CN100444330C - Insulating film material containing organic silane or organic siloxane compound, method for producing same, and semiconductor device - Google Patents

Abstract

An insulating film material from which an insulating film is formed by a chemical vapor deposition method and which is preferably used as an interlayer insulating film material for semiconductor devices is disclosed. An insulating film made from this material and a semiconductor device using such an insulating film are also disclosed. The insulating film material contains an organic silicon compound which is represented by one of the formulae (1)-(4) and composed of either an organic silane compound, wherein a silicon atom is directly bonded with a secondary hydrocarbon group and an alkenyl group or with an alkenyl group, or an organic siloxane compound, wherein a silicon atom is directly bonded with a secondary hydrocarbon group and/or an alkenyl group. With this insulating film material, an insulating film is formed through chemical vapor deposition growth of the organic silicon compound.

Description

The insulating film material, its manufacture method and the semiconductor device that contain organosilan, organosilicone compounds formation

Technical field

The present invention is the invention of the low-k interlayer insulating film material that uses in the polylaminate wiring technique that relates in logic ULSI.Particularly relate to the invention of insulating film material that the organic silane compound that contains plasma polymerization and use, any the organo-silicon compound in the organosilicone compounds form and uses thereof.

Background technology

In the manufacturing technology of the integrated circuit fields of electronics industry, the requirement of highly integrated and high speed is increased day by day.At silicon ULSI, particularly among the logic ULSI, to compare with the performance that miniaturization by MOSFE brings, the performance of relative wiring becomes more needs the problem that solves.That is, follow the problem of the wiring delay of laminates linearize, require to reduce the cloth line resistance and reduce between wiring and the electric capacity of interlayer for solution.

For this reason, now must change the aluminium wiring that is used for most of integrated circuit, and importing resistance is lower, has the copper wiring of migration patience, therefore after utilizing sputtering method or chemical vapour deposition (CVD) (below be abbreviated as CVD) method to form kind of crystalline substance, carry out copper-plated technology and be practical.

Layer insulation membrane material as low-k has various motions.As prior art, in inorganic system, use silicon dioxide (SiO is arranged ₂), the motion of silicon nitride, phosphosilicate glass, in organic system, the motion of using polyimides is arranged.Recently,, there is use in advance the tetraethoxysilane monomer to be hydrolyzed, that is, makes its polycondensation and obtain SiO for obtaining the more interlayer dielectric of homogeneous ₂, carry out the motion that polysiloxanes that polycondensation obtained uses as organic SOG as the motion of the coating material of so-called spin-coating glass (inorganic SOG) with the organoalkoxysilane monomer.

In addition, as dielectric film formation method, have with the dielectric film polymer solution with method of spin coating be coated with, the method for the application type of film forming and mainly in plasma CVD equipment, carry out plasma polymerization and two kinds of the CVD methods of film forming.

As the motion of plasma CVD method, for example, in Japanese Patent Application Laid-Open 2002-110670 communique, proposed to utilize plasma CVD method to form the method for oxidation three TMOS films from trimethyl silane and oxygen.In addition, in the flat 11-288931 communique of Japanese Patent Application Laid-Open, proposed to utilize plasma CVD method to form the method for oxidation of alkyl Silan-based Thin Films from the alkoxy silane of alkynyl such as straight chained alkyl with methyl, ethyl, n-pro-pyl etc., ethenylphenyl and aryl.With the formed dielectric film of the material of these existing plasma CVD methods, with barrier metal, good as the adhesiveness of the copper wiring material of wiring material, but on the other hand, the homogeneity of film becomes problem, and film forming speed, dielectric constant are insufficient sometimes.

On the other hand, as the motion of application type,, need coating though the homogeneity of film is good, remove desolvate, three operations of heat treatment, comparing with the CVD material is disadvantageous economically.In addition, many times, with barrier metal, as the adhesiveness of the copper wiring material of wiring material or evenly apply coating fluid itself to the board structure of miniaturization and become problem.

In addition, in the application type material, be smaller or equal to 2.5, and then, proposed the method for formation porous material smaller or equal to 2.0 ultralow k value material for realizing dielectric constant.There is the organic principle particulate that makes easy thermal decomposition to be dispersed in the matrix of organic system or inorganic based material, heat-treats the method that realizes porous; Make evaporation silicon and the formed SiO of oxygen in gas ₂Ultramicron carries out evaporation, forms SiO ₂The method of ultra fine particle film etc.

Yet the method for these porous though be effectively for low-kization, causes that sometimes mechanical strength reduces, cmp (CMP) difficulty that becomes, or absorb moisture and cause dielectric constant to rise and the wiring corrosion.

Therefore, market further require to satisfy low-k, sufficient mechanical, with the adhesiveness of barrier metal, whole performances that require of preventing copper diffusion, anti-plasma ash voltinism, anti-moisture absorption etc., and these performances material of balance well.As making these require performance to reach the method for balance to a certain extent, proposed by in organosilicon alkanes material, raising is with respect to the ratio of the carbon of the organic substituent of silane, and acquisition has the material of the intermediate features of organic polymer and inorganic polymer.

For example, in Japanese Patent Application Laid-Open 2000-302791 communique, proposed to use the silicon compound that will have adamantyl with the acidic aqueous solution coexistence under utilize be hydrolyzed polycondensation resulting coating solution of sol-gel process, obtain the method for dielectric constant smaller or equal to 2.4 interlayer dielectric without porous.

But this material is the application type material, still has the problem of application type film build method as described above.

Disclosure of an invention

The present invention is in view of the above-mentioned problems and the invention of carrying out, its purpose is, provide and contain novel advanced low-k materials, particularly be applicable to the insulating film with low dielectric constant material that the organic silane compound of PECVD device, any organo-silicon compound in the organosilicone compounds form, use the dielectric film of this insulating film with low dielectric constant material, and contained this film formed semiconductor device that insulate.

Present inventors find, sechy-drocarbyl and/or alkenyl directly are incorporated into organic silane compound on the silicon atom, any the organo-silicon compound in the organosilicone compounds, low-k interlayer insulating film material as dielectric film, particularly semiconductor device by using is fit to, thereby has finished the present invention.

