KR20130078428A - Resist underlayer composition and process for producing integrated circuit device using same - Google Patents

Abstract

PURPOSE: A composition for a resist underlayer film is provided to be able to form a resist underlayer film with an elaborate structure as the etching ability to CFx plasma, coating performance and storage stability are excellent, and the hardness is also good. CONSTITUTION: A composition for a resist underlayer film comprises organic silane polycondensate manufactured by condensation polymerization of hydrolysates produced from compounds of Chemical formula 1: [R^1O]3Si-X, Chemical formula 2: [R^2O]3Si-R^3, and Chemical formula 3: B[OR^4]3; and solvent. In Chemical formula 1, R^1 is substituted or non-substituted C1-6 alkyl, X is substituted or non-substituted C6-30 aryl. In Chemical 2, R^2 is substituted or non-substituted C1-6 alkyl, R^3 is substituted or non-substituted C1-12 alkyl. In Chemical 3, R^4 is substituted or non-substituted C1-6 alkyl. [Reference numerals] (AA) Example 1

Description

RESIST UNDERLAYER COMPOSITION AND PROCESS FOR PRODUCING INTEGRATED CIRCUIT DEVICE USING SAME}

The present invention relates to a composition for a resist underlayer film and a method for manufacturing a semiconductor integrated circuit device using the same.

As line widths used in semiconductor microcircuits decrease, the thickness of the photoresist must be thinner due to the aspect ratio of the pattern. However, when the thickness of the photoresist becomes too thin, it is difficult to serve as a mask in the pattern transfer process (etching process). That is, during the etching all of the photoresist is consumed, making it impossible to etch the substrate to the desired depth.

In the stacked structure of photoresist / (organic antireflective film) / silicon underlayer film / carbon underlayer film / lower substrate, dry etching is performed by using a photoresist as a mask and CFx plasma. Indicates significantly different etch characteristics. In addition, in order to compensate for the thin thickness of the photoresist, the etching characteristics of the CFx plasma of the silicon-based hard mask used under the resist should be improved. This is possible by using a silicon monomer capable of forming a high Si-O network structure in the resin design step, in which case there is a difficulty in synthesizing the resin, and when the product is commercialized, there is a problem in that coating property and storage stability are lowered.

One embodiment of the present invention provides a resist underlayer film composition which is not only excellent in etchability to CFx plasma but also excellent in coating property and storage stability, and exhibits excellent curing degree, thereby forming a dense underlayer film.

Another embodiment of the present invention provides a method for manufacturing a semiconductor integrated circuit device using the composition for resist underlayer film, and a semiconductor integrated circuit device manufactured therefrom.

One embodiment of the present invention provides a composition for a resist underlayer film comprising an organosilane-based condensation product prepared by condensation polymerization of hydrolyzates produced from the compounds of Formulas 1 to 3, and a solvent.

[Formula 1]

[R ¹ O] ₃ Si-X

(In the formula 1,

R ¹ is a substituted or unsubstituted C1 to C6 alkyl group, and X is a substituted or unsubstituted C6 to C30 aryl group.)

[Formula 2]

[R ² O] ₃ Si-R ³

(In the formula (2)

R ² is a substituted or unsubstituted C1 to C6 alkyl group, and R ³ is a substituted or unsubstituted C1 to C12 alkyl group.)

(3)

B [OR ⁴ ] ₃

(3)

R ⁴ is a substituted or unsubstituted C1 to C6 alkyl group.)

The hydrolyzate produced from the compounds of Formulas 1 to 3 may be compounds of Formulas 4 to 6, respectively:

[Formula 4]

[HO] _a [R ¹ O] _(3-a) Si-X

(In Formula 4, R ¹ and X are as defined above, a is a number greater than 0 and in the range of 3.)

[Chemical Formula 5]

[HO] _b [R ² O] _(3-b) Si-R ³

(In Formula 5, R ² and R ³ are as defined above, b is a number greater than 0 and in the range of 3.)

[Formula 6]

B [OH] _c [OR ⁴ ] _(3-c)

(In Formula 6, R ⁴ is as defined above, c is a number greater than 0 and in the range of 3.)

In the preparation of the organosilane condensation polymer, based on 100 parts by weight of the total amount of the compounds of Formulas 1 to 3, 5 to 90 parts by weight of the compound of Formula 1, 5 to 90 parts by weight of the compound of Formula 2, and The compound of formula 3 may be used in an amount of 5 to 90 parts by weight.

The organosilane condensation polymer may further include a repeating unit derived from a hydrolyzate produced from the compound represented by the following Formula 7.

[Formula 7]

[R ⁵ O] ₃ Si-Y-Si [OR ⁶ ] ₃

(In the above formula (7)

R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C6 alkyl group, Y is a C6 to C30 arylene group, C1 to C20 straight or branched substituted or unsubstituted alkylene group, an aromatic ring in the main chain , C1 to C20 alkylene group containing a hetero ring, urea or isocyanurate group, and C2 to C20 hydrocarbon group containing a multiple bond.

