KR100783070B1 - Organosilane composition, Hardmask Composition Coated under Photoresist and Process of producing integrated circuit devices using thereof - Google Patents

Abstract

Characterized in that it comprises a hydrolyzate and an organosilane polymer produced by reacting any one or more of the compounds represented by the formula (1) and (2), the compound represented by the formula (3), the compound represented by the formula (4) and the compound of the formula (5) The present invention relates to an organosilane compound and a method for manufacturing a semiconductor integrated circuit device using the same. The composition of the present invention has excellent film properties and storage stability, and has excellent hard mask properties, so that an excellent pattern can be transferred to the material layer.

Lithographic, Hard Mask, Anti-Reflective Film

Description

Organosilane polymer, hard mask composition for resist underlayer film comprising same, and method for manufacturing semiconductor integrated circuit device using same

The present invention relates to an organosilane polymer and a hard mask composition for a resist underlayer film and a method for manufacturing a semiconductor integrated circuit device using the same. Specifically, the pattern is excellent in reproducibility, good adhesion with a resist, and after exposure of the resist. The composition for underlayer film of the resist which is excellent in the developing film to be used and which has little film reduction at the time of plasma etching can be provided.

Most lithographic processes increase the resolution by using an antireflective coating material (ARC) to minimize the reflectivity between the imaging layer, such as a layer of resist material and the substrate. However, these ARC materials impose poor etch selectivity on the imaging layer due to the similar basic composition of the layers. Therefore, many imaging layers are also consumed during the etching of ARC after patterning, requiring further patterning during subsequent etching steps.

In addition, for some lithographic techniques, the resist material used does not provide sufficient resistance to subsequent etching steps to effectively transfer the desired pattern to the layer underlying the resist material. In many cases, for example when extremely thin resist materials are used, when the substrate to be etched is thick, when substantial etch depth is required, it is desired to use a specific etchant for a given substrate layer, or In any combination of the above cases, a hard mask for resist underlayer film is used. The hard mask for the resist underlayer film serves as an intermediate layer between the patterned resist and the substrate to be patterned. The hard mask for resist underlayer film receives a pattern from the patterned resist layer and transfers the pattern to the substrate. The hard mask layer for the resist underlayer film must be able to withstand the etching process required to transfer the pattern.

For example, when processing a substrate such as a silicon oxide film, a resist pattern is used as a mask, but since the thickness of the resist is reduced along with miniaturization, it is difficult to process the oxide film without damaging the mask property of the resist. Therefore, the process of first transferring a resist pattern to the underlayer film for oxide film processing, and performing a dry etching process to an oxide film as a mask is taken. The underlayer film for oxide film processing means a film formed under the antireflection film while also serving as a lower reflection film. In this step, since the etching rate of the resist and the underlayer film for oxide film processing is similar, it is necessary to form a mask capable of processing the underlayer film between the resist and the underlayer film. That is, a multilayer film made of an oxide film processing underlayer film-underlayer film processing mask-resist is formed on the oxide film.

In Japanese Patent 2000-0077018 (Publication No.), a condensation product of a silane compound such as RaSi (OR) 4-a is used as a material for resist underlayer film in order to obtain the same effect as described above. However, the condensation product of the patent has a problem that the Si-OH group is present in a high concentration is poor in film properties and difficult to form patterns during photoresist processing.

The present invention is to solve the problems of the prior art as described above, to provide an antireflective composition that has high etching selectivity, sufficient resistance to multiple etching, and minimizes the reflectivity between the resist and the underlying layer to be useful in lithographic processes It aims to use. Another object of the present invention is to provide a method of patterning a backing material layer on a substrate using the hardmask composition of the present invention.

In addition, the inventor of the present invention utilizes the fact that the aromatic group or the substituted aromatic group in Formula 1 or Formula 2 exhibits an absorption spectrum at 193 nm, while providing a material having high absorption at 193 nm, and at the same time, aromatic. It is a technical object of the present invention to provide a hard mask composition for a resist underlayer film having a desired absorbance and a refractive index in a specific frequency band by adjusting the concentration ratio of a) group or a substituted aromatic group.

