KR100930674B1 - Coating compositions for gap-filling, process of producing capacitorthereof - Google Patents

Abstract

PURPOSE: A compound for applying and filling micro gap in a node separation process is provided to prevent defect such as air void and enables wet etch of hole inner material. CONSTITUTION: A compound for filling gap denoted by the chemical formula 6({{SiO1.5[CH2]l[(CH2)mO]nR2}a(SiO1.5X)b(SiO1.5R4)c(SiO1.5-Y-SiO1.5)d}p(OR7)q) is prepared by condensing a condensation polymer of hydrolysates generated from one or more compound(b) among a compound of the chemical formula 1([R1]3Si-[CH2]l[(CH2)mO]nR2), a compound of the chemical formula 2([R1]3Si-X), a compound of the chemical formula 3([R1]3Si-R4) and a compound of the chemical formula 4([R1]3Si-Y-Si[R5]3) with a compound of the chemical formula 5(R63Si-R1). A composition for applying semiconductor and filling micro gap contains the compound of the chemical formula 6 and 100-10,000 weight parts of solvent per 100 weight parts of the compound of the chemical formula 6. The solvent is alcohols, acetates, esters, glymes, ethers or carboxy ketones.

Description

Compound for coating semiconductor and fine gap fill, composition comprising the same and method for manufacturing semiconductor capacitor using same {Coating Compositions for Gap-filling, Process of Producing Capacitorthereof}

The present invention relates to a compound for semiconductor coating and fine gap fill, and a composition for semiconductor coating and fine gap fill using the same.

It is important that the composition for semiconductor coating and fine gap fill of this invention has the following characteristics. That is, (1) it is possible to completely fill a hole having an aspect ratio of 1 or more and a diameter of 70 nm or less by the general spin coating, and to planarize the substrate to a certain thickness, and (2) to fill in the hole. There should be no air voids or gaps in the film, (3) the thickness of the film after coating should be constant regardless of whether the holes on the substrate are dense, and (4) the planarized film is used for treatment of aqueous ammonium solution after thermal curing. It should be able to be removed to the desired thickness by (5) It should be able to be removed at the desired speed without leaving any residue inside the hole by treatment with hydrofluoric acid solution after the process (4), (6) Excellent storage stability of the composition It is necessary to satisfy such conditions.

Conventionally, a composition containing a carbon-based polymer is used for semiconductor application and a fine gap fill, but as the size of the hole decreases to 70 nm or less as the semiconductor device becomes finer, the existing carbon-based polymer is used. When used, the surface of the hole is roughened at the last ashing step of removing the carbon-based polymer, which makes it difficult to apply the dielectric material, which is a subsequent process.

Accordingly, there is a need for a new composition capable of simultaneously eliminating the semiconductor coating fine gap fill material in the wet etching step with an aqueous hydrofluoric acid solution to remove the oxide of the hole pattern while omitting the ashing step.

The present invention enables the surface stripping by ammonium aqueous solution treatment and the etch of materials inside the hole by hydrofluoric acid solution treatment after curing by baking, the compound which can control the speed thereof, and the semiconductor coating and fine gap fill using the same. It is an object to provide a composition.

The present invention is a compound (a) represented by the formula (1); And a condensate of hydrolyzates produced from at least one compound (b) selected from the group consisting of a compound represented by Formula 2, a compound represented by Formula 3 below, and a compound represented by Formula 4 below: The compound which condensed the compound which becomes is provided.

[R ¹ ] ₃ Si- [CH ₂ ] _l [(CH ₂ ) _m O] _n R ²

(R ¹ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; l is 1 to 6; m is 1 to 5; n is 2 to 12; R ² is an alkyl group having 1 to 6 carbon atoms; Me represents a methyl group and Et represents an ethyl group.

[R ¹ ] ₃ Si-X

(R ¹ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; X is a C6-C30 functional group containing a substituted or unsubstituted aromatic ring)

[R ¹ ] ₃ Si-R ⁴

(R ¹ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; R ⁴ is H or an alkyl group having 1 to 6 carbon atoms)

[R ¹ ] ₃ Si-Y-Si [R ⁵ ] ₃

(R ¹ And R ⁵ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; Y may include an aromatic ring, a linear or branched substituted or unsubstituted alkylene group, an alkylene group having an aromatic ring or a hetero ring, a urea group or an isocyanurate group or a multiple bond in the main chain Hydrocarbon group)

R ⁶ ₃ Si-R ¹

(R ¹ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; R ⁶ is an alkyl group having 1 to 6 carbon atoms)

As an example of the compound for semiconductor coating and fine gap fill, there may be mentioned a compound represented by the following formula (6).

