole de 9- anthracèneméthylméthacrylate synthétisé dans l'Exemple IV, 0,5 mole de 2hydroxyéthylacrylate et 0,2 mole de méthylméthacrylate. On ajoute ce mélange à 300 g de tétrahydrofurane (THF) préparé séparément sous agitation. Ensuite, en présence de 0,1-3 g d'AIBN, on soumet le mélange réactionnel à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans l'éther éthylique ou l'hexane normal, et on filtre le précipité et le sèche pour obtenir un copolymère poly-[9-

H) -1-1 ------ (chemical formula 28) C-0 .C-0 Tc cc 1 J 1? OCII) 1 Cil, law Example IX

SYNTHESIS OF THE TERNAIRE COPOLYMER OF POI ~ '- [9 -NHRACENE-11RT11'1 ~ ACRYI.ATr- (4-IYDROX1'E3UTYLACR1'I.ATI:) - MHTIIl'l.- METHACRYLATE]
500 ml round-bottomed flask was charged with 0.5 mole of 9-

anthracenomethylacrylate), 0.5 mole of 4-hydrovy butylacrylate and 0.2 mole of methylmethacrylate. This mixture is added to 300 g of tetrahydrofuran (THF) prepared separately with stirring. Then, in the presence of 0.1-3 g of AIBN, the reaction mixture is subjected to polymerization at 60-75 ° C. for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane, and the precipitate is filtered and dried to obtain

a copolymer poly- [9-anthracenemethylacrylate- (4-hydroxybut) acrylate) methylmethacrylate], a polymer according to the present invention, corresponding to the following chemical formula 29. Yield 81%.

co 1 - 0 C-0 1 J02 c 1 -o - 05 '0 (chemical formula 29) cil, (Cili) 1 OH Example X
SYNTHESIS OF TERNARY COPOLYMER OF POLY- [9-ANTHRACENE-METHYLMETHACRYLATE- (2-HYDROXYETHYLACRYLATE) -METHYL-METHACRYLATE]
500 ml of a round-bottomed flask were charged with 0.3 mol of 9-anthracenemethylmethacrylate synthesized in Example IV, 0.5 mol of 2-hydroxyethylacrylate and 0.2 mol of methylmethacrylate. This mixture is added to 300 g of tetrahydrofuran (THF) prepared separately with stirring. Then, in the presence of 0.1-3 g of AIBN, the reaction mixture is subjected to polymerization at 60-75 ° C. for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane, and the precipitate is filtered off and dried to obtain a poly- [9-] copolymer.

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anthracèneméthylméthacryIate-(2-hydroxyéthylacrylate)méthylméthacrylale], un polymère scion la présente invention, répondant à la formule chimique développée suivante 30. Rendement 82%.

anthracenemethylmethacrylate- (2-hydroxyethylacrylate) methylmethacrylate], a polymer according to the present invention, having the following chemical structural formula: 30. Yield 82%.

METHYLMETHACRYLA TE-(3-HYDROXYPROPYLACRYLA TE)- METHYLMETHACRYLATE]
Dans un ballon de 500 ml à fond rond, on introduit 0,3 mole de 9- anthracèneméthylméthacrylate synthétisé dans l'Exemple IV, 0,5 mole de 3- hydroxypropylacrylate et 0,2 mole de méthylméthacrylate. On ajoute ce mélange à 300 g de tétrahydrofurane (THF) préparé séparément sous agitation. Ensuite, en présence de 0,1-3 g d'AIBN, on soumet le mélange réactionnel à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans l'éther ethnique ou l'hexane normal, et on filtre le précipité et le sèche pour obtenir un copolymère poly-[9-

anthracèneméthylacrylate-(3-hydroxypropylacrylate)-méthylméthacrylate], un polymère selon la présente invention, répondant à la formule chimique développée suivante 31, selon un rendement de 8 1 %.

