TW200827928A - Novel organosilane polymer, hardmask composition for processing resist underlayer film comprising the organosilane polymer, and process for producing semiconductor integrated circuit device using the hardmask composition - Google Patents

Abstract

A hardmask composition for processing a resist underlayer film is provided. The hardmask composition comprises: (a) an organosilane polymer prepared by reacting polycondensation products of hydrolysates of compounds represented by Formulae 1, 2 and 3 with ethyl vinyl ether of Formula 4: [RO]3Si-Ar (1) (wherein R is methyl or ethyl and Ar is an aromatic ring-containing functional group), [RO]3Si-H (2) (wherein R is methyl or ethyl), and [RO]3Si-R' (3) (wherein R is methyl or ethyl and R' is substituted or unsubstituted cyclic or acyclic alkyl) CH2CHOCH2CH3; (4) (b) a solvent; and (c) a crosslinking catalyst.

Description

200827928 IX. Description of the Invention: [Technical Field] The present invention relates to a novel organodecane polymer, a hard mask comprising 5 organic decane polymers for treating a photoresist underlayer film And a method of manufacturing a semiconductor integrated circuit device using the hard reticle composition. More particularly, the present invention relates to a composition for treating a photoresist underlayer film which exhibits improved storage stability, high pattern reproducibility, good adhesion to a photoresist, and exposure to a photoresist. After that, the developed solution is excellent in resistance (i.e., solvent), and the film loss of the electric charge is reduced. T lltr ^ [Background Art] For better resolution of most lithography methods, anti-reflective coating (arc) 15 materials are used to minimize reflection between the photoresist layer and the substrate. However, the basic (four) material between A R C and the layer of the dissimilar material causes the selectivity of the difference between the ship material and the patterned photoresist layer. Therefore, the consumption of the number of knives of the photoresist layer is unavoidable during the formation of the pattern in the ARC button. Therefore, it is necessary to further pattern the photoresist layer in the subsequent button etching step. 20 A photoresist material used in some lithography techniques does not provide a subsequent characterization step. The south photoresist is sufficient to allow the desired pattern to be effectively transferred to the layer under the photoresist material. The hard mask of the photoresist underlayer film has been used (4). For example, when the grid is used, it is necessary to be thickened by the substrate, and it is necessary to use a large amount of money X and/or a specific surname. The situation 200827928 situation. Light = hard film of the film _ plays the role of the middle layer between the substrate and the light-resisting sword and the 5 10 mask. A hard mask of the photoresist underlayer film is used to transfer the patterned photoresist pattern to the substrate. Therefore, the light: the hard mask layer of the underlying film needs to be durable to transfer the pattern. This method is required because the etching rate of the photoresist is similar to that of the underlying film for processing the oxide film. The agent and the bottom layer (4) form a photomask to process the underlying film, or form a hard mask having a very different surname rate (ie, high selectivity) to process the oxide film. Specifically, an underlayer film for processing the oxide film, a photomask for processing the underlying film (i.e., a hard mask of the photoresist underlayer film), and a photoresist are formed on the oxide film in sequence. This multi-layered w-ride county material (10), such as the oxygen film), the light Wei Wei has caused the edge to be low, making it difficult for the photoresist to act as a mask. Therefore, it is impossible to process the oxide film without any damage. According to the method for overcoming such problems, the photoresist pattern is transferred to the underlying film for processing the oxide film, and thereafter the pattern-transferred underlayer film is used as a photomask to dry the oxide film. The underlayer film for treating the oxide film means a film formed under the anti-reflection film, and serves as a bottom anti-reflection film. The 15 structure is shown in Figure 1. In this case, the most important requirements for the mask for processing the underlying film are etch resistance and high etch selectivity with respect to the underlayer for processing the oxide film. Further, the photomask needs to be insoluble in a solvent for forming an antireflection film by being applied thereon. That is, the photomask needs to have excellent solvent resistance. Various attempts have been made to meet the above requirements. For example, a polycondensation reaction of a Shi Xi Yuan compound represented by 20 200827928, 3 or 4) is used as a material for processing the underlayer film. However, the biggest problem with the cut-off compound is that the polycondensation reaction of the compound of Shi Xiyuan is in the solvent state: ^. When the polycondensation reaction product is used for a period of time after storage, the desired thickness for forming the coating 5 I _ is not achieved. Further, the polycondensation reaction product is substantially insoluble in a solvent due to the molecular weight of octa, which causes a problem of enthalpy. That is, in many cases, the polycondensation reaction is disadvantageous in terms of fine storage. The polycondensation reaction is carried out by a sterol group (Si_OH) which is present at the end of the Shixijie. In order to ensure that the desired product of the polycondensation reaction product is stored, it is necessary to limit the amount of the stagnation base or to protect it with an appropriate protective group.

SUMMARY OF THE INVENTION [Technical Problem] The present invention is based on the problems of the prior art, and an object of the present invention is to provide a novel organodecane polymer for forming a photoresist underlayer. Hard mask of film. Another object of the present invention is to provide a hard reticle composition for treating an underlying film comprising etch selectivity for improved storage of stabilized twins and sufficient resistance to multiple etches. Organic hydrazine, _ compound. Alkane-polymerized, an anti-reflective hard photocomplex of the present invention, which is used for the treatment of photoresists in a flat, good pattern due to its excellent ARC effect, and which is patterned during subsequent processing. Effectively transfer Liang Xi I gasification stone eve 20 200827928 membrane. Another object of the present invention is to provide a method of manufacturing a semiconductor integrated circuit device using the hard reticle composition. Another object of the present invention is to provide a device manufactured by this method. [Technical Solution] According to an aspect of the invention, there is provided an organodecane prepared by reacting a polycondensation reaction product of a hydrolyzate of a compound represented by Chemical Formulas 1, 2 and 3 with an ethyl vinyl ether of Chemical Formula 4. Polymer: 10 [RO]3Si-Ar (1) (wherein R is a methyl group or an ethyl group, and AH is a functional group containing an aromatic ring); [RO]3Si-H (2) (where R Methyl, or ethyl); and 15 [RO]3Si-R' (3) (wherein R is methyl, or ethyl, and R' is substituted or unsubstituted, cyclic or acyclic Alkyl): CH2CHOCH2CH3 (4) The hydrolyzate of the compounds of Chemical Formulas 1, 2 and 3 can be represented by the chemical formulas 20, 6 and 7 individually:

ArSi[OH]3 (5) (wherein Ar is a functional group containing an aromatic group); HSi[OH]3 (6); and R,Si[OH]3 (7) 8 200827928 (in which 'R , _ replaces the silk scale of the Wei scale ring of the polycondensation reaction product can be represented by the chemical formula 8 A "x -0 -s\-〇-Si -〇- 〇i -〇一: Η R1, 0- 1 1 Η 11 η η (8) wherein Ar is a functional group containing an aromatic ring, and R is a substituted or unsubstituted cyclic or acyclic group, which satisfies the relationship x + y + z 4 ' 0·04 $ X $ 〇·8〇' 〇$ y $ i 4〇, and i 8〇3 to 500. After $ z $ 3.96, and η-based organic stone sinter polymer can be expressed in chemical formula 9

Me ) 〇

Me

Mey Me

Arx -〇-S\-〇 -0-

;i-〇- Hy -Si-〇-

Me Me 10

Me

Me (9) wherein Ar is a functional group containing an aromatic ring, and r is a substituted or unsubstituted ring or acyclic group. Each -Me#f group, x, yh satisfies the relationship x + y + z S 3.96, and η is 3 to 500. 15 Hydrolyzate is selected from (4) 'acid, Wei, p-toluene 4 acid monohydrate human t, sulfuric acid dihydrate, 2,4,4,6_four desert_2,5_cyclohexanedione, and organic : Prepared in the presence of an acid catalyst of the group consisting of sulphur-based vinegar. The organodecane polymer can be prepared by mixing hydrazine to add parts by weight of the chemical compound, 0 to 35 parts by weight of the compound of the formula 2, and 45 to 99 parts by weight of 9 200827928 parts of the compound of the formula 3 (which is about 1 part by weight) a chemical formula of ruthenium, 2 and 3, such that the mixture is present in 10 to 100 parts by weight of water and 1 to 900 parts by weight of the solvent, in the presence of 1 to 5 parts by weight of the acid catalyst The intermediate reaction is obtained by the reaction of the polycondensation reaction, and the polycondensation reaction is prepared by reacting the polycondensation reaction with the ethylene ethyl group of the chemical formula 4 of the isaoo 5 heavy wound. The solvent may be selected from the group consisting of propylamine, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform-gas-fired, ethyl acetate, propylene glycol methyl-, propylene glycol ethyl-propanol-propanol, 1^ A group consisting of a mixture of diol methyl ether acetate _, propylene glycol ethyl ether acetate, propylene glycol propyl acetoacetate, lactic acid ethyl acetate, γ butyl vinegar, and the like. According to another aspect of the present invention, there is provided a hard mask shroud for treating a photoresist underlayer film, the composition comprising: - _(4) substance which is hydrolyzed by a compound which chemically licks the ball 15 The polycondensation reaction product of the product is prepared by reacting with the vinyl group of the chemical formula 4: [R〇]3Si-Ar (1) or ethyl, and the Ar-containing aromatic ring-functional [R〇]3Si-H (2) (wherein R is methyl' or ethyl), and [ROLSi-R, (3) U is 'n-mercapto' or ethyl, and R' is substituted or unsubstituted <cyclic or non- Cyclic alkyl group) ch2choch2ch3 ", (4) 10 200827928 (b) solvent; and (c) crosslinking catalyst. The hydrolysis products of the compounds of the chemical formulas 1, 2 and 3 can be represented by the chemical formulas 5, 6 and 7: 5 ArSi[OH]3 (5) (wherein Ar is a functional group containing an aromatic group); HSi[OH]3 (6); and R, Si[OH]3 (7) (wherein R' is substituted Or unsubstituted cyclic or acyclic calcined 10 base. The polycondensation reaction product can be represented by the chemical formula 8:

Wherein, Ar is a functional group containing an aromatic ring, and R' is a substituted or unsubstituted cyclic or acyclic group, and x, y and z satisfy the relationship of X + y + z = 15 4 5 0.04 < X < 0.80 5 0 < y < 1.40 9 A 1.80 < z < 3.96 5 in #, 3 to 500. The organodecane polymer can be represented by the chemical formula 9:

Me

Me ) \ Γ) / \ U π / 〕 -0-ii/-0-^Si

Arx 0-a\-0-Si-0- ;i-〇-

Me Me —\

Me

Me (9) wherein Ar is a functional group containing an aromatic ring, R' is a cyclic or acyclic alkyl group substituted or not substituted by 11 200827928, each -Me methyl group, x, y and z Satisfy the relationship x + y + z = 4, 0.04 s X $ 0·80, 0 sy $ 1.40, and 1.80 $ 2 $ 3.96, and n is 3 to 500. The hydrolyzate is selected from the group consisting of nitric acid, sulfuric acid, p-toluene acid monohydrate, diethyl sulfate, 2,4,4,6-tetrabromo-2,5-cyclohexadienone, and organic sulfonic acid. Prepared in the presence of an acid catalyst of the group consisting of alkyl esters. The organoceramic polymer can be obtained by mixing 1 to 2 parts by weight of the compound of the formula 1, 0 to 35 parts by weight of the compound of the formula 2, and 45 to 99 parts by weight of the compound of the formula 3 (which relates to 100 parts by weight) a mixture of the chemical formulas 1, 2 and 3, in the presence of from 10 to 100 parts by weight of water and from wo to 900 parts by weight of the solvent, in the presence of from 1 to 5 parts by weight of the acid catalyst, The reaction obtains a polycondensation reaction product, and a polycondensation reaction is prepared by reacting a polycondensation reaction with (10) a heavy-damaged ethylethylene ether of Chemical Formula 4. The solvent may be selected from the group consisting of acetone, tetrahydrofuran, benzene, methyl bromide, diethyl ether, gas imitation, dioxane methane, ethyl acetate, propylene glycol methyl ether, propylene glycol ethyl sulphate, propylene glycol propyl _, hexadiol methyl (iv) a group consisting of acetic acid vinegar, hexadiol ethyl ether acetate, propylene glycol propyl ether acetate, ethyl lactate, γ-butyrolactone, and the like. The hard negative mask composition of the present invention may comprise from 5 to 5 parts by weight of the organic 20 decane polymer (based on the total weight of the composition (100 parts by weight)), from 5 to 99 parts by weight. a granule (which is about the total weight of the composition ((10) parts by weight) and a cross-linking catalyst of 0.0001 to 〇·〇1 parts by weight (for 1 part by weight of the organic stone compound polymer) meter). The solvent may be selected from the group consisting of C-, tetrahydrofuran, stupid, methyl strepto, diethyl ether, 12 200827928 gas imitation, digastric hospital, ethyl acetate, propylene glycol methyl bond, propylene glycol ethyl shunt, propylene glycol propyl ether, two two a group consisting of alcohol methyl acetate, propylene glycol ethyl acetate, propylene glycol propyl acetate, lactic acid ethyl acetate, 丫-butyrolactone, and the like. The 5 + crosslinking catalyst may be selected from the group consisting of p-toluene decanoate, aramidyl phthalate betaine, (-)-camphor-10-sulfonic acid ammonium salt, ammonium formate, and triethylammonium citrate. , dimethylammonium formate, tetramethylammonium citrate, π-pyruvate, acetic acid, triethylammonium acetate, trimethylammonium acetate, tetramethylammonium acetate, pyridine acetate, tetrabutyl acetate Ammonium, tetrabutylammonium azide, tetrabutylammonium benzoate, tetrakis10-butylammonium hydrogensulfate, tetrabutylammonium bromide, tetrabutylammonium vapor, tetrabutylammonium cyanide, tetrabutyl Ammonium fluoride, tetrabutylammonium moth, tetrabutylammonium sulfate, tetrabutylammonium nitrate, tetrabutylammonium nitrite, tetrabutylammonium p-toluenesulfonate, tetrabutylammonium phosphate a group of , and a mixture of such. The hard reticle composition of the present invention may further comprise at least one additive selected from the group consisting of a crosslinking agent, a stabilizer, and a surfactant. According to another aspect of the present invention, there is provided a method of fabricating a semiconductor integrated circuit device, the method comprising the steps of (a) providing a layer of material on a substrate, and (b) forming a layer of organic material on the layer of material The hard mask 20 layer is applied to the hard mask composition of the invention to form an anti-reflective hard mask layer on the hard mask layer composed of organic materials (the anti-reflective hard mask layer) Forming a radiation sensitized imaging layer thereon, (e) imagewise exposing the imaging layer to radiation and forming an image of the radiation exposed region in the imaging layer' (f) selectively removing radiation sensitized imaging Layer and anti-reflective hard light 13 200827928 Part of the cover layer to expose a portion of the hard mask layer composed of organic material, (g) selectively remove the patterned anti-reflective hard mask layer and consist of organic material a portion of the hard mask layer to expose portions of the material layer, and (h) etching the exposed portions of the material layer to pattern the material layer. According to another aspect of the present invention, a Method of manufacturing semiconductor product [Description of the Drawings] Fig. 1 is a cross-sectional view showing a multilayer structure of an anti-reflection hard mask layer 10 formed of the hard mask composition of the present invention, which is included in the lithography method for manufacturing a semiconductor integrated circuit device. C. Mode 3: [Best Mode] The present invention will now be described in more detail. % The present invention provides an organodecane polymer which is obtained by hydrolyzing a compound represented by Chemical Formulas 1, 2 and 3 The polycondensation reaction product is reacted with ethyl vinyl ether of Chemical Formula 4 to prepare [R〇]3Si-Ar (1) group) (wherein R is a methyl group or an ethyl group, and the Ar system contains an aromatic ring) Functionality [ROJsSi-H (2) (wherein R is methyl or ethyl); and [R0]3Si-R, (3) and R, substituted or unsubstituted (wherein R is methyl, Or an ethyl group, a king-stretched or acyclic alkyl group): 14 200827928 CH2CHOCH2CH3 (4) A specific example of the compound of the formula 1 contains the following compound (la): 0

Si(0R)3 ^^^Si(0R)3

OH Ο

Si(〇R)sοό

(RO^Si-^^O

Si(〇R)3

Si(0f^3

y,^^Si〇Rh

H2C

Si(0R)3

(la) wherein each Me represents a methyl group, and each R represents a methyl group, or an ethyl group. A specific example of the compound of Chemical Formula 3 contains the following compound (3a): 15 200827928 ο ο ο 咖*((10) fe Me^O^Si(OR)3 働人〇^^^丨阙3 0 H2e<ii^0M^Si (0R)i * jI^Q^s^SiOR^ HaC^^SKORfe Me^^^iORfe M like S riding M4e Ne/\^S_3 _N^s/S_)3 n ^«^^SKORJa C^SKORfe ^C55 ^4f{OR)3 e^^Si (0%

Smm, Si(OR)3

Me^Si(0R)3 16 200827928 l ^r^Si_)3 Me 彳Me 彳\^Si(OR)a Secret e, A Coffee N^S^SKpRfe Me 贤...I we^A〇^ One coffee)3 _,_ Μβ〇

