JP2009088247A - Method of manufacturing insulation film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing an insulation film that has improved insulation film performance and adhesiveness between respective laminated films and further has improved productivity. <P>SOLUTION: In a general formula (I): (X)<SB>m</SB>-Q-(Y)<SB>n</SB>, Q indicates 5 or 6-membered nitrogen-containing heterocyclic groups, or their benzo condensed ring groups, X indicates an optional substituent, and m indicates an integer of 0-10. When m is not less than 2, X may be identical or different. Y indicates a group expressed by one of general formulae (Y-1) to (Y-6). N indicates an integer of 1-10. When n is not less than 2, Y may be identical or different. The method of manufacturing a laminated type insulation film includes: a step of forming a copper diffusion prevention film by coating a substrate with a coating liquid containing a compound polymer expressed by the general formula (I) for drying; a step of forming an inorganic polymer film by coating the copper diffusion prevention film with a coating liquid containing an inorganic polymer for drying; a step of forming an organic polymer film by coating the inorganic polymer film with a coating liquid containing a resin for insulation films for drying; and a step of simultaneously curing the copper diffusion prevention film, inorganic polymer film, and organic polymer film by heating or applying energy rays. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an insulating film that can efficiently produce multilayer wiring of an electronic device and has good characteristics such as peeling, and an electronic device having a film using the method.

  In recent years, in the field of electronic materials, with the progress of higher integration, more functions, and higher performance, circuit resistance and capacitor capacity between wirings have increased, leading to an increase in power consumption and delay time. In particular, an increase in delay time is a major factor in reducing the signal speed of the device and the occurrence of crosstalk. Therefore, in order to reduce the delay time and speed up the device, it is necessary to reduce parasitic resistance and parasitic capacitance. It has been. As a specific measure for reducing this parasitic capacitance, an attempt has been made to cover the periphery of the wiring with a low dielectric interlayer insulating film. Further, the interlayer insulating film is required to have a heat resistance that can withstand a subsequent process such as a thin film formation process, chip connection, and pinning when a mounting substrate is manufactured, and a chemical resistance that can withstand a wet process. Furthermore, in recent years, low resistance Cu wiring is being introduced from Al wiring, and along with this, planarization by CMP (Chemical Mechanical Polishing) has become common, and high mechanical strength that can withstand this process is high. It has been demanded.

  Polybenzoxazole and polyimide are widely known as organic polymer interlayer insulating films, but they are not always satisfactory from the viewpoint of various performance requirements such as low dielectric properties, low water absorption, durability, and hydrolysis resistance. Nothing has been obtained. In addition, a high heat-resistant resin having polyarylene ether as a basic main chain is known (Patent Document 1), and its relative dielectric constant is in the range of 2.6 to 2.7. However, in order to realize a high-speed device, further reduction of the dielectric constant is desired.

  In addition, when forming a wiring structure using an interlayer insulating film, not only the improvement of materials such as dielectric constant and mechanical strength, but also from the viewpoint of productivity, the application of the composition for forming the film and the baking time of the wafer There is a need to shorten the time per sheet. Conventionally, the coating type interlayer insulating film has been cured by using a furnace or the like for 30 minutes or more at 400 ° C. However, in order to cope with the recent production of a small variety of various products, Be shunned. Attempts have been made to significantly shorten the curing time itself using electron beams and ultraviolet rays (Non-patent Document 1).

US Pat. No. 6,509,415 Silicon technology NO. 91 p14 Japan Society of Applied Physics

  In order to reduce the dielectric constant of an interlayer insulating film, a laminated insulating film made up of a plurality of types of insulating films such as organic or inorganic has been studied. For example, there may be a case where a coating type organic insulating film and an insulating film obtained by vapor phase reactive growth (CVD) are stacked and mixed. However, in these stacked types, film peeling frequently occurs.

  In the case of a laminated type, it is necessary to shorten the manufacturing time of each film in order to improve productivity. However, if each insulating film is cured for a short time, the film may be peeled off. It was. These are presumed to be due to the difference in composition, the accompanying low affinity of the interface, and the decrease in adhesion due to the adsorption of chemical species such as moisture on the surface and interface of the film.

  In view of the problems as described above, it is an object of the present invention to provide a method for manufacturing an insulating film that can achieve adhesion between laminated films and has excellent productivity.

  As a result of intensive studies, the present inventors have found that the above problems are solved by the following configurations <1> to <6>.

<1> A step of applying a coating solution containing a polymer of a compound represented by the following general formula (I) on a substrate and drying to form a copper diffusion preventing film; and an inorganic layer on the copper diffusion preventing film. Applying a coating solution containing a polymer and drying to form an inorganic polymer film; applying a coating solution containing a resin for an insulating film on the inorganic polymer film; and drying to form an organic polymer film A method for producing a laminated insulating film, comprising: a step; and a step of curing the copper diffusion prevention film, the inorganic polymer film, and the organic polymer film at a time by heating or irradiation with energy rays.
(X) _m -Q- (Y) _n General formula (I)
(In general formula (I), Q represents a nitrogen-containing heterocyclic group having 5 or 6 ring members, or a benzo-fused ring group thereof. X represents an optional substituent. M represents an integer of 0 to 10. When m is 2 or more, X may be the same or different, Y represents a group represented by any one of the following general formulas (Y-1) to (Y-6), and n represents 1 to Represents an integer of 10. When n is 2 or more, Y may be the same or different.

（一般式（Ｙ−１）〜（Ｙ−６）中、Ｚは水素原子または任意の置換基を表す。Ｘ¹はＣ(Ｘ^２)_２、ＮＸ^２、Ｏ、Ｓから選ばれる原子または基を表す。Ｘ²はそれぞれ独立に水素原子または任意の置換基を表す。Ｑ²は環状またはかご型構造を有する基、またはＳｉＸ^４ _（３−ｎ ² _）を表す。Ｘ^４はそれぞれ独立に水素原子または任意の置換基を表す。Ｚ、Ｘ¹およびＱ²は複数存在する場合は、各々同一でも異なっていてもよい。ｎ²は１〜１０の整数を表す。式中＊は一般式（Ｉ）のＱとの結合位置を示す。）
＜２＞前記一般式（Ｉ）中のＱが、下記一般式（Ｑ−１）〜（Ｑ−５）のいずれかで表される基である＜１＞に記載の積層型絶縁膜の製造方法。

(In the general formulas (Y-1) to (Y-6), Z represents a hydrogen atom or an arbitrary substituent. X ¹ is an atom or group selected from C (X ² ) ₂ , NX ² , O, and S). X ² independently represents a hydrogen atom or an arbitrary substituent, Q ² represents a group having a cyclic or cage structure, or SiX ⁴ _(3-n ² _), and each X ⁴ independently represents hydrogen. Represents an atom or an arbitrary substituent, and when there are a plurality of Z, X ¹ and Q ² , they may be the same or different, and n ² represents an integer of 1 to 10. In the formula, * represents a general formula ( Shows the bonding position of I) with Q.)
<2> Production of a laminated insulating film according to <1>, wherein Q in the general formula (I) is a group represented by any one of the following general formulas (Q-1) to (Q-5) Method.

（一般式（Ｑ−１）〜（Ｑ−５）中、Ａ^１はＣ(Ｘ^３)₂、ＮＸ^３、Ｏ、Ｓから選ばれる原子または基を表す。一般式（Ｑ−４）のＡ^１には、ＮＸ^３で表される基が選ばれる。Ａ^２はそれぞれ独立にＣＸ^３、Ｎから選ばれる原子または基を表す。Ｘ^３はそれぞれ独立に水素原子、任意の置換基、または一般式（Ｉ）のＹで表される基である。Ａ^３はそれぞれ独立に水素原子または一般式（Ｉ）のＸまたはＹで表される基である。一般式（Ｑ−１）〜（Ｑ−５）で表される基は、一般式（Ｉ）におけるＸおよびＹで表される基をいずれの位置に有していてもよい。）
＜３＞前記無機ポリマーが、不飽和基を置換基として有するシルセスキオキサン化合物の重合体である＜１＞または＜２＞に記載の積層型絶縁膜の製造方法。
＜４＞前記絶縁膜用樹脂が、かご型構造を分子中に有する高分子である＜１＞〜＜３＞のいずれかに記載の積層型絶縁膜の製造方法。
＜５＞＜１＞〜＜４＞のいずれかに記載の積層型絶縁膜の製造方法により得られる絶縁膜。
＜６＞＜５＞の絶縁膜を有する電子デバイス。

(In General Formulas (Q-1) to (Q-5), A ¹ represents an atom or group selected from C (X ³ ) ₂ , NX ³ , O, and S. A in General Formula (Q-4) the ^1, the groups represented by NX ³ is selected .A ² each independently represent an atom or a group selected from the CX ^{3, N} .X ³ are each independently a hydrogen atom, any substituent or general, A group represented by Y in formula (I) A ³ is each independently a hydrogen atom or a group represented by X or Y in formula (I) General formulas (Q-1) to (Q The group represented by -5) may have a group represented by X and Y in the general formula (I) at any position.
<3> The method for producing a laminated insulating film according to <1> or <2>, wherein the inorganic polymer is a polymer of a silsesquioxane compound having an unsaturated group as a substituent.
<4> The method for producing a laminated insulating film according to any one of <1> to <3>, wherein the resin for an insulating film is a polymer having a cage structure in a molecule.
<5> An insulating film obtained by the method for manufacturing a laminated insulating film according to any one of <1> to <4>.
<6> An electronic device having the insulating film of <5>.