In order to solve the above technical problem, the inventors of the present invention have a very low concentration of Si-OH groups when the hydrolysis or condensation reaction of the present invention proceeds to form a very linear polymer under synthetic conditions, resulting in a stable material and at the same time an excellent membrane. The present invention has been completed by knowing that it produces excellent patterns in processing characteristics and photoresist.

Therefore, according to the present invention, (1) a hydrolyzate produced by reacting at least one of the compounds represented by Formula 1 and Formula 2 with the compound represented by Formula 3, the compound represented by Formula 4, and the compound represented by Formula 5, and Provided is a mixture of an organosilane polymer produced by the polymerization reaction of the hydrolyzate or (2) an organosilane compound comprising the organosilane polymer.

[Formula 1]

[RO] 3Si- (CH2) _l -R '

(R: methyl group or ethyl group, l: 0-5, R ': aromatic group or substituted aromatic group.)

[Formula 2]

[RO] 3Si-R '

(R: methyl group or ethyl group, R ': aromatic group or substituted aromatic group.)

[Formula 3]

R1-Si- (OR2) a (OR3) b (OR4) c

(R1: methyl or ethyl group, R2 to R4 are each 1-4 alkyl groups or phenyl groups, the main chain may be the same or different from each other, a, b, c are each 0 <a ≤ 3, 0 <b ≤ 3, 0 <c≤3 and a + b + c = 3.)

[Formula 4]

[RO] 3Si-H

(R is methyl or ethyl.)

[Formula 5]

[RO] 3Si- (CH2) ₁ C (O) OCH3

(l: 0-5, R is methyl or ethyl.)

In addition, the organosilane-based compound is characterized in that it further comprises an acid catalyst.

The acid catalyst is nitric acid, sulfuric acid, p-toluenesulfonic acid mono hydrate, diethylsulfate, 2,4,4,6-tetrabromocyclo Hexadienone, benzoin tosylate, 2-nitrobenzyl tosylate and an alkyl ester of organic sulfonic acid, characterized in that any one selected from the group consisting of.

The organosilane-based compound may include 5 to 85 parts by weight of any one or more compounds of Formula 1 or Formula 2, 5 to 85 parts by weight of the compound of Formula 3, 5 to 85 parts by weight of the compound of Formula 4, and 5 to 5 parts by weight of the compound of Formula 5. 85 parts by weight of the mixture is characterized in that it is produced.

The organosilane polymer is characterized in that it has a structure of formula (7).

[Formula 7]

(l은 0~5, n은 125~381)

(l is 0 ~ 5, n is 125 ~ 381)

Moreover, according to this invention, the hardmask composition for resist underlayer films which consists of the said organosilane type compound and a solvent is provided.

According to the present invention, there is provided a hard mask composition for a resist underlayer film comprising an organosilane polymer represented by the following formula (7).

[Formula 7]

(l은 0~5, n은 125~381)

(l is 0 ~ 5, n is 125 ~ 381)

The hardmask composition for a resist underlayer film may further include any one or more of a crosslinking agent, a radical stabilizer, and a surfactant.

The hardmask composition further comprises pyridine p-toluenesulfonic acid, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate and organic sulfonic acid It is characterized by comprising any one or more compounds selected from the group consisting of other alkyl esters of.

In addition, the present invention provides a method for preparing a substrate comprising: (a) providing a layer of material on a substrate; (b) forming a hardmask layer of organic material over the material layer; (c) forming an antireflective hardmask layer using the hardmask composition for resist underlayer film over the material layer; (d) forming a radiation-sensitive imaging layer over the antireflective hardmask layer; (e) generating a pattern of radiation-exposed regions within the 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 antireflective hardmask layer to expose portions of the organic-containing hardmask material layer; (g) selectively removing portions of the patterned antireflective hardmask layer and the organic-containing hardmask material layer to expose portions of the material layer; And (h) forming a patterned material shape by etching the exposed portion of the material layer.