H

0 secret 5^ one 0 person (two) peak H^smh /^rS(0R)3

Wherein each Me represents a methyl group, and each r represents a methyl group, or an ethyl group. 17 200827928 The organodecane polymer of the present invention can be obtained by mixing 1 to 20 parts by weight of the compound of the chemical formula 1, 0 to 35 parts by weight of the compound of the chemical formula 2, and 45 to 99 parts by weight of the compound of the chemical formula 3 100 parts by weight of the compound of the chemical formulas 1, 2 and 3), the mixture is contained in 10 to 100 parts by weight of water and 100 to 900 parts by weight of the solvent in the presence of 0.001 to 5 parts by weight of the acid catalyst, The reaction obtains a mixture of hydrolyzed products of the individual compounds, the polycondensation products of the hydrolyzed products are obtained by unpolymerization to obtain a mixture of the polycondensation reaction products of the individual hydrolyzates, and the polycondensation reaction product and 1 to 200 parts by weight of the ethyl group of the chemical formula 4 It is prepared by reacting vinyl ether. The acid catalyst is preferably selected from the group consisting of nitric acid, sulfuric acid, p-toluene acid monohydrate, diethyl sulfate, 2,4,4,6-tetrabromo-2,5-cyclohexadiene, and organic acid. The group consisting of the base of the burning. The hydrolysis reaction can be suitably controlled by changing the kind, amount and mode of addition of the acid catalyst. Further, the acid catalyst added for the hydrolysis reaction can be reused as a catalyst for the polycondensation reaction. 15 The acid catalyst may be used in an amount between 0.001 and 5 parts by weight in the formation reaction of the organodecane polymer. The use of an acid catalyst in an amount of less than 0.001 part by weight significantly slows down the reaction rate, while the use of an acid catalyst in an amount of more than 5 parts by weight causes an excessive increase in the reaction rate, making it impossible to prepare a polycondensation reaction product having a desired molecular weight. The solvent may be selected from the group consisting of propylene, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform, dichloromethane, ethyl acetate, propylene glycol decyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol methyl ether acetate. a group consisting of esters, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, ethyl lactate, γ-butyrolactone, and mixtures thereof. 18 200827928 The hydrolyzed products of the compounds of Chemical Formulas 1, 2 and 3 can be represented by the chemical formulas 5, 6 and 7 respectively:

ArSi[OH]3 (5) (wherein Ar is a functional group containing an aromatic group); 5 HSi[OH]3 (6); and R, Si[OH]3 (7) (wherein R' is Substituted or unsubstituted cyclic or acyclic alkyl). As a product of the polycondensation reaction, it may be an example represented by Chemical Formula 8

Arx Η Η -0 -Si VO -Si-0 II 〇〇II -O-Si/Ό -\^i-0 Hy R'z -H Ή (8) wherein Ar is a functional group containing an aromatic ring, R' is a substituted or unsubstituted cyclic or acyclic group, and x, y, and z satisfy the relationship of X + y + z = 4 9 0.04 < X < 0.80 9 0 < y < 1.40 5 ^1.80 < z < 3.96 5 JLn# 15 3 to 500 . In Chemical Formula 8, Ar, fluorene, and R' represent a functional group bonded to an individual Si atom. The number of individual functional groups is as defined in Chemical Formula 8. The organodecane polymer can be produced by reacting the polycondensation reaction product of Chemical Formula 8 with ethyl ethyl ether ether of Chemical Formula 4. 20 organononane polymers can be represented by the chemical formula 9: 19 200827928

Me (9), /, medium, Ar is a functional group containing an aromatic ring, and R is a substituted or unsubstituted % or acyclic alkyl group, each of which is a methyl group, which satisfies the relationship x + y + z = 4, 0.049m〇wim8(^ 5 z $ 3·96, and η is 3 to 500. In Chemical Formula 9 'Ar, Η and R' represent a functional group bonded to an individual Si atom. The amount of the base is as defined in Chemical Formula 9. The present invention also provides a hard reticle composition for treating a photoresist underlayer film, comprising: 10 (a) an organic decane polymer by chemical enthalpy, The polycondensation reaction product of the hydrolyzate of the compound represented by 2 and 3 is reacted with ethyl vinyl ether of Chemical Formula 4 to prepare: [R〇]3Si-Ar (1) (wherein R is a mercapto group, or an ethyl group, and Ar is an aromatic ring-containing functional group 15), 匕[R〇]3Si-H (2) (wherein R is a sulfhydryl group, or an ethyl group), and [R0]3Si_R, (3) (wherein the R system Methyl, or ethyl, and R' is a substituted or unsubstituted 20 cyclic or acyclic alkyl group) CH2CHOCH2CH3. (4) 20 200827928 (b) Solvent; and (c) crosslinking catalyst. Organic 矽The polymer may be obtained by mixing 1 to 20 parts by weight of the compound of the chemical formula 1, hydrazine to 35 parts by weight of the compound of the chemical formula 2, and 45 to 99 parts by weight of the compound of the chemical formula 3 (which is related to 100 parts by weight of the chemical formula 1) And the mixture of the compounds of 2, 3, and 10 to 100 parts by weight of water and 100 to 900 parts by weight of the solvent, in the presence of 0.001 to 5 parts by weight of an acid catalyst, to obtain a hydrolyzate of the individual compound a mixture obtained by polycondensing a hydrolyzed product without purification to obtain a mixture of 10 polycondensation reaction products of individual hydrolyzates, and reacting the polycondensation reaction product with 1 to 200 parts by weight of ethyl vinyl ether of Chemical Formula 4 to prepare a mixture Preferably, the acid catalyst is selected from the group consisting of nitric acid, sulfuric acid, p-toluenesulfonic acid monohydrate, diethyl sulfate, 2,4,4,6-tetrabromo-2,5-cyclohexadienone, and organic stone. The group consisting of the group consisting of the acid anhydride can be suitably controlled by changing the kind, amount and mode of addition of the acid catalyst 15. Further, the acid catalyst added for the hydrolysis reaction can be reused. The reminder of polycondensation In the formation reaction of the organodecane polymer, the acid catalyst can be used in an amount of between 1 and 5 parts by weight. The use of an acid catalyst in an amount of less than 0.001 part by weight significantly slows down the reaction rate, and more than 5 parts by weight is used. The amount of the acid catalyst is 20%, and the reaction rate is excessively increased, so that it cannot prepare a polycondensation reaction product having a desired molecular weight. The bathing agent may be selected from the group consisting of propylene, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform, mono-methane, Ethyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether, propanol propyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether 21 200827928 acetate, propylene glycol propyl ether acetate, ethyl lactate a group of gamma-butyrolactone, and mixtures thereof. The hydrolyzate of the compounds of Chemical Formulas 1, 2 and 3 can be represented by the chemical formulas 5, 6 and 7: 5 ArSi[OH]3 (5) (wherein the Ar-based aromatic group-containing functional group); HSi[OH]3 (6); and R, Si[OH]3 (7) (wherein R' is a substituted or unsubstituted cyclic or acyclic alkane 10 group). As a product of the polycondensation reaction, it may be an example represented by Chemical Formula 8: Η Η.