That is, the present invention is a kind of insulating film material, it is characterized in that, contains any organo-silicon compound of following general formula (1)～general formula (4), and dielectric film is to utilize the chemical vapour deposition technique of these organo-silicon compound to form.

The organic silane compound with sechy-drocarbyl and alkenyl and the direct syndeton of silicon atom of following general formula (1) expression.

(in the formula, R ¹, R ²The expression carbon number is 1～20 alkyl, R ³Expression contains an alkenyl at least or contains alkenyl and the carbon number of aryl is 1～20 alkyl, R ⁴The expression carbon number is 1～10 alkyl or hydrogen atom.M represents 1～2 integer, and n represents 1～2 integer, and m+n represents 2～3 integer).

The organosilicone compounds with sechy-drocarbyl and/or alkenyl and the direct syndeton of silicon atom of following general formula (2) expression.

(in the formula, R ¹, R ²With above-mentioned.R ⁵The expression carbon number is 1～20 alkyl or hydrogen atom.X represents the integer more than or equal to 2).

The organic silane compound with vinyl and the direct syndeton of silicon atom of following general formula (3) expression.

(in the formula, R ⁶The expression carbon number is 1～10 alkyl or hydrogen atom, and p represents 2 or 3).

The organosilicone compounds with vinyl and the direct syndeton of silicon atom of following general formula (4) expression.

(in the formula, R ⁷The expression carbon number is any one of 1～20 alkyl, alkenyl, aryl.X is with above-mentioned).

The best mode that carries out an invention

Below, the present invention is described in detail.

In above-mentioned general formula (1), R ¹, R ²Be that carbon number is 1～20 saturated or unsaturated alkyl.Any structure that can have straight chain shape, a chain, ring-type.In addition, their structures of mutually combining are also contained in the scope of the present invention.On the other hand, greater than 20 o'clock, obtain corresponding raw materials such as the organohalogen compounds difficulty that can become sometimes, even or can obtain but its purity is also low at carbon number.

When considering in the CVD device stable the use, from the vapour pressure of the organic silane compound low this point that do not become, preferred especially carbon number is 1～10 alkyl.

As R ¹, R ²The example of alkyl, there is no particular limitation, but can list carbon number is 1～20, preferred carbon number is 1～10 alkyl, aryl, aryl alkyl, alkylaryl.R ¹, R ²Can be identical, also can be different.

As R ¹, R ²Example when not mutually combining can list R ¹, R ²For being selected from least a in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, tertiary pentyl, n-hexyl, cyclohexyl, phenyl and the toluyl, or two kinds or its above sechy-drocarbyl.

As R ¹, R ²Mutually combine, and the example of the sechy-drocarbyl of the group that combines with Si by secondary carbon, can list cyclobutyl, cyclobutane base, cyclopenta, cyclopentadienyl group, cyclohexyl, cyclohexenyl group, ring octadecylene base, ring octadecane dialkylene as typical example.

As R ¹, R ²Combination, at the preferred R of economic aspect ¹, R ²Be the isopropyl of methyl, R ¹, R ²Be respectively the sec-butyl of methyl, ethyl, R ¹, R ²The cyclopenta, cyclopentadienyl group, cyclohexyl, the cyclohexenyl group that mutually combine and form.

R ³Expression contains an alkenyl at least or contains alkenyl and the carbon number of aryl is 1～20 alkyl.Alkenyl can list vinyl, 1-acrylic, 1-cyclobutenyl, 1-pentenyl, 1-hexenyl, 2-acrylic, 2-cyclobutenyl, 2-pentenyl, 2-hexenyl as typical example.Especially, alkenyl is preferably vinyl especially.In addition, as the alkyl except that alkenyl, can also use carbon number except that aryl is 1～20 alkyl, for example, and with R ¹, R ²Same group.

R ⁴The expression carbon number is 1～10 alkyl or hydrogen atom, as alkyl, is saturated or unsaturated alkyl, can have any structure of straight chain shape, a chain, ring-type.At carbon number greater than 10 o'clock, the vapour pressure step-down of the organosilan of Sheng Chenging sometimes, the difficulty that becomes of the use in the PECVD device, and not preferred.

As R ⁴, be preferably to be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group of 1～4 alkyl on raw material obtains as carbon number.

M represents 1～2 integer, and n represents 1～3 integer, and m+n represents the integer smaller or equal to 3.That is, be m=1, when n=1 or m=2, the alkyl of n=0, expression two replaces dialkoxy silicanes, be (m=1, n=2) or (m=2, n=1) or (when m=3, n=0) alkyl, represent three substituted alcoxyl base silanes.Their mixture is also contained in the scope of the present invention.

Concrete example as the organic silane compound of above-mentioned general formula (1) expression, can list, (A) isopropyl-ethylene base dimethoxy silane, isopropyl-ethylene base diethoxy silane, isopropyl-ethylene base two tert-butoxy silane, diisopropyl vinyl methoxy silane, diisopropyl vinyl Ethoxysilane, diisopropyl vinyl tert-butoxy silane, isopropyl divinyl methoxy silane, isopropyl divinyl Ethoxysilane, isopropyl divinyl tert-butoxy silane, isopropyl-ethylene ylmethyl methoxy silane, isopropyl-ethylene ylmethyl Ethoxysilane, isopropyl-ethylene ylmethyl tert-butoxy silane, isopropyl-ethylene base ethyl methoxy silane, isopropyl-ethylene base ethyl Ethoxysilane, isopropyl-ethylene base ethyl tert-butoxy silane, sec-butyl vinyl-dimethyl TMOS, sec-butyl vinyl diethoxy silane, sec-butyl vinyl two tert-butoxy silane, di-secondary butylethylene methoxylsilane, di-secondary butyl vinyl Ethoxysilane, di-secondary butyl vinyl tert-butoxy silane, sec-butyl divinyl methoxy silane, sec-butyl divinyl Ethoxysilane, sec-butyl divinyl tert-butoxy silane etc.

In above-mentioned general formula (2), for R ¹, R ², can use and the same group of above-mentioned general formula (1).R ⁵The expression carbon number is 1～20 alkyl or hydrogen atom, as alkyl, for example can use and R ¹, R ², R ³Same group.

