KR101023916B1 - Siloxane-based Resin using Molecular Polyhedral Silsesquioxane and Method for forming Dielectric Film using the Same - Google Patents

Abstract

The present invention relates to a method for forming a semiconductor interlayer insulating film using a molecular polyhedral silsesquioxane, and more particularly, using a molecular polyhedral silsesquioxane as a monomer of a siloxane resin or a molecular polyhedral silsesquioxane The present invention relates to a method for preparing an insulating film forming composition using itself as a pore-forming material, and then to forming an insulating film using the same. The method of the present invention can provide a semiconductor interlayer insulating film having excellent low dielectric properties and mechanical properties. have.

Molecular polyhedral silsesquioxane, siloxane resin, semiconductor interlayer insulation film, low dielectric, modulus, hardness

Description

Siloxane-based Resin using Molecular Polyhedral Silsesquioxane and Method for forming Dielectric Film using the Same}             

1 is a view showing a problem appearing when forming a porous thin film according to the prior art, Figure 2 is a view showing the structure of an insulating film formed by the present invention.

The present invention relates to a method for forming a semiconductor interlayer insulating film using a molecular polyhedral silsesquioxane, and more particularly, using the molecular polyhedral silsesquioxane of the present invention as a monomer of a siloxane resin or a molecular polyhedral seal The present invention relates to a method of preparing an insulating film-forming composition using sesquioxane itself as a pore-forming material, and to forming an insulating film using the same. According to the method of the present invention, the molecular polyhedral silsesquioxane itself forms internal pores. Since it has a low dielectric constant, it is possible to introduce a variety of reactors, it is possible to induce high mechanical properties through the control of the reactor.

As the degree of integration of semiconductors increases, the performance of the device depends on the wiring speed, and in order to reduce the resistance and the capacitance in the wiring, it is required to lower the storage capacitance of the interlayer insulating film. Specifically, in US Pat. Nos. 3,615,272, 4,399,266, 4,756,977 and 4,999,397, polysilicon having a dielectric constant of about 2.5 to 3.1 that allows spin on deoposition (SOD) in place of SiO ₂ having a dielectric constant of 4.00 using conventional chemical vapor deposition (Chemical Vapor Deposition) Sesquioxane (Polysilsesquioxane) was used, in this case it is possible to apply a spin coating method due to the good planarization properties.

Such hydrogen silsesquioxanes and methods for their preparation are known in the art. For example, U. S. Patent No. 3,615, 272 discloses hydrogen resins that are essentially completely condensed by a process comprising hydrolyzing trichlorosilane in a benzenesulfonic acid hydrate hydrolysis medium, followed by washing the resin with water or aqueous sulfuric acid. A manufacturing method is disclosed. U. S. Patent No. 5,010, 159 also discloses a method comprising hydrolyzing hydrosilane in an arylsulfonic acid hydrate hydrolysis medium to form a resin, and then contacting the resin with a neutralizing agent. U.S. Patent No. 6,232,424 discloses solution stability by hydrolysis and condensation reaction using water and catalyst using tetraalkoxysilane, organosilane and organotrialkoxysilane as monomers. Excellent and soluble silicone resin compositions and methods for their preparation are disclosed. US Pat. No. 6,000,339 discloses monomers selected from alkoxysilanes, fluorine-containing alkoxysilanes and alkylalkoxysilanes for the purpose of improving the resistance and properties of oxygen plasma and the formation of thick films. A silica-based compound in which a titanium (Ti) or zirconium (Zr) alkoxide compound is reacted with water and a catalyst is disclosed. U.S. Patent No. 5,853,808 discloses siloxane and silsesqui produced using compounds substituted with other elements or reactive groups at the β-position of organosilanes in order to increase the content of SiO ₂ in the thin film. An oxane (silsesquioxane) -based polymer and a thin film composition using the same are disclosed. EP 0 997 497 A1 discloses alkoxysilanes such as various monoalkoxysilanes, dialkoxysilanes, trialkoxysilanes, tetraalkoxysilanes, and trialkoxysilane dimers. It is disclosed that a composition based on a combination of an (alkoxysilane) compound and an organic polymer is used as an insulating film.