The hydrolyzate produced from the compound of Formula 7 may be a compound of Formula 8 below.

[Formula 8]

[HO] _d [R ⁵ O] _(3-d) Si-Y-Si [OH] _e [OR ⁶ ] _(3-e)

(In the formula (8)

R ⁵ , R ⁶ , and Y are as defined above, and d and e are each independently a number greater than 0 and in the range of 3.)

When the organosilane-based condensation polymer is further prepared using the compound of Formula 7, the compound of Formula 7 may be used in an amount of 5 to 400 parts by weight based on 100 parts by weight of the total amount of the compounds of Formulas 1 to 3.

The hydrolyzate may be a compound for preparing an organosilane condensation product, that is, a compound of Formulas 1 to 3 is substituted with nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, bromic acid, iodide, p-toluene sulfonic acid hydrate, 2,4,4,6- It may be prepared by hydrolysis under an acid catalyst selected from the group consisting of tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, diethyl sulfate and combinations thereof.

The compound for preparing the organosilane condensation polymer may further include the compound of Formula 7.

The acid catalyst may be used in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total amount of the compounds of Formulas 1 to 3.

The hydrolysis is acetone, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform, dichloromethane, ethyl acetate, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol monomethyl ether acetate, propylene It may be carried out in a reaction solvent selected from the group consisting of glycol ethyl ether acetate, propylene glycol propyl ether acetate, ethyl lactate, δ-butyrolactone, dimethyl ether, dibutyl ether, methanol, ethanol and combinations thereof.

The weight average molecular weight (Mw) of the organosilane condensation polymer is in the range of 2,000 to 50,000.

The organosilane-based condensation polymer may be included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the total amount of the composition for a resist underlayer film.

The solvent is acetone, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform, dichloromethane, ethyl acetate, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol propyl ether acetate, ethyl lactate, δ-butyrolactone, dimethylether, dibutylether, methanol, ethanol and combinations thereof.

The resist underlayer film composition may further include an additive selected from the group consisting of a crosslinking agent, a radical stabilizer, a surfactant, a pH adjuster, and a combination thereof.

The composition for the resist underlayer film is pyridinium p-toluenesulfonate, amidosulfobetaine-16, ammonium (-)-camphor-10-sulfonate salt, ammonium formate, alkylammonium formate, pyridinium formate, alkylammonium nitrite The additive may further include an additive selected from the group consisting of a rate and a combination thereof.

Another embodiment of the invention comprises the steps of: (a) providing a layer of material on a substrate; (b) forming a first resist underlayer film made of an organic material on the material layer; (c) spin-on-coating the composition for resist underlayer film on the first resist underlayer film to form a second resist underlayer film; (d) forming a radiation-sensitive imaging layer over the second resist underlayer film; (e) exposing the radiation-sensitive imaging layer to radiation in a patterned manner to produce a pattern of radiation-exposed areas within the radiation-sensitive imaging layer; (f) selectively removing portions of the radiation-sensitive imaging layer and the second resist underlayer film to expose portions of the first resist underlayer film; (g) selectively removing portions of the patterned second resist underlayer film and the first resist underlayer film to expose portions of the material layer; And (h) forming a patterned material shape by etching the exposed portion of the material layer using the first resist underlayer film as a mask.

The forming of the second resist underlayer film (c) may be performed by spin-on-coating the composition for the resist underlayer film and then performing heat treatment at 100 to 400 ° C.

The method may further include forming an anti-reflection film on the second resist underlayer film formed after the step (c) forming the second resist underlayer film.

Another embodiment of the present invention provides a semiconductor integrated circuit device formed by the manufacturing method.

Other details of the embodiments of the present invention are included in the following detailed description.

The resist underlayer film composition is not only excellent in etching resistance to CF _x plasma but also excellent in coating property and storage stability, and exhibits excellent degree of curing, thereby forming a resist underlayer film having a dense structure. Thereby, the composition for resist underlayer film can be used not only as an auxiliary material for the photo process, but also useful for the manufacture of the underlayer film using the etching selectivity and the manufacture of the semiconductor integrated circuit device in which the fine pattern is formed. Specifically, it may be used in a line and space or contact hole pattern forming process of several tens of nanometers.

1 is an infrared spectral spectrum for the film prepared in Example 1. FIG.
2 is an infrared spectral spectrum of the film prepared in Comparative Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited, and the present invention is defined only by the scope of the claims to be described later.

As used herein, unless otherwise defined, the term "substituted" means substituted with a C1 to C6 alkyl group or a C6 to C12 aryl group.

In the present specification, "alkyl group" means a C1 to C10 alkyl group, "C2 to C20 hydrocarbon group including a multiple bond" is a hydrocarbon group including a multiple bond including a double bond or a triple bond, C2 to C20 An alkenylene group, a C2 to C20 alkynylene group, a C3 to C20 cycloalkenylene group, a C3 to C20 cycloalkynylene group, and the like.