Concrete example as the organosilicone compounds shown in the above-mentioned general formula (2) can list,

(B) 1,3,5-triisopropyl-1,3,5-trivinyl cyclotrisiloxane, 1,3,5,7-tetra isopropyl-1,3,5,7-tetrem thiazolinyl cyclotetrasiloxane, 1,3,5,7,9-five isopropyls-1,3,5,7,9-five vinyl D5s, 1,3,5-three sec-butyls-1,3,5-trivinyl cyclotrisiloxane, 1,3,5,7-four sec-butyls-1,3,5,7-tetrem thiazolinyl cyclotetrasiloxane, 1,3,5,7,9-five sec-butyls-1,3,5,7,9-five vinyl D5s

(C) 1,3,5-triisopropyl-1,3,5-trimethyl cyclotrisiloxane, 1,3,5,7-tetra isopropyl-1,3,5,7-tetramethyl-ring tetrasiloxane, 1,3,5,7,9-five isopropyls-1,3,5,7,9-pentamethyl D5,1,3,5-triisopropyl-1,3,5-triethyl group cyclotrisiloxane, 1,3,5,7-tetra isopropyl-1,3,5,7-tetraethyl cyclotetrasiloxane, 1,3,5,7,9-five isopropyls-1,3,5,7,9-five ethyl D5s, six isopropyl cyclotrisiloxane, eight isopropyl rings, four oxygen alkane, ten isopropyl rings, five oxygen alkane, 1,3,5-three sec-butyls-1,3,5-front three basic ring tri-alkoxy, 1,3,5,7-four sec-butyls-1,3,5, the 7-tetramethyl-ring tetrasiloxane, 1,3,5,7,9-five sec-butyls-1,3,5,7,9-pentamethyl D5,1,3,5-three sec-butyls-1,3,5-triethyl group cyclotrisiloxane, 1,3,5,7-four sec-butyls-1,3,5,7-tetraethyl cyclotetrasiloxane, 1,3,5,7,9-five sec-butyls-1,3,5,7,9-five ethyl D5s

(D) 1,3,5-triisopropyl cyclotrisiloxane, 1,3,5,7-tetra isopropyl cyclotetrasiloxane, 1,3,5,7,9-five isopropyl D5s, 1,3,5-three sec-butyl cyclotrisiloxane, 1,3,5,7-four sec-butyl cyclotetrasiloxanes, 1,3,5,7,9-five sec-butyl D5s etc.

In above-mentioned general formula (3), R ⁶The expression carbon number is 1～10 alkyl or hydrogen atom, as alkyl, can use and R ⁴Same group.

Concrete example as the organic silane compound with vinyl and the direct structure that links of silicon atom shown in the above-mentioned general formula (3) can list,

(E) divinyl dimethoxy silane, divinyl diethoxy silane, divinyl two tert-butoxy silane, trivinyl methoxy silane, trivinyl Ethoxysilane, trivinyl tert-butoxy silane etc.

In above-mentioned general formula (4), R ⁷The expression carbon number is 1～20 alkyl, alkenyl, aryl, can list methyl, ethyl, vinyl, n-pro-pyl, isobutyl group etc. particularly.

Concrete example as the organosilicone compounds with vinyl and the direct structure that links of silicon atom shown in the above-mentioned general formula (4) can list,

(F) 1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrem thiazolinyl cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-five vinyl D5s, 1,3,5-triethyl group-1,3,5-trivinyl cyclotrisiloxane, 1,3,5,7-tetraethyl-1,3,5,7-tetrem thiazolinyl cyclotetrasiloxane, 1,3,5,7,9-five ethyls-1,3,5,7,9-five vinyl D5s

(G) six vinyl cyclotrisiloxane, eight vinyl cyclotetrasiloxanes, ten vinyl D5s etc.

Autofrettage to the organic silane compound of above-mentioned general formula (1), there is no particular limitation, for example, by making the reaction of organic compound shown in the following general formula (5) and organolithium or lithium metal particles produce sechy-drocarbyl and the direct compound that links of lithium atom, make the organo-halogen-silane shown in this compound and the following general formula (6), the reaction of halogenated organic alkoxy silane, can make the organic silane compound shown in the general formula (1).

(in the formula, R ¹, R ²With above-mentioned.X represents hydrogen atom, chlorine atom, bromine atoms, iodine atom).

X′ _pSiR ³ _q(OR ⁴) _4-(p+q)(6)

(in the formula, X ' expression fluorine atom, chlorine atom, bromine atoms or iodine atom, R ³, R ⁴With above-mentioned.P represents 0～4 integer, and q represents 1～2 integer, and p+q represents the integer smaller or equal to 4)

In addition, in above-mentioned manufacture method, replace organolithium or lithium metal particles, and use magnesium metal, also can make the organo-silicon compound that general formula (1) illustrates.

In the organic compound shown in the general formula (5), as X is the example of chlorine atom, bromine atoms or iodine atom, can list isopropyl chloride, isopropyl bromide, isopropyl iodide, sec-butyl chloride, sec-butyl bromide, sec-butyl iodide, cyclopenta chlorine, cyclopentyl bromide, cyclopenta iodine, cyclohexyl chloride, cyclohexyl bromide, cyclohexyl iodide etc.

In addition, in the organic compound shown in the general formula (5), be the example of hydrogen atom as X, can list cyclopentadiene, pentamethyl cyclopentadiene, 1,2,3,4-tetramethyl-1,3-cyclopentadiene etc.By organolithium and the reaction of these compounds that makes n-BuLi, tert-butyl lithium etc., can make the compound that sechy-drocarbyl and lithium atom directly link.

As the organo-halogen-silane shown in the general formula (6), the example of halogenated organic alkoxy silane or tetraalkoxysilane, for example can list, have the vinyltriethoxysilane of an alkenyl at least, vinyltrimethoxy silane, divinyl dimethoxy silane, the divinyl diethoxy silane, the vinyl methyl dimethoxysilane, vinyl ethyl dimethoxy silane, vinyl n-pro-pyl dimethoxy silane, vinyl normal-butyl dimethoxy silane, the vinyl methyl dimethoxysilane, vinyl ethyl dimethoxy silane, vinyl n-pro-pyl dimethoxy silane, vinyl normal-butyl dimethoxy silane, vinyl trichlorosilane, the divinyl dichlorosilane, the vinyl dimethyl dichlorosilane (DMCS), the vinyl ethyl dichlorosilane, the vinyl dimethyl dichlorosilane (DMCS), the vinyl ethyl dichlorosilane, vinyl n-pro-pyl dichlorosilane, vinyl normal-butyl dichlorosilane, the phenyl vinyl dichlorosilane, phenyl vinyl dimethoxy silane, phenyl vinyl diethoxy silane etc.

