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WO2011052657A1 - Composition de précurseur pour membrane poreuse et procédé de formation de membrane poreuse - Google Patents

Composition de précurseur pour membrane poreuse et procédé de formation de membrane poreuse Download PDF

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Publication number
WO2011052657A1
WO2011052657A1 PCT/JP2010/069110 JP2010069110W WO2011052657A1 WO 2011052657 A1 WO2011052657 A1 WO 2011052657A1 JP 2010069110 W JP2010069110 W JP 2010069110W WO 2011052657 A1 WO2011052657 A1 WO 2011052657A1
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alkoxysilane compound
precursor composition
film
porous
group
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PCT/JP2010/069110
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English (en)
Japanese (ja)
Inventor
一誠 東條
高博 中山
正明 平川
剛 加賀美
貴久 山崎
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株式会社 アルバック
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Priority to JP2011538465A priority Critical patent/JPWO2011052657A1/ja
Publication of WO2011052657A1 publication Critical patent/WO2011052657A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes

Definitions

  • the present invention relates to a precursor composition for a porous film applied by a spin coating method to form a porous film, in particular, a precursor composition for a porous film made of an organosilicon oxide, and the precursor composition.
  • the present invention relates to a method for forming a porous film to be used.
  • the insulating film between the wirings is made of a porous organic silicon oxide film, that is, a porous silica film. Has been intensively studied.
  • a precursor composition of the porous film is applied onto the substrate.
  • the thermally decomposable organic compound contained in the precursor composition is decomposed by heating the substrate, and the space occupied by the thermally decomposable organic compound becomes a void, that is, a porous silicon
  • a hydrophobic functional group is introduce
  • the hydrophobic functional group is also introduced into the inner surface of the pores exposed on the surface of the porous silica film.
  • the porous silica film thus formed since the hydrophilic compound is suppressed from entering the pores, the increase in the dielectric constant by the hydrophilic compound is suppressed, and the porous silica film originally has the porous silica film. A low dielectric constant is maintained.
  • the porous silica film is used as an insulating film between wirings, grooves and through holes for forming wirings, electrodes and the like are formed in the porous silica film. Since a dry etching process is generally used as a method for forming fine grooves and through-holes, the dry etching process is also performed on the porous silica film.
  • the porous silica film when a porous silica film is formed from the precursor composition described in Patent Document 1, the porous silica film has a low dielectric constant at the time of formation, but processing using a dry etching process is performed. After this time, the porous silica film may lose its low dielectric constant characteristics.
  • the present invention has been made in view of the above-described conventional situation, and the purpose thereof is a precursor composition of a porous silica film capable of suppressing an increase in the relative dielectric constant of the porous film after the etching process, Another object of the present invention is to provide a method for forming a porous silica film using the same.
  • the first aspect of the present disclosure is such that the first alkoxysilane compound, the second alkoxysilane compound, the first alkoxysilane compound, and the second alkoxysilane compound are destroyed at or above the temperature at which they are copolymerized.
  • a porous membrane precursor composition comprising nonionic surfactant micelles.
  • the first alkoxysilane compound comprises a tetraalkoxysilane, a monoalkyltrialkoxysilane, a dialkyldialkoxysilane, a tetraalkoxysilane polymer, a monoalkyltrialkoxysilane polymer, and a dialkyldialkoxysilane polymer. At least one selected from the group, and the second alkoxysilane compound is trialkoxyphenylsilane.
  • an organic silicon oxide film having a polysiloxane skeleton as a main skeleton is formed under a condition in which the first alkoxysilane compound and the second alkoxysilane compound are copolymerized, and the organic silicon oxide Nonionic surfactant micelles are contained in the membrane. Then, above the temperature at which the first alkoxysilane compound and the second alkoxysilane compound are copolymerized, the nonionic surfactant micelles contained in the organic silicon oxide film are destroyed, and the space occupied by the micelles is destroyed. Holes are formed. Therefore, the porosity of the porous film having a polysiloxane skeleton as the main skeleton, that is, the relative dielectric constant, is defined by the content of the nonionic surfactant micelle.
