JP2008019285A - Method for producing metal-containing polymer, metal-containing polymer, photosensitive resin composition and semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a metal-containing polymer by which the formation of gelled materials or particles can be suppressed and the polymer enhancing electrical characteristics can be obtained when used for composing an insulating film, etc., e.g. a semiconductor element. <P>SOLUTION: The method for producing the metal-containing polymer comprises reacting a component (A) composed of a metal compound, a hydrolyzate thereof or a condensate of the hydrolyzate with a component (B) composed of a metal compound, a hydrolyzate thereof or a condensate of the hydrolyzate. The method is carried out as follows. When the component (A) is reacted with the component (B), the component (B) has higher reactivity than that of the component (A). Furthermore, the component (A) is introduced into a container and the component (B) is then continuously or stepwise added into the container to react the component (A) with the component (B). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a metal-containing polymer obtained by reacting a plurality of components having different reactivities, and more specifically, a method for producing a metal-containing polymer in which a method for adding a plurality of components during reaction is improved, The present invention relates to a metal-containing polymer obtained by a production method, a photosensitive resin composition using the metal-containing polymer, and a semiconductor element.

  Conventionally, a metal compound-based copolymer has been synthesized by reacting a metal compound containing a metal such as silicon. A copolymer obtained by a condensation reaction of a silicon-containing compound containing silicon is used, for example, for an interlayer insulating film of a semiconductor element.

  In Patent Document 1 below, as a method for producing this type of copolymer, (A) a polysiloxane compound and (B) a polycarbosilane compound are mixed and heated in the presence of a catalyst, water and an organic solvent. A process for producing a polymer comprising steps is disclosed.

  In Patent Document 1, when both (A) the polysiloxane compound and (B) the polycarbosilane compound have Si—OH groups, (B) the Si—OH group in the polycarbosilane compound and (A) the polysiloxane compound It is said that a polymer having no phase separation can be obtained by condensing polysiloxane and polycarbosilane by condensing with Si—OH groups therein.

Even if (B) the polycarbosilane compound does not have a Si—OH group, the (B) polycarbosilane compound contains a Si—H group, or Si—OH group by hydrolysis. Si-OH group can be introduced into the (B) polycarbosilane compound. Therefore, even if (B) the polycarbosilane compound has no Si—OH group, (B) the Si—OH group in the polycarbosilane compound and (A) the Si—OH in the polysiloxane compound It is said that the polysiloxane and polycarbosilane can be combined by the condensation with the group.
JP 2005-272816 A

  In Patent Document 1, a polymer is obtained by reacting two or more different compounds of (A) a polysiloxane compound and (B) a polycarbosilane compound. When reacting two or more different compounds, if the reactivity between the compounds is greatly different, one of the highly reactive compounds will aggregate and only the highly reactive compound will react alone. In some cases, the polymer contained gelled products and particles. Alternatively, a highly reactive compound may react at a relatively high rate with a less reactive compound to generate a gelled product or particles.

  Such a gelled product or a polymer containing particles tends to be inferior in handling property, storage stability and the like. In order to improve handling property and storage stability, it was possible to filter the polymer and remove gelled products and particles to some extent, but gelled products and particles could not be completely removed. Further, when an interlayer insulating film of a semiconductor element, for example, is formed using a gelled product or a polymer containing particles, the obtained semiconductor element tends to be inferior in electrical characteristics.

  The object of the present invention is to prevent the generation of gelled substances and particles in view of the above-mentioned state of the art, and when used for forming an insulating film such as a semiconductor element, Provided are a method for producing a metal-containing polymer capable of obtaining a polymer capable of enhancing properties, a metal-containing polymer obtained by the production method, and a photosensitive resin composition and a semiconductor device using the metal-containing polymer. There is to do.

  The method for producing a metal-containing polymer according to the present invention is represented by the following formula (2), a component (A) composed of a metal compound represented by the following formula (1), a hydrolyzate thereof or a condensate of the hydrolyzate. A metal-containing polymer produced by reacting a component (B) comprising a metal compound, a hydrolyzate thereof or a condensate of the hydrolyzate, comprising the component (A) and the component (B) When the component (B) has a higher reactivity than the component (A), the component (A) is continuously put in the container after the component (A) is put in the container. Or it adds in steps, The said component (A) and the said component (B) are made to react.

_{(Xa) p Ma (Za)} i-p ··· (1)
In the above formula (1), Ma represents a trivalent, tetravalent or pentavalent metal atom, Xa represents a non-hydrolyzable organic group having 1 to 30 carbon atoms, Za represents a hydrolyzable group, i is 3, when Ma is trivalent, 4 when it is tetravalent, 5 when it is pentavalent, p <i, and p is an integer of 0-4. When there are a plurality of Xa, the plurality of Xa may be the same or different. When there are a plurality of Zas, the plurality of Zas may be the same or different.

_{(Xb) q Mb (Zb)} i-q ··· formula (2)
In the above formula (2), Mb represents a trivalent, tetravalent or pentavalent metal atom, Xb represents a non-hydrolyzable organic group having 1 to 30 carbon atoms, Zb represents a hydrolyzable group, i is 3, when Ma is trivalent, 4 when it is tetravalent, 5 when it is pentavalent, q <i, and q is an integer of 0-4. When there are a plurality of Xb, the plurality of Xb may be the same or different. When Zb is plural, the plural Zb may be the same or different.