One embodiment of the present invention provides a composition for a resist underlayer film comprising an organosilane-based condensation product prepared by condensation polymerization of hydrolyzates produced from the compounds of Formulas 1 to 3, and a solvent.

[Formula 1]

[R ¹ O] ₃ Si-X

(In the formula 1,

R ¹ is a substituted or unsubstituted C1 to C6 alkyl group, and X is a substituted or unsubstituted C6 to C30 aryl group.)

[Formula 2]

[R ² O] ₃ Si-R ³

(In the formula (2)

R ² is a substituted or unsubstituted C1 to C6 alkyl group, and R ³ is a substituted or unsubstituted C1 to C12 alkyl group.)

(3)

B [OR ⁴ ] ₃

(3)

R ⁴ is a substituted or unsubstituted C1 to C6 alkyl group.)

The alkyl group can be a linear or branched alkyl group.

The organosilane condensation polymer according to an embodiment of the present invention, when the total amount of the compound of Formula 1 to 3 is 100 parts by weight of 5 to 90 parts by weight of the compound of Formula 1, 5 to 90 parts by weight of the compound of Formula 2 and 5 to 90 parts by weight of the compound of Formula 3 may be an organosilane condensation product prepared by hydrolysis under an acid catalyst and then condensation polymerization of the resulting hydrolyzate.

When the compound of Formula 1 is used in the above range, the aromatic ring exhibits an absorption spectrum in the deep UV region, thereby providing an underlayer film having high antireflection characteristics and sufficient etching selectivity due to high Si content. can do. In addition, the content of the aromatic ring may be adjusted to provide a composition for an underlayer film having a desired absorbance and a refractive index at a specific wavelength. In addition, when the compound of Formula 2 is used in the above range, the storage stability of the polycondensate can be increased and sufficient absorbance can be obtained. In addition, when the compound of Formula 3 is used in the above range, it is possible to secure excellent etching properties with improved storage stability.

The hydrolysis is carried out in a reaction solvent under an acid catalyst.

The acid catalyst plays a role of properly adjusting the rate of the hydrolysis reaction or the polycondensation reaction of the above compounds to obtain an organosilane condensation polymer having a desired molecular weight. The type of the acid catalyst is generally used in the art, and is not particularly limited. Specifically, the acid catalyst may be nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, bromic acid, iodic acid, or the like. Inorganic acid; organic compounds such as p-toluenesulfonic acid monohydrate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and diethylsulfate Alkyl esters of sulfonic acid; Or a combination thereof. In this case, the acid catalyst is preferably used in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total amount of the compounds of Formulas 1 to 3 to form the organosilane condensation polymer, in order to properly control the reaction rate to obtain a condensation polymer having a desired molecular weight. Do.

The reaction solvent serves to increase the stability of the organosilane condensation polymer by controlling the degree of hydrolysis of Si-OR, the reaction solvent is acetone, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform, dichloro Methane, ethyl acetate, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, ethyl lactate, δ-butyrolactone, Dimethyl ether, dibutyl ether, alcohols (methanol, ethanol, etc.) and those selected from the group consisting of these can be used. The reaction solvent is preferably used in an amount of 100 to 1800 parts by weight based on 100 parts by weight of the total amount of the compounds of Formulas 1 to 3.

The organosilane condensation polymer may be a condensation product of a compound represented by the following Chemical Formulas 4 to 6, which are hydrolyzates of Chemical Formulas 1 to 3.

[Formula 4]

[HO] _a [R ¹ O] _(3-a) Si-X

(In the formula 4,

R ¹ and X are as defined above and a is a number greater than 0 and in the range of 3.)

[Chemical Formula 5]

[HO] _b [R ² O] _(3-b) Si-R ³

(In the above formula (5)

R ² and R ³ are as defined above, b is a number greater than 0 and in the range of 3.)

[Formula 6]

B [OH] _c [OR ⁴ ] _(3-c)

(6)

R ⁴ is as defined above and c is a number greater than 0 and in the range of 3.)

The alkyl group can be a linear or branched alkyl group.

The organosilane-based condensation polymer may further include a structural unit derived from a hydrolyzate produced from the compound of Formula 7.

[Formula 7]

[R ⁵ O] ₃ Si-Y-Si [OR ⁶ ] ₃

(In the above formula (7)

R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C6 alkyl group, Y is a C6 to C30 arylene group, C1 to C20 straight or branched substituted or unsubstituted alkylene group, an aromatic ring in the main chain , C1 to C20 alkylene group containing a hetero ring, urea or isocyanurate group, and C2 to C20 hydrocarbon group containing a multiple bond.

The hydrolyzate produced from the compound of Formula 7 may be a compound of Formula 8 below.

[Formula 8]

[HO] _d [R ⁵ O] _(3-d) Si-Y-Si [OH] _e [OR ⁶ ] _(3-e)

(In the formula (8)

R ⁵ and R ⁶ , and Y are as defined above, and d and e are each independently a number greater than 0 and in the range of 3.)