{{SiO _1.5 [CH ₂ ] _l [(CH ₂ ) _m O] _n R ² } _a (SiO _1.5 X) _b (SiO _1.5 R ⁴ ) _c (SiO _1.5 -Y-SiO _1.5 ) _d } _p (OR ⁷ ) _q

(R ¹ And R ⁵ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; l is 1 to 6; m is 1 to 5; n is 2 to 12; R ² is an alkyl group having 1 to 6 carbon atoms; X is a C6-C30 functional group containing a substituted or unsubstituted aromatic ring; R ⁴ is H or an alkyl group having 1 to 6 carbon atoms; Y may include an aromatic ring, a linear or branched substituted or unsubstituted alkylene group, an alkylene group having an aromatic ring or a hetero ring, a urea group or an isocyanurate group or a multiple bond in the main chain A hydrocarbon group; R ⁷ is H, R ³ Or SiR ⁶ ₃ ; R ⁶ is an alkyl group having 1 to 6 carbon atoms; a + b + c + d = 1, 0.05≤a≤0.90, 0.00≤b≤0.50, 0.00≤c, d≤0.95 (except when b = c = d = 0), p is 5 to 200 , q is from 5 to 500, where p is the number of main chain repeating units, q is -OR ⁷ Represents the number of end groups, a, b, c d and, respectively _{{SiO 1 .5 [CH 2]} l [(CH 2) m O] n R 2}, (SiO 1 .5 X), (SiO 1 _.5 R ^4), and (representing the ratio of the _{SiO 1 .5 -Y-SiO 1 .5} ) each main chain repeat units)

In addition, another aspect of the present invention relates to a composition for semiconductor coating and fine gap fill, the compound represented by the following formula (1) and the compound represented by the formula (2) and the compound represented by the formula (3) And a compound and a solvent obtained by condensation of a compound represented by the formula (5) with a condensate of hydrolyzates produced from at least one compound (b) selected from the group consisting of compounds represented.

The composition may further comprise any one or more of a crosslinking component, a crosslinking acid catalyst, a stabilizer or a surfactant.

The present invention provides a semiconductor coating and a fine gapfill composition capable of complete gap-filling without defects such as air voids by spin coating a semiconductor substrate having a hole having a diameter of 70 nm or less and an aspect ratio of 1 or more. .

In addition, according to the composition of the present invention, the residue in the hole can be cleanly removed during the treatment of aqueous ammonium solution and hydrofluoric acid solution after curing, and at the same time, the speed thereof can be controlled.

Moreover, the composition of this invention is excellent in storage stability, and is very suitable for manufacture of a semiconductor device.

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

Compound for coating a semiconductor and fine gap fill of the present invention is an acid or a base catalyst, Compound (a) represented by the formula (1); And 100 parts by weight of the compound represented by Formula 2, the compound represented by Formula 3, and the compound represented by Formula 4 and at least one compound (b) selected from the group consisting of Formula 4, Formula 1 5 to 95 parts by weight of the compound represented by the formula, 0 to 50 parts by weight of the compound represented by the formula (2), 0 to 95 parts by weight of the compound represented by the formula (3), hydrolysis of 0 to 95 parts by weight of the compound represented by the formula (4) And a condensation polymerization reaction, followed by condensation of the condensation polymer with 0.01 to 50 parts by weight of the compound represented by Formula 5 during or after the condensation polymerization reaction.

In the present invention, the acid catalyst is hydrofluoric acid, hydrochloric acid, bromic acid, iodic acid, nitric acid, sulfuric acid, p-toluenesulfonic acid mono hydrate, diethylsulfate, It is preferably at least one selected from the group consisting of 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acid.

The base catalyst is preferably one or more selected from the group consisting of triethylamine, diethylamine, ammonia, sodium hydroxide, potassium hydroxide and pyridine.