  In a specific aspect of the method for producing a metal-containing polymer according to the present invention, as the component (A), a silicon-containing compound in which Ma in the formula (1) is silicon, a hydrolyzate thereof, or a condensate of the hydrolyzate. As the component (B), a component comprising a silicon-containing compound in which Mb is silicon in the above-described formula (2), a hydrolyzate thereof, or a condensate of the hydrolyzate is used.

  In another specific aspect of the method for producing a metal-containing polymer according to the present invention, as the component (A), a silicon-containing compound in which Ma in the formula (1) is silicon is used, and as the component (B), A silicon-containing compound in which Mb in the formula (2) is silicon is used.

  In still another specific aspect of the method for producing a metal-containing polymer according to the present invention, when the reaction rate of the component (A) when only the component (A) is reacted is 10%, the component (B ) Is added continuously or intermittently in such an amount that the reaction rate of the component (B) is 5% to 40%.

  In another specific aspect of the method for producing a metal-containing polymer according to the present invention, only the component (B) is obtained when the reaction rate of the component (A) is 50% when only the component (A) is reacted. Is added continuously or intermittently in such an amount that the reaction rate of the component (B) is 30% to 70%.

  In another specific aspect of the method for producing a metal-containing polymer according to the present invention, the component (B) is added at a ratio of 0.0001 to 99.9999 parts by weight with respect to 100 parts by weight of the component (A).

  The metal-containing polymer according to the present invention is obtained by the method for producing a metal-containing polymer of the present invention.

  The photosensitive resin composition according to the present invention comprises a metal-containing polymer constituted according to the present invention and an acid or base generator that generates an acid or a base upon irradiation with light or radiation.

  The semiconductor device according to the present invention includes at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film, and the film includes the metal-containing polymer or the present invention configured according to the present invention. It is set as the film | membrane formed using the photosensitive resin composition comprised according to this.

  In the method for producing a metal-containing polymer according to the present invention, when the component (A) and the component (B) are reacted, the component (B) has higher reactivity than the component (A), and the component (B After adding A), component (B) is added continuously or stepwise into the container, and component (A) and component (B) are reacted, so that highly reactive component (B) aggregates. Only the highly reactive component (B) reacts alone, or the component (B) can be prevented from reacting at a relatively high rate with respect to the component (A). Therefore, generation | occurrence | production of a gelled material and particle | grains can be suppressed.

  As the component (A), a silicon-containing compound in which Ma is silicon in the above-described formula (1), a hydrolyzate thereof, or a hydrolyzate condensate is used, and the above-described formula is used as the component (B). (2) In the case of using a component comprising a silicon-containing compound in which Mb is silicon, a hydrolyzate thereof or a condensate of the hydrolyzate, the generation of gelled products and particles in the metal-containing polymer can be further reduced. it can.

  When the reaction rate of component (A) when only component (A) is reacted is 10%, the reaction rate of component (B) when only component (B) is reacted is from 5%. When the component (B) in an amount of 40% is added continuously or intermittently, the dispersibility of the component (A) and the component (B) can be improved, and the component (A) is aggregated. Can be suppressed. Furthermore, it is possible to effectively prevent only the component (A) from reacting alone or reacting the component (A) at a relatively high rate with respect to the component (B).

  When the reaction rate of the component (A) is 50% when only the component (A) is reacted, the component (B) is continuously added in such an amount that the reaction rate of the component (B) is 30% to 70%. Or when adding intermittently, the dispersibility of a component (A) and a component (B) can be improved, and it can suppress that a component (B) aggregates. Furthermore, it is possible to effectively prevent only the component (B) from reacting alone or reacting the component (B) with the component (A) at a relatively high rate.

  In the metal-containing polymer obtained by the method for producing a metal-containing polymer of the present invention, the contents of gelled products and particles are reduced. Therefore, when an insulating film or the like is formed using the metal-containing polymer of the present invention, the electrical characteristics can be improved.

  Since the photosensitive resin composition according to the present invention contains the metal-containing polymer of the present invention and an acid or base generator that generates an acid or a base upon irradiation with light or radiation, the photosensitive resin composition has photosensitivity and alkali development. Thus, a thin film pattern can be easily formed.

  The semiconductor device according to the present invention includes at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film, and the film includes the metal-containing polymer of the present invention or the photosensitive property of the present invention. Since it is a film formed using a resin composition, it has excellent electrical characteristics.

  Details of the present invention will be described below.

  The method for producing a metal-containing polymer according to the present invention is represented by the following formula (2), a component (A) composed of a metal compound represented by the following formula (1), a hydrolyzate thereof or a condensate of the hydrolyzate. A metal-containing polymer is obtained by reacting a component (B) comprising a metal compound, a hydrolyzate thereof or a condensate of the hydrolyzate.

_{(Xa) p Ma (Za)} i-p ··· (1)
In the above formula (1), Ma represents a trivalent, tetravalent or pentavalent metal atom, Xa represents a non-hydrolyzable organic group having 1 to 30 carbon atoms, and Za represents a hydrolyzable group. , I is 3, when Ma is trivalent, 4 when it is tetravalent, 5 when it is pentavalent, p <i, and p represents an integer of 0-4. When there are a plurality of Xa, the plurality of Xa may be the same or different. When there are a plurality of Zas, the plurality of Zas may be the same or different.