  • the surface layer of the porous film naturally includes a phenyl group in the three-dimensional polysiloxane skeleton.
  • the phenyl group is also added in a form surrounded by the polysiloxane skeleton constituting the porous film.
  • a highly hydrophobic phenyl group is imparted throughout. As a result, even when dry etching is applied to the porous film, the inner surface of the void exposed through the recessed portion after etching has a highly hydrophobic phenyl group.
  • the above-described phenyl group can be held on the inner surface of the hole regardless of the shape after the etching.
  • the hydrophobic functional group contained in the polysiloxane skeleton is an alkyl group
  • the bond between silicon and the hydrocarbon group is broken, but also the single bond between the carbons in the hydrocarbon group. Even when cleaved, the alkyl group is detached from the porous membrane.
  • the phenyl group has an arene structure including a single bond and a double bond, even if the carbon bond in the phenyl group is broken, the broken bond can be repaired. High nature.
  • the number of carbon atoms bonded to the porous film can be increased by 6 times the number of the phenyl group.
  • improving the hydrophobicity is effective.
  • the number of organic groups added to the porous membrane is smaller.
  • the above-mentioned phenyltrimethoxysilane is an alkoxysilane compound that satisfies both the hydrophobicity and mechanical strength of the porous film, and consequently suppresses the increase in the dielectric constant of the porous film after the etching process. Can do.
  • the porous membrane precursor composition contains the first alkoxysilane compound, the second alkoxysilane compound, and the nonionic surfactant.
  • a porous film having the following can be formed. That is, as compared with the case where a hydrophobic functional group is added separately after forming the porous film as in the conventional technique, the number of steps required to form such a porous film can be reduced. Also become.
  • the distance between molecules of the alkoxysilane compound generally increases during the polymerization of the alkoxysilane compound. Therefore, the degree of polymerization in the porous film is low, and the densification of the film is difficult to be promoted in the portion excluding the pores.
  • the porosity of the porous film that is, the dielectric constant of the porous film is secured by the content of the nonionic surfactant micelle, the portion excluding the pores No additional holes are required for. Rather, from the viewpoint of securing the mechanical strength of the porous membrane or protecting the hydrophobic group in the membrane, a configuration that promotes densification of the membrane is preferable.
  • the first alkoxysilane compound is methyltrimethoxysilane, n-propyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, vinyltrimethoxysilane.
  • Methyl silicate, dimethyldimethoxysilane, and dimethyldiethoxysilane which are polymers of ethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetramethoxysilane At least one selected from the group consisting of:
  • the first alkoxysilane compound is an alkoxysilane compound having an alkoxy group having 1 or 2 carbon atoms, the densification of the film is promoted in a portion excluding the vacancies. It is also possible to ensure the mechanical strength of the film and to more reliably protect the hydrophobic group in the film.
  • each alkoxy group of trialkoxyphenylsilane is an alkoxy group having 1 to 4 carbon atoms. In this case, since the densification of the membrane is promoted in the portion excluding the pores, it is possible to ensure the mechanical strength of the porous membrane and to more reliably protect the hydrophobic groups in the membrane. Also become.
  • the phenyl group of the second alkoxysilane compound is hydrophobic, when it is introduced into the porous membrane, the porous membrane is imparted with hydrophobicity. In addition, as the number of phenyl groups introduced into the porous membrane increases, the degree of hydrophobicity of the porous membrane increases.
  • the mechanical strength of the porous membrane decreases as the number of phenyl groups introduced into the porous membrane increases. This is because, for example, by adding a large number of hydrocarbon groups as side chains to the polysiloxane skeleton that becomes the skeleton of the porous film, the size per unit of the polysiloxane skeleton increases, that is, the skeleton becomes more sparse. It is thought to be. That is, a so-called trade-off relationship is established between the hydrophobicity of the porous film and the mechanical strength.
  • the substance amount of the second alkoxysilane compound is within a range that improves the hydrophobicity of the porous film and does not decrease the mechanical strength of the porous film, that is, the first alkoxysilane compound. It is adjusted to be in the range of more than 10 at% and less than 100 at% of the amount of silicon contained.