CI1 C143. ## EQU2 ## OCII = a 02 c-0 05 (tonnu) cc) nmic (c1), (C11), 1; 011 ExampleXI
SYNTHESIS OF TERNARY COPOLYMER OF POLY- [9-ANTHRACENE-

METHYLMETHACRYLA TE- (3-HYDROXYPROPYLACRYLA TE) - METHYLMETHACRYLATE]
500 ml of a round-bottomed flask were charged with 0.3 mol of 9-anthracenemethyl methacrylate synthesized in Example IV, 0.5 mol of 3-hydroxypropyl acrylate and 0.2 mol of methyl methacrylate. This mixture is added to 300 g of tetrahydrofuran (THF) prepared separately with stirring. Then, in the presence of 0.1-3 g of AIBN, the reaction mixture is subjected to polymerization at 60-75 ° C. for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in ethyl ether or normal hexane, and the precipitate is filtered off and dried to obtain a poly- [9-] copolymer.

anthracenemethylacrylate- (3-hydroxypropylacrylate) -methylmethacrylate], a polymer according to the present invention, having the following chemical structural formula 31, in a yield of 8 1%.

CW3, ---- ~ cH C = () 1 .0] C = 0 'Joi 0 f = () bones (chemical formula 31)

<Desc / Clms Page number 24>

METIIYLMETIIACRYt~ATE-(4-1IYDROXYRL1TYI~ACRYI~ATE)-METIIYI~- METHACRYLATE]
Dans un ballon de 500 ml à fond rond, on introduit 0,3 mole de 9-

aIltIlraCè11C117éthyUaCrj'IatC synthétisé dans )'Exemple IV, 0,5 mole de 4hydroxybutylacrylate et 0,2 mole de méthylméthacrylate. On ajoute ce mélange à 300 g de tétrahydrofurane (THF) préparé séparément sous agitation. Ensuite, en

présence de 0,1-3 g d 'II3il, on soumet le mélange réactionnc) à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans t'éther éthylique ou l'hexane normal, et on filtre le précipité et le sèche pour obtenir un copolymère poly-[9-

anthracèneméthylméthacrylate-(4-hydroxybutylacrylate)-méthylméthacrylate]. un polymère selon la présente invention, répondant à la formule chimique développée suivante 32. Rendement de 80%.

crl CO Jo3 0 J 02 CO os (formule chimique Ces '" CQ 1 (formule chimique 32) en, (CH,), 1 OH Exemple XIII
SYNTHESE DU COPOLYMERE BINAIRE DE POEY-[9-ANTHRACENE-

ETHYLACRYLATE-(2-HYDROXYETHYLACRYLATE)l Synthèse du 9-anthracèneéthylacrvlate
On dissous 0.5 mole de 9-anthracène éthanol et 0,5 mole de pyridine dans le THF et ensuite on ajoute 0,5 mole de chlorure d'acryloyle. Au terme de la réaction, on filtre le produit et on l'extrait à l'acétate d'éthyle. On lave l'extrait à de nombreuses reprises à l'eau distillée et on le sèche par distillation sous vide, pour

obtenir le 9-anthracènelnéthylaclylate, répondant à la formule chimique développée 33 suivante.Rendement 80 %. Example XII
SYNTHESIS OF TERNARY COPOLYMER OF POLY- [9-ANTHRACENE-

METIIYLMETIIACRYt ~ ATE- (4-1IYDROXYRL1TYI ~ ACRYI ~ ATE) -METIIYI ~ - METHACRYLATE]
500 ml of round-bottomed flask is charged with 0.3 mole of 9-

embedded image in Example IV, 0.5 mole of 4-hydroxybutylacrylate and 0.2 mole of methyl methacrylate. This mixture is added to 300 g of tetrahydrofuran (THF) prepared separately with stirring. Then, in

0.1-3 g of HCl is present, the reaction mixture is subjected to polymerization at 60 ° to 75 ° C. for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane, and the precipitate is filtered off and dried to obtain a poly- [9-] copolymer.

anthracèneméthylméthacrylate- (4-hydroxybutyl acrylate) -méthylméthacrylate]. a polymer according to the present invention, corresponding to the following chemical formula 32. Efficiency of 80%.

crl CO 0 CO 0 0 02 CO (chemical formula These '' CQ 1 (chemical formula 32) in, (CH,), 1 OH Example XIII
SYNTHESIS OF BINARY COPOLYMER OF POEY- [9-ANTHRACENE-

ETHYLACRYLATE- (2-HYDROXYETHYLACRYLATE) Synthesis of 9-anthraceneethylacrylate
0.5 mol of 9-anthracene ethanol and 0.5 mol of pyridine are dissolved in THF and then 0.5 mol of acryloyl chloride is added. At the end of the reaction, the product is filtered off and extracted with ethyl acetate. The extract is washed many times with distilled water and dried by vacuum distillation to

obtain 9-anthracenelethylaclylate, corresponding to the following chemical formula 33. Yield 80%.