Further, after synthetic reaction, in hydrocarbon substituent alkoxy silane, when remaining and the direct-connected halogen atom of silicon, can make the alkali metal alcoholates shown in the following general formula (7) and its reaction, carry out alkoxylate as product.

R ⁴OM(7)

(in the formula, M is an alkali metal, R ⁴With above-mentioned).

Example as the alkali metal alcoholates shown in the general formula (7) can list lithium methoxide, lithium ethoxide, isopropyl alcohol lithium, sodium methoxide, caustic alcohol, sodium isopropylate, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium tert-butoxide etc.

By adopting this manufacture method, can suppress the generation of accessory substance, obtain the organic silane compound shown in the highly purified general formula (1) with high yield.

To creating conditions of sechy-drocarbyl and the direct-connected compound of lithium atom, there is no particular limitation, and the one example is shown below.

Lithium metal as using can use lithium silk, lithium band, lithium grain etc., but from the reaction efficiency aspect, the preferred lithium particulate that has smaller or equal to the particle diameter of 500 μ m that uses.

Magnesium metal as using can use magnesium ribbon, magnesium particle, magnesium powder etc.

Organolithium as using can use the hexane solution of n-BuLi, the pentane solution of tert-butyl lithium etc.

As the solvent that in above-mentioned reaction, uses, so long as at the operable solvent in present technique field, just there is no particular limitation, for example, can use the ethers of the unsaturated hydro carbons, ether, propyl ether, t-butyl methyl ether, butyl ether, cyclopentyl-methyl ether etc. of the saturated hydrocarbons, toluene, dimethylbenzene, 1-decene etc. of pentane, isopentane, n-hexane, cyclohexane, normal heptane, n-decane etc.In addition, also can use their mixed solvent.

For the reaction temperature in above-mentioned reaction, preferably in compound that the secondary carbon that generates combines with lithium atom or sechy-drocarbyl and the not resolvent temperature range of the direct-connected compound of magnesium atom, carry out.Usually, in-100～200 ℃ scope, carry out, preferably in-85～150 ℃ scope, carry out as the temperature of industrial use.The pressure condition of reaction, can for pressurize down, arbitrary condition under the normal pressure, under reducing pressure.

For the sechy-drocarbyl that synthesizes and the direct-connected compound of lithium atom or sechy-drocarbyl and the direct-connected compound of magnesium atom, after manufacturing, can directly use, in addition, also can with unreacted organohalogen compounds, lithium metal, magnesium metal, remove the back as lithium halide, the magnesium halide of byproduct of reaction and use.

For operating sechy-drocarbyl and the direct-connected compound of lithium atom or sechy-drocarbyl and the direct-connected compound of magnesium atom that is obtained like this, condition with the reaction of the organo-halogen-silane of above-mentioned general formula (6), halogenated organic alkoxy silane, there is no particular limitation, and the one example is shown below.

Spendable reaction dissolvent can use and the same solvent of operable solvent in the reaction of above-mentioned secondary carbon and the direct-connected compound of lithium atom (or magnesium atom).For this reaction temperature, preferably in sechy-drocarbyl and/or alkenyl and the not resolvent temperature range of the direct-connected compound of lithium atom (or magnesium atom), carry out.Usually, in-100～200 ℃ scope, carry out, preferably in-85～150 ℃ scope, carry out as the temperature of industrial use.The pressure condition of reaction, can for pressurize down, arbitrary condition under the normal pressure, under reducing pressure.

To the autofrettage of the organosilicone compounds of above-mentioned general formula (2), there is no particular limitation, for example, and can be by making following general formula (8):

(in the formula, R ¹, R ², R ⁴, R ⁵, X is with above-mentioned.S represents 0～2 integer) shown in the sechy-drocarbyl with sechy-drocarbyl and the direct-connected structure of silicon atom replace the halogenated alkoxy silane compound, with acid or alkali coexistence under, react with water and to make.The compound that for example can use the sechy-drocarbyl of above-mentioned (A) in the example of the organic silane compound shown in the above-mentioned general formula (1) to replace dialkoxy silicane or their alkoxyl is replaced with chlorine, bromine, iodine, fluorine.

These compounds can with above-mentioned general formula (1) same autofrettage in, obtained by the form that chlorine, bromine, iodine, fluorine have replaced with alkoxyl by the change condition.The compound that in the compound of operating the above-mentioned general formula (8) that is obtained like this, can comprise in addition, above-mentioned general formula (1) or (3).

In when reaction,, can use the organic acid of the inorganic acid of hydrochloric acid, nitric acid, sulfuric acid etc. and toluenesulfonic acid etc. as the acid of coexistence.

When making the organosilicone compounds of general formula (2) expression, to operable reaction dissolvent, so long as at the operable solvent of this technical field, just there is no particular limitation.For example, can use the saturated hydrocarbons of pentane, isopentane, n-hexane, cyclohexane, normal heptane, n-decane etc., the unsaturated hydro carbons of toluene, dimethylbenzene, 1-decene etc., the ethers of ether, propyl ether, t-butyl methyl ether, butyl ether, cyclopentyl-methyl ether, oxolane etc., the alcohol of methyl alcohol, ethanol, isopropyl alcohol, n-butanol, the tert-butyl alcohol, 2-Ethylhexyl Alcohol etc.In addition, also can use their mixed solvent.Especially, using ethers or pure time-like, can make the organosilicone compounds of general formula (2) sometimes with high yield with specific molecular weight.

For the reaction temperature when making the organosilicone compounds of general formula (2) expression, usually, in-100～200 ℃ scope of the temperature of using as industry, carry out, preferably in-85～150 ℃ scope, carry out.The pressure condition of reaction, can for pressurize down, arbitrary condition under the normal pressure, under reducing pressure.