The acid catalyst or base catalyst may be suitably controlled to control the hydrolysis or condensation reaction during the semiconductor coating and synthesis of the fine gap fill compound by adjusting the type, the amount and the method of adding the acid catalyst.

The acid catalyst or the base catalyst in the reaction, the compound represented by the formula (1); And 0.001 to 5 weights based on 100 parts by weight of the sum of the compound represented by Formula 2, the compound represented by Formula 3, and the at least one compound (b) selected from the group consisting of the compound represented by Formula 4. Can be used as a wealth.

In addition, during the hydrolysis or condensation reaction, the solvent may be used in an amount of 100 to 900 parts by weight.

The semiconductor coating and fine gap fill compound is characterized in that it has a weight average molecular weight of 1,000 to 50,000. More preferably, it has a weight average molecular weight of 2,000-30,000. If the weight average molecular weight is less than 1,000, the coating property is poor, and if the weight average molecular weight exceeds 50,000, gap-fill characteristics such as voids are reduced.

The semiconductor coating and fine gap fill compound includes a hydrophilic portion derived from the compound represented by Formula 1 and a hydrophobic portion at the end of the condensation polymer produced by the compound represented by Formula 5. At this time, by adjusting the ratio of the compound represented by the formula (1) and the compound represented by the formula (5), it is possible to control the coating property, peeling rate, wet etch rate and storage stability required in the composition for semiconductor coating and fine gap fill. That is, as the amount of the compound represented by Chemical Formula 1 increases, the hydrophilicity is increased, so that the peeling rate and the wet etch rate are increased.

Compound (a) represented by Formula 1; And 100 parts by weight of the compound represented by Formula 2, the compound represented by Formula 3, and the compound represented by Formula 4 and at least one compound (b) selected from the group consisting of Formula 4, Formula 1 The compound represented by is preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight. When used in less than 5 parts by weight there is a problem in expressing hydrophilicity in the polymer, when used in excess of 95 parts by weight there is a problem in coating properties.

In addition, the compound represented by the formula (5) increases the storage stability, it is not preferable to include more than 50 parts by weight since it greatly increases the hydrophobicity. If the hydrophobicity is greatly increased, the peeling rate and the wet etch rate may be reduced or the coating may be defective.

On the other hand, the compounds represented by Formula 2, Formula 3 and Formula 4 serve to maintain the skeleton of the condensation polymer.

In addition, another aspect of the present invention relates to a composition for semiconductor coating fine gap fill, comprising the compound and a solvent for the semiconductor coating fine gap fill.

In the present invention, the semiconductor coating fine gap fill composition is preferably 1 to 60 parts by weight, more preferably 5 to 30 parts by weight based on the total composition of the semiconductor coating fine gap fill compound.

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

The solvent may be selected from the group consisting of alcohols, acetates, esters, glymes, ethers and carboxy ketones. As a specific example, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, ethyl-3-ethoxy propionate, methyl-3-methoxy propionate, cyclopentanone, cyclohexanone, propylene glycol mono Preference is given to using those selected from the group consisting of methyl ether acetate, propylene glycol dimethyl ether acetate, 1-methoxy-2-propanol, ethyl lactate, cyclopentanone, ethyl hydroxy acetate and the like. These solvents may be used alone or in combination of two or more thereof.

The compound for semiconductor-coated fine gap fill included in the composition of the present invention may be cured by self-crosslinking during baking. That is, the coating coating film can be formed only by baking without a separate crosslinking component. However, in the case of additionally including a crosslinking component, an improved effect on the crosslinking reaction can be expected.

As the crosslinking component that may be included in the composition of the present invention, a melamine-based, substituted urea-based, polymer-containing epoxy group or a compound derived therefrom may be used, but is not limited thereto. The crosslinking component in the semiconductor coating fine gap fill composition may be included in an amount of 0.1 to 30 parts by weight per 100 parts by weight of the semiconductor coating and fine gap fill compound.

The crosslinking component included in the composition of the present invention is activated by a crosslinking acid catalyst. Therefore, it is preferable that the composition of this invention contains a crosslinking acid catalyst with a crosslinking component. The crosslinking acid catalyst may include inorganic acid, sulfonic acid, oxalic acid, maleic acid, hexamic cyclohexylsulfonic acid, phthalic acid, and salts thereof. Any one or more selected from the group consisting of can be used. The acid catalyst may be included in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the semiconductor coating fine gap fill compound.