Arx -s\-o-s

Si-Ο I I 〇 〇 I I 0-Si/-0-'\Si-0

H R'7 -H Ή (8) wherein Ar is a functional group containing an aromatic ring, and R' is a cyclic or acyclic group which is substituted or not substituted, and x, y and z satisfy the relationship. Formula X + y + z = 4 5 0.04 < x < 0.80 9 0<y< 1.40 5 A1.80<z<3.96 5 3 to 500. In Chemical Formula 8, Ar, H and R' represent a functional group bonded to an individual Si atom. The number of individual functional groups is as defined in Chemical Formula 8. The organic stone sinter polymer can be produced by reacting the polycondensation reaction product of Chemical Formula 8 with ethyl vinyl ether of Chemical Formula 4. The organic stone kiln polymer can be represented by the chemical formula 9: 22 (9) 200827928

Me

Me Me

Arx 0-s\-0-Si-0 i 6 〇 ~ ^/-0 -\^Si —〇 Hv R'z

Me

Wherein Ar is a functional group containing an aromatic ring, R is a substituted or unsubstituted cyclic or acyclic group, and each Me methyl group, x, y and z satisfy the relationship X + y + z = 4,0.04 $x2〇.80,〇2y2 1·4〇, and 1.80 $ 5 ζ $ 3·96, and η is 3 to 500. In Chemical Formula 9, Ar, Η and R represent a functional group bonded to an individual Si atom. The number of individual functional groups is as defined in Chemical Formula 9. The hard ray composition of the present invention using the aromatic group contained in the compound of Chemical Formula 1 exhibits excellent antireflection properties due to the UV absorbability of the organic zeocary polymer. At the same time, the hard reticle composition of the present invention has a desired absorption ratio and refractive index in a specific wavelength region by controlling the number of aromatic groups in the organic pulverized polymer. It is preferred to use a compound of the formula 1 in an amount of from 1 to 20 parts by weight based on the total weight (100 parts by weight of the compound of the chemical formulas 1, 2 and 3). The compound of Chemical Formula 1 is used in an amount of less than 1 part by weight to cause a low absorptivity of the hard reticle composition. At the same time, the use of more than 20 parts by weight of the chemical formula results in a problem that sufficient etching selectivity cannot be ensured due to low content. Suitable antireflective properties can be achieved by controlling the relative amounts of the compounds of the formula. For example, when the compound of the formula has a phenyl group as the aryl 2 sulfonyl group and is used in an amount of 10 parts by weight, the hard reticle composition has an absorptance (k) of about 0.2. 23 200827928 On the other hand, an increase in the relative amount of the compound of Chemical Formula 2 used results in an increase in the Si content in the hard reticle composition of the present invention. This change in the Si content of the hard reticle composition imparts suitable etch selectivity to the hard reticle composition of the present invention and the overlying photoresist layer composed of the organic material and the underlying hard mask layer 5 . Preferably, a compound of the formula 2 is used in an amount of not more than 35 parts by weight based on the total weight of the compound of the formulas 1, 2 and 3 (1 part by weight). When the compound of Chemical Formula 2 is used in an amount of more than 35 parts by weight, the storage stability of the hard mask composition is impaired by the unstable Si-H bond. 10 The increase in the relative amount of the compound of Chemical Formula 3 used results in an improvement in the storage stability of the hard mask composition. It is preferred to use a compound of Chemical Formula 3 in an amount of from 45 to 99 parts by weight based on the total weight (100 parts by weight of the compound of Chemical Formulas 1, 2 and 3). The use of a compound of Chemical Formula 3 in an amount of less than 45 parts by weight causes a poor storage stability of the hard reticle composition, and at the same time, the use of a compound of Chemical Formula 3 in an amount exceeding 99 parts by weight causes a hard reticle composition. The problem of reduced absorption rate. The ethyl vinyl ether of Chemical Formula 4 reacts with the Si-〇H group to form a Si-OCH(CH3)〇CH2CH3 group and serves to protect the Si-OH group, thereby ensuring the stability of the final composition. Meanwhile, Si_〇CH(CH3)〇CH2CH3 is easily converted into a Si-OH group in the presence of a crosslinking catalyst based on 20 high temperatures, which will be described later. When the hard reticle composition is coated and heated during its post-treatment, the Si-OH groups are recovered and cross-linked to each other. This crosslinking results in the formation of a rigid film. Preferably, the compound of Chemical Formula 4 is used in an amount of from 1 to 200 parts by weight based on 1 part by weight of the compound of the formulae i, 2 and 3. When the chemical formula 4 2008 20082828 is used in an amount of less than 1 part by weight, the improvement in the storage stability of the hard mask composition cannot be expected. At the same time, all of the Si-OH groups have been reacted with the compound of the chemical formula 4 in an amount of not more than 200 parts by weight, so that it is not expected to further improve the storage stability of the hard mask composition. The organodecane polymer is preferably present in an amount of from 1 to 50 parts by weight, and more preferably from 1 to 30 parts by weight based on the total weight (100 parts by weight) of the hard mask composition. When the content of the organodecane polymer is outside the preferred range, the coatability of the hard mask composition is deteriorated. Examples of the solvent used in the hard reticle composition of the present invention include propylene ketone, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform, methylene chloride, ethyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether. , propylene glycol propyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether ethyl ester, ethyl lactate, γ-butyrolactone, and the like. The solvent may be the same as or different from the solvent used for the formation reaction of the organodecane polymer. 15 The solvent may be used in an amount of from 50 to 99 parts by weight based on the total weight (100 parts by weight) of the hard mask composition. When the amount of the solvent used is outside the above range, the coatability of the hard mask composition is deteriorated. Examples of suitable crosslinking catalysts include: sulfonates of organic bases, such as acridine p-toluenesulfonate, tetrabutylammonium p-toluenesulfonate, decylamine 20 acid beet test-16, (a) - camphor-10-supply acid ammonium salt; organic test formate, such as ammonium formate, triethylammonium formate, trimethylammonium formate, tetramethylammonium formate, and picolinate; and organic base Acetate, such as ammonium acetate, triethylammonium acetate, trimethylammonium acetate, tetramethylammonium acetate, and pyridine acetate, tetrabutylammonium acetate; tetrabutylammonium azide, tetrabutyl benzoate 25 200827928 money tetrabutyl hydroxyhydrogen sulfate, tetrabutylammonium desert, tetrabutyl butyl tetrabutylammonium cyanide; tetrabutyl hydroxy fluoride; tetrabutyl hydride; tetrabutyl ammonium sulphate a salt; tetrabutylammonium nitrate; tetrabutylammonium acid hypophosphite; tetrabutylammonium phosphate; and mixtures thereof. 5 _ cross-linking catalyst compound promotes the cross-linking of the organic stone light polymer to improve the durability of the hard reticle composition and the solvent property plays an important role. The crosslinking catalyst compound is preferably used in an amount of from 0,0001 to 1 part by weight based on 100 parts by weight of the organodecane polymer. Below 0.0001 parts by weight, the above effects are not expected. Above 1 part by weight of 〇, the storage stability of the hard reticle composition is insufficient. If desired, the hard reticle composition of the present invention may further comprise at least one additive from the parent, the benzoate, and the surfactant. The present invention also provides a method of fabricating a semiconductor integrated circuit device, the method comprising the steps of: (a) providing a layer of material on a substrate, and (b) forming a layer of organic material on the layer of material I5 a hard mask layer, (c) coating the hard mask layer of the present invention on the first hard mask layer to form a second hard mask layer, and (d) forming a radiation sensitive layer on the second hard mask layer The imaging layer '(e) imagewise exposes the imaging layer to radiation and forms a pattern of light exposed areas in the imaging layer, (f) selectively removes the radiation sensitized imaging layer 20 and the second hard a portion of the mask layer to expose a portion of the first hard mask layer, (g) selectively removing the patterned second hard mask layer and portions of the first hard mask layer to expose the layer of material And (h) etching the exposed portion of the material layer to pattern the material layer. The present invention also provides a semiconductor integrated circuit 26 200827928 device manufactured by this method. [Mode for Invention] Hereinafter, the present invention will be explained in more detail with reference to the following examples. However, the examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention. EXAMPLES [Comparative Example 1] 1,750 g of decyltrimethoxy decane, 34 g of phenyltrimethoxy sylvestre, and 313 g of dimethoxy sulphur were dissolved in a magnetic stirrer, and cooled 10 5,600 g of propylene glycol methyl ether acetate (pgmea) in a 1 liter four-necked flask of a condenser, a dropping funnel, and a nitrogen introduction tube, and then 925 g of an aqueous nitric acid solution (1, 〇 00 ppm) was added. The resulting mixture was removed after 6 hours of reaction at 6 〇 QC. The reaction was continued for a week while maintaining the reaction temperature at 50. (: After the reaction is completed, hexane is added to the reaction mixture 15 to precipitate the polymer of Chemical Formula 10: Η Η