Autofrettage to the organic silane compound of above-mentioned general formula (3), there is no particular limitation, the alkoxy silane of vinyl organo-metallic compound that for example, can be by making vinyl lithium, vinyl chlorination magnesium, vinyl chlorination magnesium etc. and tetramethoxy-silicane, tetraethoxysilane etc. reacts to be made.In addition, also can the alkali metal alcoholates of above-mentioned general formula (7) and its reaction be made by after the halogenated silanes reaction of vinyl organo-metallic compound that makes vinyl lithium, vinyl chlorination magnesium, vinyl chlorination magnesium etc. and tetrachloro silicane etc.Condition during for manufacturing can be used the same condition of manufacture method with above-mentioned general formula (1).

Autofrettage to the organosilicone compounds of above-mentioned general formula (4), there is no particular limitation, for example, with the organo-halogen-silane with at least one alkenyl, the halogenated organic alkoxy silane shown in the above-mentioned general formula (6) is raw material, uses with the same method of the manufacture method of above-mentioned general formula (2) and makes.

At the organic silane compound shown in any of general formula (1)～(4) that use produces or organosilicone compounds during as insulating film material, preferred its water content is less than 50ppm, and the content that derives from the impurity element of making raw material beyond silicon, carbon, oxygen, the hydrogen is less than 10ppb.Therefore, these organo-silicon compound preferably will be as lithium salts, the magnesium salts of accessory substance, by using the filtration of glass filter, sintered porous bodies etc.; Normal pressure or reduced pressure distillation; Or use the method for the post separation etc. of silicon dioxide, aluminium oxide, high-molecular gel to make with extra care.At this moment, also can as required above-mentioned process for purification be used in combination.In general organic synthesis technology, use, to wait in the method for extracting as lithium salts, the magnesium salts water of accessory substance, the content of organic silane compound shown in one of any institute of final sometimes general formula (1)～(4) that obtain or the moisture in the organosilicone compounds or silicon, carbon, oxygen, hydrogen impurity element in addition, particularly the metal impurities residue to contain quantitative change big, becoming is not suitable as insulating film material.

In addition, when containing the accessory substance that comprises the silanol structure, can be at the hydroxyl that makes silanol with NaOH or potassium hydroxide etc. as sodium salt or sylvite and post precipitation utilizes distillation to separate the alkyl substituted alcoxyl base silane of acquisition as principal product.

During fabrication, be according to the method in the synthetic field of this organo-metallic compound.That is, dewatering, carrying out under the nitrogen of deoxidation or the argon gas atmosphere, the solvent of use and the column packing of refining usefulness etc. have preferably carried out dehydrating operations in advance.In addition, preferably remove the impurity of metallic residue and particle etc. in advance.

Organic silane compound or organosilicone compounds shown in any of general formula of the present invention (1)～(4) all is to be adapted to pass through the PECVD device carries out film forming as low dielectric constant insulating material material.

To the manufacture method of insulating film material of the present invention, there is no particular limitation, and can use normally used PECVD device in this technical field in field of semiconductor manufacture, LCD manufacturing field etc., forms dielectric film.So-called PECVD device is meant, the insulating film material of organosilan etc. is gasified by gasifier, import in the film forming room, utilize the electrode making alive of high-frequency power in film forming room, produce plasma, form the device of plasma polymerization film on the silicon substrate in film forming room etc.At this moment, in order to produce plasma, also can import the oxidant of the gas, oxygen, nitrous oxide etc. of argon, chlorine etc.When using insulating film material of the present invention to carry out film forming, can form suitable film as the advanced low-k materials (Low-k material) of semiconductor device by using by the PECVD device.

Under the PECVD condition of the annular siloxane structure of any organosilicone compounds of keeping above-mentioned general formula (2), (4), form dielectric film, also in scope of the present invention.Dielectric film with this method acquisition, become fine pore with organic cyclic siloxane compound and be the porous insulating film of main fine pore smaller or equal to 1nm, as having the low-k characteristic, and the semiconductor device by using advanced low-k materials (Low-k material) with high mechanical-physical character and high thermal conductivity can form specially suitable film.As PECVD condition at this moment, in order not destroy the annular siloxane structure, preference as, as shown in the Examples, at lower plasma power (W; Voltage * electric current) implements the PECVD film forming down.Particularly, at 1W～2000W, preferably in the scope of 1W～1000W, carry out.In addition, at this moment,, can high film forming speed formation have the more dielectric film of low-k characteristic by using the organic annular siloxane that on same silicon atom, is combined with vinyl and isopropyl.

After any materials of general formula (1)～(4) carried out film forming with CVD, by sechy-drocarbyl, alkenyl, alkyl, aryl and silicon atom fracture more than or equal to 350 ℃ temperature under heat-treat, can obtain the insulating film with low dielectric constant of porous.Preferred heat treatment temperature is, porous finish more than or equal to 350 ℃ and do not make the semiconductor device deterioration smaller or equal to 500 ℃ temperature.

Advanced low-k materials of the present invention, the ULSI of multilayer wiring has been used in suitable manufacturing, has used the semiconductor device of ULSI also to be contained in the category of the present invention.

Embodiment is shown below, but the present invention is not subjected to any restriction of these embodiment.

Embodiment 1

[manufacturing of sechy-drocarbyl and the direct-connected organic-magnesium of magnesium atom]

Under nitrogen current, in the four neck flasks of the 2L that is equipped with dropping funel, agitating device, add 53.4g (2.20mol) magnesium metal and 1.60L dry ether, be cooled to 0 ℃.Stir on one side, with 100 minute in clockwise flask drip 246g isopropyl bromide (2.00mol) and be diluted in 200ml dry ether formed solution on one side, at room temperature reacted the diethyl ether solution of acquisition isopropyl bromination magnesium 14 hours.