  • the porous film precursor composition was formed by two alkyl groups of the dialkylalkoxysilane. Hydrophobicity is imparted to the porous membrane.
  • the silicon atom of dialkyl dialkoxysilane has two of the four covalent bonds that can be used for bonding to the alkyl group, all of the above covalent bonds are bonded to the alkoxyl group. Compared to those used, it becomes easier to form a linear polysiloxane skeleton. That is, when the dialkyl dialkoxysilane is used, it is difficult to ensure the mechanical strength as the porous film.
  • the second alkoxysilane compound is adjusted to 3 to 5 times the amount of dialkyldialkoxysilane.
  • the second alkoxysilane compound having more alkoxy groups a linear polysiloxane skeleton is hardly formed, and as a result, the mechanical strength as a porous film is ensured.
  • Another aspect of the present disclosure is that the first alkoxysilane compound, the second alkoxysilane compound, the first alkoxysilane compound, and the second alkoxysilane compound are destroyed at a temperature higher than the copolymerization temperature.
  • a method for forming a porous film using a porous film precursor composition containing ionic surfactant micelles wherein the porous film precursor composition is applied to a substrate by spin coating And heating the substrate coated with the porous membrane precursor composition to a temperature at which the first alkoxysilane compound and the second alkoxysilane compound are copolymerized, and the nonionic property
  • a method for forming a porous film comprising the step of destroying a surfactant micelle and removing it from the copolymer of the first alkoxysilane compound and the second alkoxysilane compound is provided. That.
  • the first alkoxysilane compound is composed of tetraalkoxysilane, monoalkyltrialkoxysilane, dialkyldialkoxysilane, tetraalkoxysilane polymer, monoalkyltrialkoxysilane polymer, and dialkyldialkoxysilane polymer.
  • the second alkoxysilane compound is trialkoxyphenylsilane.
  • porous film formed using the precursor composition according to the present embodiment is a porous organosilicon oxide film, that is, a porous silica film, and the structural unit of this porous silica film is as follows: It is represented by chemical formula (1) (subscripts a, b and c are integers).
  • a porous silica membrane is formed from a precursor composition comprising (a) a first alkoxysilane compound, (b) a second alkoxysilane compound, and (c) a nonionic surfactant micelle. .
  • the first alkoxysilane compound is at least selected from the group consisting of tetraalkoxysilane, dialkyldialkoxysilane, tetraalkoxysilane polymer, and dialkyldialkoxysilane polymer.
  • an alkoxy group it is preferable to employ
  • As the alkyl group a methyl group, an ethyl group, and a propyl group are preferably employed, and combinations thereof are also arbitrary.
  • Such first alkoxysilane compounds include, for example, tetramethoxysilane, tetraethoxysilane, methyl silicate, dimethyldimethoxysilane, and dimethyldiethoxysilane, methyltrimethoxysilane, n-propyltrimethoxysilane, hexyltrimethoxysilane, decyl.
  • Examples include trimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-glycidoxypropyltriethoxysilane.
  • the methyl silicate is a tetramethoxysilane multimer, for example, a tetramethoxysilane tetramer (see chemical formula (2)).
  • a polysiloxane skeleton represented as a part of the above chemical formula (1) is obtained by causing a silanol condensation polymerization reaction between two or more molecules of the monomer or polymer constituting the compound.
  • the chemical formula (3) below is formed.
  • a second alkoxysilane compound second alkoxysilane compound has three alkoxy groups (OR-) with one phenyl group (C 6 H 5 -) and are trialkoxy phenylsilane bonded to silicon, It is represented by the following chemical formula (4).
  • the number of carbon atoms of each alkoxy group is preferably 1 to 4. Within this range, the combination of the above three alkoxy groups is also arbitrary.
  • the 2nd alkoxysilane compound is used independently, and 2 or more types may be used together. Examples of such a second alkoxysilane compound include trimethoxyphenylsilane, triethoxyphenylsilane, tripropoxyphenylsilane, and tributoxyphenylsilane.