  According to the present invention, there is provided an insulating film manufacturing method capable of forming an insulating film suitable for multilayer wiring of a semiconductor integrated circuit with high productivity by using the method of the present invention, and having good productivity. Can do.

Next, the present invention will be described in more detail with reference to preferred embodiments.
In the present invention, the insulating film is manufactured in the following four steps.
<1> Obtained in step <2> step <1> in which a coating solution containing a polymer of a compound represented by formula (I) is applied on a substrate and dried to form a copper diffusion prevention film. Applying a coating solution containing an inorganic polymer on the copper diffusion prevention film and drying to form an inorganic polymer film <3> A resin for an insulating film is formed on the inorganic polymer film obtained in the step <2> Step 4 of applying and drying to form an organic polymer film <4> Thereafter, the copper diffusion preventing film, the inorganic polymer film, and the organic polymer film are formed at a time by heating or irradiation with energy rays. Step of curing Each step will be described in detail below.

<1> Step <1> Step is a step of forming a copper diffusion prevention film by applying a coating solution containing a polymer of a compound represented by the general formula (I) on a substrate and drying it.
(X) _m -Q- (Y) _n General formula (I)
(In general formula (I), Q represents a nitrogen-containing heterocyclic group having 5 or 6 ring members, or a benzo-fused ring group thereof. X represents an optional substituent. M represents an integer of 0 to 10. When m is 2 or more, X may be the same or different, Y represents a group represented by any one of the following general formulas (Y-1) to (Y-6), and n represents 1 to Represents an integer of 10. When n is 2 or more, Y may be the same or different.

（一般式（Ｙ−１）〜（Ｙ−６）中、Ｚは水素原子または任意の置換基を表す。Ｘ¹はＣ(Ｘ^２)_２、ＮＸ^２、Ｏ、Ｓから選ばれる原子または基を表す。Ｘ²はそれぞれ独立に水素原子または任意の置換基を表す。Ｑ²は環状またはかご型構造を有する基、またはＳｉＸ^４ _（３−ｎ ² _）を表す。Ｘ^４はそれぞれ独立に水素原子または任意の置換基を表す。Ｚ、Ｘ¹およびＱ²は複数存在する場合は、各々同一でも異なっていてもよい。ｎ²は１〜１０の整数を表す。式中＊は一般式（Ｉ）のＱとの結合位置を示す。）

(In the general formulas (Y-1) to (Y-6), Z represents a hydrogen atom or an arbitrary substituent. X ¹ is an atom or group selected from C (X ² ) ₂ , NX ² , O, and S). X ² independently represents a hydrogen atom or an arbitrary substituent, Q ² represents a group having a cyclic or cage structure, or SiX ⁴ _(3-n ² _), and each X ⁴ independently represents hydrogen. Represents an atom or an arbitrary substituent, and when there are a plurality of Z, X ¹ and Q ² , they may be the same or different, and n ² represents an integer of 1 to 10. In the formula, * represents a general formula ( Shows the bonding position of I) with Q.)

  In general formula (I), Q represents a nitrogen-containing heterocyclic group having 5 or 6 ring members, or a benzo-fused ring group thereof. The nitrogen-containing heterocyclic group represented by Q may contain a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, or a boron atom in addition to a carbon atom, a hydrogen atom, or a nitrogen atom. Good. The heterocycle may be aromatic or non-aromatic, but is preferably aromatic. In general formula (I), Q may have a group represented by X and Y in general formula (I) at any position. Q may be a group in which a plurality of ring structures selected from nitrogen-containing heterocyclic rings having 5 or 6 ring members or benzo-fused rings thereof are bonded via a linking group.

  Examples of the nitrogen-containing heterocyclic group represented by Q or the benzo-fused ring group thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a thiazole ring, an isothiazole ring, an oxazole ring, an isoxazole ring, a pyridine ring, and a pyrazine. Ring, pyrimidine ring, pyridazine ring, pyridin ring, indolizine ring, indole ring, indazole ring, quinolidine ring, isoquinoline ring, quinoline ring, phthalazine ring, quinoxaline ring, quinazoline ring, cinnoline ring, acridine ring, perimidine ring, carbazole ring Phenazine ring, thiadiazole ring, oxadiazole ring, triazine ring, 1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, Nzofuroxane ring, benzotriazole ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, isoxazolidine ring, isothiazolidine ring, piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, indoline ring, isoindoline ring, etc. Can be selected.

  In general formula (I), X represents an arbitrary substituent. The optional substituent may be any substituent as long as the effects of the present invention are not impaired. Specifically, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (regardless of the position of substitution), an acyl group, an alkoxy group Carbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group (the carbamoyl group having a substituent includes, for example, N-hydroxycarbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl group) Group, thiocarbamoyl group, N-sulfamoylcarbamoyl group), carbazoyl group, carboxy group or a salt thereof, oxalyl group, oxamoyl group, cyano group, carbonimidoyl group (Carbonimidoyl group), formyl group, hydroxy group, alkoxy (Including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, a carbamoyloxy group, a sulfonyloxy group, an amino group, (Alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamido group, ureido group, thioureido group, N-hydroxyureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, Semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, N- (alkyl or aryl) sulfonylureido group, N-acylureido group, N-acylsulfamoylamino group, hydroxya Group, nitro group, heterocyclic group containing a quaternized nitrogen atom (for example, pyridinio group, imidazolio group, quinolinio group, isoquinolinio group), isocyano group, imino group, mercapto group, (alkyl, aryl, or hetero Ring) thio group, (alkyl, aryl, or heterocyclic) dithio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group (sulfamoyl group having a substituent) And N-acylsulfamoyl group, N-sulfonylsulfamoyl group) or a salt thereof, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group and the like.

  M in the general formula (I) represents an integer of 0 to 10, preferably 0 to 5, and more preferably 0 to 2. When m is 2 or more, X may be the same or different.

  Y in the general formula (I) represents a group represented by any one of the following general formulas (Y-1) to (Y-6), preferably the general formulas (Y-1), (Y-2) and (Y-3), particularly preferably general formula (Y-1).

  In general formulas (Y-1) to (Y-6), Z represents a hydrogen atom or an arbitrary substituent. The definition of the arbitrary substituent represented by Z is the same as the definition of the arbitrary substituent of X in the said general formula (I). Among them, Z is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or a phenyl group.

X ¹ in the general formulas (Y-1) to (Y-6) represents an atom or group selected from C (X ² ) ₂ , NX ² , O, and S.

X ² each independently represents a hydrogen atom or an arbitrary substituent. Defining optional substituent represented by X ² is the same definition of any substituent of X in the general formula (I). When there are a plurality of X ^{2 s} , they may be the same or different.

Q ² in the general formulas (Y-1) to (Y-6) represents a group having a cyclic or cage structure, or SiX ⁴ _(3-n ² ₎ .

  The group having a cyclic structure may be any group having a cyclic structure as long as the effects of the present invention are not impaired. Specific examples include alicyclic hydrocarbon groups (which may be monocyclic or polycyclic), aromatic hydrocarbon groups, and heterocyclic groups.

  The alicyclic hydrocarbon group may be monocyclic (such as a cycloalkyl group) or polycyclic (such as a bicycloalkyl group). Specific examples include a cyclohexyl group.

  The aromatic hydrocarbon group is not particularly limited as long as it is an aromatic ring, and specific examples include a phenyl group and a naphthyl group.

  The heterocyclic group contains one or more hetero atoms such as a sulfur atom, an oxygen atom, and a nitrogen atom, and the number of ring members is not particularly limited, and may be a single ring or a polycyclic ring having a condensed ring. Specific examples include an imidazole ring group.

The “cage structure” of Q ^{2 in} the general formulas (Y-1) to (Y-6) means that the volume is determined by a plurality of rings formed by covalently bonded atoms, and the point located within the volume is a ring. A molecule that cannot leave the volume without passing through. For example, an adamantane structure is considered a cage structure. In contrast, a ring structure having a single bridge such as norbornane (bicyclo [2.2.1] heptane) is not considered a cage structure because the ring of the single bridged cyclic compound does not define volume. .

  The group having a cage structure is, for example, an adamantane group, a biadamantane group, a diamantane group, a triamantane group, a tetramantane group, or a dodecahedrane group, more preferably an adamantane group, a biadamantane group, or a diamantane group. In terms of the dielectric constant, a biadamantan group or a diamantane group is particularly preferable. The cage structure may contain either a saturated or unsaturated bond and may contain a heteroatom such as oxygen, nitrogen or sulfur, but a saturated hydrocarbon is preferred from the viewpoint of a low dielectric constant.

X ⁴ each independently represents a hydrogen atom or an arbitrary substituent. Defining optional substituents represented by X ⁴ are the same definition of any substituent of X in the general formula (I). X ⁴ is preferably a hydrogen atom, an alkyl group, or an aryl group, and particularly preferably a methyl group.

N < ² > in general formula (I) represents the integer of 1-10, Preferably it is 1-5, More preferably, it is 1-2. When n ² is 2 or more, Z may be the same or different.

When a plurality of Z, X ¹ and Q ² are present, they may be the same or different.

  The molecular weight of the compound represented by the general formula (I) is preferably 80 to 1500, more preferably 100 to 1000, and particularly preferably 150 to 500 from the viewpoint of solubility.

  Q in the general formula (I) is preferably a group represented by any one of the following general formulas (Q-1) to (Q-5) from the viewpoint of barrier against copper diffusion.

In general formulas (Q-1) to (Q-5), A ¹ represents an atom or group selected from C (X ³ ) ₂ , NX ³ , O, and S. For A ¹ in the general formula (Q-4), a group represented by NX ³ is selected.