[manufacturing] with organic silane compound of sechy-drocarbyl and vinyl and the direct-connected structure of silicon atom

Under nitrogen current, in the four neck flasks of the 2L that is equipped with dropping funel, agitating device, add 206g (1.39mol) vinyltrimethoxy silane and 300ml dry ether, be cooled to 0 ℃.Stir on one side,, at room temperature reacted 2 hours on one side with the diethyl ether solution that drips the above-mentioned isopropyl bromination magnesium that modulates of 1.67mol in 120 fens clockwise flasks.After reaction finishes, by removing by filter magnesium methoxide residue, and the filtrate that obtains is carried out reduced pressure distillation as accessory substance, obtain the isopropyl-ethylene base dimethoxy silane of 141g (0.882mol) as object.Yield is 63.5%.

Isolated isopropyl-ethylene base dimethoxy silane is used ¹H-NMR, ¹³C-NMR, GC-MS analyze, and the result is as follows.

¹H-NMR；δ1.07ppm(s，6H，2CH ₃)、δ1.08ppm(s，1H，CH)、δ3.62ppm(s，6H，2OCH ₃)、δ5.95～6.30ppm(m，3H，CH＝CH ₂)

¹³C-NMR；δ12.0ppm、16.7ppm、50.7ppm、δ130.2ppm、δ136.4ppm

GC-MS；Mw＝160、C ₇H ₁₆O ₂Si

In addition, utilize Ka Er-Fischer moisture teller and ICP-MS (high-frequency plasma is luminous-mass spectrometer, Yokogawa ア Na リ テ イ カ Le シ ス テ system society system, trade name " HP4500 ") to measure moisture and content of magnesium in the isopropyl-ethylene base dimethoxy silane that 100g obtains, the result is H ₂O=5ppm, Mg＜10ppb, it is useful as insulating film material.

Embodiment 2

[manufacturing] with organic silane compound of 2 vinyl and the direct-connected structure of silicon atom

Under nitrogen current, in the four neck flasks of the 5L that is equipped with dropping funel, agitating device, add the dry hexane of 306g (2.00mol) divinyl dichlorosilane, 539g (4.80mol) potassium tert-butoxide and 3.0L, under the hexane counterflow condition, make its reaction 17 hours.After reaction finishes, by removing by filter potassium chloride residue, and the filtrate that obtains is carried out reduced pressure distillation, obtain the divinyl two tert-butoxy silane of 257g (1.13mol) as object as accessory substance.Yield is 56.5%.

Isolated divinyl two tert-butoxy silane are used ¹H-NMR, GC-MS analyze, and the result is as follows.

¹H-NMR；δ1.39ppm(s，18H，2 ^tBuO)、δ5.87～6.28ppm(m，6H，2CH＝CH ₂)

GC-MS；Mw＝228、C ₁₂H ₂₄O ₂Si

In addition, utilize Ka Er-Fischer moisture teller and ICP-MS (high-frequency plasma is luminous-mass spectrometer, Yokogawa ア Na リ テ イ カ Le シ ス テ system society system, trade name " HP4500 ") to measure moisture and potassium content in the divinyl two tert-butoxy silane that 100g obtains, the result is H ₂O=4ppm, K＜10ppb, it is useful as insulating film material.

Embodiment 3

[manufacturing] with organosilicone compounds of sechy-drocarbyl and vinyl and the direct-connected structure of silicon atom

In the four neck flasks of the 5L that is equipped with agitating device, add 500g (3.09mol) isopropyl-ethylene base dimethoxy silane, 556g (30.9mol) pure water, 152g (1.55mol) sulfuric acid, 3.00L oxolane, under refluxad, make its reaction 1 hour.After reaction finishes, THF and water distillation are removed, the organic layer that obtains is carried out drying with molecular sieve.After the drying,, obtain 255g (0.746mol) as 1,3 of object, 5-triisopropyl-1,3,5-trivinyl cyclotrisiloxane by organic layer is carried out decompression distillation.Yield is 24.1%, and the conversion ratio of isopropyl-ethylene base dimethoxy silane is 72.4%.

With isolated 1,3,5-triisopropyl-1,3,5-trivinyl cyclotrisiloxane is used ¹H-NMR, GC-MS analyze, and the result is as follows.

¹H-NMR；δ1.05～1.14(m，21H， ¹Pr)、δ5.88～6.23ppm(m，9H，CH＝CH ₂)

¹³C-NMR；δ14.4ppm、δ14.5ppm、δ16.3ppm、δ133.1ppm、δ133.2ppm、δ133.4ppm、δ134.6ppm、δ134.8ppm、δ135.0ppm

GC-MS；Mw＝342、C ₁₅H ₃₀O ₃Si ₃

In addition, utilize that Ka Er-Fischer moisture teller and ICP-MS (high-frequency plasma is luminous-mass spectrometer, Yokogawa ア Na リ テ イ カ Le シ ス テ system society system, trade name " HP4500 ") measure that 100g obtains 1,3,5-triisopropyl-1,3, moisture and content of magnesium in the 5-trivinyl cyclotrisiloxane, the result is H ₂O=8ppm, Mg＜10ppb, it is useful as insulating film material.

Embodiment 4

Except 500g (3.09mol) the isopropyl-ethylene base dimethoxy silane of replacement in embodiment 3, and use outside 458g (3.09mol) the isopropyl methyl dimethoxy silane, all operation makes 1 similarly to Example 3,3,5-triisopropyl-1,3,5-trimethyl cyclotrisiloxane.Yield is 25.3%, and the conversion ratio of isopropyl methyl dimethoxy silane is 75.8%.

With isolated 1,3,5-triisopropyl-1,3,5-trimethyl cyclotrisiloxane is used ¹H-NMR, ¹³C-NMR, GC-MS analyze, and the result is as follows.

¹H-NMR；δ0.197～0.213ppm(m，9H，CH ₃)、δ1.06～1.10(m，21H， ¹Pr)、

¹³C-NMR；δ15.3ppm、δ15.5ppm、δ16.4ppm、δ16.5ppm

GC-MS；Mw＝306、C ₁₂H ₃₀O ₃Si ₃

In addition, utilize that Ka Er-Fischer moisture teller and ICP-MS (high-frequency plasma is luminous-mass spectrometer, Yokogawa ア Na リ テ イ カ Le シ ス テ system society system, trade name " HP4500 ") measure that 100g obtains 1,3,5-triisopropyl-1,3, moisture and content of magnesium in the 5-trimethyl cyclotrisiloxane, the result is H ₂O=9ppm, Mg＜10ppb, it is useful as insulating film material.