In order to lower the dielectric constant of the semiconductor interlayer insulating film below 2.5, a porogen-forming material is formulated into the siloxane-based resin and pyrolyzed and removed in a temperature range of 250 ° C to 350 ° C. -template) method is proposed. However, in this method, as shown in FIG. 1, when the Si-OH is formed on the pore surface or porogen is removed, pores collapse and are connected to each other. Problems appear, which degrades the process applicability in applying a porous dielectric film as an insulating film of a semiconductor.

For example, a cage-type siloxane monomer represented by the following formula (1), which has been studied in the past, has the following structure but has a diagonal length of about 5.3 μs, and when forming an insulating film using the same, it has a dielectric constant of 3.0 to 2.7. Therefore, in order to lower the dielectric constant below, the addition of porogen is essential and the above problems also occur.

The present invention is to solve the problems of the prior art as described above, by using a molecular polyhedral silsesquioxane having pores therein as a monomer of the siloxane-based resin to be used in the insulation film composition or when forming the insulation film composition The present invention provides a method of forming an insulating film between semiconductor layers which can obtain a low dielectric constant and can induce mechanical properties, thermal stability, crack resistance, and the like by the functional groups introduced by introducing various reactors.

That is, one aspect of the present invention is a mixture of one or more molecular polyhedral silsesquioxanes represented by the following formula (2) alone or optionally with one or more silane monomers to form water and an acid or base catalyst in an organic solvent. It is to provide a siloxane-based resin produced by hydrolysis and condensation polymerization in the presence.

[SiO _1.5 ] _n- (R) _n

Wherein R is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkene group, an alkyne group, an aryl group or an alkoxy group, or -OSir ₁ r ₂ r ₃ , wherein r ₁ , r ₂ , And r ₃ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkene group, an alkyne group, an aryl group, or an alkoxy group, and the plurality of Rs may be different from each other, and at least one of Rs Hydrolysable functional group, n is 10, 12, 14 or 16.

Another aspect of the present invention is to provide a composition for forming an insulating film comprising the prepared siloxane resin and an organic solvent.

Another aspect of the present invention is to provide a composition for forming an insulating film comprising a molecular polyhedral silsesquioxane of Formula 2, a thermally stable siloxane precursor, and a solvent for dissolving the material.                         

Another aspect of the present invention is to provide a method of forming an insulating film comprising the step of applying the composition for forming the insulating film on a substrate and thermosetting.

Another aspect of the invention relates to a semiconductor interlayer insulating film formed by the above method.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In the present invention, one or more molecular polyhedral silsesquioxanes represented by the following Chemical Formula 2 may be used directly for the polymerization of the siloxane-based resin used for forming the insulating film, or used as a material for introducing pores as a component of the insulating film forming composition. Can be.

[Formula 2]

[SiO _1.5 ] _n- (R) _n

Wherein R is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkene group, an alkyne group, an aryl group or an alkoxy group, or -OSir ₁ r ₂ r ₃ , wherein r ₁ , r ₂ , And r ₃ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkene group, an alkyne group, an aryl group, or an alkoxy group, and the plurality of Rs may be different from each other, and at least one of Rs Hydrolysable functional group, n is 10, 12, 14 or 16.

Hereinafter, a process in which the molecular polyhedral silsesquioxane is used for polymerization of the siloxane resin will be described in more detail.

That is, the molecular polyhedral silsesquioxane of the formula (2) alone or optionally mixed with at least one silane monomer selected from the group consisting of compounds represented by the following formulas (3), (4), (5) and (6), The siloxane resin is prepared by condensation polymerization in the presence of an acid or a base catalyst in water.

Wherein R ₁ is a hydrogen atom, an alkyl group of C ₁ to C ₃ or an aryl group of C ₆ to C ₁₅ ; R ₂ is a hydrogen atom, an alkyl group of C ₁ to C ₁₀ or SiX ₁ X ₂ X ₃ (wherein X ₁ , X ₂ , X ₃ are each independently a hydrogen atom, an alkyl group of C ₁ to C ₃ , C ₁ To alkoxy or halogen atom of C ₁₀ , at least one of which is a hydrolyzable functional group; p is an integer of 3-8.

