CN1739190A - Fluorine-free plasma curing process for porous Low-K-materials - Google Patents
Fluorine-free plasma curing process for porous Low-K-materials Download PDFInfo
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- CN1739190A CN1739190A CN 200480002329 CN200480002329A CN1739190A CN 1739190 A CN1739190 A CN 1739190A CN 200480002329 CN200480002329 CN 200480002329 CN 200480002329 A CN200480002329 A CN 200480002329A CN 1739190 A CN1739190 A CN 1739190A
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Abstract
Low dielectric constant porous materials with improved elastic modulus and material hardness. The process of making such porous materials involves providing a porous dielectric material and plasma curing the porous dielectric material with a fluorine-free plasma gas to produce a fluorine-free plasma cured porous dielectric material. Fluorine-free plasma curing of the porous dielectric material yields a material with improved modulus and material hardness, and with comparable dielectric constant. The improvement in elastic modulus is typically greater than or about 50%.
Description
The present invention relates generally to be used to produce the method for semiconductor chip.In more detail, the present invention relates to improve the method for the structural property that is used as the more dielectric porous materials of integrated circuit (IC).
The potential use of new material (being called " low-K dielectric " in the prior art) as insulator in semiconductor chip design with low-k just is studied.Advanced low-k materials can help further to reduce the integrated circuit characteristic size.The material of lowest dielectric constant is air (k=1.0).Therefore, porous dielectric is very promising candidate, because they have the potentiality that low-down dielectric constant is provided.Yet unfortunately, generally there is the not enough difficult problem of mechanical strength in these porous low dielectric constant dielectrics.
Film dielectric coat on the electric device is known in the prior art.For example, the United States Patent (USP) 4,749,631 and 4,756,977 of Haluska etc. discloses by respectively the solution of silicon alkoxide or hydrogen silsesquioxane being coated onto on the matrix, heats this coated substrate then between 200-1000 ℃ and the silica dioxide coating of preparation.The dielectric constant of these coatings is too high usually for some electronic devices and loop.
The United States Patent (USP) 4,847,162 and 4,842,888 of Haluska etc. has been instructed by respectively hydrogen silsesquioxane resin and esters of silicon acis being formed the nitrided silicon dioxide coating being heated in the presence of the ammonia between 200-1000 ℃.
Glasser etc., Journal of Non-Crystalline Solids, 64 (1984), the 209-221 page or leaf has been instructed by heating tetraethoxysilane in the presence of ammonia and has been formed ceramic coating.This reference teaches the application of anhydrous ammonia and the silica dioxide coating that obtains by ammonification.
The United States Patent (USP) 4,636,440 of Jada discloses the method for matrix drying time of reduction sol-gel coating, comprises matrix is exposed in moisture quaternary ammonium base and/or the chain triacontanol amine compound.Jada requires first dry coating before heating.The method is limited to the silicon alkoxide of hydrolysis or partial hydrolysis especially.
The United States Patent (USP) 5,116,637 of the United States Patent (USP) 5,262,201 of Chandra etc. and Baney etc. has been instructed the use base catalyst, reduces to make the various pre-ceramic materials that comprise hydrogen silsesquioxane change into the necessary temperature of ceramic coating.These reference teaches before coating is exposed to base catalyst, want earlier solvent is removed.
The United States Patent (USP) 5,547,703 of Camilletti etc. has been instructed and formed the method that low-k contains the Si-O coating on matrix, comprises successively and heat hydrogen silsesquioxane resin in wet ammonia, dried ammonia and oxygen.The coating of Xing Chenging has low 2.42 the dielectric constant that reaches under 1MHz thus.This reference teaches before coating is converted into pottery, remove solvent.
The United States Patent (USP) 5,523,163 of Balance etc. has been instructed and formed the method that contains the Si-O coating on matrix, comprises the heating hydrogen silsesquioxane resin, makes it be converted into the ceramic coating that contains Si-O, subsequently this coating is exposed in the annealing atmosphere of hydrogen.The coating that obtains thus has low 2.773 the dielectric constant that reaches.The document proposes, and before coating is converted into pottery, remove solvent.
The United States Patent (USP) 5,618,878 of Syktich etc. discloses and has been used to form the coating composition that be dissolved in the hydrogen silsesquioxane resin in the saturated alkane containing of thick ceramic coating.Alkane disclosed herein is the longest to be dodecane.This list of references is not taught in except that before desolvating coated substrates is exposed in the base catalyst.