On the other hand, in the composition for a gap fill for semiconductors of the present invention in order to improve the dispersibility, film thickness uniformity and semiconductor coating and fine gap fill characteristics in addition to the above-described semiconductor coating and fine gap fill compound, crosslinking component, crosslinking acid catalyst and solvent. Surfactants may be added. As said surfactant, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, or polyoxyethylene oleyl ether; Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonyl phenol ether; polyoxyethylene polyoxypropylene block copolymers; Sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate or polyoxyethylene sorbitan tristearate Nonionic surfactants, such as polyoxyethylene sorbitan fatty acid ester, such as F-top EF301, EF303, EF352 (made by Tochem Products), Megapack F171, F173 (made by Dainippon Ink), Prorad Fluorine-based surfactants such as FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.) or Asahigard AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.); Silicone surfactant, such as organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), is mentioned.

It is preferable to add the said surfactant in the ratio of 0.001-10 weight part per 100 weight part of total solid content of the composition of this invention. These surfactants may be added alone or in combination of two or more kinds.

The present invention also includes forming an oxide mold (pattern oxide) on a semiconductor substrate to form patterned holes; Depositing an electrode material on the oxide mold (pattern oxide); Gap-filling the patterned hole in which the electrode material is deposited with the composition for semiconductor application and fine gap fill of the present invention; Developing with a developing solution such as an aqueous ammonium solution and the like to remove and bake the composition coated on the upper end of the electrode material; Etching back the upper end of the electrode material and removing the electrode material; And wet-etching to simultaneously remove the remaining material of the composition filled in the patterned oxide and the patterned hole to form a lower electrode to form a lower electrode. To provide.

In the wet etching process, any material having both an oxide and a solubility in the composition of the present invention may be used, but it is preferable to proceed using an aqueous hydrofluoric acid solution. Ti / TiN may be used as the electrode material.

After the lower electrode is formed through the above process, a dielectric layer may be formed, and then an upper electrode may be formed on the upper portion thereof to complete a semiconductor capacitor.

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

Comparative Example 1

In a 2-liter four-necked flask equipped with a mechanical stirrer, a cooling tube, a dropping funnel, and a nitrogen gas introduction tube, 25 g of phenyltrimethoxysilane and 275 g of methyltrimethoxysilane were propylene glycol monomethyl ether. After dissolving in 700 g of acetate, 80 g of 1000 ppm nitric acid aqueous solution was added to the solution. The reaction was run for one week while maintaining the reaction temperature at 60 degrees. The reaction was terminated to obtain Polymer A1 (weight average molecular weight = 6,500, polydispersity (PD) = 2). 10 g of the polymer A1 was added to 100 g of propylene glycol monomethyl ether acetate, and sufficiently stirred to prepare a fine gap fill composition for a semiconductor.

Comparative Example 2

10 g of the polymer A1 obtained in Comparative Example 1 was added to 100 g of propylene glycol monomethyl ether acetate, and further stirred with 1 g of hexamethyldisiloxane to prepare a fine gap fill composition for a semiconductor.

Comparative Example 3

2-methoxypolyethyleneoxypropyltrimethoxysilane (2- [Methoxy (polyethyleneoxy) propyl] trimethoxysilane, manufactured by Gelest) in a 3 L four-necked flask equipped with a mechanical stirrer, cooling tube, dropping funnel, and nitrogen gas introduction tube 25 g and 575 g of methyltrimethoxysilane were dissolved in 1400 g of propylene glycol monomethyl ether acetate, and then 149 g of an aqueous 2000 ppm nitric acid solution was added to the solution. The reaction was run for one week while maintaining the reaction temperature at 60 degrees. The reaction was terminated to obtain polymer B1 (weight average molecular weight = 5,500, polydispersity (PD) = 2). 10 g of the polymer B1 was added to 100 g of propylene glycol monomethyl ether acetate, and sufficiently stirred to prepare a fine gap fill composition for a semiconductor.