In General Formulas (Q-1) to (Q-5), A ² independently represents an atom or group selected from CX ³ and N.

X ³ is each independently a hydrogen atom or an arbitrary substituent, but may be a group represented by Y in formula (I). Defining optional substituent represented by X ³ is the same definition of any substituent of X in the general formula (I).

In General Formulas (Q-1) to (Q-5), A ³ is each independently a hydrogen atom or a group represented by X or Y in General Formula (I). The groups represented by the general formulas (Q-1) to (Q-5) may have groups represented by X and Y in the general formula (I) at any position.

  Q in the general formula (I) is preferably a ring represented by the general formula (Q-1), and most preferably a ring represented by the following general formula (Q-6).

Definition of the general formula (Q-6) ^{A 3} in is the same definition as in formula (Q-1) ~ (Q -5) in ^{A 3.}

  The compounds represented by the general formula (I) may be used alone or in admixture of two or more. Although the specific example of a compound represented with general formula (I) below is described, this invention is not limited to these.

  The compound of the general formula (I) is synthesized according to, for example, the method described in Macromolecules, 36, 16 (2003), 5947-5959, or Helv. Chim. Acta, 54, 1971, 2060- Using (Ib) synthesized according to the method described in 2068, etc., it can be synthesized by performing a known heterocycle formation reaction described in Experimental Chemistry Course 4th edition Volume 24, etc. In another method, synthesis can be performed by substituting the halogen atom bonded to the aromatic ring with (Ic). In that case, you may use catalysts, such as copper and palladium, as needed. In still another method, it can be synthesized by converting an acetyl group or a vinyl group into an ethynyl group by a known method.

  The copper diffusion preventing film used in the present invention is obtained by applying a coating solution containing a polymer of the compound represented by the general formula (I) on a substrate and drying it.

  The polymer of the compound represented by the general formula (I) may be a copolymer of two or more compounds represented by the general formula (I), or a compound represented by the general formula (I). And other reactive compounds having a reactive group (such as an ethynyl group, a vinyl group, or a diene functional group) may be a copolymer.

  The polymer of the compound represented by the general formula (I) preferably has sufficient solubility in an organic solvent. The solubility is preferably 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more in cyclohexanone or anisole at 25 ° C.

  The reaction in synthesizing the polymer contained in the copper diffusion prevention film used in the present invention by polymerizing the compound of the general formula (I) is preferably a reaction of a polymerizable group substituted with the compound. Examples of the polymerizable group include a group containing a carbon-carbon double bond or a carbon-carbon triple bond, and a group containing a carbon-carbon triple bond is preferable. Examples of the polymerization reaction include radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polyaddition, transition metal catalyst polymerization, thermal polymerization and the like, and radical polymerization reaction is preferable.

  The polymerization reaction of the compound of the general formula (I) is preferably performed in the presence of a nonmetallic polymerization initiator. For example, the presence of a polymerization initiator which exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating a compound of general formula (I) having a polymerizable carbon-carbon double bond or carbon-carbon triple bond. Can be polymerized under. As the polymerization initiator, an organic peroxide or an organic azo compound is preferably used, and an organic peroxide is particularly preferable. Examples of organic peroxides include ketone peroxides such as Perhexa H, peroxyketals such as Perhexa TMH, hydroperoxides such as Perbutyl H-69, Parkmill D, and Perbutyl C, which are commercially available from Nippon Oil & Fat Co., Ltd. Dialkyl peroxides such as perbutyl D, diacyl peroxides such as Nyper BW, peroxyesters such as perbutyl Z and perbutyl L, and peroxydicarbonates such as peroyl TCP are preferably used. Examples of the organic azo compound include azonitrile compounds such as V-30, V-40, V-59, V-60, V-65, and V-70 that are commercially available from Wako Pure Chemical Industries, Ltd., VA-080. Azoamide compounds such as VA-085, VA-086, VF-096, VAm-110 and VAm-111, cyclic azoamidine compounds such as VA-044 and VA-061, and azoamidines such as V-50 and VA-057 Compounds and the like are preferably used.

  Only one polymerization initiator or a mixture of two or more polymerization initiators may be used. The amount of the polymerization initiator used is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, and particularly preferably 0.05 to 0.5 mol, relative to 1 mol of the compound of general formula (I). Is a mole.

Any solvent can be used in the polymerization reaction as long as the compound of the general formula (I) as a raw material can be dissolved at a necessary concentration and does not adversely affect the characteristics of the film formed from the obtained polymer. You may use anything. For example, alcohol solvents such as water, methanol, ethanol, propanol, alcohol solvents such as alcohol acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, methyl benzoate Ester solvents such as dibutyl ether, anisole, etc., toluene, xylene, mesitylene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, isopropylbenzene, 1,4-diisopropylbenzene, t- Butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-triethylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-orthoxylate , Aromatic hydrocarbon solvents such as 1-methylnaphthalene and 1,3,5-triisopropylbenzene, amide solvents such as N-methylpyrrolidinone and dimethylacetamide, carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane Halogen solvents such as chlorobenzene, 1,2-dichlorobenzene and 1,2,4-trichlorobenzene, and aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane can be used.
Among these, more preferred solvents are acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, anisole, tetrahydrofuran, toluene, xylene, mesitylene, 1, 2, 4, 5-tetramethylbenzene, isopropylbenzene, t-butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-orthoxylene, 1-methyl Naphthalene, 1,3,5-triisopropylbenzene, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, more preferably tetrahydrofuran, γ-butyrolactone, Nisole, toluene, xylene, mesitylene, isopropylbenzene, t-butylbenzene, 1,3,5-tri-t-butylbenzene, 1-methylnaphthalene, 1,3,5-triisopropylbenzene, 1,2-dichloroethane, Chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, particularly preferably γ-butyrolactone, anisole, mesitylene, 1,3,5-triisopropylbenzene, 1,2-dichlorobenzene, 1, 2,4-trichlorobenzene. These may be used alone or in admixture of two or more. The concentration of the compound of the general formula (I) in the reaction solution is appropriately selected depending on the type of compound and the polymerization initiator.

  Optimum conditions for the polymerization reaction are 0 ° C to 220 ° C, more preferably 40 ° C to 210 ° C, particularly preferably 80 ° C to 200 ° C, preferably 1 to 50 hours, more preferably 2 to 20 hours, particularly preferably. Is in the range of 3 to 10 hours. Moreover, in order to suppress inactivation of the polymerization initiator by oxygen, it is preferable to make it react in inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.

  The preferred range of the weight average molecular weight of the polymer obtained by polymerizing the compound of general formula (I) is 1,000 to 500,000, more preferably 5,000 to 300,000, particularly preferably 10,000 to 200. , 000.

  The coating liquid applied onto the substrate contains a polymer obtained by polymerizing the compound of general formula (I). The polymer may be used alone or in combination of two or more.

  The coating solution applied on the substrate contains an organic solvent. Examples of the organic solvent include 1-methoxy-2-propanol, 2-propanol, acetylacetone, cyclohexanone, propylene glycol monomethyl ether acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, anisole, mesitylene, and t-butylbenzene. Particularly preferred are 1-methoxy-2-propanol, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, t-butylbenzene, and anisole, preferably cyclohexanone.

  The concentration of the polymer of the compound of general formula (I) in the coating solution applied onto the substrate is appropriately selected depending on the type of the polymer of the compound of the compound of general formula (I).

  Furthermore, in the coating solution applied on the substrate, radical generators and colloidal silica are used as long as the properties of the resulting insulating film (heat resistance, dielectric constant, mechanical strength, coating properties, adhesion, etc.) are not impaired. In addition, additives such as a surfactant, a silane coupling agent, and an adhesion promoter may be added.

  Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants, and also include silicone surfactants, fluorine-containing surfactants, polyalkylene oxide surfactants. Agents and acrylic surfactants. The surfactant that can be used in the present invention may be one type or two or more types. As the surfactant, silicone surfactants, nonionic surfactants, fluorine-containing surfactants, and acrylic surfactants are preferable, and silicone surfactants are particularly preferable. The content of the surfactant that can be used in the present invention is preferably 0.01% by mass or more and 1% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass with respect to the total amount of the film-forming coating solution. More preferably, it is at most mass%.

  The film containing the polymer of the compound of the general formula (I) may contain colloidal silica. For example, a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent or water, usually having an average particle size of 5 to 30 nm, preferably 10 to 20 nm, and a solid content concentration of 5 to 40% by mass. is there.

  Any silane coupling agent may be used for the film containing the polymer of the compound of the general formula (I) as long as the effects of the present invention are not impaired. Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1 -Methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarboni -3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) 3-aminopropyl trimethoxysilane, etc. N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like. The silane coupling agent that can be used in the present invention may be used alone or in combination of two or more.

  Any adhesion promoter may be used for the film containing the polymer of the compound of the general formula (I) as long as the effects of the present invention are not impaired. Examples of the adhesion promoter include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane. , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, trimethoxyvinylsilane, γ-aminopropyltriethoxysilane, aluminum monoethylacetoacetate diisopropylate, vinyltris (2-methoxyethoxy) silane, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylto Limethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane , Dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, benzotriazole, benzimidazole, Indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole , Mention may be made of 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethylurea, 1,3-dimethylurea, and thiourea compounds. Functional silane coupling agents are preferred as adhesion promoters. The amount of the adhesion promoter used is preferably 10 parts by mass or less, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total solid content.