The present invention also provides a semiconductor integrated circuit device which is formed by the above manufacturing method.

Hereinafter, the present invention will be described in more detail.

In the present invention, (1) the hydrolyzate and the hydrolyzate produced by reacting at least one of the compounds represented by Formula 1 and Formula 2 with the compound represented by Formula 3, the compound represented by Formula 4, and the compound of Formula 5 Provided is a mixture of an organosilane polymer produced by a polymerization reaction or (2) an organosilane compound comprising the organosilane polymer.

[Formula 1]

[RO] 3Si- (CH2) _l -R '

(R: methyl group or ethyl group, l: 0-5, R ': aromatic group or substituted aromatic group.)

[Formula 2]

[RO] 3Si-R '

(R: methyl group or ethyl group, R ': aromatic group or substituted aromatic group.)

[Formula 3]

R1-Si- (OR2) a (OR3) b (OR4) c

(R1: methyl or ethyl group, R2 to R4 are each 1-4 alkyl groups or phenyl groups, the main chain may be the same or different from each other, a, b, c are each 0 <a ≤ 3, 0 <b ≤ 3, 0 <c≤3 and a + b + c = 3.)

[Formula 4]

[RO] 3Si-H

(R is methyl or ethyl.)

[Formula 5]

[RO] 3 Si- (CH 2) _l C (= O) OCH 3

(l: 0-5, R is methyl or ethyl.)

In the present invention, 5 to 85 parts by weight of any one or more compounds of Formula 1 or Formula 2 and 5 to 85 parts by weight of Compound 3, 5 to 85 parts by weight of Compound 4 and 5 to 85 parts by weight of Compound 5 The organosilane compound produced by reacting the mixture may be provided.

The organosilane-based compound may be provided in the form of an organosilane-based polymer or a mixture of a hydrolyzate and an organosilane-based polymer.

In addition, the organosilane-based compound may include an acid catalyst.

The acid catalyst is nitric acid, sulfuric acid, p-toluenesulfonic acid mono hydrate, diethylsulfate, 2,4,4,6-tetrabromocyclo It is preferably at least one selected from the group consisting of hexadienone, benzoin tosylate, 2-nitrobenzyl tosylate and alkyl esters of organic sulfonic acid. The acid catalyst can appropriately control the hydrolysis or condensation reaction during the synthesis of the resin by adjusting the type, the amount and the addition method.

The aromatic group or substituted aromatic group included in the compound of Formula 1 or Formula 2 provides a material having a high anti-reflective property by utilizing the point of absorption spectrum in the DUV region and at the same time an aromatic group Or by adjusting the concentration ratio of substituted aromatic groups to provide a hardmask composition having the desired absorbance and refractive index at a particular wavelength.

Increasing the relative dose of the compound of Formula 4 may increase the Si content. By controlling the Si content it is possible to impart an etch selectivity between the top photoresist layer and the hard mask layer consisting of the bottom organic material.

The ester group of Formula 5 may show a crosslinking characteristic of itself by performing a transesterification reaction at a high temperature (see Scheme 1) with a Si—OH group.

Scheme 1

Si-OH + Si- (CH2) nC (= O) OCH3 → Si- (CH2) nC (= O) O-Si

 When the compound of Formula 1 or Formula 2 is 10 parts by weight in Scheme 1, a k (absorbance) value of about 193 nm is obtained. Therefore, in order to have appropriate antireflection properties, it is preferable to adjust the relative amount of the compound of Formula 1 or Formula 2.

In the present invention, the structure of the hydrolyzate is preferably represented by the following formula (6).

[Formula 6]

    Ph [CH2] nSi [OH] 3, HSi [OH] 3, CH3Si [OH] 3, (OH) 3Si- (CH2) nC (= O) OCH3

In addition, the structure of the organosilane polymer is preferably represented by the following formula (7).

[Formula 7]

(l은 0~5, n은 125~381)

(l is 0 ~ 5, n is 125 ~ 381)

Further, another aspect of the present invention relates to a composition for resist underlayer film, comprising the organosilane compound and a solvent.