Wherein R ₁ is a hydrogen atom, an alkyl group of C ₁ to C ₃ or an aryl group of C ₆ to C ₁₅ ; X ₁ , X ₂ and X ₃ are each independently a hydrogen atom, an alkyl group of C ₁ to C ₃ , an alkoxy group or halogen atom of C ₁ to C ₁₀ , at least one of which is a hydrolyzable functional group; m is an integer of 0-10, p is an integer of 3-8.

Wherein X ₁ , X ₂ and X ₃ are each independently a hydrogen atom, an alkyl group of C ₁ to C ₃ , an alkoxy group or halogen atom of C ₁ to C ₁₀ , at least one being a hydrolyzable functional group; M is a single bond or an alkylene group of C ₁ to C ₁₀ or an arylene group of C ₆ to C ₁₅ .

(R ₁ ) _n Si (OR ₂ ) _4-n

Wherein R ₁ is a hydrogen atom, an alkyl group of C ₁ to C ₃ , a halogen group or an aryl group of C ₆ to C ₁₅ , and R ₂ is a hydrogen atom, an alkyl group of C ₁ to C ₃ or C ₆ to C ₁₅ As an aryl group, at least one of R ₁ and OR ₂ is a hydrolyzable functional group; n is an integer of 0-3.

As a specific example of the molecular polyhedral silsesquioxane, the basic structure of the compound used in the present invention may include a structure represented by the following Chemical Formula 7.

In the above formula, various substituents may be bonded to Si. By modifying the Si—H bond to Si—OH, Si—OR, Si—CH═CH _2, etc., a sol-gel reaction or a polymer polymerization reaction is possible. The functional group may be used as an additive because of good compatibility with the siloxane resin, and may use pores inside the molecular polyhedron.

Since the silsesquioxane in which the hydrogen atom is bonded to the Si atom of the compound has a length of about 8.3 μm of the body diagonal of the skeleton of Si—O—Si, the dielectric constant of the insulating film including the same is 2.5 to 1.8. It may also be possible to lower it. In the above structure, when a polymer is prepared using an oligomer having a hydrogen atom bonded to an oxygen atom directed toward the outside of a molecule as a starting monomer, and an insulating film is formed using the polymer, the Si atoms in the molecule all have a Q structure. The mechanical properties such as modulus and hardness are excellent and the coefficient of thermal expansion (CTE) is low.                     

In addition, when the molecular polyhedral silsesquioxane having the above structure is used, an insulating film having a pore wall as shown in FIG. 2 can be manufactured. That is, a porous insulating film can be formed by introducing a spherical insulator having pores therein into the film. In this case, since the insulator has a completed form at the molecular level, the Si-OH is not formed as in the prior art or the aggregation of pore-forming materials does not cause a problem in that the pores in the thin film are connected to each other. In addition, when applied to the semiconductor process, since the molecules such as HF or H ₂ O, which may be generated in the insulating film, cannot enter the pores, the process applicability can be fundamentally improved, and the overall pore volume is increased. In order to reduce the dielectric constant below 2.0, there is no problem. In addition, the dielectric constant is lowered due to pore formation, but it is expected that the decrease in mechanical properties relative to the dielectric constant is small since it is not removed by heat like conventional pore-forming materials.

Molecular polyhedral silsesquioxanes having various substituents used in the present invention are specifically prepared through the same route as in Scheme 1.

In the present invention, preferably at least one silane selected from the group consisting of compounds represented by the following formula (8) as the molecular polyhedral silsesquioxane alone or optionally selected from formulas (3), (4), (5) and (6). The siloxane resin may be prepared by mixing with a monomer and condensation polymerization in the presence of an acid, a base, or a metal catalyst in water in an organic solvent.

[SiO _1.5 ] _n (H) _n

In the preparation of the siloxane resin, when polymerizing one or more silane monomers selected from the group consisting of molecular polyhedral silsesquioxane and the compounds of Formulas 3 to 6, the reaction ratio is 9.999: 0.001 to 0.001: 9.999. It is preferable.