When the organosilane condensation polymer further comprises a structural unit derived from a hydrolyzate produced from the compound of Formula 7, the compound of Formula 7 in the preparation of the organosilane condensation polymer is the total amount of the compounds of Formulas 1 to 3 It can be used from 5 to 400 parts by weight based on 100 parts by weight. When the compound of Formula 7 is used in the above range, it is possible to increase the content of Si and O in the polycondensate with improvement of storage stability, thereby securing sufficient etching property for CFx plasma.

A condensation polymer according to an embodiment of the present invention includes a structural unit of formula 9 or 10 below:

[Chemical Formula 9]

^{_{{(R 3 SiO 1 .5 (}} OR 2) 1.5-p) 0.7 (XSiO 1 .5 (OR 1) 1.5-q) 0.1 (BO 1 .5 (OH) 1.5-r) 0.2} m

Wherein R ¹ to R ³ and X are the same as defined in Formulas 1 and 2, 0.001 ≦ p ≦ 0.9, 0.001 ≦ q ≦ 0.9 and 0.001 ≦ r ≦ 0.9, p + q + r = 1, m Is in the range of 50 to 300. In addition, in the structural units in the above formula _{^{9 (R 3 SiO 1 .5 (}} OR 2) 1.5-p), (XSiO 1.5 (OR 1) 1.5-q) and _{(BO 1 .5 (OH) 1.5} -r) of the order Is random.

[Formula 10]

^{_{{(SiO 1 .5 (OR 5}} ) 1.5-s -Y-SiO 1 .5 (OR 6) 1.5-s) 0.5 (R 3 SiO 1 .5 (OR 2) 1.5-p) 0.3 (XSiO 1 .5 (OR ¹ ) _1.5-q ) _0.1 (BO _1.5 (OH) _1.5-r ) _0.1 } _n

Wherein R ¹ to R ³ , R ⁵ , R ⁶ , X, and Y are the same as defined in Formulas 1 to 3 and 7, and 0.001 ≦ p ≦ 0.9, 0.001 ≦ q ≦ 0.9, 0.001 ≦ r ≦ 0.9 And 0.001 ≦ s ≦ 0.9, p + q + r + s = 1, and n is in the range of 50 to 300. In addition, in the structural unit in Formula ^{_{10 (SiO 1 .5 (OR 5}} ) 1.5-s -Y-SiO 1 .5 (OR 6) 1.5-s), (R 3 SiO 1 .5 (OR 2) 1.5-p ), a sequence of _{^{(XSiO 1.5 (OR 1) 1.5}} -q) and _{(BO 1 .5 (OH) 1.5} -r) is random.

Such organosilane-based condensation polymer may be used that has a weight average molecular weight (Mw) of 2,000 to 50,000. In particular, it is preferable to consider the coating performance on the substrate, and to use a range of 3,000 to 20,000 in order to prevent gel formation.

In addition, the organosilane-based condensation polymer may be included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the total amount of the composition for resist underlayer film. In particular, it is preferable to include 0.5 to 10 parts by weight in consideration of the coating performance on the substrate.

In addition, in the resist underlayer film composition, the solvent serves to prevent voids and to improve flatness by slowly drying the film. The kind of the solvent is generally used in the art, and is not particularly limited, but more specifically, volatilization near a temperature lower than the temperature during coating, drying and curing of the composition for resist underlayer film according to one embodiment of the present invention. A high boiling solvent can be used. More specifically, acetone, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform, dichloromethane, ethyl acetate, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene Propylene glycol propyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, Ethyl lactate, δ-butyrolactone, dimethyl ether, dibutyl ether, methanol, ethanol, and combinations thereof may be used.

The resist underlayer film composition may further include an additive selected from the group consisting of crosslinking agents, radical stabilizers, surfactants, pH adjusting agents, and combinations thereof.

Specifically, as the crosslinking agent, tetrabutyl ammonium acetate, tetrabutyl ammonium azide, tetrabutyl ammonium benzoate, tetrabutyl ammonium bisulfate, brominated Tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium cyanide, tetrabutyl ammonium fluoride, tetrabutyl ammonium iodide, tetra Tetrabutyl ammonium sulfate, tetrabutyl ammonium nitrite, tetrabutyl ammonium p-toluene sulfonate, tetrabutyl ammonium phosphate, and their In the group of mixtures You can use that tag.

In addition, the composition for the resist underlayer film is a sulfonic acid salt of organic base (for example, pyridinium p-toluenesulfonate, amidosulfobetaine-16, ammonium (-)-camphor -10-sulfonate (ammonium (-)-camphor-10-sulfonic acid ammonium salt, etc.), ammonium formate, alkylammonium formate (e.g. triethylammonium formate ( triethylammonium formate, trimethylammonium formate, tetramethylammonium formate, tetrabutylammonium formate, etc., pyridinium formate, alkylammonium nitrate (e.g. For example, tetramethylammonium nitrate, tetrabutyl ammonium nitrate, and the like, and combinations thereof. Crosslinking catalyst may be further included as an additive.