<Desc / Clms Page number 25>

co (formule chimique 33) o (CH2)2

Synthèse du copolvmère de poly [9-anthracèneéthlacry-late-(?hydroxycthylacrylate)] Dans un ballon de 500 ml à fond rond, on introduit 0,5 mole de 9-

anthracèneéthylacrylate et 0,5 mole de 2-hydroxy'éthylacrylate. On ajoute ce mélange à 300 g de THF préparé à part sous agitation. Ensuite, en présence de 0,1-3 g d'AIBN, on soumet la réaction à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans l'éther éthylique ou l'hexane normal, et on filtre le précipité et le sèche pour obtenir un copolymère poly [9-anthracèneéthylacrylate-(2-hydroxyéthylacrylate)], une résine selon la présente invention, répondant à la formule chimique développée suivante 34, selon un rendement de 82 %.

co (chemical formula 33) o (CH2) 2

Synthesis of poly [9-anthraceneethlacry-late- (β-hydroxyethylacrylate)] copolymer In a 500 ml round-bottomed flask, 0.5 mole of

anthraceneethylacrylate and 0.5 mole of 2-hydroxyethylacrylate. This mixture is added to 300 g of THF prepared separately with stirring. Then, in the presence of 0.1-3 g of AIBN, the reaction is subjected to polymerization at 60-75 C for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane, and the precipitate is filtered and dried to obtain a poly [9-anthraceneethylacrylate- (2-hydroxyethylacrylate)] copolymer, a resin according to The present invention, according to the following developed chemical formula 34, has a yield of 82%.

Co 1 05 0 y = O os o 1 (CH) 1 on f! 1 (chemical formula 34) Example XIV
SYNTHESIS OF BINARY COPOLYMER OF POLY- [9-ANTHRACENE-ETHYLACRYLATE- (3-HYDROXYPROPYLACRYLATE)]
500 ml of round bottom flask are charged with 0.5 mol of 9-anthracethylethyl acrylate synthesized in Example XIII and 0.5 mol of 3-

<Desc / Clms Page number 26>

un copolymère poly-(9-anthracèneéthylacrylate-(3-h-droy-propy-lacrylatc)], un polymère selon la présente invention, répondant à la formule chimique développée suivante 35, selon un rendement de 81%.

hydroxypropyl acrylate. This mixture is added to 300 g of tetrahydrofuran (THF) prepared separately with stirring. Then, in the presence of 0.1-3 g of AIBN, the reaction mixture is subjected to polymerization at 60-75 ° C. for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane, and the precipitate is filtered and dried to obtain

a poly- (9-anthraceneethylacrylate- (3-h-droypropyl-lacrylate)] copolymer, a polymer according to the present invention, having the following chemical structural formula 35, in a yield of 81%.

SYNTHESE DU COPOLYMERE POLY-[9-ANTHRACENE-ETIÏYLACRYLATE- (4-HYDROXYBUTYLACRYLATE)]
Dans un ballon de 500 ml à fond rond, on introduit 0,5 mole de 9- anthracèneéthylacrylate et 0,5 mole de 4-hydroxybutylacrylate. On ajoute ce mélange à 300 g de tétrahydrofurane (THF) préparé séparément sous agitation. Ensuite, en présence de 0,1-3 g d'AIBN, on soumet la solution réactionnelle à une polymérisation à 60-75 C pendant 5-20 heures sous atmosphère d'azote. Au terme de la polymérisation, on précipite la solution dans l'éther éthylique ou l'hexane normal, et on filtre le précipité et le sèche pour obtenir un copolymère poly-[9-

anthracèneéthylacrylate-( 4-hydroxybutylacry latc)1, un polymère selon la présente invention, répondant à la formule chimique développée suivante 36. Rendement 80%.