  • a dealcoholization polycondensation reaction occurs between two or more molecules, whereby a skeleton represented as a part of the chemical formula (1), that is, a skeleton containing a silicon and a phenyl group as a structural unit ( (See chemical formula (5) below). Then, a dealcohol alcohol condensation polymerization reaction occurs between two or more molecules between the first alkoxysilane compound and the second alkoxysilane compound, so that a skeleton having the chemical formula (1) as a structural unit is formed. It is formed.
  • Nonionic surfactant that is, a surfactant having a nonionic hydrophilic group
  • Nonionic surfactant includes, for example, an alkyl polyoxyethylene ether, a fatty acid polyoxy, generally called polyethylene glycol type Ethylene ester, fatty acid polyoxyethylene sorbitan ester, polypropylene glycol polyoxyethylene adduct and the like are used.
  • fatty acid sorbitan esters, fatty acid sucrose esters, fatty acid polyglycerol esters, and the like which are generally called polyhydric alcohol types, can also be used.
  • nonionic surfactants are associated by hydrophobic interaction between molecules in a non-aqueous solvent in which (a) the first alkoxysilane compound, (b) the second alkoxysilane compound, etc. are dissolved,
  • a micelle which is a spherical structure that forms an outer surface with a hydrophilic group, is formed around the end of the molecule on the hydrophobic group side.
  • the nonionic surfactant micelle has a temperature characteristic that it is structurally destroyed when the temperature exceeds the temperature at which the first alkoxysilane compound or the second alkoxysilane compound is copolymerized.
  • the first alkoxysilane compound and the second Two alkoxysilane compounds collect around the micelles.
  • the polycondensation reaction as described above proceeds with the first alkoxysilane compound and the second alkoxysilane compound gathered around the micelle in this way, the first alkoxysilane compound and the second alkoxysilane compound Is formed so as to surround the micelle.
  • micelles are removed from the copolymer of the first alkoxysilane compound and the second alkoxysilane compound, voids are formed in the region where the micelles are present.
  • the diameter of the vacancies thus formed is proportional to the molecular weight of the nonionic surfactant, it is sufficient to select a surfactant having a higher molecular weight when it is desired to increase the vacancy diameter.
  • a surfactant having a smaller molecular weight may be selected.
  • Non-aqueous solvent in the precursor composition, in addition to the above-mentioned first alkoxysilane compound, second alkoxysilane compound, and nonionic surfactant micelle, a non-aqueous solvent for dissolving them Is used.
  • a non-aqueous solvent include alcohol-based, acetone-based, ether-based, and ester-based solvents, and the non-aqueous solvent should be removed from the precursor composition before or when the above polymerization reaction proceeds.
  • a solvent having a boiling point higher than 75 ° C. and lower than 130 ° C. can be used.
  • solvents examples include ethanol (boiling point: 78.4 ° C.) belonging to alcohol, methyl ethyl ketone (boiling point: 79.6 ° C.), methyl isobutyl ketone (boiling point: 116.8 ° C.), and methyl-normal belonging to acetone.
  • Butyl ketone (boiling point: 127 ° C), 1,4-dioxane (boiling point: 101.1 ° C) belonging to the ether system, and isobutyl acetate (boiling point: 118 ° C) and normal-propyl acetate (boiling point: 102 ° C) belonging to the ester system ), Normal-butyl acetate (boiling point: 125-126 ° C.).
  • (E) Reaction catalyst In the precursor composition, in addition to these various compounds, a catalyst for promoting a polycondensation reaction between the first alkoxysilane compound and the second alkoxysilane compound and a polymerization start temperature are adjusted. It is possible to use a catalyst for this as a reaction catalyst.
  • a catalyst for this As the reaction catalyst, an acid catalyst or a base catalyst can be used, and examples thereof include dilute nitric acid or triethylammonium hydroxide.
  • alkalis such as a trimethyl ammonium hydroxide.
  • the basification of the precursor composition resulting from the addition of triethylammonium hydroxide as a reaction catalyst may be neutralized by adding an acid such as dilute nitric acid.