Acids, bases or metal catalysts used in the production of the siloxane resin may be hydrochloric acid, nitric acid, benzene sulfonic acid, oxalic acid, formic acid, Potassium hydroxide, sodium hydroxide, triethylamine, sodium bicarbonate, pyridine, Pt, Pd derivatives, and the like can be used. The catalyst is preferably used in a molar ratio of catalyst to monomer in a range of 1: 0.00001 to 1:10.

Water used in the hydrolysis and condensation reaction is used in the molar ratio of water to monomers in the range of 1: 1 to 1: 100.

As the organic solvent, Preferably, an aliphatic hydrocarbon solvent such as hexane; Aromatic hydrocarbon solvents such as anisol, mesitylene and xylene; Ketone-based solvents such as methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, 1-methyl-2-pyrrolidinone, cyclohexanone, and acetone ); Ether-based solvents such as tetrahydrofuran and isopropyl ether; Acetate-based solvents such as ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate; Alcohol-based solvents such as isopropyl alcohol and butyl alcohol; Amide solvents such as dimethylacetamide and dimethylformamide; Silicon-based solvents; Or mixtures thereof.

The hydrolysis and condensation reaction is more preferably carried out at a temperature of 0 to 200 ℃ for 0.1 to 100 hours.

The siloxane resin prepared above preferably has a weight average molecular weight of 1000 to 300,000.

The siloxane resin obtained by the condensation polymerization is dissolved in the solvent exemplified above to prepare an insulating film forming composition, and at this time, a known pore-forming material may be optionally added.

On the other hand, the molecular polyhedral silsesquioxane represented by the formula (2) in the present invention can be used in the preparation of the composition for forming a porous insulating film with a thermally stable siloxane precursor and a solvent dissolving them as a pore-forming material. In this case the molecular polyhedral silsesquioxane may act as the pore-forming material alone but may optionally be used in combination with all known pore-forming materials.

Preferred examples of the pore-forming material which can be used in combination include cyclodextrin, polycaprolactone, Brij surfactant, polyethylene glycol-polypropyleneglycol-polyethylene glycol triblock copolymer-based surfactants and derivatives thereof.

In the insulating film forming composition, the pore-forming material is present in an amount of 0.1 to 99.9% by weight, preferably 1 to 70% by weight, based on the total weight of solids (ie, siloxane precursor + pore-forming material) in the composition. It is not limited to this.

When the molecular polyhedral silsesquioxane is used as the pore-forming material in the present invention, as the thermally stable siloxane precursor, a siloxane monomer selected from the group consisting of Formulas 3, 4, 5, and 6 may be used. It can be prepared and used in the same manner.                     

The organic solvent that can be used when preparing the insulating film forming composition is not particularly limited, and preferably all organic solvents described above can be used.

Although the content of solids in the composition is not particularly limited, it is more preferable that the solids content is 5 to 70% by weight based on the weight of the total composition including the organic solvent and the solids.

The insulating film forming composition comprising a siloxane-based resin prepared using the molecular polyhedral silsesquioxane prepared above or the insulating film forming composition comprising a molecular polyhedral silsesquioxane as a pore-forming material is coated on a substrate By curing, an insulating film is formed.

The substrate is not particularly limited as long as the object of the present invention is not impaired, and any substrate capable of withstanding thermosetting conditions, for example, a glass substrate, a silicon wafer, a plastic substrate, and the like may be selected and used depending on the application. Examples of coating methods usable in the present invention include, but are not limited to, spin coating, dip coating, spray coating, flow coating, and screen printing. It doesn't work. The most preferred coating method in terms of convenience and uniformity is spin coating. When spin coating is performed, the spin speed is preferably adjusted within the range of 800 to 5,000 rpm.

After the coating is completed, it may include a process of drying the film by evaporating the solvent, if necessary. The film drying process can be carried out simply by exposing to the ambient environment, applying a vacuum at the initial stage of the curing process, or by heating to a relatively low temperature of 200 ° C. or less.