In the present invention, the hard mask composition is a hydrolyzate and an organosilane produced by reacting at least one of the compounds represented by Formula 1 or Formula 2 with the compound represented by Formula 3, the compound represented by Formula 4, and the compound of Formula 5 It is preferable that the organosilane type compound containing a system polymer is 1-50 weight part with respect to the whole composition, More preferably, it is 1-30 weight part.

In addition, the hard mask composition may optionally include only an organosilane polymer obtained by separating the hydrolyzate from the composition including the hydrolyzate and the organosilane-based polymer. Particularly preferred are organosilane polymers of the general formula (7).

    In the present invention, the solvent may be used alone or in combination of two or more, at least one of which uses a high boiling solvent. High boiling solvent prevents voids and improves flatness by drying the film at low speed. Here, "high boiling solvent" means a solvent that volatilizes near a temperature lower than the temperature at the time of coating, drying and curing the invention.

In addition, in the present invention, the hard mask composition further comprises pyridine p-toluenesulfonic acid, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl It may further comprise a compound which is selected from the group consisting of tosylate and other alkyl esters of organic sulfonic acids. The compound serves to promote crosslinking of the resin to improve the etching resistance and solvent resistance.

    In addition, the present invention may further include any one or more of a crosslinking agent, a radical stabilizer, and a surfactant in the hard mask composition as necessary.

(A) providing a layer of material on a substrate; (b) forming a hardmask layer of organic material over the material layer; (c) forming an antireflective hardmask layer using the hardmask composition for resist underlayer film over the material layer; (d) forming a radiation-sensitive imaging layer over the antireflective hardmask layer; (e) generating a pattern of radiation-exposed regions within the 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 antireflective hardmask layer to expose portions of the organic-containing hardmask material layer; (g) selectively removing portions of the patterned antireflective hardmask layer and the organic-containing hardmask material layer to expose portions of the material layer; And (h) forming a patterned material shape by etching the exposed portion of the material layer.

The invention forms patterned material layer structures, such as metal wiring lines, contact holes or vias, insulation sections such as damask trench or shallow trench isolation, trenches for capacitor structures, such as those that may be used in the design of integrated circuit devices. Can be used to The invention is particularly useful with regard to forming patterned layers of oxides, nitrides, polysilicones and chromium.

In addition, the present invention provides a semiconductor integrated circuit device, which is formed by the above manufacturing method.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

[Comparative Example]

1,4-Bis (methoxymethyl) benzene with nitrogen gas flowing into a 1 liter four-necked flask equipped with a mechanical stirrer, a cooling tube, a 300 ml dropping funnel, and a nitrogen gas introduction tube. Stir well with 8.31 g (0.05 mole), 0.154 g (0.001 mole) diethyl sulfate and 200 g of γ-butyrolactone. After 10 minutes, a solution of 28.02 g (0.08 mol) of 4,4 '-(9-fluorenylidene) diphenol in 200 g of γ-butyrolactone was slowly added dropwise for 30 minutes, followed by reaction for 12 hours. . After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. It was then diluted with MAK and methanol and adjusted to a solution of 15 wt% MAK / methanol = 4/1 (weight ratio). The solution was placed in a 3 L separatory funnel, and n-heptane was added thereto to remove the low molecular weight containing the monomer to obtain the desired resin (Mw = 12,000, polydispersity = 2.0, n = 23).

0.8 g of the phenolic resin prepared and 0.2 g of an oligomeric crosslinking agent (Powderlink 1174) consisting of repetition of the following structural units and 2 mg of pyridinium P-toluene sulfonate were dissolved in 9 g of PGMEA, followed by filtration. A solution was made.

Powderlink 1174 structure

The sample was coated on a silicon wafer by spin-coating to bake at 200 ° C. for 60 seconds to form a film having a thickness of 1500 Å.