The crosslinking catalyst may be added to the composition including the organosilane-based polymer and the solvent alone or in addition to the additive selected from the group consisting of the crosslinking agent, radical stabilizer, surfactant, and combinations thereof.

In the case where the resist underlayer film composition further includes the above additives, it is preferable to include 0.0001 to 1 parts by weight of each of the additives based on 100 parts by weight of the organosilane condensation polymer.

The composition for resist underlayer film according to one embodiment of the present invention includes CF _x by including a silane-based condensation polymer including a structural unit derived from a hydrolyzate of a compound containing a BO or BO-Si bond.  Not only excellent etching property for plasma but also excellent coating property and storage stability. In addition, a resist underlayer film excellent in antireflection characteristics and etching selectivity can be provided.

According to one embodiment of the invention, (a) providing a material layer on a substrate; (b) forming a first resist underlayer film made of an organic material on the material layer; (c) spin-on-coating the composition for resist underlayer film on the first resist underlayer film to form a second resist underlayer film; (d) forming a radiation-sensitive imaging layer over the second resist underlayer film; (e) generating a pattern of radiation-exposed regions within the radiation-sensitive imaging layer by exposing the radiation-sensitive imaging layer to radiation in a patterned manner; (f) selectively removing portions of the radiation-sensitive imaging layer and the second resist underlayer film to expose portions of the first resist underlayer film; (g) selectively removing portions of the patterned second resist underlayer film and the first resist underlayer film to expose portions of the material layer; And (h) forming a patterned material shape by etching the exposed portion of the material layer using the first resist underlayer film as a mask.

The method of patterning the material on the substrate according to the present invention can be carried out more specifically as follows.

First, a material to be patterned, such as aluminum and SiN (silicon nitride), is formed on a silicon substrate according to a conventional method. The material to be patterned in which the composition for resist underlayer film of the present invention is used may be all conductive, semiconducting, magnetic or insulating materials.

A first resist underlayer film made of an organic material is formed on the material to be patterned. In this case, the first resist underlayer film may be formed to have a thickness of 200 kPa to 12000 kPa using an organic material mainly including carbon, hydrogen, and oxygen. In this case, the type and the thickness of the first resist underlayer film are not limited to the above-described range, but may be manufactured in various forms, and those skilled in the art will recognize that the technical idea of the present invention, It will be appreciated that the invention may be embodied in other specific forms without modification.

Subsequently, the second resist underlayer film is formed by spin-on-coating to a thickness of 100 kPa to 4000 kPa using a composition for a resist underlayer film according to an embodiment of the present invention and then performing heat treatment.

The heat treatment process for forming the second resist underlayer film may be performed at 100 ° C to 400 ° C. When heat-treated in the above range, the content of Si in the underlayer film is increased to provide a dense underlayer film.

When the second resist lower layer film is formed, a radiation-sensitive imaging layer is formed and a developing process is performed to expose a region to be patterned by an exposure process through the imaging layer. Subsequently, the imaging layer and the antireflective layer are selectively removed to expose portions of the material layer, and dry etching is performed using an etching gas. As a general example of the etching gas may be selected from the group consisting of CHF ₃ , CH ₂ F ₂ , CF ₄ , CH ₄ , N ₂ , O ₂ , Cl ₂ , BCl ₃ and mixtures thereof. After the patterned material shape is formed, any remaining radiation-sensitive imaging layer can be removed by conventional photoresist strippers.

According to another exemplary embodiment of the present disclosure, the method may further include forming an anti-reflection film on the second resist underlayer film formed after the step (c) forming the second resist underlayer film. Although the composition for resist underlayer film according to the present invention includes a structural unit derived from the hydrolyzate of the compound of Formula 1, a sufficient antireflection effect can be obtained, so that it is not necessary to form a separate antireflection film. It can further form an additional anti-reflection film. At this time, the anti-reflection film can be prepared according to a conventional method.

A device patterned by the above manufacturing method is provided. The device may be a semiconductor integrated circuit device. In particular, a patterned material layer structure, such as a hole for a metal wiring line, contact or bias; Insulation sections such as multimask trenches or cellrow trench insulation; A trench for a capacitor structure such as a design of an integrated circuit device, and the like. It can also be very usefully applied to form patterned layers of oxides, nitrides, polysilicon and chromium. It should also be understood that the invention is not limited to any particular lithographic technique or device structure.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

Comparative example  One

In a 1 L four-necked flask equipped with a mechanical stirrer, a cooling tube, a dropping funnel, and a nitrogen gas introduction tube, 190.7 g of methyltrimethoxysilane and 34.3 g of phenyltrimethoxysilane were mixed with PGMEA (propylene glycol monomethyl). ether acetate) and 59.5 g of 0.5% nitric acid solution were added to the solution. Thereafter, the reaction was carried out at room temperature for 1 hour, and then negative pressure was applied to remove methanol and ethanol. After the reaction was carried out for 7 days while maintaining the reaction temperature at 90 ℃. After the reaction, 98 g of PGMEA was added to 2 g of a solution of the polymerized organosilane condensation product (weight average molecular weight: 10,000) to prepare a dilute solution.