In the present invention, within the range allowed by the mechanical strength of the film containing the polymer of the compound of the general formula (I), the film can be made porous by using a pore forming factor to achieve a low dielectric constant. There are no particular limitations on the pore-forming factor as an additive that serves as a pore-forming agent, but a non-metallic compound is preferably used to simultaneously satisfy the solubility in the solvent used and the compatibility with the membrane. is required.
A polymer can also be used as the pore-forming agent. Examples of the polymer that can be used as the pore-forming agent include polyvinyl aromatic compounds (polystyrene, polyvinyl pyridine, halogenated polyvinyl aromatic compounds, etc.), polyacrylonitrile, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.), polyethylene, poly Lactic acid, polysiloxane, polycaprolactone, polycaprolactam, polyurethane, polymethacrylate (such as polymethyl methacrylate) or polymethacrylic acid, polyacrylate (such as polymethyl acrylate) and polyacrylic acid, polydiene (such as polybutadiene and polyisoprene), polyvinyl chloride , Polyacetal, and amine-capped alkylene oxide, other polyphenylene oxide, poly (dimethyl) Siloxane), polytetrahydrofuran, poly cyclohexyl ethylene, polyethyl oxazoline, polyvinyl pyridine, may be a polycaprolactone.
In particular, polystyrene can be suitably used as a pore forming agent. Examples of polystyrene include anionic polymerized polystyrene, syndiotactic polystyrene, unsubstituted and substituted polystyrene (for example, poly (α-methylstyrene)), and unsubstituted polystyrene is preferred.

  The method for producing the coating solution to be coated on the substrate is not particularly limited. For example, the polymer of the compound of the general formula (I) in the reaction vessel and, if necessary, each of the above optional components are mixed, A method of sufficiently stirring using a stirrer can be used.

The substrate used in this step is not particularly limited, and a substrate such as a silicon wafer, a SiO ₂ wafer, or a SiN wafer is used. In particular, a substrate having metal wiring, for example, a semiconductor integrated circuit having wiring containing copper is preferable.

  The film containing the polymer of the compound of the general formula (I) can be applied to any coating solution containing the polymer of the compound of the general formula (I) such as a spin coating method, a roller coating method, a dip coating method, a scanning method, and an ink jet method. After coating on the substrate by the above method, it can be formed by removing the solvent by applying a drying treatment by heating. In addition, in the case of a drying process, it implements on the temperature conditions which a film | membrane does not harden | cure. Curing means that reactive groups such as carbon-carbon double bonds and carbon-carbon triple bonds contained in the polymer of the compound of general formula (I) are further polymerized and reacted by heating to cause crosslinking of the film. It means to progress and harden. Therefore, the temperature condition at the time of the drying treatment means that a reactive group such as a carbon-carbon double bond or a carbon-carbon triple bond contained in the polymer of the compound of the general formula (I) is not substantially consumed. This means that the temperature conditions can remain. Specifically, the heating for drying the solvent is preferably performed at 100 ° C. to 250 ° C. for 1 minute or more and less than 5 minutes. The drying process may be performed in a plurality of times under different conditions. The drying atmosphere is not particularly limited, and is appropriately selected in the air or in an inert gas (nitrogen, argon, etc.). As a method of applying to the substrate, a spin coating method is particularly preferable. For spin coating, commercially available equipment can be used. The spin coating conditions may be any rotational speed, but from the viewpoint of in-plane uniformity of the film, a rotational speed of about 1300 rpm is preferable for a 300 mm silicon substrate. The spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate. The heat treatment method is preferably a hot plate heating method or a heating method using a furnace. A commercially available device can be preferably used as the hot plate, and the clean track series (manufactured by Tokyo Electron), D-Spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo) can be preferably used. As the furnace, α series (manufactured by Tokyo Electron) and the like can be preferably used.

  The film thickness of the film containing the polymer of the compound of general formula (I) is usually 50 nm to 1000 nm, preferably 60 nm to 500 nm.

<2> Process <2> Process is a process of apply | coating the coating liquid containing an inorganic polymer on the said copper diffusion prevention film obtained at <1> process, and drying and forming an inorganic polymer film.

  The inorganic polymer used in this step may be any inorganic polymer as long as the effects of the present invention are not impaired. Among them, silsesquioxane is preferable, and a polymer having a silsesquioxane structure is particularly preferable. Silsesquioxane is a silsesquioxane structure in which each silicon atom is bonded to three oxygen atoms, and each oxygen atom is bonded to two silicon atoms (the number of oxygen atoms is 1. 5) is a class name indicating a compound including, for example, a ladder structure, a cage structure, or a partially modified version thereof. As the polymer having a silsesquioxane structure, a polymer of a silsesquioxane compound having an unsaturated group as a substituent is preferable from the viewpoint of low dielectric properties, adhesion, and the like. A substituted cage-type silsesquioxane compound polymer is preferred.

Any silsesquioxane compound may be used as long as it does not impair the effects of the present invention, and examples thereof include a ladder type, a cage type, an incomplete cage type in which a part of the cage type is lost, and a cage type from the viewpoint of heat resistance. Is preferred. The cage-type silsesquioxane compound (hereinafter also referred to as compound (II)) substituted with two or more unsaturated groups is, for example, m RSi (O _0.5 ) ₃ units (m is an integer of 8 to 16). And each R independently represents a non-hydrolyzable group, and at least two of R are groups containing a vinyl group or an ethynyl group), and each unit shares an oxygen atom in each unit Examples thereof include a compound linked to another unit to form a cage structure (hereinafter also referred to as compound (II ′)). For example, m in compound (II ′) is preferably 8, 10, 12, 14, or 16 from the viewpoint of the effect of lowering the dielectric constant, and 8, 10, or 12 is more preferable from the viewpoint of availability. The cage structure is a structure in which the volume is determined by a plurality of rings formed of covalently bonded atoms, and a point located in the volume cannot be separated from the volume without passing through the ring.

  Each R independently represents a non-hydrolyzable group. The non-hydrolyzable group is a group that remains at least 95% when brought into contact with 1 equivalent of neutral water at room temperature for 1 hour. It is preferable that 99% or more remain. Specific examples include a substituted or unsubstituted hydrocarbon group, a silicon atom-containing group, and a group obtained by combining them. The hydrocarbon group refers to an aliphatic hydrocarbon group or an aryl group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. When there are a plurality of Rs, they may be the same or different.

  The alkyl group is not particularly limited, and may be linear, branched, or cyclic. Specific examples include a methyl group, a tert-butyl group, a cyclopentyl group, and a cyclohexyl group.

  The alkenyl group is not particularly limited, and may be linear, branched, or cyclic. Specific examples include a vinyl group and an allyl group.

  The alkynyl group is not particularly limited, and may be linear, branched or cyclic, and specifically includes an ethynyl group.

  The aryl group is not particularly limited as long as it is an aromatic ring, but specific examples include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

  Preferable examples of the silicon atom-containing group include silyloxy groups. Specific examples include a trimethylsilyloxy group, a triethylsilyloxy group, a t-butyldimethylsilyloxy group, and the like.

  The cage-type silsesquioxane compound substituted with two or more unsaturated groups refers to a compound in which at least two of R are groups containing a vinyl group or an ethynyl group. When the group represented by R includes a vinyl group or an ethynyl group, the vinyl group or ethynyl group is preferably bonded to the silicon atom to which R is bonded, particularly directly or via a divalent linking group. The group or ethynyl group is preferably bonded directly to the silicon atom to which R is bonded.

  In the cage-type silsesquioxane compound in which two or more unsaturated groups are substituted, at least two of R are preferably vinyl groups, and at least half of R are preferably vinyl groups. All are preferably vinyl groups.

  Specific examples of compound (II) include the following. The present invention is not limited to these.

  Compound (II) may be commercially available or synthesized by a known method.

  It is also preferable that R in the compound (II) is a group represented by the following general formula (II-1). In this case, the compound represented by the following general formula (II-2) and the following general formula (II-3) ) Can be synthesized by reaction.

(R ¹ ) ₃ —Si—O— (II-1)
[MO-Si (O _0.5 ) ₃ ] _m (II-2)
(R ¹ ) ₃ -Si-Cl (II-3)

The compound represented by the general formula (II-2) can be synthesized according to the method described in, for example, Angew. Chem. Int. Ed. Engl. 1997, 36, No. 7, 743-745. R ^{1 in} general formulas (II-1) and (II-3) each independently represents a non-hydrolyzable group. The definition of the non-hydrolyzable group is the same as the definition of the non-hydrolyzable group of R. The non-hydrolyzable group represented by R ¹ is preferably an alkyl group, an aryl group, a vinyl group, or an ethynyl group. The definition of m in general formula (II-2) is the same as the definition of m of compound (II '). M represents a metal atom (for example, Na, K, Cu, Ni, Mn) or an onium cation (for example, tetramethylammonium). In addition, when M is a polyvalent metal atom, it means a form in which a plurality of —O—Si (O _0.5 ) ₃ is bonded to the polyvalent metal atom M.

  The reaction between the compound represented by the general formula (II-2) and the compound represented by the general formula (II-3) is carried out, for example, with a compound represented by the general formula (II-2) in a solvent. The compound represented by the general formula (II-3) is added in an amount of 1 to 100 times the number of Si-OM groups contained in the compound represented by the general formula (II-2). ˜180 ° C., 10 minutes to 20 hours. As the solvent, organic solvents such as toluene, hexane, and tetrahydrofuran (THF) are preferable.