(10) 100 g of PGMEA and 100 g of lactic acid B were added to 4.0 g of the polymer to prepare a dilute solution of the polymer. The resulting solution was spin coated onto the twin circles. Thereafter, it was baked at 240 ° C for 60 seconds to form a film of 500 person thick. 20 [Example 1] 1750 g of methyltrimethoxydecane, 34 g of phenyltrimethoxy 27 200827928 decane, and 313 g of trimethoxydecane dissolved in a magnetic sandal mixer, condensation concentrating, dropping funnel 'And 5,600 g of PGMEA in a 10 liter four-necked flask of nitrogen gas introduction tube, then, 925 g of aqueous nitric acid solution 〇, 〇〇〇 ppm). The resulting mixture was reacted at 6 ° C for 1 hour. Thereafter, the formed methanol 5 is removed under dust reduction. The reaction was continued for 1 week while maintaining the reaction temperature at 5 °C. After the reaction temperature was lowered to 25 ° C, 185 g of ethyl vinyl ether was added. The resulting mixture was reacted at room temperature for 18 hours. After the reaction is completed, hexane is added to the reaction mixture to precipitate the polymer of Chemical Formula 11:

A dilute solution of the polymer was prepared by adding 100 g of PGMEA and 100 g of ethyl lactate to 40 g of polya. To this dilute solution, 〇·(8) 4 g of a ratio of cis-methyl sulfonate was added. The resulting solution is spin coated onto the Shi Xi wafer, followed by 240. (: Baking for 60 seconds to form a film of 500 A_thickness. [Experimental Example 1] The solutions prepared in Comparative Example 1 and Example 被 were tested for stability during storage. Each solution was stored at 40 Torr. At intervals, the state of the solution is observed 'and the film thickness after coating the solution is measured. The result side is shown in the table! Table 0 ... Large sample size is normalized by the normalization of molecular weight normalization - drought and molecular weight Thickness 28 200827928 Comparative Example 1 1.1 512 A 1.8 Example 1 1.0 502 A 1.0

532 A observed particle difference coating 502 A 1.0 503 A The molecular weight of the corresponding polymer measured after the normalization time shown in Table 1 was divided by the molecular weight of the polymer measured immediately after preparation of the polymer. The value obtained. The increase in molecular weight of the polymer prepared in Comparative Example 1 after the time interval of (4) was observed, and the condensation occurred between the shoe compounds of the solution prepared in Comparative Example (4). Conversely, the molecular weight of the polymer of the examples was maintained even after the crosslinking time was over, indicating improved storage stability of the yarn. [Experimental Example 2] Comparative example! And the refractive index (8) and extinction coefficient (9) of the film formed by m were measured using an elliptical thickness gauge (J. A. Woollam). The results are shown in Table 2. Sample No. 2 for forming a film Comparative Example 1 iL Properties Π93 3 Rate (8) 171 0.23 Example 1______ ^JV78_ 0.23 As seen from the second table, the film formed by Comparative Example 1 and Example 1 showed good exposure at 193 nmi. Optical properties. The protection of the Si-fluorenyl group by the ethyl vinyl ether of Chemical Formula 4 in the polymer prepared in Example 1 was confirmed to have no adverse effect on the optical properties of the reticle. [Experimental Example 3]