Pyridinium p-toluenesulfonate (0.004 g) was added to this dilution solution to prepare a resist underlayer film composition.

The composition for resist underlayer film was coated on a silicon wafer by spin-on-coating, and baked at 240 ° C. for 60 seconds to form a film having a thickness of 400 mm 3.

Comparative example  2

In a 1 L four-necked flask equipped with a mechanical stirrer, cooling tube, dropping funnel, and nitrogen gas introduction tube, 48.7 g of methyltrimethoxysilane, 17.7 g of phenyltrimethoxysilane, and 158.5 g of bistriethoxysilylethane were added to 525 g of PGMEA. After dissolution, 50.7 g of 0.5% nitric acid aqueous solution was added to the solution. Then, after reacting at room temperature for 1 hour, negative pressure was applied to remove the generated methanol and ethanol. The reaction was then carried out for 5 days while maintaining the reaction temperature at 50 ℃. After the reaction, 98 g of PGMEA was added to 2 g of a solution of the polymerized organosilane condensation product (weight average molecular weight: 10,000) to prepare a dilute solution.

0.004 g of pyridinium p-toluenesulfonate was added to this dilution solution to prepare a composition for resist underlayer film.

The resist underlayer film was coated on a silicon wafer by spin-on-coating to bake at 240 ° C. for 60 seconds to form a film having a thickness of 400 μs.

Example  One

In a 1 L four-necked flask equipped with a mechanical stirrer, cooling tube, dropping funnel, and nitrogen gas introduction tube, 110.0 g of methyltrimethoxysilane, 25.5 g of phenyltrimethoxysilane, and 14.5 g of boric acid were charged with 600 g of PGMEA. After dissolving in, 44.3 g of 0.5% nitric acid aqueous solution was added to the solution. Then, after reacting at room temperature for 1 hour, negative pressure was applied to remove the generated methanol and ethanol. After the reaction was carried out for 4 days while maintaining the reaction temperature at 50 ℃. After the reaction, 98 g of PGMEA was added to 2 g of a solution of the polymerized organosilane condensation product (weight average molecular weight: 10,000) to prepare a dilute solution.

0.004 g of pyridinium p-toluenesulfonate was added to this diluted solution to prepare a composition for resist underlayer film.

The resist underlayer film composition was coated on a silicon wafer by spin-on-coating to bake at 240 ° C. for 60 seconds to form a film having a thickness of 400 μs.

Example  2

In a 1 L four-necked flask equipped with a mechanical stirrer, cooling tube, dropping funnel, and nitrogen gas introduction tube, 21.8 g of methyltrimethoxysilane, 10.6 g of phenyltrimethoxysilane, 94.4 g of bistriethoxysilylethane, and boric acid 3.3 g was dissolved in 520 g of PGMEA and 90.6 g of ethanol, and then 60.4 g of 0.5% nitric acid solution was added to the solution. Then, after reacting at room temperature for 1 hour, negative pressure was applied to remove the generated methanol and ethanol. After the reaction was carried out for 3 days while maintaining the reaction temperature at 50 ℃. After the reaction, 98 g of PGMEA was added to 2 g of a solution of the polymerized organosilane condensation product (weight average molecular weight: 10,000) to prepare a dilute solution.

0.004 g of pyridinium p-toluenesulfonate was added to this diluted solution to prepare a composition for resist underlayer film.

The resist underlayer film was coated on a silicon wafer by spin-on-coating to bake at 240 ° C. for 60 seconds to form a film having a thickness of 400 μs.

Experimental Example  1: Storage stability evaluation

Storage stability of the organosilane condensation polymer solution prepared in Comparative Examples 1 and 2 and Examples # 1 and 2 was evaluated.

In detail, the organosilane condensation polymer solution prepared in Comparative Examples 1 and 2 and Examples 1 and 2 was stored at 40 ° C. for 30 days, and the state of the solution and the thickness after coating were measured.

As a result of the measurement, in Comparative Examples 1 and 2 and Examples # 1 and 2, the molecular weight at the time of manufacture was maintained even after a certain time elapsed, and there was almost no change in thickness even after coating (<10 ms). From these results, it was confirmed that both the organosilane condensation solution solutions of Comparative Examples 1 and 2 and Examples 1 and 2 had excellent retention stability.