Example 1

In a 10 liter four-necked flask equipped with a mechanical stirrer, a cooling tube, a dropping funnel and a nitrogen gas introduction tube, 1279 g of methyltrimethoxysilane, 310 g of phenyltrimethoxysilane, and 288 g of trimethoxysilane And 523 g of methyltrimethoxysilylbutyrate were dissolved in 5600 g of PGMEA, and 833 g of an aqueous 1000 ppm nitric acid solution was added to the solution. Thereafter, the reaction was carried out at 60 ° C. for 1 hour, and then negative pressure was applied to remove the generated methanol. The reaction was run for 1 week while maintaining the reaction temperature at 50 ° C. After the reaction, hexanes were added to separate the produced solids, thereby obtaining a polymer having Mw (weight average molecular weight) = 23,000 and polydispersity = 4.6. 10 g of this solid was dissolved in 100 g of PGMEA and 100 g of ethyl lactate to make a solution.

The sample was coated on a silicon wafer by spin-coating to bake at 200 ° C. for 60 seconds to form a film having a thickness of 600 μs.

The refractive index n and extinction coefficient k of the films prepared in Comparative Example and Example 1 were obtained. The instrument used was Ellipsometer (J. A. Woollam) and the measurement results are shown in Table 1.

delete

Sample used to make film Optical properties (193nm) Optical properties (248nm) n (refractive index) k (absorption coefficient) n (refractive index) k (absorption coefficient) Comparative example 1.44 0.70 2.02 0.27 Example 1 1.72 0.20 1.53 0.00

Example 2

The ArF photoresist was coated on the wafer prepared in Comparative Example and Example 1, baked at 110 ° C. for 60 seconds, exposed using an ArF exposure apparatus ASML1250 (FN70 5.0 active, NA 0.82), and then exposed to TMAH (2.38 wt% aqueous solution). Developed. And using a FE-SEM to examine the line and space (line and space) pattern of 80nm as shown in Table 2 below. The exposure latitude (EL) margin according to the change of the exposure dose and the depth of focus (DoF) margin according to the distance change with the light source are considered and recorded in Table 2.

Sample used to make film Pattern EL margin (△ mJ / exposure energy mJ) DoF margin (μm) Comparative example 0.2 0.2 Example 2 0.2 0.2

The patterned specimens of Table 2 CHF ₃ / CF ₄ with a mixed gas proceeds to dry etching, and then proceeds to dry etching again using a CHF ₃ / CF ₄ gas mixture containing oxygen, and then, CHF ₃ / Dry etching was again performed using a CF ₄ mixed gas. Finally, after removing all remaining organics using O ₂ gas, the cross section was examined by FE SEM and the results are listed in Table 3.

Sample used to make film Pattern shape after etching Comparative example Tapered shape, rough surface Example 2 Vertical shape

Resist excellent in pattern reproducibility, good adhesion with resist, excellent resistance to developing film used after exposing resist and low film reduction during plasma etching using organosilane compound according to the present invention The composition for underlayer film can be provided.

Claims (11)