_{(Xb) q Mb (Zb)} i-q ··· formula (2)
In the above formula (2), Mb represents a trivalent, tetravalent or pentavalent metal atom, Xb represents a non-hydrolyzable organic group having 1 to 30 carbon atoms, and Zb represents a hydrolyzable group. , I is 3, when Ma is trivalent, 4 when it is tetravalent, 5 when it is pentavalent, q <i, and q is an integer of 0-4. When there are a plurality of Xb, the plurality of Xb may be the same or different. When Zb is plural, the plural Zb may be the same or different.

  The hydrolyzable groups Za and Zb are usually hydrolyzed to form silanol groups by heating within the temperature range of room temperature (25 ° C.) to 100 ° C. without catalyst in the presence of excess water. A group that can be condensed or further condensed to form a siloxane bond.

  Examples of the hydrolyzable groups Za and Zb include C1-C6 alkoxy groups such as a methoxy group, an ethoxy group, and a propoxy group. The hydrolyzable groups Za and Zb may be hydrogen, halogens such as chlorine and bromine, amino groups, hydroxyl groups, or carboxyl groups.

  Examples of the non-hydrolyzable organic groups Xa and Xb include organic groups having 1 to 30 carbon atoms, which are hardly hydrolyzed and are stable hydrophobic groups. As the organic group having 1 to 30 carbon atoms which is a stable hydrophobic group, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group, pentyl group, decyl group, dodecyl group, tetradecyl group, Alkyl groups having 1 to 30 carbon atoms such as hexadecyl group, octadecyl group and eicosyl group, and alkyl halide groups such as fluorinated, chlorinated and brominated alkyl groups (for example, 3-chloropropyl group, 6-chloropropyl group) , 6-chlorohexyl group, 6,6,6-trifluorohexyl group, etc.), aromatic substituted alkyl groups such as halogen-substituted benzyl groups (for example, benzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, etc.) ), Aryl groups (eg phenyl group, tolyl group, mesityl group, naphthyl group, etc.), vinyl groups and epoxy groups Group, an organic group containing an amino group, and the like organic group containing a thiol group.

  Examples of the trivalent, tetravalent or pentavalent metal atoms Ma and Mb include tetravalent metal atoms such as silicon, titanium and zirconium, trivalent metal atoms such as aluminum, and pentavalent metal atoms such as tantalum. It is done.

  In the present invention, as the component (A), a component comprising a silicon-containing compound in which Ma in the formula (1) is silicon, a hydrolyzate thereof or a condensate of the hydrolyzate is used, and the component (B) is used. It is preferable to use a component comprising a silicon-containing compound in which Mb in the formula (2) is silicon, a hydrolyzate thereof or a condensate of the hydrolyzate. In this case, generation | occurrence | production of the gelled material and particle | grains in a metal containing polymer can be reduced further.

  Specific examples of the silicon-containing compound include, for example, trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyl-tri-n-propoxysilane. , Ethyltrimethoxysilane, ethyltriethoxysilane, ethyl-tri-n-propoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyl-tri-n-propoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyl Tripropoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n- Xyltripropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecyltripropoxysilane, Tetradecyltrimethoxysilane, tetradecyltriethoxysilane, tetradecyltripropoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, hexadecyltripropoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltripropoxysilane , Eicosyldecyltrimethoxysilane, eicosyltriethoxysilane, Icosyltripropoxysilane, 6-chlorohexyltrimethoxysilane, 6,6,6-trifluorohexyltrimethoxysilane; benzyltrimethoxysilane, 4-chlorobenzyltrimethoxysilane, 4-bromobenzyltri-n-propoxysilane Dodecyltrichlorosilane, dodecyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxysilane), β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyl Examples include trimethoxysilane.

  In the present invention, a silicon-containing compound in which Ma in the formula (1) is silicon is used as the component (A), and a silicon-containing compound in which Mb in the formula (2) is silicon as the component (B). More preferably, a compound is used. In this case, the generation of gelled products and particles in the metal-containing polymer can be further reduced.

  Since component (A) can suppress the generation of gelled products and particles, phenyltriethoxysilane, isobutyltrimethoxysilane, and ethyltriethoxysilane are more preferably used. As component (B), the generation of gelled products and particles can be suppressed, so that triethoxysilane, trimethoxysilane, and vinyltriethoxysilane are more preferably used.

  Since generation of gelled products and particles can be further suppressed, it is more preferable to use phenyltriethoxysilane as the component (A) and triethoxysilane as the component (B).

  When the tetravalent metal atoms Ma and Mb are metal atoms other than silicon, specific examples of the metal compound represented by the above formula (1) and the metal compound represented by the above formula (2) are as follows: Examples include tetrabutoxy titanium, tetrapropoxy titanium, tetraethoxy zirconium, tetraisopropoxy hafnium, and triisopropoxy aluminum.

  In this invention, the component (A) which consists of a metal compound represented by Formula (1) mentioned above, the hydrolyzate of a metal compound, or the condensate of the hydrolyzate of a metal compound is used. As the component (A), the metal compound, the hydrolyzate of the metal compound, or the condensate of the hydrolyzate of the metal compound may be used alone or in combination of two or more. As the component (A), it is preferable that one of these components is used alone.

  In the present invention, in addition to the component (A), the component (B) comprising the metal compound represented by the above formula (2), the hydrolyzate of the metal compound, or the condensate of the hydrolyzate of the metal compound is further included. Used. As the component (B), the metal compound, the hydrolyzate of the metal compound, or the condensate of the hydrolyzate of the metal compound may be used alone or in combination of two or more. As the component (B), it is preferable that one of these components is used alone.