ArF photoresist was applied to each of the films formed in Comparative Example 1 and Example 1 on 2008 2972828, baked at 110 ° C for 60 seconds, and exposed using an ArF exposure coefficient (ASML 1250, FN70 5.0 activity, NA 0.82). The pattern of lines and gaps of 80 nm was developed by developing an aqueous solution of TMAH (2.38 wt%). The pattern was observed using a field emission scanning electron microscope (FE-SEM). The pattern is measured as the exposure latitude (EL) limit of the 5 function of exposure energy and the depth of focus (DoF) limit as a function of distance from the group source. The results are recorded in Table 3. Sample for forming a film Pattern characteristics EL limit (AmJ/exposure energy mJ) DoF limit (μηι) Comparative Example 1 0.2 0.2 Example 1 0.2 0.2 Patterns all showed good optical profiles. From the results, it was confirmed that the protection of the 10 Si-〇H group by the ethyl vinyl ether of Chemical Formula 4 in the polymer prepared in Example 1 did not adversely affect the optical profile of the photoresist. [Experimental Example 4] The patterned samples obtained in Experimental Example 3 were sequentially dried using cfx electric 堕, 〇2 plasma, and CFX plasma. The remaining organic material was completely removed using 〇2, and the cross section of the etched sample was observed using FE_SEM. The result series is shown in Table 4. Table 4 ------------ '^ _______________ Pattern shape after etching of the sample used to form the film ______---------____ Comparative Example 1 Vertical Reality; Column 1__ Vertical samples all show good surname characteristics. These results show that the ethyl vinyl ether of Chemical Formula 4 protects the si-〇H group 30 in the polymer prepared in Example 1. 200827928 Resistant to the mask, the last name selectivity and the residual wheel corridor are not bad. influences. [Industrial Applicability] The present invention provides a hard reticle composition for treating a photoresist underlayer film, which does not adversely affect the reticle resistance, the stencil selectivity, the stencil, and the optical properties. And optical contours. Further, the hard reticle of the present invention. The composition is highly stable during storage. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a multilayer structure of an antireflection hard mask layer 10 formed of a hard mask composition of the present invention, which is included in a lithography method for fabricating a semiconductor integrated circuit device. [Main component symbol description] (none) 31

Claims (1)