Comparative Example 4

10 g of the polymer B1 obtained in Comparative Example 3 was placed in 100 g of propylene glycol monomethyl ether acetate, and further stirred with 1 g of hexamethyldisiloxane to prepare a fine gap fill composition for a semiconductor.

Comparative Example 5

2-methoxypolyethyleneoxypropyltrimethoxysilane (2- [Methoxy (polyethyleneoxy) propyl] trimethoxysilane, manufactured by Gelest) in a 3 L four-necked flask equipped with a mechanical stirrer, cooling tube, dropping funnel, and nitrogen gas introduction tube 301 g and 220 g of methyltrimethoxysilane were dissolved in 1400 g of propylene glycol monomethyl ether acetate, and then 100 g of 2000 ppm nitric acid solution was added to the solution. The reaction was run for 1 week while maintaining the reaction temperature at 70 degrees. The reaction was terminated and polymer C1 (weight average molecular weight = 5,000, polydispersity (PD) = 2) was obtained. 10 g of polymer C1 was added to 100 g of propylene glycol monomethyl ether acetate, followed by stirring sufficiently to prepare a fine gap fill composition for a semiconductor.

Example 1

10 g of the polymer C1 obtained in Comparative Example 5 was added to 100 g of propylene glycol monomethyl ether acetate, and further stirred with 1 g of hexamethyldisiloxane to prepare a fine gap fill composition for a semiconductor.

Comparative Example 6

2-methoxypolyethyleneoxypropyltrimethoxysilane (2- [Methoxy (polyethyleneoxy) propyl] trimethoxysilane, manufactured by Gelest) in a 3 L four-necked flask equipped with a mechanical stirrer, cooling tube, dropping funnel, and nitrogen gas introduction tube 558 g and 40 g of bistriethoxysilyl methane (Shin-Etsu Co., Ltd.) were dissolved in 1400 g of propylene glycol monomethyl ether acetate, and then 50 g of 2000 ppm nitric acid solution was added to the solution. The reaction was run for 1 week while maintaining the reaction temperature at 70 degrees. The reaction was terminated and polymer D1 (weight average molecular weight = 6,000, polydispersity (PD) = 2) was obtained. 10 g of polymer D1 was added to 100 g of propylene glycol monomethyl ether acetate, and the mixture was sufficiently stirred to prepare a fine gap fill composition for a semiconductor.

Example 2

10 g of the polymer D1 obtained in Comparative Example 6 was placed in 100 g of propylene glycol monomethyl ether acetate, and further stirred with 1 g of hexamethyldisiloxane to prepare a fine gap fill composition for a semiconductor.

Comparative Example 7

2-methoxypolyethyleneoxypropyltrimethoxysilane (2- [Methoxy (polyethyleneoxy) propyl] trimethoxysilane, Gelest Co., Ltd. 1) 270 g, bis (triethoxysilyl) methane (100 g) and 400 g of methyltrimethoxysilane were dissolved in 1400 g of propylene glycol monomethyl ether acetate, and 130 g of 2000 ppm nitric acid solution was dissolved in the solution. Added. The reaction was run for one week while maintaining the reaction temperature at 60 degrees. The reaction was terminated to obtain polymer E1 (weight average molecular weight = 7,000, polydispersity (PD) = 2). 10 g of the polymer E1 was added to 100 g of propylene glycol monomethyl ether acetate, and sufficiently stirred to prepare a fine gap fill composition for a semiconductor.

Example 3

10 g of the polymer E1 obtained in Comparative Example 7 was added to 100 g of propylene glycol monomethyl ether acetate, and further stirred with 1 g of hexamethyldisiloxane to prepare a fine gap fill composition for a semiconductor.

For the fine gap fill composition for semiconductors in the above Examples and Comparative Examples, the gap fill characteristics, the peeling rate to the aqueous ammonium solution, the removal rate and the removal performance by the aqueous hydrofluoric acid solution, and the storage stability (molecular weight change, coating) were as follows. Thickness change) and the results are shown in Table 1 below.

(1) gap fill characteristics

After spin-coating a silicon pattern wafer having a hole of 68 nm in diameter and a height of 1600 nm under the same coating conditions, baking at 160 ° C. for 50 seconds to cure, the cross section of the wafer was observed with a scanning electron microscope. It was confirmed that the composition filled in the hole was completely filled without defects such as voids.