C = 0 Jos C-0 Jas 1 (chemical formula 35) (at Y >>> JL OH Example XV

SYNTHESIS OF POLY- [9-ANTHRACENE-ETIYLACRYLATE- (4-HYDROXYBUTYLACRYLATE) COPOLYMER]
500 ml of round bottom flask are charged with 0.5 moles of 9-anthraceneethylacrylate and 0.5 moles of 4-hydroxybutylacrylate. This mixture is added to 300 g of tetrahydrofuran (THF) prepared separately with stirring. Then, in the presence of 0.1-3 g of AIBN, the reaction solution is subjected to polymerization at 60-75 ° C. for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane, and the precipitate is filtered off and dried to obtain a poly- [9-] copolymer.

anthraceneethylacrylate- (4-hydroxybutylacrylate) 1, a polymer according to the present invention, having the following chemical formula 36. Yield 80%.

Jos i-o i 0 ZH,), yHal, (chemical formula 36)

<Desc / Clms Page number 27>

nIMETHOXYMETHl'L)PHENYLMETHACRYLATE) Synthèse dupolv f4-formylphénylméthacl-latcl
Dans un bal lon de 300 ml à fond rond, on dissout complètement 31,3 g (0,3 mole) de chlorure de méthacryloyle dans 200 g de THF sous agitation et on ajoute 26 g de pyridine. A cette solution,on ajoute goutte à goutte 36,6 g (0,3 mole) de 4- hydroxybenzaldéhyde puis, on laisse les réactifs réagir pendant 24 heures ou davantage. On lave la solution du produit à !'eau déminéralisée pour séparer une couche aqueuse d'où on extrait et sèche le composé désiré.

Example XVI
SYNTHESIS OF POLY- [4- (1,1

nIMETHOXYMETHL'L) PHENYLMETHACRYLATE) Synthesis dupolv f4-formylphenylmethacl-latch
In a 300 ml round-bottomed flask, 31.3 g (0.3 mol) of methacryloyl chloride are completely dissolved in 200 g of THF with stirring and 26 g of pyridine are added. To this solution is added dropwise 36.6 g (0.3 mole) of 4-hydroxybenzaldehyde and then the reactants are allowed to react for 24 hours or more. The product solution is washed with deionized water to separate an aqueous layer from which the desired compound is extracted and dried.

0.4 mol of the resulting 4-chlorothymethylcellulose with 300 g of THF are introduced into a 500 ml round bottom flask and 0.1-3 g of AIBN are added with stirring. The polymerization is continued at 60-75 ° C. for 5-20 hours under a nitrogen atmosphere. At the end of the polymerization, the solution is precipitated in normal ethyl ether or hexane and the precipitate is filtered off and dried to obtain a poly [4-formylphenylmethacrylate] polymer in a yield of 80%.

et sèche le précipité pour obtenir le poly [4-(l.l-diméthoxyméth\l)phényl- méthacrylate]. un polymère selon la présente invention, répondant à la formule chimique développée 37 suivante. Rendement 82 %.

t-4-1 --OCH, (formule chimique ( formule chimique 37) CH,0-OCt<. Exemple XVII

SYNTHESE DU POLY [4-(l,l-DIETHOXYMETHY)PHENYL- METHACRYLATE]
Dans une fiole d'Erlenmeyer de 400 ml, on introduit 15g du poly [4formylméthacrylate] synthétisé dans l'Exemple VI et 200 ml de THF et ensuite, on Synthesis of poly (4- (1,1-dimethoxymethylphenyl) methacrylate]
400 g of Erlenmeyer flask are charged with 15 g of the polymer obtained above and 200 ml of THF, then 100 g of methanol are added with 0.5 g of IICI, after which the reactants are allowed to react at 60 ° C. for about 12 hours. The solution of the product is precipitated in normal ethyl ether or hexane and filtered,

and drying the precipitate to obtain poly [4- (11-dimethoxymethyl) phenylmethacrylate]. a polymer according to the present invention, corresponding to the following developed chemical formula. Yield 82%.