200827928 X. Patent Application Range: 1. An organic decane polymer prepared by reacting a polycondensation reaction product of a hydrolyzate of a compound represented by Chemical Formulas 2 and 3 with ethyl vinyl ether of Chemical Formula 4: 5 [RO]3Si-Ar (1) (wherein R is a methyl group or an ethyl group, and Ar is a functional group containing an aromatic ring); [RO]3Si-H (2) (wherein R is a methyl group) , or ethyl); and [RO]3Si_R, (3) 10 (wherein R is a methyl group, or an ethyl group, and R' is a substituted or unsubstituted cyclic or acyclic alkyl group): CH2CHOCH2CH3 (4). 2. The organodecane polymer according to claim 1, wherein the hydrolyzate of the compound of the chemical formulas 1, 2 and 3 is independently represented by the chemical formulas 5, 6 15 and 7 by ArSi[OH]3 (5) (wherein Ar is a functional group containing an aromatic ring); HSi[OH]3 (6); and R,Si[OH]3 (7) 20 (wherein R' is a substituted or unsubstituted ring Amorphous or acyclic alkyl). 3. The organodecane polymer according to claim 1, wherein the polycondensation reaction product is represented by Chemical Formula 8: 32 200827928 Arx )-s\-( -0 -Si VO -Si -〇_ 〇0 II ~0—Si/-0 Hy V II Η η η (8) = a functional group containing an aromatic ring, (iv) a substituted or unsubstituted cyclic or acyclic alkyl group, x, y And z satisfy the relational fork ^ °.〇4&lt;x&lt;〇e8〇, 〇&lt;y &lt; ! 4〇, ^1.80 &lt;z&lt; 3 9β is 3 to 500. — y + ζ and η 4· An organic (four) polymer as claimed in claim 1, wherein the organodecane polymer is represented by the chemical formula 9: Me (9) l〇15 /, medium, Ar is a functional group containing an aromatic ring, and R is a substituted or unsubstituted cyclic or acyclic alkyl group, each Me methyl group, hydrazine, y and ζ satisfy the relationship x + y + ζ = 4,0·04 £ X $ 0.80,0 ^ y $ ι·4〇, and 1·80 S ζ $ 3.96, and n is 3 to 500. 5. The organodecane polymer according to claim 1, wherein the hydrolyzate is selected from the group consisting of nitric acid, sulfuric acid, p-toluenesulfonic acid monohydrate, sulfuric acid diethyl sulfate, 2, 4, 4, 6- It is prepared in the presence of an acid catalyst of the group consisting of tetrabromo-2,5-cyclohexadienone and an organic sulfonic acid. 6. The organodecane polymer according to claim 1, wherein the organodecane polymer is obtained by mixing 1 to 2 parts by weight of the compound of Chemical Formula 1, and hydrazine to 35 parts by weight of the compound of Chemical Formula 2 And 45 to 99 parts by weight of the compound of the formula 3 (which is based on 100 parts by weight of the compound of the chemical formulas 1, 2 and 3), and the mixture is made up of 1 to 1 part by weight of water and 100 to 900 parts by weight of a solvent, in the presence of 1 to 5 parts by weight of an acid catalyst, to obtain a polycondensation reaction product, and to make the polycondensation reaction product and 1 to 200 parts by weight of the chemical formula 4 It is prepared by reacting ethyl vinyl ether. 7. The organodecane polymer according to claim 1, wherein the solvent is selected from the group consisting of acetone, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform, dichloromethane, ethyl acetate, propylene glycol methyl ether. , propylene glycol ethyl ether, 10 propylene glycol propyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, ethyl lactate, butyrolactone, and the like The ethnic group. 8. A hard reticle composition for treating a photoresist underlayer film, the composition comprising: 15 (a) an organodecane polymer which is obtained by hydrolyzing a compound represented by Chemical Formulas 2 and 3 The polycondensation reaction product is reacted with ethyl vinyl ether of Chemical Formula 4 to prepare: [RO]3Si-Ar (1) (wherein R is a mercapto group, or an ethyl group, and the Ar system contains an aromatic ring-containing functional group), 20 [R〇]3Si-H (2) (wherein R is a methyl group, or an ethyl group), and [R〇]3Si-R9 (3) (wherein R is a methyl group, or an ethyl group, and R' a substituted or unsubstituted cyclic or acyclic alkyl group) 34 200827928 (4) CH2CHOCH2CH3 5 (b) a solvent; and (c) a crosslinking catalyst. 9. The hydrolyzed product of the compound of the hard reticle compositions 1, 2 and 3 of claim 8 of the patent application is individually and 7: 'wherein the chemical formula is the chemical formula 5, 6 ArSi[OH]3 (5) (wherein Ar is a functional group containing an aromatic ring); HSi[〇H]3 (6); and 10 R,Si[OH]3 (7) (wherein R' is a substituted or unsubstituted ring or The sleek base). 10. The hard reticle composition of claim 8 of the patent, wherein +, the polycondensation reaction product is represented by the chemical formula: -0 - Si \ - 〇 - - Si - 〇 I I 15 wherein 'Ar is a functional group containing an aromatic ring, R is a substituted or unsubstituted cyclic or acyclic alkyl group, and x, y and z satisfy the relationship X + y + z = 4 ' 0.04$ Xm 1.40, and 1·80<ζ$3·96, j^n are 3 to 500. U. The hard reticle composition of claim 8, wherein the organo decane polymer is represented by Chemical Formula 1: 35 200827928 Wherein 'Αι· is a functional group containing a aryl phase ring, r is a substituted or unsubstituted cyclic or acyclic group, and each of the -Me thiol groups, x, yAz satisfy the relationship x + y + z = 4, 〇〇4^x^〇8〇, 4〇, and 5 I·80 $ z $ 3·96, and η is 3 to 500. 12. The hard reticle composition of claim 8, wherein the hydrolyzate is selected from the group consisting of nitric acid, sulfuric acid, p-toluenesulfonic acid monohydrate, diethyl sulfonate sulfate, 2, 4, 4, It is prepared in the presence of an acid catalyst of a group consisting of 6-tetrabromo-2,5-cyclohexanedione, and an organic acid-based alkyl ester. The hard reticle composition of claim 8, wherein the organodecane polymer is obtained by mixing 1 to 20 parts by weight of the compound of Chemical Formula 1, 0 to 35 parts by weight of Chemical Formula 2 a compound, and 45 to 99 parts by weight of the compound of Chemical Formula 3, which is based on 100 parts by weight of the compound of Chemical Formulas 1, 2 and 3, such that the mixture is in an amount of from 1 to 1 part by weight of 15 water and 1 to 900 parts by weight of a solvent, in the presence of 0.001 to 5 parts by weight of an acid catalyst, the reaction obtains a polycondensation reaction product, and the polycondensation reaction is carried out with 1 to 200 parts by weight of an ethyl vinyl group of Chemical Formula 4 Prepared by ether reaction. 14. The hard reticle composition of claim 13, wherein the bismuth bismuth agent is selected from the group consisting of propylene, tetrahydroethylene, benzene, toluene, diethyl, chloroform, dichloromethane, and acetic acid Ester, propylene glycol methyl ether, propylene glycol ethyl ether, 36 200827928 propanol propyl ether, propylene glycol methyl acetate, propylene glycol ethyl ether acetic acid, propylene glycol propyl squaric acid, lactic acid B, γ-butane Stuffed, and a mixture of its specialties. 15. The hard reticle composition of claim 8, wherein the hard 5 reticle composition comprises from 1 to 50 parts by weight of the organodecane polymer, based on the total weight of the composition ( 5 〇 to 99 parts by weight of the solvent, based on 1 part by weight of the total weight of the composition (1 Å by weight), and 0.0001 to 0.01 parts by weight of the crosslinking catalyst, It is based on the 100% heavy organic stone polymer. b. The hard reticle composition of claim 8, wherein the solvent is selected from the group consisting of acetone, tetrahydrofuran, benzene, toluene, diethyl ether, gas, methane, ethyl acetate, propylene glycol methyl Ether, propylene glycol ethyl ether, propylene glycol propyl scale, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetamidine, propylene glycol propyl ether acetate, ethyl lactate, butyrolactone, and mixtures thereof The group of people. 17. The hard reticle composition of claim 8, wherein the crosslinking catalyst is selected from the group consisting of pyridine p-toluenesulfonate, decyl sulfobetaine 16, (-) _ camphor_1 〇 _ acid ammonium salt, ammonium formate, triethyl sulphate, dimethyl ammonium formate, tetramethylammonium formate, pyridine formate, ammonium acetate, diethylammonium acetate, trimethylammonium acetate, tetramethyl acetate Alkyl ammonium, pyridine acetate, tetrabutylammonium acetate, tetrabutylammonium azide, tetrabutylammonium benzoate tetrabutylammonium hydrogen sulfate, tetrabutylammonium bromide, tetrabutylammonium chloride tetrabutyl Base ammonium cyanide, tetrabutylammonium fluoride, tetrabutylammonium moth, tetrabutylammonium sulfate, tetrabutylammonium nitrate, tetrabutylammonium 37 200827928 nitrate, tetrabutylammonium p-toluene a group of sulfonates, tetrabutylammonium phosphates, and mixtures thereof. 18. The hard reticle composition of claim 8 further comprising at least one agent selected from the group consisting of a crosslinking agent, a free radical stabilizer, and a surfactant. 19. A method of fabricating a semiconductor integrated circuit device, the method comprising the steps of: (a) providing a layer of material on a substrate; (b) forming a hard mask layer of organic material on the layer of material; 10 (c) applying a hard mask composition according to any one of claims 8 to 18 to the hard mask layer composed of an organic material to form an anti-reflective hard mask layer; d) forming a radiation sensitized imaging layer on the anti-reflective hard mask layer; 15 (e) imagewise exposing the imaging layer to radiation to form an image of the radiation exposed region in the imaging layer; (f) selectively removing the portion of the radiation-sensitized imaging layer and the anti-reflective hard mask layer to expose a portion of the hard mask layer composed of an organic material; 20 (g) selectively removing a patterned anti-reflective hard mask layer and a portion of the hard mask layer composed of an organic material to expose a portion of the material layer; and (h) etching the exposed portion of the material layer to cause etching The layer of material forms a pattern. 38 200827928 20. A semiconductor integrated circuit device manufactured by the method of claim 19 of the patent application. 39