Embodiment 5

[manufacturing] with organosilicone compounds of vinyl and the direct-connected structure of silicon atom

Under nitrogen current, in the four neck flasks of the 5L that is equipped with dropping funel, agitating device, add 1250g (69.4mol) pure water and 1250g (16.9mol) tert-butyl alcohol, at room temperature with the 1 hour 500g that drips (3.27mol) divinyl dichlorosilane, further make its reaction 1 hour with dropping funel.After reaction finishes,, the pentane layer that obtains is carried out drying with molecular sieve with the eight vinyl cyclotetrasiloxanes of 1.0L pentane extraction as object.After the drying,, obtain the eight vinyl cyclotetrasiloxanes of 144g (0.368mol) as object by pentane layer is carried out decompression distillation.Yield is 11.3%, and the conversion ratio of divinyl dichlorosilane is 45.0%.

Isolated eight vinyl cyclotetrasiloxanes are used ¹H-NMR, GC-MS analyze, and the result is as follows.

¹H-NMR；δ5.90～6.32ppm(m，CH＝CH ₂)

GC-MS；Mw＝392、C ₁₆H ₂₄O ₄Si ₄

In addition, utilize Ka Er-Fischer moisture teller and ICP-MS (high-frequency plasma is luminous-mass spectrometer, Yokogawa ア Na リ テ イ カ Le シ ス テ system society system, trade name " HP4500 ") to measure moisture and content of magnesium in the eight vinyl cyclotetrasiloxanes that 100g obtains, the result is H ₂O=9ppm, Mg＜10ppb, it is useful as insulating film material.

Embodiment 6

[manufacturing] with organosilicone compounds of vinyl and alkyl and the direct-connected structure of silicon atom

Except 500g (3.27mol) the divinyl dichlorosilane silane of replacement in embodiment 5, and use outside 500g (3.55mol) the vinyl dimethyl dichlorosilane (DMCS), all operation makes 1 similarly to Example 5,3,5,7-tetrem thiazolinyl-1,3,5, the 7-tetramethyl-ring tetrasiloxane.Yield is 16.5%, and the conversion ratio of vinyl dimethyl dichlorosilane (DMCS) is 66.0%.

With isolated 1,3,5,7-tetrem thiazolinyl-1,3,5, the 7-tetramethyl-ring tetrasiloxane is used ¹H-NMR, GC-MS analyze, and the result is as follows.

¹H-NMR；δ0.255～0.290ppm(m，12H，CH ₃)δ5.90～6.32ppm(m，12H，CH＝CH ₂)

GC-MS；Mw＝344、C ₁₂H ₂₄O ₄Si ₄

In addition, utilize that Ka Er-Fischer moisture teller and ICP-MS (high-frequency plasma is luminous-mass spectrometer, Yokogawa ア Na リ テ イ カ Le シ ス テ system society system, trade name " HP4500 ") measure that 100g obtains 1,3,5,7-tetrem thiazolinyl-1,3,5, moisture in the 7-tetramethyl-ring tetrasiloxane and content of magnesium, the result is H ₂O=9ppm, Mg＜10ppb, it is useful as insulating film material.

Embodiment 7

[plasma polymerization]

Use the system plasma polymerization NL-OP50FT of Japanese レ one ザ, one electronics (strain) society, at discharge voltage is 2.1kV, discharging current is that 5.0mA, divinyl two tert-butoxy silane partial pressure are 0.7torr, room temperature, polymerization (discharge) time are under 12 minutes the condition, divinyl two tert-butoxy silane are carried out plasma polymerization, film forming on silicon substrate.

The result is:

Film forming speed=46.7nm/min.

Film composition (XPS) C=41.3 atom %, O=36.7 atom %,

Si=22.0 atom %,

The C/Si=1.88 atomic ratio,

The O/Si=1.67 atomic ratio

The SEM thin-membrane section is observed: smooth dense film,

With respect to silicon, the ratio height of carbon (organic substituent) is suitable film as insulating film material.

Comparative example 1

Except the polymerization single polymerization monomer among the embodiment 7 being replaced to dimethyldimethoxysil,ne, the plasma polymerization film forming is implemented in all operations similarly to Example 7 on silicon substrate.

The result is:

Film forming speed=10.8nm/min.

Film composition (XPS) C=32.2 atom %, O=40.6 atom %,

Si=27.1 atom %,

The C/Si=1.19 atomic ratio,

The O/Si=1.50 atomic ratio

The SEM thin-membrane section is observed: smooth dense film

Compare with embodiment 7, film forming speed is slow, and is low with respect to the ratio of the carbon (organic substituent) of silicon, has to as the inappropriate film of insulating film material.

Embodiment 8

[plasma polymerization]

Except polymerization single polymerization monomer being replaced to isopropyl-ethylene base dimethoxy silane, the plasma polymerization film forming is implemented in all operations similarly to Example 7 on silicon substrate.

The result is:

Film forming speed=100nm/min.

Film composition (XPS) C=56.6 atom %, O=25.1 atom %,

Si=18.3 atom %,

The C/Si=3.09 atomic ratio,

The O/Si=1.37 atomic ratio

The SEM thin-membrane section is observed: smooth dense film

Be the ratio height of carbon (organic substituent), as the suitable film of insulating film material with respect to silicon.

Embodiment 9

[plasma polymerization]

Except polymerization single polymerization monomer is replaced to 1,3,5,7-tetrem thiazolinyl-1,3,5 beyond the 7-tetramethyl-ring tetrasiloxane, is all operated similarly to Example 7, implements the plasma polymerization film forming on silicon substrate.

The result is:

Film forming speed=153nm/min.

Film composition (XPS) C=58.7 atom %, O=20.9 atom %,

Si=20.4 atom %,

The C/Si=2.88 atomic ratio,

The O/Si=1.02 atomic ratio

The SEM thin-membrane section is observed: smooth dense film

Be the ratio height of carbon (organic substituent), as the suitable film of insulating film material with respect to silicon.In addition, hinted and kept the O/Si=1.00 atomic ratio in the monomer, kept the monomer circulus.