Experimental Example  2: Refractive index and Extinction coefficient  Measure

In general, the refractive index and the extinction coefficient are factors that inform the function of the reflectivity and thickness prior to the exposure experiment. Accordingly, for the films prepared in Comparative Examples 1 and 2 and Examples 1 and 2, the refractive index (n) and the absorption coefficient (refractive index, n) at 193 nm were measured using an ellipsometer (manufactured by JA Woollam, Inc.). extinction coefficient (k) was measured. The results are shown in Table 1 below.

n, k (@ 193nm) Comparative Example 1 n = 1.70, k = 0.21 Example 1 n = 1.73, k = 0.27 Comparative Example 2 n = 1.69, k = 0.14 Example 2 n = 1.70, k = 0.16

As shown in Table 1, even when the same chromophore content was used, Examples 1 and 2 including the boric acid-derived structural unit in the organosilane condensate increased n and compared with Comparative Examples 1 and 2 The k value is shown. This is because chromophore / Si was relatively increased when boron was included in organosilane condensate.

Experimental Example  3: Contact angle  Measure

Contact angles of the films prepared in Comparative Examples 1 and 2 and Examples 1 and 2 were measured. The instrument used was DAS-100 (Kruess Co., Ltd.) dropping 3 μl of water by 5 points on each surface to measure the angle between each surface and water droplets. The results are shown in Table 2 below.

Contact angle (˚) Comparative Example 1 83 Example 1 78 Comparative Example 2 69 Example 2 66

As shown in Table 2, Examples 1 and 2 in which the organosilane-based polycondensate contained a boron component showed lower contact angles than Comparative Examples 1 and 2.

Experimental Example  4: Measurement of Infrared Spectroscopy Spectrum

Infrared spectroscopy (FT-IR Spectrum) was measured on the films prepared in Comparative Example 1 and Example 1. The results are shown in FIGS. 1 and 2, respectively.

As shown in Figure 1 and 2, in the film prepared in Example 1 was observed BO (1351 cm ^-1 ) and BO-Si (886 cm ^-1 ) peaks that were not observed in Comparative Example 1, respectively, through the boron It can be seen that the organosilane condensation polymer is present in the form of a chemical bond.

Experimental Example  5: Etch rate  Measure

The silicon wafers prepared in Comparative Examples 1 and 2 and Examples 1 and 2 were subjected to etching conditions of 50 CF ₄ , 20 O ₂ , 10 CH ₂ F ₂ , 80 CHF ₃ , 800 Ar, 27 MHz 600 W, 2 MHz 850 W, and 200 mTorr. After 5 seconds of bulk dry etching, the thickness was measured to measure the etch rate per unit time. In this experiment, Ar was used as the flowing gas, and CFx and O ₂ were used as the main etching gas.

Etch rate (Å / sec) Comparative Example 1 80 Example 1 90 Comparative Example 2 85 Example 2 100

As shown in Table 3, the silicon wafers of Examples 1 and 2 including boron exhibited increased etch rates under CFx-based etching gases compared to Comparative Examples 1 and 2. From these results, it was confirmed that Example 1 and 2 both have excellent etching property with respect to CFx plasma.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (19)