  • the precursor composition having the above structure when the precursor composition is heated near the boiling point of the non-aqueous solvent, evaporation of the non-aqueous solvent contained in the precursor composition is promoted, and the first alkoxy The silane compound and the second alkoxysilane compound gather around the nonionic surfactant micelle. Further, when the precursor composition is heated to a temperature at which the first alkoxysilane compound and the second alkoxysilane compound start copolymerization, an organic silicon oxide film having a polysiloxane skeleton as a main skeleton is formed. Accordingly, nonionic surfactant micelles are included in the organic silicon oxide film.
  • the nonionic surfactant micelles contained in the organic silicon oxide film are destroyed.
  • holes are formed in the space occupied by the micelle. Therefore, the porosity of the porous silica film having a polysiloxane skeleton as the main skeleton, that is, the relative dielectric constant, is defined by the content of the non-surfactant micelle.
  • the surface layer of the porous silica film is naturally a polysiloxane skeleton which is a three-dimensional main skeleton.
  • a phenyl group is also contained inside. That is, the phenyl group is added in such a manner as to be included in the polysiloxane skeleton constituting the porous silica film. And the highly hydrophobic phenyl group will be provided over the whole porous silica film.
  • the inner surface of the void exposed through the recessed portion after etching has a highly hydrophobic phenyl group.
  • the above-described phenyl group can be held on the inner surface of the hole regardless of the shape after the etching.
  • the dissociation of the phenyl group by the etchant proceeds, since the hydrophobicity of the phenyl group is higher than the hydrophobicity of the alkyl group, the dissociation of the phenyl group proceeds to the same extent as the dissociation of the alkyl group. If it exists, it becomes easy to maintain the hydrophobicity of a porous membrane compared with the structure which uses an alkyl group as a hydrophobic group. Therefore, a decrease in hydrophobicity in the porous silica film can be suppressed, and an increase in the dielectric constant of the porous silica film after the processing can be suppressed.
  • hexamethyldisiloxane may be added to the precursor composition in order to modify the alkoxy group bonded to the terminal of the polysiloxane skeleton that becomes the skeleton of the porous silica film.
  • a cyclic molecule such as tetramethylcyclotetrasiloxane or octamethylcyclotetrasiloxane may be added. Since these molecules are included in the polysiloxane skeleton by ring-opening polymerization, it is possible to add 4 or 8 hydrocarbon groups per molecule to the polysiloxane skeleton. Can be improved.
  • the intermolecular distance between the alkoxylsilane compounds generally becomes longer, and the densification of the film is promoted in the portion excluding the vacancies. It becomes difficult to be done.
  • the porous silica film as described above since the porosity of the porous silica film, that is, the dielectric constant of the porous silica film is secured by the content of the non-surfactant micelles, the pores were excluded. No additional holes are required for the part.
  • the first alkoxysilane compound is preferably tetramethoxysilane, tetraethoxysilane, or a polymer of tetramethoxysilane, methyl silicate, dimethyldimethoxysilane, or dimethyldiethoxysilane.
  • the alkoxyl group in the second alkoxysilane compound is also preferably an alkoxyl group having 1 to 4 carbon atoms.
  • the Si atom composition ratio percentage of the first alkoxysilane compound in the precursor composition has a large three-dimensional spread of the polysiloxane skeleton, which is the main skeleton, and is an indicator of the mechanical hardness of the porous silica film. From the viewpoint of increasing the Young's modulus, it is preferably 30 at% or more and 92 at% or less, and more preferably 44 at% or more and 87 at% or less.
  • the Si atom composition percentage of the second alkoxysilane compound in the precursor composition is preferably 5 at% or more and 50 at% or less from the above viewpoint, and more preferably 8 at% or more and 46 at% or less.
  • the Si atom composition percentage of tetramethoxysilane is 44 at% or more and 87 at% or less.
  • the Si atom composition percentage of triethoxyphenylsilane is 13 at% or more and 46 at% or less.