     (1) Hydrolyzate and polymerization of the hydrolyzate produced by reacting at least one of the compounds represented by Formula 1 and Formula 2 with the compound represented by Formula 3, the compound represented by Formula 4, and the compound represented by Formula 5 A mixture of an organosilane polymer produced by the reaction or (2) an organosilane compound comprising the organosilane polymer. [Formula 1] [RO] 3Si- (CH2) _l -R ' (R: methyl group or ethyl group, l: 0-5, R ': aromatic group or substituted aromatic group.) [Formula 2] [RO] 3Si-R ' (R: methyl group or ethyl group, R ': aromatic group or substituted aromatic group.) [Formula 3] R1-Si- (OR2) a (OR3) b (OR4) c (R1: methyl or ethyl group, R2 to R4 are each 1-4 alkyl groups or phenyl groups, the main chain may be the same or different from each other, a, b, c are each 0 <a ≤ 3, 0 <b ≤ 3, 0 <c≤3 and a + b + c = 3.) [Formula 4] [RO] 3Si-H (R is methyl or ethyl.) [Formula 5] [RO] 3 Si- (CH 2) _l C (= O) OCH 3 (l: 0-5, R is methyl or ethyl.)    According to claim 1, wherein any one or more of the compounds represented by Formula 1 and Formula 2 and the compound represented by Formula 3, the compound represented by Formula 4 and the compound represented by Formula 5 are produced by reacting in the presence of an acid catalyst An organosilane compound, characterized in that. The method of claim 2, wherein the acid catalyst is nitric acid (sulfuric acid), sulfuric acid (sulfuric acid), p-toluenesulfonic acid mono hydrate (p-toluenesulfonic acid mono hydrate), diethylsulfate (diethylsulfate), 2,4,4, An organosilane-based compound, which is at least one selected from the group consisting of 6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acid. According to claim 1, wherein the organosilane compound is 5 to 85 parts by weight of any one or more of the compound of Formula 1 or Formula 2, 5 to 85 parts by weight of the compound of Formula 3, 5 to 85 parts by weight of the compound of Formula 4 and An organosilane compound, which is produced by reacting a mixture of 5 to 85 parts by weight of a compound of Formula 5. The method of claim 1, wherein the organosilane-based polymer is 5 to 85 parts by weight of any one or more of the compound of Formula 1 or Formula 2 and 5 to 85 parts by weight of the compound of Formula 3, 5 to 85 of the compound of Formula 4 An organosilane compound, which is produced by reacting 5 parts by weight to 85 parts by weight of the compound of Formula 5, and has the structure of Formula 7. [Formula 7]

(l is 0 ~ 5, n is 125 ~ 381) A hard mask composition for a resist underlayer film comprising the organosilane compound according to claim 1 and a solvent. A mixture of 5 to 85 parts by weight of any one or more compounds of Formula 1 or Formula 2, 5 to 85 parts by weight of the compound of Formula 3, 5 to 85 parts by weight of the compound of Formula 4 and 5 to 85 parts by weight of the compound of Formula 5 Hardmask composition for a resist underlayer film comprising an organosilane-based polymer of the formula (7) generated by. [Formula 1] [RO] 3Si- (CH2) _l -R ' (R: methyl group or ethyl group, l: 0-5, R ': aromatic group or substituted aromatic group.) [Formula 2] [RO] 3Si-R ' (R: methyl group or ethyl group, R ': aromatic group or substituted aromatic group.) [Formula 3] R1-Si- (OR2) a (OR3) b (OR4) c (R1: methyl or ethyl group, R2 to R4 are each 1-4 alkyl groups or phenyl groups, the main chain may be the same or different from each other, a, b, c are each 0 <a ≤ 3, 0 <b ≤ 3, 0 <c≤3 and a + b + c = 3.) [Formula 4] [RO] 3Si-H (R is methyl or ethyl.) [Formula 5] [RO] 3 Si- (CH 2) _l C (= O) OCH 3 (l: 0-5, R is methyl or ethyl.) [Formula 7]

(l is 0 ~ 5, n is 125 ~ 381) The hard mask composition for a resist underlayer film of claim 6, wherein the hard mask composition further comprises at least one of a crosslinking agent, a radical stabilizer, and a surfactant. 7. The method of claim 6, wherein the hard mask composition further comprises pyridine p-toluenesulfonic acid, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitro A hard mask composition for a resist underlayer film comprising at least one compound selected from the group consisting of benzyl tosylate and other alkyl esters of organic sulfonic acid. (a) providing a layer of material on the substrate; (b) forming a hardmask layer of organic material over the material layer; (c) forming an antireflective hardmask layer using the hardmask composition for a resist underlayer film according to any one of claims 6 to 9 over the material layer; (d) forming a radiation-sensitive imaging layer over the antireflective hardmask layer; (e) generating a pattern of radiation-exposed regions within the 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 antireflective hardmask layer to expose portions of the organic-containing hardmask material layer; (g) selectively removing portions of the patterned antireflective hardmask layer and the organic-containing hardmask material layer to expose portions of the material layer; And (h) forming a patterned material shape by etching the exposed portion of the material layer. A semiconductor integrated circuit device formed by the manufacturing method of claim 10.