Organosilane-based polycondensates prepared by condensation polymerization of hydrolyzates produced from compounds of Formulas 1 to 3; And a composition for a resist underlayer film containing a solvent.
[Formula 1]
[R ¹ O] ₃ Si-X
(In Formula 1,
R ¹ is a substituted or unsubstituted C1 to C6 alkyl group, and X is a substituted or unsubstituted C6 to C30 aryl group.)
(2)
[R ² O] ₃ Si-R ³
(In the formula (2)
R ² is a substituted or unsubstituted C1 to C6 alkyl group, and R ³ is a substituted or unsubstituted C1 to C12 alkyl group.)
(3)
B [OR ⁴ ] ₃
(3)
R ⁴ is a substituted or unsubstituted C1 to C6 alkyl group.)
The method of claim 1,
Wherein the hydrolyzate produced from the compounds of formulas (1) to (3) is a compound of the following formulas (4) to (6), respectively.
[Chemical Formula 4]
[HO] _a [R ¹ O] _(3-a) Si-X
(In Formula 4, R ¹ and X are as defined in claim 1, a is a number greater than 0 and in the range of 3.)
[Chemical Formula 5]
[HO] _b [R ² O] _(3-b) Si-R ³
(In Formula 5, R ² and R ³ are as defined in claim 1, b is a number greater than 0 and in the range of 3.)
[Chemical Formula 6]
B [OH] _c [OR ⁴ ] _(3-c)
(6)
R ⁴ is as defined in claim 1, where c is a number greater than 0 and in the range of 3.)
The method of claim 1,
With respect to 100 parts by weight of the compound represented by Formula 1 to 3, the compound represented by Formula 1 is 5 to 90 parts by weight, the compound represented by Formula 2 is 5 to 90 parts by weight, and is represented by Formula 3 The compound is a resist underlayer film composition used in the amount of 5 to 90 parts by weight.
The method of claim 1,
The composition for resist underlayer film, wherein the organosilane condensation polymer further comprises a structural unit derived from a hydrolyzate produced from the compound represented by the following Formula 7.
(7)
[R ⁵ O] ₃ Si-Y-Si [OR ⁶ ] ₃
(In the above formula (7)
R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C6 alkyl group, Y is a C6 to C30 arylene group, C1 to C20 straight or branched substituted or unsubstituted alkylene group, an aromatic ring in the main chain , C1 to C20 alkylene group containing a hetero ring, urea group or isocyanurate group, and C2 to C20 hydrocarbon group including a multiple bond.
5. The method of claim 4,
A composition for resist underlayer film wherein the hydrolyzate produced from the compound of Formula 7 is a compound of Formula 8.
[Chemical Formula 8]
[HO] _d [R ⁵ O] _(3-d) Si-Y-Si [OH] _e [OR ⁵ ] _(3-e)
(In the formula (8)
R ⁵ , R ⁶ , and Y are as defined in claim 4, wherein d and e are each independently a number greater than 0 and in the range of 3.)
5. The method of claim 4,
The compound of Formula 7 is a composition for a resist underlayer film further comprises 5 to 400 parts by weight based on 100 parts by weight of the total amount of compounds of Formulas 1 to 3.
The method of claim 1,
The hydrolyzate is a compound for the formation of the organosilane condensation product is a compound of formula 1 to 3 nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, bromic acid, iodic acid, p-toluene sulfonic acid hydrate, 2,4,4,6-tetra A composition for a resist underlayer film which is prepared by hydrolysis under an acid catalyst selected from the group consisting of bromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, diethyl sulfate, and combinations thereof.
The method of claim 7, wherein
The compound for forming the organosilane-based polycondensation composition further comprises a compound of the formula (7).
(7)
[R ⁵ O] ₃ Si-Y-Si [OR ⁶ ] ₃
(In Formula 7, R ⁵ , R ⁶ , and Y are as defined in claim 4)
The method of claim 7, wherein
The acid catalyst is a composition for resist underlayer film which is used in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total amount of the compound of Formulas 1 to 3.
The method of claim 7, wherein
The hydrolysis is acetone, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform, dichloromethane, ethyl acetate, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol monomethyl ether acetate, propylene Resist underlayer which is carried out in a reaction solvent selected from the group consisting of glycol ethyl ether acetate, propylene glycol propyl ether acetate, ethyl lactate, δ-butyrolactone, dimethyl ether, dibutyl ether, methanol, ethanol and combinations thereof Membrane composition.
The method of claim 1,
The organosilane-based condensation polymer is a composition for resist underlayer film having a weight average molecular weight of 2,000 to 50,000 range.
The method of claim 1,
The organosilane-based condensation polymer is 0.1 to 50 parts by weight based on 100 parts by weight of the composition for a resist underlayer film composition for a resist underlayer film.
The method of claim 1,
The solvent is acetone, tetrahydrofuran, benzene, toluene, diethyl ether, chloroform, dichloromethane, ethyl acetate, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol propyl ether acetate, ethyl lactate, δ-butyrolactone, dimethyl ether, dibutyl ether, methanol, ethanol and a composition for a resist underlayer film is selected from the group consisting of these.
The method of claim 1,
The resist underlayer film composition further comprises an additive selected from the group consisting of a crosslinking agent, a radical stabilizer, a surfactant, a pH adjusting agent and a combination thereof.
The method of claim 1,
The composition for the resist underlayer film is pyridinium p-toluene sulfonate, amidosulfobetaine-16, ammonium (-)-camphor-10-sulfonate, ammonium formate, alkylammonium formate, pyridinium formate, alkylammonium nitrite The composition for a resist underlayer film further comprising an additive selected from the group consisting of a rate and a combination thereof.
(a) providing a layer of material on the substrate;
(b) forming a first resist underlayer film made of an organic material on the material layer;
(c) forming a second resist underlayer film by spin-on-coating the composition for resist underlayer film according to any one of claims 1 to 15 on the first resist underlayer film;
(d) forming a radiation-sensitive imaging layer over said second resist underlayer;
(e) generating a pattern of radiation-exposed regions within the radiation-sensitive imaging layer by exposing the radiation-sensitive imaging layer to radiation in a patterned manner;
(f) selectively removing portions of the radiation-sensitive imaging layer and the second resist underlayer film to expose portions of the first resist underlayer film;
(g) selectively removing portions of the patterned second resist underlayer film and portions of the first resist underlayer film to expose portions of the material layer; And
(h) forming a patterned material shape by etching the exposed portion of the material layer using the first resist underlayer film as a mask;
Method for manufacturing a semiconductor integrated circuit device comprising a.
17. The method of claim 16,
Wherein (c) the second resist underlayer film forming step is a method for manufacturing a semiconductor integrated circuit device is carried out by spin-on-coating the composition for a resist underlayer film followed by heat treatment at 100 to 400 ℃.
17. The method of claim 16,
And (c) forming an anti-reflection film on the second resist underlayer film formed after the step of forming the second resist underlayer film.
A semiconductor integrated circuit device formed by the manufacturing method according to claim 16.

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