The film is then thermally cured at temperatures between 150 ° C. and 600 ° C., preferably between 200 ° C. and 450 ° C. for 1 to 180 minutes to form an insoluble coating that is free of cracks. 'No cracks' refers to a film that does not show any cracks visible to the naked eye when viewed under an optical microscope of 1000x magnification. An insoluble film is a solvent or resin that forms a film by depositing a siloxane-based polymer. Refers to a coating that is essentially insoluble in a solvent described as useful. When the pore forming material other than the molecular polyhedral silsesquioxane is included, the thermosetting temperature is determined in consideration of the decomposition temperature of the pore forming material.

Since the insulating film using the molecular polyhedral silsesquioxane has a dielectric constant of 3.0 or less depending on the content of the polyhedral material, it can be used as a low dielectric semiconductor interlayer insulating film. The insulating film prepared according to the present invention is excellent in mechanical properties such as toughness, elasticity, low carbon content in the film can be usefully used as a semiconductor interlayer insulating film.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for the purpose of explanation and are not intended to limit the present invention.

First, a method of measuring the performance of the insulating film manufactured in the following examples will be described in detail.

① Dielectric constant measurement:                     

A silicon thermal oxide film is deposited on a boron-doped p-type silicon wafer with 3000 microns of silicon, 100 microns of aluminum, 2000 microns of aluminum, and 100 microns of titanium by a metal evaporator, and then an insulating film to be measured is formed thereon. A low dielectric thin film for measuring dielectric constant of MIM (metal-insulator-metal) structure is completed by depositing a circular titanium 100Å and an aluminum thin film 5000 1 having a diameter of 1 mm using a hard mask having an electrode diameter of 1 mm on the insulating film. . The finished thin film was measured using a PRECISION LCR METER (HP4284A) equipped with a probe station (micromanipulatior 6200 probe station) at the frequencies of about 10 kHz, 100 kHz, and 1 MHz, and the thickness of the thin film using a prism coupler. The dielectric constant is then calculated from the following equation:

k = C xd / ε _o x A

Where k is the relative permittivity, C is the capacitance, ε _o is the dielectric constant of the vacuum (ε _o = 8.8542 × 10-12 Fm-1), and d is the insulating film Is the thickness of A, and A is the contact cross-sectional area of the electrode.)

② Hardness and modulus:

Hardness and modulus of elasticity are determined by quantitatively analyzing the insulating film using MTS Nanoindenter II. More specifically, the thin film is indented with a nanoindenter, and the hardness and elastic modulus of the thin film are obtained when the indentation depth is 10% of the thin film thickness. The thickness of the thin film is measured using a prism coupler. In the present example and the comparative example, in order to ensure the reliability, nine points on the insulating film were press-fitted to obtain respective hardness and elastic modulus from the average value.

Preparation of Molecular Polyhedral Silsesquioxanes

Preparation Example 1

In a well-dried flask, 80 g of sulfuric acid (H ₂ SO ₄ ) and fuming H ₂ SO ₄ containing 15% of SO ₃ were mixed well with 200 ml of benzene, followed by rapid stirring. Put it. After the addition of trichlorosilane, the organic layer is washed several times with 50% H ₂ SO ₄ solution and then with distilled water. The organic layer was concentrated after filtering to remove insoluble and unremovable substances in the organic layer to obtain 4.8 g of a molecular polyhedral silsesquioxane precursor having n = 12, 14, and 16 (Formula 8). The mixture thus obtained was separated from each other by sublimation.

Production Example 2

Of n = 14 obtained in Preparative Example 1 [Si ₁₄ O _21] and H into the flask after ₁₄ 1g to 8 hours at room temperature into the Pd / C 0.1g was dissolved in methanol _{20ml [Si 14 O 21] OMe} 14 0.8 g was obtained.

Preparation of Polymers Containing Molecular Polyhedral Silsesquioxanes

Production Example 3

5 g of the monomer [Si ₁₄ O ₂₁ ] H ₁₄ obtained in Preparation Example 1 was added to the flask, and the mixture was diluted with benzene so that the concentration of the total solution was 0.05 to 0.07 M, and then 0.01 mmol% of the PtCl ₂ catalyst was added to the flask. After the addition was carried out for 12 hours at room temperature. After the reaction was completed, the solution was removed from the catalyst using a celite (cellite), it was filtered through a filter having a pore of 0.2㎛ and then the solvent was removed. The white powder was dried for 4 hours at a temperature of 0 to 20 ° C. and 0.9 Torr pressure to obtain 3.5 g of a siloxane polymer (hereinafter referred to as (a-1)). Si-OH content and Si-CH ₃ content in the polymer were 38.70% and 61.30%, respectively.