t-4-1 --OCH, (chemical formula (chemical formula 37) CH, O-OCt <Example XVII

SYNTHESIS OF POLY [4- (1,1-DIETHOXYMETHY) PHENYL METHACRYLATE]
400 g of Erlenmeyer flask are charged with 15 g of the poly [4formylmethacrylate] synthesized in Example VI and 200 ml of THF and then

<Desc / Clms Page number 28>

diétliox'iiiétii,I)pliéii-Iiiiétliacrylate]. une résine selon la présente invention, répondant à la formule chimique développée suivante 38. Rendement 80 %.

c=c (formule chimique 38) Cf I3CH2O OCIICH Exemple XVIII
Préparation de l'ARC
On dissout un polymère préparé dans chacun des exemples I à XV et un polymère préparé dans l'exemple XVI ou XVII dans le propylèneglycol méthyléther acétate (PGMEA). Cette solution, seule ou en combinaison avec 0,1-30 % en poids d'au moins un additif choisi parmi les composés de formules chimiques 1 à 18 et dans le tableau 1, est filtrée, appliquée sur une plaquette et durcie par cuisson à 100- 300 C pendant 10 à 1 000 secondes pour former une ARC. On peut appliquer une substance photosensible sur l'ARC ainsi formée et la transformer en image en un réseau ultrafin d'une manière classique. 150 g of ethanol are added with 0.5 g of HCl, after which the reactants are allowed to react for approximately 12 hours at 60 ° C. The solution is precipitated in normal ethyl ether or hexane, the precipitate is filtered off and dry it to obtain poly [4- (l, l-

diétliox'iiiétii, I) pliéii-Iiiiétliacrylate]. a resin according to the present invention, corresponding to the following chemical formula 38. Yield 80%.

c = c (chemical formula 38) Cf I3CH2O OCIICH Example XVIII
ARC Preparation
A polymer prepared in each of Examples I to XV and a polymer prepared in Example XVI or XVII are dissolved in propylene glycol methyl ether acetate (PGMEA). This solution, alone or in combination with 0.1-30% by weight of at least one additive selected from the compounds of chemical formulas 1 to 18 and in Table 1, is filtered, applied to a wafer and cured by baking. 100-300 C for 10 to 1000 seconds to form an ARC. A photosensitive substance can be applied to the ARC thus formed and transformed into an image in an ultrafine network in a conventional manner.

sub-microlithographie. As described above, the ARCs of the present invention, obtained from a mixture comprising a polymer of the general formula I or II and a polymer of the general formula III, alone or in combination with an additive of chemical formulas 1 to 18 in Table I, contains sufficient chromophore substituents to exhibit absorbance at useful wavelengths for

Sub-microlithography.

 In particular, the ARC of the present invention provides maximum crosslinking reaction efficiency and storage stability. The ARC polymer resins of the present invention exhibit superior solubility in all hydrocarbon solvents, but after heating cure exhibit such high solvent resistance that they do not dissolve at all in any solvent. These advantages make it possible to apply the resin without any problem and the coatings obtained prevent the overhanging areas and the spreading of the base which can occur when forming images on photosensitive substances. In addition,

<Desc / Clms Page number 29>

 Coatings obtained from the acrylic polymers of the present invention have a faster etch rate than the photosensitive films, which improves the etch selection ratio between them.

 Thus, the ARCs of the present invention can play an excellent role in the formation of ultrafine networks. For example, they can prevent retroreflection of the light from the lower layers or the surface of the semiconductor elements, as well as the elimination of light-induced stationary waves and thickness variations in the photoresist layer itself, in a submicrolithographic method using KrF 248 11111, ArF 193 nm or F2 lasers at 157 nm. This leads to the stable formation of ultra-fine circuits that are suitable for 64M, 256M, 1G, 4G and 16G DRAM semiconductor devices and a great improvement in productivity.

 The present invention has been described by way of illustration and it is understood that the terminology used is descriptive rather than limiting. Many variations and modifications can be made to the present invention in light of the above teachings. Therefore, it is understood that within the scope of the appended claims, the present invention may be practiced otherwise than specifically described.