  • the ratio of (a) the first alkoxysilane compound, (b) the second alkoxysilane compound, and (c) the nonionic surfactant micelle is described above in any of the above (d) non-aqueous solvents. Mix in an appropriate ratio and stir at 25 ° C. for 30 minutes, for example.
  • an acid catalyst or a base catalyst, which is a reaction catalyst is added and, for example, stirred at 25 ° C. for 3 hours.
  • the precursor composition of the said porous membrane can be obtained by adding the alkali which neutralizes this acid catalyst, or the acid which neutralizes a base catalyst, and stirring for 24 hours, for example.
  • the precursor composition is preferably liquid at room temperature.
  • the precursor composition thus produced is applied to a film formation target.
  • the precursor composition is applied to a silicon substrate, which is a film formation target, by a spin coat method under the condition of 1200 rpm, for example.
  • Nonionic surfactant micelles are formed in the film made of the precursor composition applied to the substrate, and the first alkoxysilane compound or the second alkoxysilane compound is formed around each micelle particle. Are gathering.
  • the non-aqueous solvent is removed from the precursor composition applied to the substrate.
  • the substrate coated with the precursor composition is heated in a vacuum atmosphere, and the temperature is raised to 350 ° C., for example, for 35 seconds to volatilize the non-aqueous solvent of the precursor composition.
  • the time for heating the substrate may be set to a time during which the non-aqueous solvent contained in the precursor composition can be volatilized.
  • the substrate When the substrate is irradiated with ultraviolet rays in this way, the association state of the nonionic surfactant or the nonionic surfactant itself is destroyed by the ultraviolet rays, so that the nonionic surfactant micelles are removed from the substrate. Removed.
  • these heat treatment and ultraviolet irradiation treatment are not limited to a vacuum atmosphere, and can be performed in a nitrogen atmosphere or an oxygen-containing atmosphere.
  • the surface of the porous silica film is further silylated by exposing the surface of the porous silica film to vapor of hexamethyldisilazane. You may make it implement.
  • a porous silica film precursor composition was prepared using the various compounds described above, and applied to the surface of the substrate to form the porous silica film of the example. Thereafter, the dielectric constant of the porous silica film of the example and the Young's modulus, which is an index of mechanical strength, were measured, and the dielectric constant after the reactive dry etching treatment was performed on the porous silica film was also measured.
  • the first alkoxysilane compound, the second alkoxysilane compound, and the nonionic surfactant were added to a nonaqueous solvent and stirred at 25 ° C. for 30 minutes.
  • an acid catalyst was added and stirred at 25 ° C. for 3 hours, and then an alkali neutralizing the acid catalyst was added and stirred for 24 hours.
  • the precursor composition When forming a porous silica film with the precursor composition thus prepared, first, the precursor composition was spin-coated on the surface of the silicon substrate under the condition of 1200 rpm. The substrate coated with this precursor composition was placed in a vacuum atmosphere, and the temperature was raised to 350 ° C. in 35 seconds. Next, ultraviolet rays having an illuminance of 40 mW / cm 2 and a wavelength of 172 nm were irradiated at 350 ° C. for 20 seconds.
  • the thickness of the porous silica film thus formed was measured with an ellipsometer, and the relative dielectric constant was calculated from the CV characteristics measured using the mercury probe method.
  • the Young's modulus of the porous silica film was measured with a nanoindenter (manufactured by Nanoinstrument).
  • Example 1 Various compounds shown in the above (a) to (e) and (f) a pH adjuster were blended and mixed as follows to prepare the precursor composition of the porous silica film.
  • Non-aqueous solvent ethanol 22.0 ml
  • Reaction catalyst nitric acid solution (0.5%) 15.8 g
  • pH adjuster trimethylammonium hydroxide / propylene glycol monomethyl ether solution 0.00006 mol / 62.0 ml
  • Si atom composition ratio percentage of the said tetraethoxysilane in the said precursor composition is 87 at%
  • Si atom composition ratio percentage of the said trimethoxyphenylsilane in the same precursor composition is 13 at%.
  • the film thickness, relative dielectric constant, and Young's modulus were measured.