Si-OH (%) = Area (Si-OH) x [Area (Si-OH) + Area (Si-OCH ₃ ) / 3 + Area (Si-CH ₃ ) / 3] x 100;

Si-OCH ₃ (%) = Area (Si-OCH ₃ ) / 3 ÷ [Area (Si-OH) + Area (Si-OCH ₃ ) / 3 + Area (Si-CH ₃ ) / 3] × 100;

Si-CH ₃ (%) = Area (Si-CH ₃ ) / 3 ÷ [Area (Si-OH) + Area (Si-OCH ₃ ) / 3 + Area (Si-CH ₃ ) / 3] × 100

Preparation Example 4

After reacting for 6 hours at room temperature in the same manner as in Preparation Example 3, except that tetrahydrofuran was used instead of benzene as a solvent, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis 5 g of (trimethoxysilyl) cyclosiloxane (2,4,6,8-tetramethyl-2,4,6,8-tetrakis (trimethoxysilyl) cyclosiloxane) was placed in a flask, and the reaction solution temperature was -78 ° C. After adding 0.484 mmol of hydrochloric acid and 241.2 mmol of water to the flask, the temperature of the reaction solution was gradually raised from -78 ° C to 70 ° C, and the reaction was carried out for 6 hours. After the reaction solution was transferred to a separatory funnel, the same amount of tetraethylfuran and tetrahydrofuran in the same amount were added, washed three times with about 1/8 of the total solvent, and then the volatiles were removed under reduced pressure. Removal to obtain a polymer in the form of a white powder. The polymer obtained by the above method was dissolved in tetrahydrofuran to form a transparent solution, which was filtered through a filter having a pore of 0.2 μm, and water was slowly added to the filtrate to obtain a precipitate of white powder. The white powder was dried for 8 hours at a temperature of 0 to 20 ° C. and 0.9 Torr pressure to obtain 6.2 g of a siloxane polymer (hereinafter referred to as (a-2)). The Si-OH content, Si-OCH ₃ content and Si-CH ₃ content in the polymer were 39.50%, 0.65% and 59.85%, respectively.

Preparation Example 5

2,4,6,8-tetramethyl-2,4,6,8-tetrakis (trimethoxysilyl) cyclosiloxane (2,4,6,8-tetramethyl-2,4,6,8-tetrakis ( trimethoxysilyl) cyclosiloxane): T4Q4) and the polymer by the same method as in Preparation Example 4, except that methyltrimethoxysilane (MTMS, manufactured by Aaldrich) was used as the acyclic alkoxy silane monomer. ). The amount of each monomer used, the amount of HCl and water used in the preparation of each polymer is shown in Table 1. On the other hand, the polymer amount, Si-OH content, Si-OCH ₃ content, and Si-CH ₃ content, respectively obtained, are also shown in Table 1.

Example 1

0.207 g of the polymer (a-3) as the siloxane polymer and 0.046 g of the molecular polyhedral silsesquioxane (n = 14) of Preparation Example 1 were used as the pore-forming substance, and propylene glycol methyl ether acetate was used as the solvent. methyl ether acetate) was used to prepare a coating liquid having a solid content of 24% by weight. The coating solution was spin-coated on a silicon wafer for 30 seconds at 2000 rpm, and preheated at 150 ° C. for 1 minute and at 250 ° C. for 1 minute on a hot plate in a nitrogen atmosphere to prepare a film. The film was heat-treated at 420 ° C. (heating rate: 3 ° C./min) for 1 hour in a vacuum atmosphere to prepare an insulating film (C-1). The thickness, refractive index, dielectric constant, hardness, modulus, and carbon content of the prepared insulating film were measured and the results are shown in Table 2 below.