  The inorganic polymer film is formed by applying a coating solution containing an inorganic polymer, preferably a polymer having a silsesquioxane structure, particularly preferably a polymer of compound (II), onto the copper diffusion prevention film and drying. Is done.

  The polymer of the compound (II) is preferably produced by using a polymerization reaction between carbon-carbon unsaturated bonds. In particular, the compound (II) is dissolved in a solvent, a polymerization initiator is added, and a vinyl group or ethynyl is added. It is preferred to react the groups. The polymerization reaction may be any polymerization reaction, and examples thereof include radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polycondensation, polyaddition, addition condensation, and transition metal catalyst polymerization.

  The compound (II) remaining at the end of the polymerization reaction is preferably 25% by mass or less, more preferably 20% by mass or less, and most preferably 15% by mass or less of the addition amount. If this condition is satisfied at the time of polymerization, a film-forming composition having a good coated surface shape and a small film loss at the time of firing can be produced with a high yield.

  The weight average molecular weight (Mw) of the polymer of the compound (II) at the end of the polymerization reaction is more preferably 30,000 to 160,000, further preferably 40,000 to 140,000, and 50,000 to 120,000. Most preferably it is. The polymer of the compound (II) at the end of the polymerization reaction is preferably substantially free of components having a molecular weight of 3 million or more, more preferably substantially free of components of 2 million or more, and 1 million or more. It is most preferable not to contain these components.

  The polymerization reaction of compound (II) is preferably carried out in the presence of a nonmetallic polymerization initiator. For example, in the presence of a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating. It can be polymerized. As the polymerization initiator, an organic peroxide or an organic azo compound is particularly preferable, and an organic azo compound is preferable in view of the safety of the reagent itself and the molecular weight reproducibility of the polymerization reaction, and harmful cyano is taken into the polymer. Most preferred are azoester compounds such as V-601.

  Any solvent can be used for the polymerization reaction as long as it can dissolve the compound (II) at a necessary concentration and does not adversely affect the properties of the film formed from the polymer obtained. However, a more preferable solvent is an ester solvent, and particularly preferable are ethyl acetate and butyl acetate.

  The boiling point of the organic solvent is preferably 75 ° C. or higher and 140 ° C. or lower so that the reaction solution can be heated to a temperature necessary for decomposing the polymerization initiator during the reaction and the organic solvent can be distilled off after completion of the reaction. The polymerization initiator can be added by batch addition, divided addition, continuous addition, etc., but it can be increased in molecular weight with a small amount of polymerization initiator added, and it is advantageous from the viewpoint of film strength. Is preferred.

  Optimum conditions for the polymerization reaction in the present invention vary depending on the polymerization initiator, monomer, solvent type, concentration, etc., but preferably the internal temperature is 0 ° C. to 200 ° C., more preferably 40 ° C. to 170 ° C., particularly preferably 70. C. to 140.degree. C., preferably 1 to 50 hours, more preferably 2 to 20 hours, and particularly preferably 3 to 10 hours. Moreover, in order to suppress the inactivation of the polymerization initiator by oxygen, it is preferable to make it react under inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.

  When producing the coating solution, the reaction solution obtained by subjecting the polymerization reaction of compound (II) may be used as it is as the composition for forming an insulating film, but it is preferable to distill off the reaction solvent and concentrate it. . Moreover, it is preferable to use after performing a reprecipitation process.

  Furthermore, in the coating solution containing the inorganic polymer applied on the copper diffusion prevention film, as long as the properties of the insulating film obtained (heat resistance, dielectric constant, mechanical strength, applicability, adhesion, etc.) are not impaired, Additives such as radical generators, colloidal silica, surfactants, silane coupling agents, and adhesives may be added.

  An organic solvent is contained in the coating liquid containing the inorganic polymer applied on the copper diffusion prevention film. Usable organic solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, ethylene carbonate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, tetrahydrofuran, methyl isobutyl ketone, xylene, mesitylene And diisopropylbenzene.

  The total solid content concentration in the coating solution containing the inorganic polymer applied on the copper diffusion prevention film is preferably 1 to 30% by mass, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the coating liquid is 1 to 30% by mass, the film thickness of the coating film is in an appropriate range, and the storage stability of the coating liquid is further improved.

  Within the range allowed by the mechanical strength of the inorganic polymer film, pore formation factors can be used to make the film porous and to achieve a low dielectric constant. In particular, polystyrene can be suitably used as a pore forming agent.

  It is preferable to use the coating liquid containing the inorganic polymer coated on the copper diffusion prevention film for film formation after removing insoluble matter, gel-like components and the like by filter filtration. The pore size of the filter used at that time is preferably 0.001 to 0.2 μm, more preferably 0.005 to 0.05 μm, and most preferably 0.005 to 0.03 μm. The material of the filter is preferably PTFE, polyethylene, or nylon, and more preferably polyethylene or nylon.

  The method for producing a coating solution containing an inorganic polymer coated on the copper diffusion prevention film is not particularly limited. For example, the polymer of compound (II) and, if necessary, each of the above optional components are placed in a reaction vessel. A method of sufficiently stirring using a stirrer such as a mixing mixer can be used.

  The inorganic polymer film is formed by applying a coating solution containing an inorganic polymer on the copper diffusion prevention film by any method such as spin coating method, roller coating method, dip coating method, scan method, spray method, bar coating method, It can form by removing a solvent by performing the drying process by heating. In addition, in the case of a drying process, it implements on the temperature conditions which a film | membrane does not harden | cure. The meaning of drying is synonymous with the drying with the said copper diffusion prevention film. Specifically, the heating for drying the solvent is preferably performed at 100 ° C. to 250 ° C. for 1 minute or more and less than 5 minutes. The drying process may be performed in a plurality of times under different conditions. The drying process may be performed in a plurality of times under different conditions. The drying atmosphere is not particularly limited, and is appropriately selected in the air or in an inert gas (nitrogen, argon, etc.). As a method of applying to the substrate, a spin coating method or a scanning method is preferable. Particularly preferred is the spin coating method. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate.

  Among the inorganic polymer films, the total of the polymers obtained by reacting the compounds (II) is preferably 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. Preferably, it is 95% by mass or more. Moreover, it is preferable that 10-90 mol% remains unreacted among the vinyl group or ethynyl group of compound (II), and it is preferable that 20-80 mol% remains unreacted, 30 Most preferably, ˜70 mol% remains unreacted.

  The film thickness of the inorganic polymer film is usually 50 nm to 1000 nm, preferably 60 nm to 500 nm, particularly preferably 70 nm to 400 nm. The film thickness is preferably within this range from the viewpoint of low dielectric properties and heat resistance of the film.

<3> Step <3> Step is a step of forming an organic polymer film by applying a coating liquid containing an insulating film resin on the obtained inorganic polymer film and drying it.

The insulating film resin is not particularly limited as long as it is a low dielectric constant polymer compound or a precursor compound for forming the insulating film. Specific examples include polyarylene, polybenzoxazole, polyimide, polyarylene ether, and a compound having a cage structure. From the viewpoint of low dielectric constant and high mechanical strength, a compound having a cage structure is preferable. A compound having a cage structure is a polymer having a cage structure in the molecule, and the cage structure may be a part of the polymer main chain, and the cage structure is incorporated as a pendant group in the polymer main chain. It may be. The definition of the cage structure is the same as the definition of the cage structure at Q ² in the general formulas (Y-1) to (Y-6). The organic insulating film material does not include a polymer of the compound represented by the general formula (I).

  The cage structure is, for example, a polycyclic hydrocarbon such as adamantane, biadamantane, diamantane, triamantane, tetramantane, or dodecahedrane, and more preferably adamantane, diamantane, or triadamantane from the viewpoint of high heat resistance. Diamantane is particularly preferred because it has a low dielectric constant and is easily synthesized. The cage structure may contain either a saturated or unsaturated bond and may contain a heteroatom such as oxygen, nitrogen or sulfur, but a saturated hydrocarbon is preferred from the viewpoint of a low dielectric constant.

  The cage structure may have a substituent as long as the effects of the present invention are not impaired. For example, a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), an alkyl group (which may be linear, branched or cyclic, preferably 1 to 5 carbon atoms), an alkenyl group (preferably Alkynyl group (preferably having 2 to 5 carbon atoms), silyl group (triethoxysilyl, methyldiethoxysilyl, trivinylsilyl, etc.) and the like.

  The cage structure is preferably 1 to 4 valent, more preferably 2 to 3 valent, and particularly preferably 2 valent. At this time, the group bonded to the cage structure may be a monovalent or higher valent substituent or a divalent or higher valent linking group.

  The compound having a cage structure may be a polymer having a cage structure in the molecule, and the weight average molecular weight is preferably 1,000 to 500,000, more preferably 5,000 to 300,000, particularly preferably 10,000 to 200,000. . When the weight average molecular weight is within this range, various film properties such as low dielectric properties and heat resistance are excellent.

  The cage structure may be incorporated as a monovalent or higher pendant group in the polymer main chain. Preferred polymer main chains to which the cage compound is bonded include, for example, conjugated unsaturated bond chains such as poly (arylene), poly (arylene ether), poly (ether), polyacetylene, polyethylene, etc. Among them, heat resistance is good. From these points, poly (arylene ether) and polyacetylene are more preferable.

The cage structure may be incorporated as part of the polymer backbone. In this embodiment, the cage structures are directly single-bonded between the cage structures or connected by an appropriate divalent or higher linking group. Examples of the linking group include, for example, C (R ₁₁ ) (R ₁₂ ) —, —CH═CH—, —C≡C—, an arylene group, —O—, —Si (R ₁₃ ) (R ₁₄ ) — or A group in which these are combined, and —CH═CH—, —C≡C—, —O—, —Si (R ₁₃ ) (R ₁₄ ) — or a combination thereof is particularly preferable. R _{11 to} R ₁₄ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an alkoxy group.