  In the method for producing a metal-containing polymer according to the present invention, when the component (A) and the component (B) are reacted, the component (B) has higher reactivity than the component (A), and the component (B After putting A), component (B) is added continuously or stepwise into the container to react component (A) with component (B). In this production method, the reaction can be performed in an inert gas atmosphere as necessary.

  The feature of the present invention is that the component (A) and the component (B) are not simultaneously put into the container to start the reaction, but the component (B) having a higher reactivity than the component (A) is added to the component (A). The component (A) and the component (B) are reacted while being added continuously or stepwise. By reacting in this way, it is possible to effectively prevent only the highly reactive component (B) from reacting alone or reacting with the component (A) at a relatively high rate. be able to. Therefore, generation | occurrence | production of a gelled material and particle | grains can be suppressed effectively.

In the present invention, when component (A) and component (B) are reacted, component (B) has a higher reactivity than component (A). This is because when component (A) and component (B) coexist in the production environment of the metal-containing polymer of the present invention, the rate of hydrolysis of component (B) is the rate of hydrolysis of component (A). This means that the reaction of the component (B) is easier to proceed than the component (A). The level of reactivity between the component (B) and the component (A) is attributed to hydrolysis of the alkoxide or hydroxyl group by, for example, calculating the rate of increase of the weight average molecular weight by GPC, or by ¹ H NMR measurement in the solution. This can be confirmed by experiment by measuring the half width of the resonance line.

  In producing the metal-containing polymer, it is preferable to continuously add the component (B) into the container. By continuously adding the component (B) to the component (A), the component (A) and the component (B) can be effectively reacted.

  In the production of the metal-containing polymer, the component (B) when only the component (B) is reacted when the reaction rate of the component (A) when only the component (A) is reacted becomes 10%. It is preferable to add component (B) in such an amount that the reaction rate of 5% to 40% is continuously or intermittently added. More preferably, the reaction rate of the component (B) when only the component (B) is reacted at the time when the reaction rate of the component (A) when the component (A) alone is reacted is 50%. Component (B) in an amount from 30% to 70% is added continuously or intermittently. When the added amount of component (B) is such that the reaction rate of component (B) exceeds 40%, the dispersibility between component (A) and component (B) is poor, and only component (B) reacts alone. Or the component (B) is likely to react with the component (A) at a relatively high rate, and gelled products and particles are easily generated. When the reaction rate of the component (B) is less than 5%, only the component (A) is likely to condense first.

  Before adding the component (B), it is preferable to dilute the component (A) by a volume ratio of 1.1 to 1000 times using water and / or a solvent. More preferably, it is a diluted solution obtained by diluting component (A) 1.2 to 20 times. More preferably, it is a diluted solution obtained by diluting the component (A) 5 times. When the dilution ratio of the component (A) is less than 1.2 times, the dispersibility between the component (A) and the component (B) is inferior, and only the component (A) reacts alone or the component (B). On the other hand, component (A) may react at a relatively high rate. When the dilution ratio of the component (A) exceeds 20 times, the diluted solution of the component (A) may be too much.

  It is preferable to dilute the component (B) 1.2 to 20 times in volume ratio using water and / or a solvent, and add the component (B) as a diluted solution to the component (A). More preferably, it is a diluted solution obtained by diluting component (B) 1.2 to 20 times. More preferably, it is a diluted solution obtained by diluting the component (B) 5 times. When the dilution ratio of the component (B) is less than 1.2 times, the dispersibility between the component (A) and the component (B) is inferior, and only the component (B) reacts alone, or the component (A) On the other hand, component (B) may react at a relatively high rate. When the dilution ratio of the component (B) exceeds 20 times, the diluted solution of the component (B) may be too much.

  The solvent used for diluting the component (A) or the component (B) is not particularly limited as long as the silicon-containing polymer (P) can be dissolved, but benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene. , Aromatic hydrocarbon compounds such as diethylbenzene; cyclohexane, cyclohexene, dipentene, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, Saturated or unsaturated hydrocarbon compounds such as isodecane, tetrahydronaphthalene, squalane; diethyl ether, di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethylpropyl ether, diphenyl ether, diethyl Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethylene glycol dipropyl ether, ethylene glycol methyl ethyl ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol Rumonoethyl ether acetate, ethylcyclohexane, methylcyclohexane, p-menthane, o-menthane, m-menthane; ethers such as dipropyl ether, dibutyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl Ketones such as amyl ketone, cyclopentanone, cyclohexanone, cycloheptanone; ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, lactic acid Examples thereof include esters such as butyl, isoamyl lactate and butyl stearate. These solvents may be used independently and 2 or more types may be used together.

  In the production of the metal-containing polymer, it is preferable to add the component (B) at a ratio of 0.0001 to 99.9999 parts by weight with respect to 100 parts by weight of the component (A). More preferably, component (B) is added in a proportion of 0.1 to 50 parts by weight. When the component (B) is less than 0.0001 parts by weight, the dispersibility between the component (A) and the component (B) is inferior, and only the component (A) reacts alone or with respect to the component (B). The component (A) is likely to react at a very high ratio, and gelled products and particles are easily generated. When the component (B) exceeds 99.9999 parts by weight, the dispersibility between the component (A) and the component (B) is inferior, and only the component (B) reacts alone, or the component (A) with respect to the component (A) (B) is likely to react at a very high rate, and gelled products and particles are likely to be generated.