Claims (19)

1. An antireflective coating composition comprising: a polymer according to one of the following general formulas: ## STR1 ## (general formula (CH 2) rn 1 1 (formula in which R and R ', which may be identical or different, each represents hydrogen or -CH 2, R 3 to R 9, which may be identical or different, each represent a hydrogen or a hydroxyl group; methoxycarbonyl, carboxyl, hydroxymethyl or linear or branched, substituted or unsubstituted C 1 -C 6 alkyl or alkoxyalkyl; x and y are each a mole fraction in the range of 0.01 to 0.99; and m is 1 or 2 and n is an integer of 2 to 4, or R 1 R n C = O x C = O z C = O-OCH, (CH 2) m (CH 2) n 1 R, O 11 (general formula II) R, R, Ra Wherein R, R 'and R ", which are the same or different, are each hydrogen or -CH-, R, to R ,, which are the same or different from each other; , each represent a hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl or linear or branched, substituted or unsubstituted C 1 -C 6 alkyl or alkoxyalkyl; x, y and z each represents a mole fraction in the range of 0.01 to 0.99; and m is 1 or 2 and n is an integer of 2 to 4; and a polymer comprising repeating units of the following general formula III: ## STR2 ## in which R '"is hydrogen or -CH, and R0 is - CI I3 or -CH2CH3.  An anti-reflective coating composition according to claim 1, wherein in the polymer of general formula I, R 1 to R 9 are each hydrogen, R 1 is hydrogen; and y are each 0.5; and m is 1 and n is 2.  An anti-reflective coating composition according to claim 1, wherein in the polymer of the general formula I, R 1 to R 9 are each hydrogen; R 'is hydrogen; x and y are each 0.5 and m is worth and n is 3.  An anti-reflective coating composition according to claim 1, wherein in the polymer of the general formula I, R 1 to R 1 are each hydrogen; R1 is hydrogen; and y are each 0.5 and m is 1 and n is 4.  An anti-reflective coating composition according to claim 1, wherein in the polymer of the general formula I, R 1 to R 2 are each hydrogen; R 'is -CH3: x and y are each 0.5 and m is 1 and n is 2.  An anti-reflective coating composition according to claim 1, wherein in the polymer of the general formula I, R 3 is each a hydrogen; R 'is CH3; x and y are each 0.5 and m is 1 and n is 3. <Desc / Clms Page number 32>  An anti-reflective coating composition according to claim 1, wherein in the polymer of the general formula I, R 1 to R 9 are each hydrogen; R 'is -CH3; x and y are each 0.5 and m is 1 and n is 4.  An anti-reflective coating composition according to claim 1, wherein in the polymer of the general formula T, R 1 to R 9 are each hydrogen; R1 is hydrogen; x and y are each 0.5 and m is 2 and n is 2.  An anti-reflective coating composition according to claim 1, wherein in the polymer of general formula I, R1 to R9 each represent hydrogen; R1 is hydrogen; x and y are each 0.5 and m is 2 and n is 3.  An anti-reflective coating composition according to claim 1, wherein in the polymer of the general formula T, R 1 to R 9 are each hydrogen; R1 is hydrogen; x and y are each 0.5 and m is 2 and n is 4.  He. Anti-reflective coating composition according to one of claims 1 to 10, wherein in the polymer of the general formula II R 1 to R 9 are each hydrogen; R1 is hydrogen; x, y and z are 0.3, 0.5 and 0.2, respectively, and m is 1 and n is 2.  12. anti-reflective coating composition according to one of claims 1 to 10, wherein in the polymer of general formula II, R, R9 each represent a hydrogen, R 'is a hydrogen, x, y and z valent 0.3, 0.5 and 0.2, respectively; and m is 1 and n is 3.  Anti-reflective coating composition according to one of claims 1 to 10, wherein in the polymer of the general formula II R 1 to R 9 are each hydrogen; R1 is hydrogen; x, y and z are 0.3, 0.5 and 0.2, respectively; m is 1 and n is 4.  14. Anti-reflection coating composition according to one of claims 1 to 10, wherein in the polymer of general formula II, R, R9 are each hydrogen, R1 is -CH3; x, y and z are 0.3, 0.5 and 0.2, respectively; and m is worth! 1 and n is 2.  Anti-reflective coating composition according to one of claims 1 to 10, wherein in the polymer of the general formula II, R1 to R9 are each hydrogen; R1 is -CH3; x, y and z are 0.3, 0.5 and 0.2 respectively and m is 1 and n is 3. <Desc / Clms Page number 33>  An anti-reflective coating composition according to one of claims 1 to 10, wherein in the polymer of the general formula II R 1 to R 9 are each hydrogen, R 'is -CH 3; x, y and z are 0.3, 0.5 and 0.2, respectively, and m is 1 and n is 4.  17. An anti-reflective coating composition according to one of claims 1 to 16, further comprising an anthracene derivative.  The anti-reflective coating composition according to claim 17, wherein the anthracene derivative is selected from the group consisting of anthracene, 9-anthracene methanol, 9-anthracene carbonitrile, 9-anthracene carboxylic acid, dithranol, 1,2,10-anthracenetriol, anthraflavic acid, 9-anthraldehyde