Comparative Example 1

As a siloxane-based polymer, a coating liquid having a solid content of 24% by weight was prepared by using propylene glycol methyl ether acetate as a solvent without using a pore-forming substance in 0.459 g of the polymer (a-3). Except for producing an insulating film (C-2) in the same manner as in Example 1. The thickness, refractive index, dielectric constant, hardness, modulus, and carbon content of the prepared insulating film were measured and the results are shown in Table 2.

Comparative Example 2

0.413 g of the above polymer (a-3) as a siloxane-based polymer, and heptakis [2,3,6-tri-methoxy] -beta-cyclodextrin [2,3,6-tri- as a pore-forming substance; An insulating film (C-3) was prepared in the same manner as in Example 1, except that 0.046 g of O-methyl) -β-cyclodextrin) was used. The thickness, refractive index, dielectric constant, hardness, modulus, and carbon content of the prepared insulating film were measured and the results are shown in Table 2.

The molecular polyhedral silsesquioxane according to the present invention has excellent compatibility with existing siloxane resins and is easy to introduce various derivatives, and when used to form a polymer, it has excellent compatibility with other pore-forming materials, and manufactured using the same. Films are useful in the field of semiconductor devices because of their excellent mechanical properties, thermal stability and crack resistance, low carbon content, high SiO ₂ content and excellent insulation properties. Can be used.

Claims (21)

A siloxane-based resin prepared by condensation polymerization of molecular polyhedral silsesquioxane containing pores within at least one of the following Chemical Formulas 2 alone in an organic solvent in the presence of water and an acid or a base catalyst: [Formula 2] [SiO _1.5 ] _n- (R) _n [Wherein R is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkene group, an alkyn group, an aryl group or an alkoxy group, or -OSir ₁ r ₂ r ₃ , wherein r ₁ , r ₂ , And r ₃ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkene group, an alkyne group, an aryl group, or an alkoxy group, and the plurality of R may be different from each other, and at least one of the R's Is a hydrolyzable functional group and n is 10, 12, 14 or 16; An organic solvent is obtained by mixing a molecular polyhedral silsesquioxane containing pores in at least one interior represented by Formula 2 with at least one monomer selected from the group consisting of compounds represented by Formulas 3, 4, 5, and 6. Siloxane-based resins prepared by condensation polymerization in the presence of water and an acid or base catalyst in: [Formula 2] [SiO _1.5 ] _n- (R) _n [Wherein R is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkene group, an alkyn group, an aryl group or an alkoxy group, or -OSir ₁ r ₂ r ₃ , wherein r ₁ , r ₂ , And r ₃ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkene group, an alkyne group, an aryl group, or an alkoxy group, and the plurality of R may be different from each other, and at least one of the R's Is a hydrolyzable functional group and n is 10, 12, 14 or 16; (3)

[Wherein, R ₁ is a hydrogen atom, an alkyl group of C ₁ to C ₃ or an aryl group of C ₆ to C ₁₅ ; R ₂ is a hydrogen atom, an alkyl group of C ₁ to C ₁₀ or SiX ₁ X ₂ X ₃ (wherein X ₁ , X ₂ , X ₃ are each independently a hydrogen atom, an alkyl group of C ₁ to C ₃ , C ₁ To alkoxy or halogen atom of C ₁₀ , at least one of which is a hydrolyzable functional group; p is an integer from 3 to 8; [Formula 4]

[Wherein, R ₁ is a hydrogen atom, an alkyl group of C ₁ to C ₃ or an aryl group of C ₆ to C ₁₅ ; X ₁ , X ₂ and X ₃ are each independently a hydrogen atom, an alkyl group of C ₁ to C ₃ , an alkoxy group or halogen atom of C ₁ to C ₁₀ , at least one of which is a hydrolyzable functional group; m is an integer from 0 to 10, p is an integer from 3 to 8; [Chemical Formula 5]