  The compound having a cage structure may contain one or more cage structures in the molecule. Specific examples of the “compound having a cage structure” of the present invention are shown below, but the present invention is of course not limited thereto.

  The compound having a cage structure of the present invention is particularly preferably a polymer of a compound represented by the following general formula (III).

  R in the general formula (III) represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a silyl group. When R is other than a hydrogen atom, R may be further substituted with another substituent. Among these, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a silyl group is preferable, and a hydrogen atom or a silyl group having 0 to 10 carbon atoms is more preferable.

  M in general formula (III) represents the integer of 1-14, Preferably it is an integer of 1-4, More preferably, it is an integer of 1-3, Most preferably, it is 2 or 3. When m in general formula (III) is 2 or more, R may be the same or different.

  X in the general formula (III) is a halogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), an alkenyl group (preferably having 2 to 10 carbon atoms), an aryl group (preferably having 6 to 6 carbon atoms). 20) and a silyl group (preferably having 0 to 20 carbon atoms). X may be further substituted with another substituent.

  N in the general formula (III) represents an integer of 0 to 13, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When n in general formula (III) is 2 or more, X may be the same or different.

  Optimum polymerization reaction conditions for the compound of the general formula (III) are preferably in an organic solvent, preferably an internal temperature of 0 ° C to 220 ° C, more preferably 50 ° C to 210 ° C, particularly preferably 100 ° C to 200 ° C, preferably It is preferable to carry out for 1 to 50 hours, more preferably 2 to 20 hours, particularly 3 to 10 hours. If desired, a metal catalyst such as palladium, nickel, tungsten, or molybdenum may be used.

  The preferable range of the weight average molecular weight of the polymer obtained by polymerizing the compound of the general formula (III) is 1000 to 500000, more preferably 5000 to 300000, and particularly preferably 10000 to 200000. Within this range, various film properties such as low dielectric properties and heat resistance are excellent.

  Specific examples of the compound of the general formula (III) are shown below. The present invention is not limited to the following specific examples.

  The compound having a cage structure preferably has a reactive group that forms a covalent bond with another molecule by electron beam or heat. Such a reactive group is not particularly limited, and for example, a substituent that causes a cycloaddition reaction or a radical polymerization reaction can be preferably used. For example, a combination of a group having a double bond (such as a vinyl group or an allyl group), a group having a triple bond (such as an ethynyl group or a phenylethynyl group), a diene group for causing a Diels-Alder reaction, or a combination of a dienophile group is effective. In particular, an ethynyl group and a phenylethynyl group are effective.

  From the viewpoint of imparting good characteristics (dielectric constant, mechanical strength) to the insulating film of the present invention, the ratio of the total carbon number of the cage structure to the total carbon number contained in the organic polymer film is 30% or more. Is preferable, more preferably 50 to 95%, still more preferably 60% to 90%.

  The organic polymer film is formed by applying a coating solution containing an insulating film resin on the inorganic polymer film and drying it.

  The coating liquid applied on the inorganic polymer film contains an organic solvent. The organic solvent is not particularly limited, but more preferable solvents are acetone, propanol, cyclohexanone, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, γ-butyrolactone, anisole, mesitylene, and 1,2-dichlorobenzene.

  The concentration of the insulating film resin in the coating solution applied on the inorganic polymer film is preferably 1.0 to 20% by mass, more preferably 1.0 to 15% by mass, and particularly preferably 1.5 to 10% by mass. %. When it is in this range, the film thickness of the coating film is in an appropriate range, and the storage stability of the coating solution is more excellent and preferable.

  Furthermore, in the coating solution applied on the inorganic polymer film, radical generators and colloids are used as long as the properties of the resulting insulating film (heat resistance, dielectric constant, mechanical strength, coating properties, adhesion, etc.) are not impaired. Additives such as glassy silica, surfactants, silane coupling agents and adhesion promoters may be added.

  The production method in the coating solution applied onto the inorganic polymer film is not particularly limited. For example, the polymer of compound (III) and, if necessary, the above optional components are added to a reaction vessel, A method of sufficiently stirring using a stirrer can be used.

  The organic polymer film is formed by applying a coating solution containing a resin for an insulating film on the inorganic polymer film by any method such as a spin coating method, a roller coating method, a dip coating method, a scanning method, a spray method, or a bar coating method. It can be formed by removing the solvent by performing a drying treatment by heating. In addition, in the case of a drying process, it implements on the temperature conditions which a film | membrane does not harden | cure. Curing means, for example, that a reactive group such as a carbon-carbon double bond or carbon-carbon triple bond contained in a compound having a cage structure is further polymerized and reacted by heating to be cured. Therefore, the temperature condition during the drying process is a temperature condition in which reactive groups such as carbon-carbon double bonds and carbon-carbon triple bonds contained in the insulating film resin are not substantially consumed and can remain. It means that there is. Specifically, the heating for drying the solvent is preferably performed at 50 ° C. to 250 ° C. for 1 minute to less than 5 minutes, and particularly preferably performed at 80 ° C. to 200 ° C. for 1 minute to less than 5 minutes. The drying process may be performed in a plurality of times under different conditions. The drying atmosphere is not particularly limited, and is appropriately selected in the air or in an inert gas (nitrogen, argon, etc.). As a method of applying to the substrate, a spin coating method or a scanning method is preferable. Particularly preferred is the spin coating method. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate.

  The film thickness of the organic polymer film is usually 50 nm to 1000 nm, preferably 60 nm to 500 nm, particularly preferably 70 nm to 150 nm. The film thickness is preferably within this range from the viewpoint of low dielectric properties and heat resistance of the film.

<4> Step <4> Step is a step of curing the copper diffusion prevention film, the inorganic polymer film, and the organic polymer film at once by heating or irradiation with energy rays after the <3> step. In this step, the copper diffusion prevention film, inorganic polymer film, and organic polymer film coated on the substrate are collectively cured (fired). As a method for the curing treatment, there is heating or irradiation with energy rays.

  Polymerization of reactive groups such as carbon-carbon triple bonds remaining in the film composition by heating the laminated film composed of the copper diffusion preventing film, inorganic polymer film, and organic polymer film obtained in the <3> step A reaction / crosslinking reaction is caused to increase the crosslink density in the film and promote the curing of the laminated film. The heating conditions are preferably 100 to 450 ° C., more preferably 200 to 420 ° C., particularly preferably 350 to 400 ° C., preferably 5 minutes to 2 hours, more preferably 10 minutes to 1.5 hours, particularly Preferably, it is in the range of 30 minutes to 1 hour. The heat treatment may be performed in several times. The pressure during firing is usually 0.001 to 2000 torr, preferably 0.001 to 800 torr. This heat treatment is particularly preferably performed in a nitrogen atmosphere or at an atmospheric pressure of 10 Torr or less in order to prevent thermal oxidation by oxygen.

As another method, it may be cured by causing a polymerization reaction / crosslinking reaction of a reactive group such as a carbon-carbon triple bond remaining in the polymer by irradiation with high energy rays. Examples of high energy rays include electron beams, ultraviolet rays, and X-rays. The energy when an electron beam is used as the high energy beam is preferably 50 keV or less, more preferably 30 keV or less, and particularly preferably 20 keV or less. The total dose of the electron beam is preferably 5 μC / cm ² or less, more preferably ² μC / cm ² or less, and particularly preferably 0 to 1 μC / cm ² or less. The substrate temperature at the time of irradiation with an electron beam is preferably 0 to 450 ° C, more preferably 0 to 400 ° C, and particularly preferably 0 to 350 ° C. The pressure is preferably 0 to 133 kPa, more preferably 0 to 60 kPa, and particularly preferably 0 to 20 kPa. From the viewpoint of preventing oxidation of the film composition, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, a gas such as oxygen, hydrocarbon, or ammonia may be added for the purpose of reaction with plasma, electromagnetic waves, or chemical species generated by interaction with an electron beam. The electron beam irradiation may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same each time, and may be performed under different conditions each time.

Ultraviolet rays may be used as the high energy rays. The irradiation wavelength region when using ultraviolet rays is preferably 190 to 400 nm, and the output is preferably 0.1 to 2000 mWcm ⁻² immediately above the substrate. The substrate temperature at the time of ultraviolet irradiation is preferably 250 to 450 ° C, more preferably 250 to 400 ° C, and particularly preferably 250 to 350 ° C. From the viewpoint of preventing oxidation of the film composition, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, the pressure at that time is preferably 0 to 133 kPa. The ultraviolet irradiation may be performed a plurality of times. In this case, the ultraviolet irradiation conditions need not be the same every time, and may be performed under different conditions each time.

  When the curing treatment is performed in a state where the films are laminated in the <4> step, a laminated insulating film having excellent adhesion can be produced in a short time. Although the detailed mechanism for improving the adhesion is unknown, first, the reaction by the reactive group such as carbon-carbon double bond or carbon-carbon triple bond remaining in the film composition at the time of curing treatment, It is presumed that a cross-linked structure is formed between the film compositions due to a hydrogen abstraction reaction and the like, and peeling at each film interface is suppressed. In addition, the heat-curing treatment in the laminated state causes mutual diffusion of each film composition at the interface between each film, resulting in a structure in which each component enters, and peeling is suppressed by a so-called anchoring effect. The effect is also speculated. Furthermore, even if the linear expansion coefficient of each film is different, it is speculated that it is possible to cure while releasing the stress generated at the film interface by lump-curing, thereby suppressing the generation of internal stress and suppressing peeling. Is done. In particular, when the inorganic polymer is a polymer of a silsesquioxane compound (preferably cage silsesquioxane) having an unsaturated group as a substituent, and the insulating film resin is a polymer having a cage structure in the molecule. Has a three-dimensional and bulky functional group, so that the curing shrinkage is expected to be small, and the occurrence of internal stress at the time of curing is further reduced and the adhesion is estimated to be improved.