  In the production of the metal-containing polymer, in addition to the components (A) and (B), water, and a solvent, a catalyst, an organic polymer, and the like may be further added as necessary.

  The photosensitive resin composition according to the present invention contains a metal-containing polymer produced as described above, and an acid or base generator that generates an acid or a base by irradiation with light or radiation. A metal containing polymer may be used independently and 2 or more types may be used together.

Although it does not specifically limit as said acid or base generator, For example, onium salt etc. are mentioned. More specifically, diazonium, phosphonium, and iodonium salts such as BF ₄ ⁻ , PF ₆ ⁻ , SBF ₆ ⁻ , and ClO ₄ ^— , and other organic halogen compounds, organic metals, and organic halides can be used. .

  The acid generator that generates an acid upon irradiation with light or radiation is not particularly limited, but triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethaneantimonate, triphenylsulfonium benzosulfonate, cyclohexylmethyl (2- Sulfonium salt compounds such as oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, and diphenyliodonium trifluoromethanesulfonate Iodonium salts such as N-hydroxysuccini De trifluoromethanesulfonate, and the like. An acid generator may be used independently and 2 or more types may be used together.

  The acid generator is not particularly limited, but preferably, at least one compound selected from the group consisting of a more reactive onium salt, diazonium salt, and sulfonic acid ester is used.

  The content ratio of the acid generator is desirably in the range of 0.05 to 50 parts by weight with respect to 100 parts by weight of the metal-containing polymer. If the acid generator is less than 0.05 parts by weight, the sensitivity may not be sufficient, and formation of a thin film pattern may be difficult. When the acid generator exceeds 50 parts by weight, it is difficult to uniformly apply the photosensitive resin composition, and a residue may be generated after development.

  In addition to these photosensitizer acid or base generators, a sensitizer may be further added to increase sensitivity.

  The sensitizer is not particularly limited. Specifically, benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, Anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2- Chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-t rt-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis ( 5,7-dimethoxycarbonylcoumarin) and coronene, and the like are preferable.

  The base generator that generates a base upon irradiation with light or radiation is not particularly limited, and examples thereof include cobaltamine complexes, o-acyloximes, carbamic acid derivatives, formamide derivatives, quaternary ammonium salts, tosylamines, carbamates, and amine imides. A compound etc. can be mentioned. Specific examples include 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide, 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate, and the like. . A base generator may be used independently and 2 or more types may be used together.

  As the base generator, an amine imide compound that generates a base by irradiation with light or radiation is preferably used. Such an amine imide compound is not particularly limited as long as it generates a base when irradiated with light or radiation. Examples of such amine imide compounds include compounds represented by the following general formula (3) or (4).

In the above formulas (3) and (4), R ¹ , R ² and R ³ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkylidene having 1 to 8 carbon atoms. Group, a cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, a phenoxyalkyl group having 7 to 12 carbon atoms, a phenyl group, an electron donating group and / or an electron withdrawing group And a benzyl group substituted with a group, a benzyl group, an electron donating group and / or an electron withdrawing group. As a C1-C8 alkyl group, the alkyl group which has a substituent other than a linear alkyl group, for example, an isopropyl group, an isobutyl group, t-butyl group etc. are included. Among these substituents, from the viewpoint of ease of synthesis, solubility of amine imide, etc., an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, and a phenoxyalkyl group having 7 to 12 carbon atoms. Is preferred. R ⁴ independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a cycloalkyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group. Ar ¹ in the general formula (3) is an aromatic group, and such an amine imide compound is known prior to the filing of the present application as disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-35949. Are available. In the general formula (4), Ar ² is an aromatic group.

  The amine imide compound has a higher base generation efficiency than a compound that generates a primary or secondary amine when irradiated with light or radiation. Therefore, it is desirable to include an amine imide compound because the exposure time can be shortened and the manufacturing process can be shortened.

  The content ratio of the base generator is desirably in the range of 0.05 to 50 parts by weight with respect to 100 parts by weight of the metal-containing polymer. If the base generator is less than 0.05 parts by weight, the sensitivity may not be sufficient and it may be difficult to form a thin film pattern. When the base generator exceeds 50 parts by weight, it is difficult to uniformly apply the photosensitive resin composition, and a residue may be generated after development.

  In addition, in order to obtain an optimal resist shape, the acid generator generating the acid and the base generator generating the base may be used in combination of two or more.

  In the present invention, an appropriate solvent may be added in addition to the metal-containing polymer and the acid or base generator that generates an acid or a base upon irradiation with light or radiation. By adding a solvent, a photosensitive resin composition that can be easily applied can be provided.

  The solvent is not particularly limited as long as it can dissolve the metal-containing polymer, but is an aromatic hydrocarbon compound such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene; cyclohexane, cyclohexene, dipentene, n-pentane. Saturated or unsaturated hydrocarbon compounds such as isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane; Di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, Ethylene glycol methyl ethyl ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl cyclohexane, methyl Cyclohexane, p-menthane, o-menthane, m-menthane; ethers such as dipropyl ether and dibutyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, Ketones such as cycloheptanone; ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, butyl stearate, etc. And the like. These solvents may be used independently and 2 or more types may be used together.