 oxime, 9-anthraldehyde, 2-amino-7-methyl-5-oxo-SH- [1] -benzopyrano [2,3b] pyridine-3-carbonitrile, 1-aminoanthraquinone, 2-anthraquinone carboxylic acid, dihydroxyanthraquinone, anthrone, 9-anthryl-trifluoromethyl ketone, 9-alkylanthracene derivatives represented by the following structural formula 16, the 9-carboxyl anthracene derivatives having the following structural formula 17, the 1-carboxyl anthracene derivatives having the formula developed following 1 8 and their combinations:

 (chemical formula 16) (chemical formula 17) (chemical formula 18)

 where R11, R1, R3, R1 "and R1, which are the same or different, each represent -H-, OH, -CII, O11, - (CH1) ,, CH3 p being an integer of 1 to 3, or a linear or branched substituted or unsubstituted alkyl or alkoxyalkyl containing from 1 to 5 carbon atoms.  19. A process for preparing an anti-reflective coating composition which comprises dissolving a mixture of a polymer according to the general formula (I) or the general formula (II) and a polymer according to the general formula (III) in an organic solvent, and then adding thereto an anthracene additive selected from the group consisting of anthracene, 9-anthracene methanol, 9-anthracene

 carbonitrile, 9-anthracene carboxylic acid, dithranol, t, 2-O-anthracenetratriot, anthraflavic acid, 9-anthraldehyde oxime, 9-allylaldehyde, 2-amino-7-methyl-5-oxo [1] benzopyrano, 3-b] pyridine-3-carbonitrile, 1-aminoanthraquinone, 2-anthraquinone carboxylic acid, 1,5-dihydroxyanthraquinone, anthrone, 9-anthryl- <Desc / Clms Page number 34>  trifluoromethyl ketone, 9-alkylanthracene derivatives represented by the following structural formula 16, 9-carboxyl anthracene derivatives having the following structural formula 17, 1-carboxy-anthracene derivatives having the following formula 18, and combinations thereof:

 (chemical formula 16) (chemical formula 17) (chemical formula 18)

 wherein R ", 1, R12, R1, R4 and R1, which are the same or different, each represents -H-, -OH, -CH3, -CH, OH, - (CH2) pCH3 p being a an integer of 1 to 3, or substituted or unsubstituted, linear or branched alkyl or alkoxyalkyl containing from 1 to 5 carbon atoms.  20. - The method of claim 19, wherein the additive derived from anthracene is used in a proportion of 0.1 to 30% by weight.  21. A process according to claim 19 or claim 20, wherein the organic solvent is selected from the group consisting of ethyl 3-ethoxypropionate,

 methyl 3-ethoxypropionate, cyclohexanone and propylene glycol methyl ether acetate.  22. A process for forming an antireflective coating in which an anti-reflective coating composition according to any one of claims 1 to 18 is applied to a wafer and the wafer is cured at 80-300 ° C. .  23. - Semiconductor device manufactured using an anti-reflective coating composition according to one of claims 1 to 18.