  The multilayer structure obtained by using the film forming composition of the present invention can be used for various purposes. For example, it is suitable as an insulating film in electronic devices such as semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and multi-chip module multilayer wiring boards. Interlayer insulating film for semiconductor, etching stopper film, surface protection In addition to a film and a buffer coat film, it can be used as a passivation film in an LSI, an α-ray blocking film, or the like.

  EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by these examples.

<Coating liquid preparation example 1>
According to the synthesis method described in Macromolecules, 5266 (1991), 4,9-diethynyldiamantane was synthesized. Next, 2 g of 4,9-diethynyldiamantane, 0.22 g of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation), and 10 ml of t-butylbenzene were stirred and polymerized at an internal temperature of 150 ° C. for 7 hours under a nitrogen stream. . After the reaction solution was brought to room temperature, it was added to 60 ml of isopropyl alcohol, and the precipitated solid was filtered and thoroughly washed with isopropyl alcohol. 0.8 g of a polymer (A) having a weight average molecular weight of about 15,000 was obtained.
0.35 g of the polymer (A) was completely dissolved in 7 g of cyclohexanone. This solution was filtered through a 0.1 μm tetrafluoroethylene filter to obtain coating solution A.

<Coating liquid preparation example 2>
1 g of exemplary compound (II-d) (manufactured by Aldrich) was added to 80 g of butyl acetate. While heating under reflux (internal temperature 127 ° C.) in a nitrogen stream, a solution obtained by diluting 5 mg of V-601 (10 hours half-temperature 66 ° C.) manufactured by Wako Pure Chemical Industries, Ltd. with 4 ml of butyl acetate as a polymerization initiator is taken over 2 hours. The mixture was added dropwise, and heated to reflux for 1 hour after the completion of the addition. After adding 20 mg of 4-methoxyphenol as a polymerization inhibitor, the mixture was cooled to room temperature, concentrated under reduced pressure to a liquid weight of 2 g, added with 20 ml of methanol and stirred for 1 hour, and then the solid was collected by filtration and dried. This was dissolved in 10 ml of tetrahydrofuran, and 1.8 ml of water was added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation, and 10 ml of methanol was added. The solid content was collected by filtration and dried to obtain 0.49 g of solid content. When the solid content was analyzed by GPC, components having a molecular weight larger than that of the exemplary compound (II-d) were Mw = 1580, M _{Z + 1} = 310,000, and Mn = 89,000 (M _{Z + 1} was Z + 1 average) Molecular weight). The unreacted exemplary compound (II-d) in the solid was 3% by mass or less. No component with a molecular weight of 3 million or more was contained. When ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, the proton peak derived from the alkyl group formed by polymerization of the vinyl group and the remaining proton peak derived from the vinyl group were integrated at 48:52. The ratio was observed and it was found that vinyl groups were polymerized.
When 0.3 ml of this composition was added with 5 ml of propylene glycol methyl ether acetate and stirred at 40 ° C. for 3 hours, it was uniformly dissolved. This was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to obtain a coating liquid B for forming an inorganic polymer film of the present invention. From the weight of the remaining monomer and the weight of the additive, it is apparent that the polymer obtained by the reaction of the vinyl groups of the monomers in the solid content in the composition is 70% by mass or more.

<Coating liquid preparation example 3>
1 g of exemplified compound (II-d) (manufactured by Aldrich) was added to 26.4 g of butyl acetate. While heating and refluxing (internal temperature 127 ° C.) in a nitrogen stream, a solution obtained by diluting 1.8 mg of Wako Pure Chemical Industries, Ltd. V-601 (10 hours half-temperature 66 ° C.) with 2 ml of butyl acetate as a polymerization initiator for 2 hours The solution was added dropwise, and after completion of the addition, the mixture was heated to reflux for 1 hour. After adding 20 mg of 4-methoxyphenol as a polymerization inhibitor, the mixture was cooled to room temperature, concentrated under reduced pressure to a liquid weight of 2 g, added with 20 ml of methanol and stirred for 1 hour, and then the solid was collected by filtration and dried. This was dissolved in 15 ml of tetrahydrofuran, and 5 ml of water was added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation, and 10 ml of methanol was added. The solid content was collected by filtration and dried to obtain 0.60 g of solid content. When the solid content was analyzed by GPC, the parts having a molecular weight larger than that of the compound (II-d) were Mn = 31,000, Mw = 118,000, and M _{z + 1} = 270,000. The unreacted exemplary compound (II-d) in the solid was 3% by mass or less. No component with a molecular weight of 3 million or more was contained. When ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, the proton peak derived from the alkyl group formed by polymerization of the vinyl group and the proton peak derived from the remaining vinyl group were integrated at 42:58. The ratio was observed and it was found that vinyl groups were polymerized.
When 0.3 ml of this composition was added with 5 ml of propylene glycol methyl ether acetate and stirred at 40 ° C. for 3 hours, it was uniformly dissolved. This was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to obtain a coating liquid C for forming an inorganic polymer film of the present invention. From the weight of the remaining monomer and the weight of the additive, it is apparent that the polymer obtained by the reaction of the vinyl groups of the monomers in the solid content in the composition is 70% by mass or more.

<Coating liquid preparation example 4>
Chem. Heterocycl. Compd. (Engl. Transl) (12) 1976; 1109-1110, 5-bromo-2- (3-bromophenyl) benzoxazole (14-a) 10 g (0. 0283 mol) was added 50 ml of triethylamine and 13.36 g (0.136 mol) of trimethylsilylacetylene, and 0.8 g of (Ph ₃ P) ₂ PdCl ₂ and 0.6 g of Ph ₃ P were added under a nitrogen stream. The mixture was refluxed for 4 hours and then cooled to room temperature. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 6.1 g (0.0157 mol) of (14-b).
This was dissolved in 50 ml of chloroform, 20 ml of tetrabutylammonium fluoride (1 mol / liter THF solution) was added, and the mixture was stirred at room temperature for 1 hour. The organic layer was washed with water, dehydrated with anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by column chromatography to obtain 2.92 g (0.012 mol) of Exemplified Compound (I-14).

  Next, 2 g of exemplary compound (I-14), 0.11 g of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) and 5 ml of t-butylbenzene were stirred and polymerized at an internal temperature of 150 ° C. for 7 hours in a nitrogen stream. After the reaction solution was brought to room temperature, it was added to 30 ml of isopropyl alcohol, and the precipitated solid was filtered and thoroughly washed with isopropyl alcohol. 0.35 g of polymer (B) having a weight average molecular weight of about 7000 was obtained. The solubility of the polymer (B) in cyclohexanone was 5% by mass or more at 25 ° C. 0.35 g of the polymer (B) was completely dissolved in 7 g of cyclohexanone. This solution was filtered through a 0.1 μm tetrafluoroethylene filter to obtain coating solution D.

<Example 1>
The SCT unit (SOD spin coat unit) in ACT8SOD manufactured by Tokyo Electron was set at a temperature of 23 ° C and humidity of 45%, and was applied using a nitrogen pressure (0.05 MPa) line with a PTFE 0.1 µm filter. 3 ml of the liquid D was discharged, and spin coating was performed on the Si wafer at 1200 rpm. Thereafter, a heat drying treatment was performed at 110 ° C. for 1 minute using LHP (atmosphere atmosphere hot plate) and at 200 ° C. for 1 minute using DLB (low oxygen concentration hot plate) to obtain a 200 nm coating film D. Continuously, the Si wafer was again introduced into the SCT unit, 3 ml of coating solution B was discharged using a nitrogen pressure (0.05 MPa) line on which a PTFE 0.1 μm filter was set, and spin coating was performed at 1200 rpm. It was. Thereafter, heat drying was performed at 110 ° C. for 1 minute with LHP (atmospheric atmosphere hot plate) and at 200 ° C. for 1 minute with DLB (low oxygen concentration hot plate) to obtain 380 nm coating film B on coating film D. . Continuously, the Si wafer was again introduced into the SCT unit, 3 ml of coating solution A was discharged using a nitrogen pressure (0.05 MPa) line on which a PTFE 0.1 μm filter was set, and spin coating was performed at 1200 rpm. It was. Thereafter, a heat drying treatment was performed at 110 ° C. for 1 minute using LHP (atmospheric atmosphere hot plate) and at 200 ° C. for 1 minute using DLB (low oxygen concentration hot plate) to obtain 200 nm coating film A on coating film B. . The laminate composed of the coating films D and B and the coating film A thus formed was heat-cured in nitrogen at 400 ° C. for 30 minutes using a clean oven. Thereafter, a cross-cut peel test was performed. Specifically, 10 × 10 squares (100 lattice grids) having a 1 mm interval were formed on the laminate by scribing with a diamond pen, and an adhesive tape was adhered to the grid grids. Later, when peeled, no peeling of the grid was observed with the naked eye.