(2) Peeling rate by aqueous ammonium solution

A silicon pattern wafer having a diameter of 68 nm and a hole having a height of 1600 nm was spin-coated under the same coating conditions, baked and cured at 160 ° C. for 50 seconds, immersed in an aqueous ammonium solution for 1 minute, washed with distilled water, and sufficiently dried. Then, the cross section of the wafer was observed with a scanning electron microscope, and compared with the height of the composition remaining from the bottom, it was determined that the lower the height, the faster the removal rate by the aqueous ammonium solution.

(3) Removal performance by hydrofluoric acid aqueous solution

Spin-coated a silicon pattern wafer having a hole of 68 nm in diameter and a height of 1600 nm under the same coating conditions, baked and cured at 180 ° C. for 50 seconds. Washed and dried well. Then, the cross section of the wafer was observed with a scanning electron microscope, and it was confirmed whether the composition filled in the hole remained. At this time, the hydrofluoric acid solution concentration was 6.6%, and the temperature was 23.0 ° C.

(4) Storage stability (molecular weight change)

Samples stored at 40 ° C. for 30 days were prepared, the respective molecular weights were measured, and compared with the molecular weights measured immediately after preparation. .

(5) Storage stability (film thickness change)

Samples stored at 40 ° C. for 30 days were prepared, spin coated on 8 inch silicon wafers under the same coating conditions, and baked at 160 ° C. for 50 seconds to form a coating film. When the film thicknesses were measured and compared with the film thicknesses measured immediately after the manufacture, the cases where the difference in film thickness was within 5% were evaluated as good and the case when the film thickness was exceeded by 5% was poor.

According to the above table, the composition of the present invention has a diameter of 70 nm or less, and a perfect gap fill is formed on a semiconductor substrate having a hole having an aspect ratio of 1 or more, without defects such as air voids, by spin coating. After curing by baking, it was possible to control the speed and remove the residues inside the hole without any residue by treating with aqueous ammonium solution and hydrofluoric acid solution. It was also confirmed that the storage stability was excellent.

This node separation material is particularly useful for the manufacture of capacitor electrodes, and wet-etched simultaneously in hydrofluoric acid solution used to remove silicon oxide for pattern after gap-filling patterned holes. This is a new concept material that can omit the ashing step.

Claims (14)