  What is necessary is just to select the mixing | blending ratio of the said solvent suitably so that it may apply uniformly, for example when apply | coating the photosensitive resin composition on a board | substrate and forming the photosensitive resin composition layer. Preferably, the concentration of the photosensitive resin composition is 0.5 to 60% by weight, more preferably about 2 to 40% by weight in terms of solid content.

  If necessary, other additives may be further added to the photosensitive resin composition according to the present invention. Such additives include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, UV absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, plasticizers, plasticizers. Examples include accelerators and sagging inhibitors.

  As a method for forming a pattern using the photosensitive resin composition according to the present invention, for example, as shown in FIG. 1A, a photosensitive resin composition layer 1 made of the photosensitive resin composition according to the present invention is used. A step of forming, and then a step of selectively exposing the photosensitive resin composition layer 1 using a photomask 3 corresponding to the pattern to form a patterned latent image 1A (FIG. 1B); And a step of developing the photosensitive layer 1B on which the latent image is formed with an alkaline aqueous solution (FIG. 1C). Here, development means an operation of immersing the photosensitive layer 1B on which a latent image is formed in an alkaline aqueous solution, an operation of washing the surface of the photosensitive layer 1B with an alkaline aqueous solution, or an alkaline aqueous solution on the surface of the photosensitive layer 1B. It includes various operations for treating the photosensitive layer 1B with an alkaline aqueous solution, such as a spraying operation. The developing solution is not limited to an alkaline aqueous solution, and an acidic aqueous solution or various solvents may be used. Examples of the solvent include the various solvents described above. Examples of the acidic aqueous solution include oxalic acid, formic acid, acetic acid and the like.

  Although the process of forming the said photosensitive resin composition layer is not specifically limited, For example, the photosensitive resin composition which concerns on this invention is provided on the board | substrate 2 shown in FIG. 1, and the photosensitive resin composition layer 1 is formed. A method is mentioned. As a specific method in this case, a general coating method can be used, for example, dip coating, roll coating, bar coating, brush coating, spray coating, spin coating, extrusion coating. Work, gravure coating, etc. can be used. As the substrate on which the photosensitive resin composition is applied, a silicon substrate, a glass substrate, a metal plate, a plastics plate, or the like is used depending on the application. The thickness of the photosensitive resin composition layer varies depending on the use, but 10 nm to 10 μm is a standard. When the photosensitive resin composition layer coated on the substrate uses a solvent to dissolve the photosensitive resin, it is preferable to heat-treat the solvent to dry the solvent. The heat treatment temperature is generally 40 ° C. to 200 ° C., and is appropriately selected according to the boiling point and vapor pressure of the solvent.

  A photosensitive resin composition layer is formed on a substrate, heat-treated as necessary, and then the photosensitive resin composition layer is covered with a photomask and irradiated with light in a pattern. Thereby, a latent image having a necessary pattern shape can be formed. What is necessary is just to use the common thing marketed as a photomask.

The light source for irradiating light rays such as ultraviolet rays and visible rays, or radiation is not particularly limited, and an ultrahigh pressure mercury lamp, a deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer laser, etc. can be used. . These light sources are appropriately selected according to the photosensitive wavelength of the sensitizer. The light irradiation energy is generally in the range of 10 to 1000 mJ / cm ² , although it depends on the desired film thickness and type of sensitizer. When it is less than 10 mJ / cm ² , the metal-containing polymer is not sufficiently exposed. On the other hand, if it is larger than 1000 mJ / cm ² , the exposure time may be long, and the production efficiency per pattern time may be reduced.

  In the exposed portion of the photosensitive resin composition layer irradiated with light in the pattern shape, as described above, crosslinking of the metal-containing polymer proceeds by the action of an acid or base generator or the like by exposure. Therefore, the exposed portion becomes insoluble in the developer as a result of the progress of crosslinking. By developing the exposed photosensitive resin composition layer using a developer, the unexposed portion of the photosensitive resin composition layer is dissolved and removed in the developer, and the exposed portion remains on the substrate. As a result, a film pattern is formed. This film pattern is called a negative pattern because the unexposed part is removed.

  As the developer, an explosion-proof facility is unnecessary, and the burden on the facility due to corrosion or the like is small, so an alkaline aqueous solution is preferably used. For example, alkaline aqueous solutions, such as tetramethylammonium hydroxide aqueous solution, sodium silicate aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, are mentioned. The time required for development depends on the thickness of the photosensitive resin composition layer and the type of solvent, but is generally 10 seconds to 5 minutes. After development, the film pattern is preferably washed with distilled water to remove the aqueous alkali solution remaining on the film.

  In addition, although the photosensitive resin composition which concerns on this invention is used suitably for forming a film | membrane pattern in various apparatuses, the said film | membrane pattern is used suitably for the insulation protective film of an electronic device. By using a film pattern formed using the photosensitive resin composition according to the present invention as an insulating protective film of an electronic device, the shape stability of the obtained insulating protective film can be effectively increased. Examples of such an insulating protective film for an electronic device include a TFT protective film for protecting a thin film transistor (TFT) in a liquid crystal display element, and a protective film for protecting a filter in a color filter.

  In addition, the photosensitive resin composition according to the present invention is more preferably used to constitute an interlayer insulating film or a passivation film of a semiconductor element.

  FIG. 2 is a front cross-sectional view schematically showing a semiconductor element including a passivation film and an interlayer insulating film made of the photosensitive resin composition according to the present invention.