<Example 2>
The SCT unit (SOD spin coat unit) in ACT8SOD manufactured by Tokyo Electron was set at a temperature of 23 ° C and humidity of 45%, and was applied using a nitrogen pressure (0.05 MPa) line with a PTFE 0.1 µm filter. 3 ml of the liquid D was discharged, and spin coating was performed on the Si wafer at 1200 rpm. Thereafter, a heat drying treatment was performed at 110 ° C. for 1 minute using LHP (atmospheric atmosphere hot plate) and at 200 ° C. for 1 minute using DLB (low oxygen concentration hot plate) to obtain 200 nm coating film D. Continuously, the Si wafer was again introduced into the SCT unit, 3 ml of coating solution C was discharged using a nitrogen pressure (0.05 MPa) line on which a PTFE 0.1 μm filter was set, and spin coating was performed at 1200 rpm. It was. Thereafter, a heat drying treatment was performed at 110 ° C. for 1 minute with LHP (atmosphere atmosphere hot plate) and at 200 ° C. for 1 minute with DLB (low oxygen concentration hot plate) to obtain a coating film C of 380 nm on coating film D. . Continuously, the Si wafer was again introduced into the SCT unit, 3 ml of coating solution A was discharged using a nitrogen pressure (0.05 MPa) line on which a PTFE 0.1 μm filter was set, and spin coating was performed at 1200 rpm. It was. Thereafter, a heat drying treatment was performed at 110 ° C. for 1 minute using LHP (atmospheric atmosphere hot plate) and at 200 ° C. for 1 minute using DLB (low oxygen concentration hot plate) to obtain 200 nm coating film A on coating film C. . The laminate composed of the coating films D and C and the coating film A thus formed was heated and cured in nitrogen at 350 ° C. for 1 hour using a clean oven. After the curing treatment, a peel test was performed in the same manner as in <Example 1>. When the diamond is scratched with a diamond pen, 10 × 10 squares (100 lattice grids) are formed on the laminate, and the adhesive tape is adhered to the grid grids and then peeled off. The naked eye did not peel off the grid.

<Example 3>
The SCT unit (SOD spin coat unit) in ACT8SOD manufactured by Tokyo Electron was set at a temperature of 23 ° C and humidity of 45%, and was applied using a nitrogen pressure (0.05 MPa) line with a PTFE 0.1 µm filter. 3 ml of the liquid D was discharged, and spin coating was performed on the Si wafer at 1200 rpm. Thereafter, a heat drying treatment was performed at 110 ° C. for 1 minute using LHP (atmosphere atmosphere hot plate) and at 200 ° C. for 1 minute using DLB (low oxygen concentration hot plate) to obtain a 200 nm coating film D. Continuously, the Si wafer was again introduced into the SCT unit, 3 ml of coating solution C was discharged using a nitrogen pressure (0.05 MPa) line on which a PTFE 0.1 μm filter was set, and spin coating was performed at 1200 rpm. It was. Thereafter, a heat drying treatment was performed at 110 ° C. for 1 minute with LHP (atmospheric atmosphere hot plate) and at 200 ° C. for 1 minute with DLB (low oxygen concentration hot plate) to obtain 380 nm of coating film C on coating film D. . Continuously, the Si wafer was again introduced into the SCT unit, 3 ml of coating solution A was discharged using a nitrogen pressure (0.05 MPa) line on which a PTFE 0.1 μm filter was set, and spin coating was performed at 1200 rpm. It was. Thereafter, heat treatment was performed at 110 ° C. for 1 minute with LHP (atmosphere atmosphere hot plate) and at 200 ° C. for 1 minute with DLB (low oxygen concentration hot plate) to obtain 200 nm of coating film A on coating film C. The laminate composed of the coating films D and C and the coating film A thus formed was divided into about 8 cm square. Ultraviolet irradiation with a high-pressure mercury lamp (nitrogen atmosphere, substrate temperature 350 ° C., wavelength 220 to 600 nm, illuminance 800 mW (240 to 320 nm)) was irradiated for 15 minutes for simultaneous curing. After the curing treatment, a peel test was performed in the same manner as in <Example 1>. When the diamond is scratched with a diamond pen, 10 × 10 squares (100 lattice grids) are formed on the laminate, and the adhesive tape is adhered to the grid grids and then peeled off. The naked eye did not peel off the grid.

<Comparative Example 1>
The SCT unit (SOD spin coat unit) in ACT8SOD manufactured by Tokyo Electron was set at a temperature of 23 ° C and humidity of 45%, and was applied using a nitrogen pressure (0.05 MPa) line with a PTFE 0.1 µm filter. 3 ml of the liquid D was discharged, and spin coating was performed on the Si wafer at 1200 rpm. Thereafter, a heat drying treatment was performed at 110 ° C. for 1 minute using LHP (atmosphere atmosphere hot plate) and at 200 ° C. for 1 minute using DLB (low oxygen concentration hot plate) to obtain a 200 nm coating film D. Thereafter, heat curing was performed in nitrogen at 400 ° C. for 30 minutes using a clean oven. Continuously, the Si wafer was again introduced into the SCT unit, 3 ml of coating solution B was discharged using a nitrogen pressure (0.05 MPa) line on which a PTFE 0.1 μm filter was set, and spin coating was performed at 1200 rpm. It was. Thereafter, a heat drying treatment was performed at 110 ° C. for 1 minute with LHP (atmosphere atmosphere hot plate) and at 200 ° C. for 1 minute with DLB (low oxygen concentration hot plate) to obtain 380 nm coating film B on coating film D. . Thereafter, heat curing was performed in nitrogen at 400 ° C. for 30 minutes using a clean oven. Continuously, the Si wafer was again introduced into the SCT unit, 3 ml of coating solution A was discharged using a nitrogen pressure (0.05 MPa) line on which a PTFE 0.1 μm filter was set, and spin coating was performed at 1200 rpm. It was. Thereafter, a heat drying treatment was performed at 110 ° C. for 1 minute using LHP (atmospheric atmosphere hot plate) and at 200 ° C. for 1 minute using DLB (low oxygen concentration hot plate) to obtain 200 nm coating film A on coating film B. . Thereafter, heat curing was performed in nitrogen at 400 ° C. for 30 minutes using a clean oven. When a peel test was performed on the laminate composed of the coating films D and B and the coating film A formed in this manner in the same manner as in <Example 1>, 32 squares in 100 square grids were peeled off and can be confirmed with a microscope. It was found that the interface between the film A and the film B was almost the peeling interface in the range.

<Comparative example 2>
Evaluation was conducted in the same manner as in Comparative Example 2 except that the coating liquid B was changed to C. As a result, 74 squares in 100 square grids were peeled off, and the peeling interface was an interface between the coating film D and the coating film C.

  From the results shown in Table 1, by using the present invention, a laminated structure of insulating films used in a multilayer structure of a semiconductor device can be formed in a short time, and there is no need to use an expensive CVD apparatus.

Claims (6)

A step of applying a coating solution containing a polymer of a compound represented by the following general formula (I) on a substrate and drying to form a copper diffusion prevention film, and containing an inorganic polymer on the copper diffusion prevention film Applying a coating liquid to be dried and forming an inorganic polymer film; applying a coating liquid containing an insulating film resin on the inorganic polymer film; and drying to form an organic polymer film; Then, the manufacturing method of the laminated insulation film which has the process of hardening | curing the said copper diffusion prevention film, the said inorganic polymer film, and the said organic polymer film at once by heating or irradiation of an energy ray.
(X) _m -Q- (Y) _n General formula (I)
(In general formula (I), Q represents a nitrogen-containing heterocyclic group having 5 or 6 ring members, or a benzo-fused ring group thereof. X represents an optional substituent. M represents an integer of 0 to 10. When m is 2 or more, X may be the same or different, Y represents a group represented by any one of the following general formulas (Y-1) to (Y-6), and n represents 1 to Represents an integer of 10. When n is 2 or more, Y may be the same or different.

(In the general formulas (Y-1) to (Y-6), Z represents a hydrogen atom or an arbitrary substituent. X ¹ is an atom or group selected from C (X ² ) ₂ , NX ² , O, and S). X ² independently represents a hydrogen atom or an arbitrary substituent, Q ² represents a group having a cyclic or cage structure, or SiX ⁴ _(3-n ² _), and each X ⁴ independently represents hydrogen. Represents an atom or an arbitrary substituent, and when there are a plurality of Z, X ¹ and Q ² , they may be the same or different, and n ² represents an integer of 1 to 10. In the formula, * represents a general formula ( Shows the bonding position of I) with Q.) The method for producing a multilayer insulating film according to claim 1, wherein Q in the general formula (I) is a group represented by any one of the following general formulas (Q-1) to (Q-5).

(In General Formulas (Q-1) to (Q-5), A ¹ represents an atom or group selected from C (X ³ ) ₂ , NX ³ , O, and S. A in General Formula (Q-4) the ^1, the groups represented by NX ³ is selected .A ² each independently represent an atom or a group selected from the CX ^{3, N} .X ³ are each independently a hydrogen atom, any substituent or general, A group represented by Y in formula (I) A ³ is each independently a hydrogen atom or a group represented by X or Y in formula (I), represented by formulas (Q-1) to ( The group represented by Q-5) may have a group represented by X and Y in the general formula (I) at any position.   The method for producing a laminated insulating film according to claim 1 or 2, wherein the inorganic polymer is a polymer of a silsesquioxane compound having an unsaturated group as a substituent.   The method for producing a laminated insulating film according to any one of claims 1 to 3, wherein the resin for an insulating film is a polymer having a cage structure in the molecule.   The insulating film obtained by the manufacturing method of the lamination type insulating film in any one of Claims 1-4.   An electronic device having the insulating film according to claim 5.