Compound (a) represented by the following formula (1); And a condensate of hydrolyzates produced from at least one compound (b) selected from the group consisting of a compound represented by Formula 2, a compound represented by Formula 3 below, and a compound represented by Formula 4 below: A compound characterized by condensation with the compound represented. [Formula 1] [R ¹ ] ₃ Si- [CH ₂ ] _l [(CH ₂ ) _m O] _n R ² (R ¹ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; l is 1 to 6; m is 1 to 5; n is 2 to 12; R ² is an alkyl group having 1 to 6 carbon atoms) [Formula 2] [R ¹ ] ₃ Si-X (R ¹ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; X is a C6-C30 functional group containing a substituted or unsubstituted aromatic ring) [Formula 3] [R ¹ ] ₃ Si-R ⁴ (R ¹ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; R ⁴ is H or an alkyl group having 1 to 6 carbon atoms) [Formula 4] [R ¹ ] ₃ Si-Y-Si [R ⁵ ] ₃ (R ¹ And R ⁵ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; Y may include an aromatic ring, a linear or branched substituted or unsubstituted alkylene group, an alkylene group having an aromatic ring or a hetero ring, a urea group or an isocyanurate group or a multiple bond in the main chain Hydrocarbon group) [Formula 5] R ⁶ ₃ Si-R ¹ (R ¹ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; R ⁶ is an alkyl group having 1 to 6 carbon atoms) The compound of claim 1, wherein the compound is represented by Chemical Formula 1 under an acid or base catalyst; And 100 parts by weight of the sum of the compound represented by Formula 2, the compound represented by Formula 3, and the at least one compound selected from the group consisting of the compound represented by Formula 4, 5 to 95 parts by weight of the compound represented by Formula 1, 0 to 50 parts by weight of the compound represented by Formula 2, 0 to 95 parts by weight of the compound represented by Formula 3, 0 to 95 parts by weight of the compound represented by Formula 4 Hydrolysis and polycondensation reaction Compounds, characterized in that prepared by condensation of the condensation polymer to 0.01 to 50 parts by weight of the compound represented by the formula (5) during or after the condensation polymerization reaction. The compound of claim 1, wherein the compound is represented by the following Chemical Formula 6. [Formula 6] _{{{SiO 1 .5 [CH 2} ] l [(CH 2) m O] n R 2} a (SiO 1 .5 X) b (SiO 1 .5 R 4) c (SiO 1 .5 -Y-SiO _{1 .5} ) _d } _p (OR ⁷ ) _q (R ¹ And R ⁵ is halogen, OH, OR ³ (R ³ is an alkyl group having 1 to 6 carbon atoms), O ₂ CCH ₃ , CN, O ₃ SCF ₃ , NSiMe ₃ , OSiMe ₃ , NEt ₂ Or NMe ₂ ; l is 1 to 6; m is 1 to 5; n is 2 to 12; R ² is an alkyl group having 1 to 6 carbon atoms; X is a C6-C30 functional group containing a substituted or unsubstituted aromatic ring; R ⁴ is H or an alkyl group having 1 to 6 carbon atoms; Y may include an aromatic ring, a linear or branched substituted or unsubstituted alkylene group, an alkylene group having an aromatic ring or a hetero ring, a urea group or an isocyanurate group or a multiple bond in the main chain A hydrocarbon group; R ⁷ is H, R ³ or SiR ⁶ ₃ ; R ⁶ is an alkyl group having 1 to 6 carbon atoms; a + b + c + d = 1, 0.05 ≦ a ≦ 0.90, 0.00 ≦ b ≦ 0.50, 0.00 ≦ c, d ≦ 0.95, p is 5 to 200, q is 5 to 500, where p is the number of main chain repeating units And q is -OR ⁷ Represents the number of end groups, a, b, c and d are each _{{SiO 1 .5 [CH 2]} l [(CH 2) m O] n R 2}, (SiO 1 .5 X), (SiO 1 _.5 R ^4), and (representing the ratio of the _{SiO 1 .5 -Y-SiO 1 .5} ) each main chain repeat units) The compound of claim 1 having a weight average molecular weight of 1,000 to 50,000. The composition of claim 1 and 100 to 10,000 parts by weight of the solvent per 100 parts by weight of the compound of claim 1 comprising a semiconductor coating and fine gap fill composition. 6. The composition of claim 5, wherein the solvent is at least one selected from the group consisting of alcohols, acetates, esters, glymes, ethers, and carboxy ketones. The composition for semiconductor application and fine gap fill according to claim 5, wherein the composition further contains a surfactant. 6. The composition for semiconductor application and fine gap fill according to claim 5, wherein the composition further contains a crosslinking component alone or a mixture of a crosslinking acid catalyst and a crosslinking component. The composition of claim 8, wherein the crosslinking component is selected from melamine-based, substituted urea-based, epoxy-containing polymers and derivatives thereof. The composition of claim 8, wherein the crosslinking component is included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the compound of claim 1. The method of claim 8, wherein the cross-linking acid catalyst is a mineral acid (mineral acid), sulfonic acid (sulfonic acid), oxalic acid (oxalic acid), maleic acid (maleic acid), hexamic cyclohexylsulfonic acid (hexamic cyclohexylsulfonic acid), phthalic acid (phthalic acid) And at least one selected from the group consisting of salts thereof. The composition of claim 8, wherein the crosslinking acid catalyst is included in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the compound of claim 1. Forming an oxide mold (pattern oxide) on the semiconductor substrate to form patterned holes; Depositing an electrode material on the oxide mold (pattern oxide); Filling the patterned hole in which the electrode material is deposited with the composition for semiconductor fine gap fill according to any one of claims 5 to 12; Developing with a developer to remove and bake the composition coated on the upper electrode material; Etching away the upper electrode material; And And wet-etching to simultaneously remove residual material of the composition filled in the patterned oxide and the patterned hole to form a lower electrode. The method of manufacturing a semiconductor capacitor according to claim 13, wherein the method is wet etched using an aqueous hydrofluoric acid solution.