[Wherein, X ₁ , X ₂ and X ₃ are each independently a hydrogen atom, an alkyl group of C ₁ to C ₃ , an alkoxy group or halogen atom of C ₁ to C ₁₀ , at least one being a hydrolyzable functional group; M is a single bond or a C ₁ to C ₁₀ alkylene group or a C ₆ to C ₁₅ arylene group; And [Formula 6] (R ₁ ) _n Si (OR ₂ ) _4-n [Wherein, R ₁ is hydrogen atom, C ₁ to C ₃ alkyl group, halogen group or C ₆ to C ₁₅ aryl group, R ₂ is hydrogen atom, C ₁ to C ₃ alkyl group or C ₆ to C ₁₅ As an aryl group, at least one of R ₁ and OR ₂ is a hydrolyzable functional group; n is an integer of 0 to 3; The method of claim 1 or 2, wherein the acid catalyst is hydrochloric acid, nitric acid, benzene sulfonic acider, oxalic acid, formic acid or a mixture thereof. The base catalyst is a siloxane-based resin, characterized in that the potassium hydroxide (potassium hydroxide), sodium hydroxide (sodium hydroxide), triethylamine (triethylamine), sodium bicarbonate, pyridine (pyridine) or a mixture thereof . The siloxane-based resin according to claim 1 or 2, wherein the molar ratio between the total monomers and the acid or base catalyst used is from 1 × 10 ⁻⁵ to 1:10. The siloxane-based resin according to claim 1 or 2, wherein the molar ratio of the total monomers and the water used is 1: 1 to 1: 100. The siloxane-based resin according to claim 1 or 2, wherein the polymerization reaction is performed at a temperature of 0 to 200 ° C for 0.1 to 100 hours. The method of claim 1 or 2, wherein the organic solvent is aliphatic hydrocarbon solvent (aliphatic hydrocarbon solvent) of hexane or heptane; Aromatic hydrocarbon solvents of anisol, mesitylene or xylene; Ketone-based solvents of methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, 1-methyl-2-pyrrolidinone, cyclohexanone or acetone ; Ether-based solvents of tetrahydrofuran or isopropyl ether; Acetate-based solvents of ethyl acetate, butyl acetate or propylene glycol methyl ether acetate; Alcohol-based solvents of isopropyl alcohol or butyl alcohol; Amide solvents such as dimethylacetamide or dimethylformamide; Silicon-based solvents; Or a mixture of the above solvents. The siloxane-based resin according to claim 1 or 2, wherein the weight average molecular weight of the siloxane-based resin is 1,000 to 300,000. The composition for insulating film formation containing the siloxane-type resin of Claim 1 or 2, and an organic solvent. 10. The method of claim 9, wherein the solvent is aliphatic hydrocarbon solvent of hexane or heptane; Aromatic hydrocarbon solvents of anisol, mesitylene or xylene; Ketone-based solvents of methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, 1-methyl-2-pyrrolidinone, cyclohexanone or acetone ; Ether-based solvents of tetrahydrofuran or isopropyl ether; Acetate-based solvents of ethyl acetate, butyl acetate or propylene glycol methyl ether acetate; Alcohol-based solvents of isopropyl alcohol or butyl alcohol; Amide solvents such as dimethylacetamide or dimethylformamide; Silicon-based solvents; Or a mixture of the solvents. 10. The method of claim 9, wherein the insulating film forming composition further comprises cyclodextrin, polycaprolactone, Brij-based surfactant (surfactant), polyethylene glycol-polypropylene glycol-polyethylene glycol tertiary block copolymer ( Polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer) A composition for forming an insulating film comprising a pore-forming material selected from the group consisting of surfactants and derivatives thereof. delete delete delete delete delete Preparing a composition according to claim 9; And coating the composition on a substrate and thermally curing. 18. The composition of claim 17, wherein the composition is cyclodextrin, polycaprolactone, Brij-based surfactant, polyethylene glycol-polypropylene glycol-polyethylene glycol terpolymer Polyethylene glycol triblock copolymer) A method of forming a semiconductor interlayer insulating film further comprising a pore-forming material selected from the group consisting of surfactants and derivatives thereof. 18. The method of claim 17, wherein the coating is performed by spin coating, dip coating, spray coating, flow coating, or screen printing. A method of forming a semiconductor interlayer insulating film. The method of claim 17, wherein the thermal curing is performed at a temperature of 150 ° C. to 600 ° C. for 1 to 180 minutes. A semiconductor interlayer insulating film formed by the method of claim 17.

Images