  • the film thickness was 151 nm
  • the relative dielectric constant was 2.1
  • the Young's modulus was 6 0.0 GPa.
  • the film thickness was 103 nm and the relative dielectric constant was 2.7. That is, it was recognized that the dielectric constant of the porous silica film was increased by 0.7 by performing the dry etching process.
  • Example 2 Various compounds shown in the above (a) to (e) and (f) a pH adjuster were blended and mixed as follows to prepare the precursor composition of the porous silica film.
  • pH adjuster trimethylammonium hydroxide / propylene glycol monomethyl ether solution 0.00009 mol / 93.0 ml
  • pH adjuster trimethylam
  • the film thickness, relative dielectric constant, and Young's modulus were measured.
  • the film thickness was 202 nm
  • the relative dielectric constant was 2.0
  • the Young's modulus was 5 It was 5 GPa.
  • the film thickness was 110 nm and the relative dielectric constant was 3.0. That is, the dielectric constant of the porous silica film increased by 1.0 due to the dry etching process.
  • the film thickness, relative dielectric constant, and Young's modulus were measured.
  • the film thickness was 213 nm
  • the relative dielectric constant was 2.0
  • the Young's modulus was 5 0.7 GPa.
  • the film thickness was 100 nm and the relative dielectric constant was 2.7. That is, the dielectric constant of the porous silica film increased by 0.7 due to the dry etching process.
  • the film thickness was 191 nm, the relative dielectric constant was 2.0, and the Young's modulus was 6 It was 5 GPa.
  • the film thickness was 102 nm and the relative dielectric constant was 3.8. That is, the relative dielectric constant of the porous silica film increased by 1.8 due to the dry etching process.
  • the increase in the dielectric constant after the dry etching process in the example was 0.7, while the increase in the dielectric constant after the dry etching process in the comparative example was 1.8. That is, in the above example, the polysiloxane skeleton constituting the porous silica film contains a hydrophobic phenyl group, so that hydrocarbon group detachment is suppressed even after dry etching treatment, and the ratio is reduced. It can be said that the increase in dielectric constant was suppressed.
  • the Young's modulus of the example was 6.0 GPa, and it was confirmed that the Young's modulus of the comparative example was substantially the same.
  • the mechanical strength of the porous membrane is ensured if the number of carbon atoms of each alkoxy group of the trialkoxysilane group is 1 to 4. It is possible to protect the hydrophobic group in the film more reliably.
  • the precursor composition of the porous silica film is equal to or higher than the temperature at which the first alkoxysilane compound, the second alkoxysilane compound, the first alkoxysilane compound, and the second alkoxysilane compound are copolymerized.
  • nonionic surfactant micelles that break down.
  • an organic silicon oxide film having a polysiloxane skeleton as a main skeleton is formed under a condition in which the first alkoxysilane compound and the second alkoxysilane compound are copolymerized, and the organic silicon oxide film is formed in the organic silicon oxide film.
  • Nonionic surfactant micelles are included.
  • the nonionic surfactant micelles contained in the organic silicon oxide film are destroyed, and the spaces occupied by the micelles are destroyed. Holes are formed. Therefore, the porosity of the porous silica film having a polysiloxane skeleton as the main skeleton, that is, the relative dielectric constant, is defined by the content of the nonionic surfactant micelle.
  • the surface layer of the porous silica film includes phenyl groups in the three-dimensional polysiloxane skeleton.
  • the phenyl group is also added to the porous silica film surrounded by the polysiloxane skeleton.
  • a highly hydrophobic phenyl group is imparted over the entire silica film.
  • the inner surface of the void exposed through the etched surface has a highly hydrophobic phenyl group.
  • the above-described phenyl group can be held on the inner surface of the hole regardless of the shape after the etching.
  • the dissociation of the phenyl group by the etchant proceeds, since the hydrophobicity of the phenyl group is higher than the hydrophobicity of the alkyl group, the dissociation of the phenyl group proceeds to the same extent as the dissociation of the alkyl group. If it exists, it becomes easy to maintain the hydrophobicity of a porous membrane compared with the structure which uses an alkyl group as a hydrophobic group. Therefore, it can suppress that the dielectric constant of a porous silica film increases after the process.