  In the semiconductor element 11 shown in FIG. 2, a gate electrode 13 is provided at the center of the upper surface of the substrate 12. A gate insulating film 14 is formed on the upper surface of the substrate 12 so as to cover the gate electrode 13. A source electrode 15 and a drain electrode 16 are provided on the gate insulating film 14. A semiconductor layer 17 is formed on the gate insulating film 14 so as to cover part of the source electrode 15 and part of the drain electrode 16. Further, a passivation film 18 is formed so as to cover the portion of the source electrode 15 and the drain electrode 16 that are not covered with the semiconductor layer 17 and the semiconductor layer 17. In the semiconductor element 11, the gate insulating film 14 and the passivation film 18 are films formed using the photosensitive resin composition according to the present invention.

  The film | membrane formed using the photosensitive resin composition is used for various uses. Here, the “film formed using the photosensitive resin composition” is a film obtained by introducing energy such as heat, light or radiation to the photosensitive resin composition and introducing a crosslinked structure. Means.

  The photosensitive resin composition according to the present invention can be widely used as an insulating protective film for various electronic devices such as a TFT protective film for organic EL elements, an interlayer protective film for IC chips, and an insulating layer for sensors.

  The present invention is implemented as follows.

Add to component (A) an amount of solvent and the required amount of water to achieve the desired concentration in the synthesis. A desired catalyst is added there. In the spectrum obtained using the solution NMR method, the integral value of the resonance line attributed to the hydrolyzable group is obtained, and the time T _10a at which 10% of the total amount of the component (A) reacts and the time T at which 50% reacts _50a is obtained.

  Next, with respect to component (B), an amount of a solvent and a necessary amount of water to a desired concentration at the time of synthesis are added. A desired catalyst is added there. From the spectrum obtained using the solution NMR method, the integral value of the resonance line attributed to the hydrolyzable group is determined, and the rate of hydrolysis is determined.

  The addition rate used in the present invention is defined as follows.

First reaction of the component (B) in _{T 10a} is such that 5% to 40%, continuously or intermittently added to component (B). Next, the component (B) is continuously or intermittently added so that the reaction rate of the component (B) at T _50a is 30% to 70%.

  Hereinafter, the present invention will be clarified by giving examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.

(Examples 1-8)
20 g (99 mmol) of phenyltriethoxysilane as component (A) was diluted with water: PEGMEA solvent = 1: 10 to prepare 100 mL of a diluted solution of component (A). Separately, 16.4 g (99 mmol) of triethoxysilane as component (B) was diluted with a PEGMEA solvent to prepare 100 mL of a diluted solution of component (B).

  Next, after putting 100 mL of the diluted solution of component (A) into the container, 5 g of dilute hydrochloric acid as a catalyst was further added to the container, and heating and stirring were started. Simultaneously with the start of the reaction in the container, 100 mL of the diluted solution of the component (B) was continuously added to the container as shown in Table 1 below, and the component (A) and the component (B) were reacted. After 3 hours from the start of the reaction, the mixture was allowed to cool to obtain a solution containing a metal-containing polymer.

(Comparative Example 1)
20 g (99 mmol) of phenyltriethoxysilane as component (A) was diluted with water: PEGMEA solvent = 1: 10 to prepare 100 mL of a diluted solution of component (A). Separately, 16.4 g (99 mmol) of triethoxysilane as component (B) was diluted with a PEGMEA solvent to prepare 100 mL of a diluted solution of component (B).

  Next, after 100 mL of the diluted solution of component (A) and 100 mL of component (B) were put together in a container, 5 g of dilute hydrochloric acid as a catalyst was further added to the container, and heating and stirring were started. A) and component (B) were reacted. After 3 hours from the start of the reaction, the mixture was allowed to cool to obtain a solution containing a metal-containing polymer.

(Evaluation of metal-containing polymer)
(1) Number of gelled products generated The solution containing the obtained metal-containing polymer was applied on a glass plate and then dried. The number of gelled products per unit area existing on the glass plate after drying was confirmed with a microscope. The results are shown in Table 1 below.

(2) Dielectric withstand voltage 500 g of the obtained silicon-containing polymer mixture, and a sulfonium salt photoacid generator (CAS No. 83697-56-7), green as a compound that generates an acid or a base upon irradiation with light or radiation. 5 g of a chemical company, trade name: NAI-106) was mixed and dissolved to prepare a silicon-containing photosensitive composition.

The obtained photosensitive resin composition was spin-coated at a rotation speed of 1000 rpm on a 0.75 mm thick silicon wafer. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film. Next, ultraviolet rays having a wavelength of 365 nm are applied to the coating film through a photomask having a predetermined pattern (USHIO Inc., Spot Cure SP-5), and the irradiation energy is 500 mJ / cm ² . It was irradiated for 5 seconds with an ultraviolet illuminance of 100 mW / cm ² . After irradiation, the coating film was heated in a hot air oven at 80 ° C. for 5 minutes. Thereafter, the coating film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to obtain a thin film pattern.

  With respect to the thin film having a thickness of 500 nm formed as described above, withstand voltage was measured as an electrical characteristic using R8252 (electrometer) (manufactured by Advantest). The results are shown in Table 1 below.

  As a result of evaluating the IV characteristics of the thin film having a thickness of 500 nm formed as described above, dielectric breakdown was observed at 50 V in the thin film formed using the metal-containing polymer of Comparative Example 1. In contrast, the thin film formed using the metal-containing polymer of Example 2 had a withstand voltage characteristic of 300V. Moreover, in the thin film comprised using the metal containing polymer of Example 2, reduction of leakage current was seen.