Embodiment 10

[plasma polymerization]

Except polymerization single polymerization monomer is replaced to 1,3,5-triisopropyl-1,3 beyond the 5-trivinyl cyclotrisiloxane, is all operated similarly to Example 7, implements the plasma polymerization film forming on silicon substrate.

The result is:

Film forming speed=215nm/min.

Film composition (XPS) C=68.5 atom %, O=15.8 atom %,

Si=15.7 atom %,

The C/Si=4.36 atomic ratio,

The O/Si=1.01 atomic ratio

The SEM thin-membrane section is observed: smooth dense film

For the ratio with respect to the carbon (organic substituent) of silicon is higher than embodiment 9, as the suitable film of insulating film material.In addition, hinted and kept the O/Si=1.00 atomic ratio in the monomer, kept the monomer circulus.

Embodiment 11

[plasma polymerization]

Except polymerization single polymerization monomer is replaced to 1,3,5-triisopropyl-1,3 beyond the 5-trimethyl cyclotrisiloxane, is all operated similarly to Example 7, implements the plasma polymerization film forming on silicon substrate.

The result is:

Film forming speed=117nm/min.

Film composition (XPS) C=60.8 atom %, O=20.1 atom %,

Si=19.1 atom %,

The C/Si=3.18 atomic ratio,

The O/Si=1.05 atomic ratio

The SEM thin-membrane section is observed: smooth dense film

For the ratio with respect to the carbon (organic substituent) of silicon is higher than embodiment 9, as the suitable film of insulating film material.In addition, hinted and kept the O/Si=1.00 atomic ratio in the monomer, kept the monomer circulus.

The industry utilizability

According to the present invention, can realize following significant effect. That is, as first effect of the present invention Fruit is, the application of the invention have sechy-drocarbyl and/or alkenyl and a direct syndeton of silicon atom Organic silane compound and/or organosilicone compounds can provide low-k and high machinery strong The material of degree is as the advanced low-k materials in the semiconductor devices interlayer dielectric film. In addition, at this In bright, can make efficiently highly purified useful as PECVD method layer insulation membrane material Have the organic silane compound of sechy-drocarbyl and/or alkenyl and the direct syndeton of silicon atom and/or have The organic siloxane compound.

Claims (13)

1. an insulating film material is characterized in that, contains any organo-silicon compound of following general formula (1), and dielectric film is to utilize the chemical vapour deposition technique of these organo-silicon compound to form,

The organic silane compound with sechy-drocarbyl and alkenyl and the direct syndeton of silicon atom of following general formula (1) expression,

In the formula, R ¹, R ²The expression carbon number is 1～20 alkyl, R ¹And R ²Mutually combine or not combination R ³Expression contains an alkenyl at least or contains alkenyl and the carbon number of aryl is 1～20 alkyl, R ⁴The expression carbon number is 1～10 alkyl or hydrogen atom, and m represents 1～2 integer, and n represents 1～2 integer, and m+n represents 2～3 integer, wherein, and except isopropyl-ethylene base dimethoxy silane and the isopropyl-ethylene base diethoxy silane.

2. insulating film material as claimed in claim 1, the sechy-drocarbyl of general formula (1) are any of isopropyl, sec-butyl, cyclopenta, cyclohexyl, cyclohexenyl group, cyclopentadienyl group.

3. insulating film material as claimed in claim 1 is combined with vinyl and isopropyl on the same silicon atom of general formula (1).

4. insulating film material as claimed in claim 1, the impurity level of making raw material as deriving from of the element beyond the silica removal, carbon, oxygen, hydrogen is less than 10ppb, and water content is less than 50ppm.

5. insulating film material as claimed in claim 1, chemical vapour deposition technique are the chemical vapour deposition technique that plasma strengthens.

6. the manufacture method of the organic silane compound shown in the general formula as claimed in claim 1 (1), by making organic compound and the organolithium shown in the following general formula (5), any of lithium metal particles or magnesium metal reacted and made the compound that sechy-drocarbyl and lithium atom or magnesium atom directly link, make the reaction of organo-halogen-silane shown in this compound and the following general formula (6) or halogenated organic alkoxy silane, further, after making the reaction of alkali metal alkoxide shown in the following general formula (7), by filtering, distillation or post separate to be made with extra care

In the formula, R ¹, R ², R ³, R ⁴, m, n and m+n be with claim 1,

In the formula, R ¹, R ²With claim 1, X represents hydrogen atom, chlorine atom, bromine atoms or iodine atom,

X′ _rSiR ³ _n(OR ⁴) _4-(r+n)(6)

In the formula, X ' expression fluorine atom, chlorine atom, bromine atoms or iodine atom, R ³, R ⁴With claim 1, r represents 0～4 integer, and n represents 1～2 integer, and r+n represents the integer smaller or equal to 4,

R ⁴OM (7)

In the formula, M is an alkali metal, R ⁴With claim 1.

7. a dielectric film uses each described insulating film material of claim 1～5, and the chemical vapor deposition unit that utilizes plasma to strengthen carries out film forming and forms.

8. dielectric film as claimed in claim 7, with dielectric film sechy-drocarbyl, alkyl, alkenyl and aryl any with cut temperature of combining of silicon atom or the temperature more than it under heat-treat, carried out porous.

9. a semiconductor device has used claim 7 or 8 described dielectric films.

10. isopropyl-ethylene base two tert-butoxy silane, diisopropyl vinyl methoxy silane, diisopropyl vinyl Ethoxysilane or diisopropyl vinyl tert-butoxy silane;

Sec-butyl vinyl-dimethyl TMOS, sec-butyl vinyl diethoxy silane, sec-butyl vinyl two tert-butoxy silane, di-secondary butylethylene methoxylsilane, di-secondary butyl vinyl Ethoxysilane or di-secondary butyl vinyl tert-butoxy silane.

11. a dielectric film uses isopropyl-ethylene base dimethoxy silane or isopropyl-ethylene base diethoxy silane, the chemical vapor deposition unit that utilizes plasma to strengthen carries out film forming and forms.

12. dielectric film as claimed in claim 11 is heat-treated dielectric film under isopropyl or vinyl and cut temperature of combining of silicon atom or the temperature more than it, carried out porous.

13. a semiconductor device has used claim 11 or 12 described dielectric films.