  • a hydrophobic functional group added to the polysiloxane skeleton.
  • the first alkoxysilane compound is methyltrimethoxysilane, n-propyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, vinyltriethoxy.
  • the porous film is formed of an alkoxysilane compound having an alkoxy group having 1 or 2 carbon atoms. This promotes densification of the membrane in the area excluding the pores, so it is possible to ensure the mechanical strength of the porous silica membrane and to protect the hydrophobic groups in the membrane more reliably. It also becomes.
  • Each alkoxy group of trialkoxyphenylsilane is an alkoxy group having 1 to 4 carbon atoms. This promotes densification of the membrane in the area excluding the pores, so it is possible to ensure the mechanical strength of the porous silica membrane and to protect the hydrophobic groups in the membrane more reliably. It also becomes.
  • the substance amount of the second alkoxysilane compound is included in the first alkoxysilane compound in a range that improves the hydrophobicity of the porous film and does not reduce the mechanical strength of the porous film.
  • the amount is adjusted to be greater than 10% and less than 100% of the amount of silicon.
  • the second alkoxysilane compound is formed 3 to 5 times the amount of the first alkoxysilane compound to form a polysiloxane skeleton.
  • a polysiloxane skeleton is formed by the second alkoxysilane compound having more possible alkoxyl groups, and as a result, the mechanical strength as a porous film is secured.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Paints Or Removers (AREA)
  • Formation Of Insulating Films (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Silicon Polymers (AREA)

Abstract

Selon l'invention, la composition de précurseur pour membrane poreuse présente une structure telle qu'elle contient : un premier composé d'alcoxysilane, un second composé d'alcoxysilane, et des micelles tensioactives non ioniques détruites à une température supérieure ou égale à celle de la copolymérisation dudit premier composé d'alcoxysilane et dudit second composé d'alcoxysilane. Parmi ces composants, le premier composé d'alcoxysilane est au moins un élément choisi dans un groupe constitué de tétraalcoxysilane, monoalkyltrialcoxysilane, dialkyldialcoxysilane, polymère de tétraalcoxysilane, polymère de monoalkyltrialcoxysilane et polymère de dialkyldialcoxysilane; et le second composé d'alcoxysilane est un trialkoxyphénylsilane.
PCT/JP2010/069110 2009-10-27 2010-10-27 Composition de précurseur pour membrane poreuse et procédé de formation de membrane poreuse WO2011052657A1 (fr)

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JP2013200389A (ja) * 2012-03-23 2013-10-03 Fuji Xerox Co Ltd 静電荷像現像用トナー、静電荷像現像剤、トナーカートリッジ、現像剤カートリッジ、プロセスカートリッジ、画像形成装置、及び、画像形成方法
JP2014080304A (ja) * 2012-10-12 2014-05-08 Ulvac Japan Ltd 多孔質シリカ膜前駆体組成物、多孔質シリカ膜の製造方法及び多孔質シリカ膜並びに半導体素子

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JP2003277042A (ja) * 2002-03-19 2003-10-02 Mitsui Chemicals Inc 表面平滑性に優れる多孔質シリカフィルムの製造方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012251119A (ja) * 2011-06-07 2012-12-20 Ulvac Japan Ltd ポーラスシリカ前駆体組成物及びその作製方法、ポーラスシリカ膜及びその作製方法、並びに半導体素子
JP2013200389A (ja) * 2012-03-23 2013-10-03 Fuji Xerox Co Ltd 静電荷像現像用トナー、静電荷像現像剤、トナーカートリッジ、現像剤カートリッジ、プロセスカートリッジ、画像形成装置、及び、画像形成方法
JP2014080304A (ja) * 2012-10-12 2014-05-08 Ulvac Japan Ltd 多孔質シリカ膜前駆体組成物、多孔質シリカ膜の製造方法及び多孔質シリカ膜並びに半導体素子

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