  Further, for the thin film having a thickness of 500 nm formed as described above, the ion mobility was confirmed using impedance spectroscopy. In the thin film configured using the metal-containing polymer of Examples 1 to 8, The ion mobility was reduced, the resistance value was improved, and the stability of the dielectric constant with respect to the alternating current frequency was excellent.

  Furthermore, when the NOESY spectrum was measured using the NMR apparatus about the solution of the metal containing polymer of Examples 1-8 and the comparative example 1, in the solution of the metal containing polymer of Examples 1-3, the resonance line of Si-Me And a spectrum in which the correlation between the resonance line and Si-Ph resonance line appeared stronger was obtained. This suggests that the dispersibility of the component (A) and the component (B) is improved at the nano level.

  Further, the molecular weight distributions of the metal-containing polymer solutions of Examples 1 to 8 were analyzed by gel permeation chromatography. The metal-containing polymer solutions of Examples 1 to 8 were compared with the metal-containing polymer solution of Comparative Example 1. The distribution was narrow. It is expected that the dispersibility of the component (A) and the component (B) is improved and the polymer is uniform.

(A)-(c) is sectional drawing of each process for demonstrating the method of forming a thin film pattern using the photosensitive resin composition which concerns on this invention. The front sectional view showing the semiconductor element provided with the passivation film and interlayer insulation film which consist of the photosensitive resin composition concerning the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive resin composition layer 1A ... Latent image 1B ... Photosensitive layer 1C ... Thin film pattern 2 ... Substrate 3 ... Photomask 11 ... Semiconductor element 12 ... Substrate 13 ... Gate electrode 14 ... Gate insulating film 15 ... Source electrode 16 ... Drain Electrode 17 ... Semiconductor layer 18 ... Passivation film

Claims (10)

Component (A) comprising a metal compound represented by the following formula (1), a hydrolyzate thereof or a condensate of the hydrolyzate, a metal compound represented by the following formula (2), a hydrolyzate thereof or a hydrolysis A method for producing a metal-containing polymer obtained by reacting a component (B) comprising a condensate of a product,
When reacting the component (A) and the component (B), the component (B) has a higher reactivity than the component (A),
After putting the component (A) in a container, the component (B) is added continuously or stepwise into the container, and the component (A) and the component (B) are reacted. A method for producing a metal-containing polymer.
_{(Xa) p Ma (Za)} i-p ··· (1)
In the above formula (1), Ma represents a trivalent, tetravalent or pentavalent metal atom, Xa represents a non-hydrolyzable organic group having 1 to 30 carbon atoms, Za represents a hydrolyzable group, i is 3, when Ma is trivalent, 4 when it is tetravalent, 5 when it is pentavalent, p <i, and p is an integer of 0-4. When there are a plurality of Xa, the plurality of Xa may be the same or different. When there are a plurality of Zas, the plurality of Zas may be the same or different.
_{(Xb) q Mb (Zb)} i-q ··· formula (2)
In the above formula (2), Mb represents a trivalent, tetravalent or pentavalent metal atom, Xb represents a non-hydrolyzable organic group having 1 to 30 carbon atoms, Zb represents a hydrolyzable group, i is 3, when Ma is trivalent, 4 when it is tetravalent, 5 when it is pentavalent, q <i, and q is an integer of 0-4. When there are a plurality of Xb, the plurality of Xb may be the same or different. When Zb is plural, the plural Zb may be the same or different.   As the component (A), a component comprising a silicon-containing compound in which Ma in the formula (1) is silicon, a hydrolyzate thereof, or a condensate of the hydrolyzate is used, and as the component (B), the above formula (2) The method for producing a metal-containing polymer according to claim 1, wherein a component comprising a silicon-containing compound in which Mb is silicon, a hydrolyzate thereof or a condensate of the hydrolyzate is used.   A silicon-containing compound in which Ma is silicon in the formula (1) is used as the component (A), and a silicon-containing compound in which Mb is silicon in the formula (2) is used as the component (B). The method for producing a metal-containing polymer according to claim 1, wherein:   When only the component (A) is reacted, the reaction rate of the component (B) when only the component (B) is reacted when the reaction rate of the component (A) becomes 10% is 5% to 40 The manufacturing method of the metal containing polymer of Claims 1-3 which adds the quantity of the component (B) used as% continuously or intermittently.   When only the component (A) is reacted, when the reaction rate of the component (A) reaches 50%, the reaction rate of the component (B) when only the component (B) is reacted is 30% to 70%. The manufacturing method of the metal containing polymer of Claims 1-4 which adds the quantity of the component (B) used as% continuously or intermittently.   The metal-containing polymer according to any one of claims 1 to 5, wherein the component (B) is added at a ratio of 0.0001 to 99.9999 parts by weight with respect to 100 parts by weight of the component (A). Production method.   The metal containing polymer obtained by the manufacturing method of the metal containing polymer of any one of Claims 1-6.   A photosensitive resin composition comprising the metal-containing polymer according to claim 7 and an acid or base generator that generates an acid or a base upon irradiation with light or radiation.   It comprises at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film, and the film is a film formed using the metal-containing polymer according to claim 7. A semiconductor element.   It is provided with at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film, and the film is a film formed using the photosensitive resin composition according to claim 8. A semiconductor element that is characterized.

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