The United States Patent (USP) 6,231,989 of Chung etc., title are " method that forms coating ", disclose the method for the porous network coating of preparation low-k.The method comprises that this solution contains resin and the solvent that comprises at least two Si-H groups with solution deposited coatings on matrix, and depositional mode will make the solvent that keeps at least 5 volume % in the post-depositional coating.Subsequently this is coated with and is placed in the environment that contains base catalyst and water.At last, evaporation removes the formation porous network that desolvates from coating.If desired, this coating can be pottery by being heating and curing.Film dielectric constant by the method preparation is 1.5 to 2.4, and modulus of elasticity is about 2 to about 3Gpa.
Porous low-k dielectric constant material by spin coating (Spin-on) and chemical vapour deposition (CVD) preparation needs a solidification process usually after deposition.The typical process condition of solidifying these low-k films is included in about 350 and annealed 30 to 180 minutes with the nitrogen purge heating furnace to about 450 ℃ temperature.As in Application No. 09/681,332,09/952,649,09/906,276 and 09/952, as described in 398, its content is hereby incorporated by, and the porous network coating can replace hot curing and plasma treatment with plasma or ultraviolet curing, has got rid of necessity that aforementioned heating furnace solidifies.
Yet, still needing to prepare the method for porous low-k material, these materials should have improved structural property, for example modulus of elasticity of Ti Gaoing and material hardness, and do not damage or destroy its electrical property.
The fluorine-free plasma curing process that the invention provides a kind of porous low-k material satisfies above-mentioned needs.
Although the present invention is not limited to specific advantage or function, what deserves to be mentioned is that the material of the method production has the modulus of elasticity and the material hardness of low dielectric constant and improvement.Except that having avoided that dielectric is exposed to the advantage of fluoro plasma material, this method is compared with conventional hot curing technology, also significantly reduces the cured time, and makes to be solidificated under the lower chip temperature and carry out.
According to an embodiment of the invention, the invention provides a kind of method for preparing the fluorine-free plasma curing material, comprise a kind of porous dielectric material with first dielectric constant, first modulus of elasticity and first material hardness is provided.This porous dielectric material is carried out plasma curing with fluorine-free plasma gas, with preparation have second dielectric constant suitable with first dielectric constant and than first modulus of elasticity bigger second modulus of elasticity and than first material hardness fluorine-free plasma curing porous dielectric material of the second higher material hardness.We refer to herein " quite " and equal and be lower than slightly, for example, and second permittivity ratio, first dielectric constant low 0.05.The increase of modulus of elasticity generally greater than or be approximately 50%, more typically for greater than or be approximately 100%.The increase of material hardness generally greater than or be approximately 50%.
Therefore, target of the present invention is to produce to have the modulus of elasticity of raising and the porous dielectric material of material hardness and low-k.
These and other characteristic of the present invention and advantage can deeply be understood from the detailed description below the present invention.Scope that what deserves to be mentioned is claim limits by narration, rather than the qualification that goes through by characteristics that this specification is illustrated and advantage.
The present invention is based upon on the discovery basis that in fact plasma can solidify any porous dielectric material, it does not need this material of hot curing, can improve the modulus of elasticity (Young's modulus) and the material hardness of material, keep the curing time significantly reduce simultaneously and do not damage the character of its low-k.Porous dielectric material comprises, but be not limited to for example hydrogen silsesquioxane (HSQ) of organic dielectric materials, methyl silsesquioxane (MSQ), with their combination, Inorganic Dielectric Material and its combination, they can be deposited on dielectric coat on the matrix by the method for utilizing spin coating or chemical vapor deposition (CVD) and prepare.Porous dielectric material can have pore former-generation, solvent-formation, or the hole of molecular engineering reinforcing, these holes can be interconnective or isolated (closed), can be arbitrarily to distribute or regular distribution, for example vertical pores.
Method of the present invention is particularly useful for the coating deposition of electronic installation or circuit board, they can be as layer inner-dielectric-ayer, doping (doped) dielectric layer in production transistor-like device, in silicon on producing capacitor or capacitor class device, multilayer device, three-dimension device, insulator device, the superlattice device etc., as containing silicon ribbon pigment deposition binder system.Yet, intend selection with the matrix of the present invention's coating and device only be subjected to matrix under the used temperature and pressure of the present invention thermal stability and the restriction of chemical stability.Therefore, porous dielectric material of the present invention can be used on the following matrix, for example comprises plastics, pottery, leather, fabric and metal as polyimides, epoxides, polytetrafluoroethylene and copolymer thereof, Merlon, acrylic compounds and polyester and so on or the like.
Be used for the present invention, term " pottery " comprises as pottery of indefiniteness silicon dioxide and so on and class ceramic material, as is not have carbon and/or hydrogen fully but the indefiniteness class earth silicon material that is ceramic characteristics.Term " electronic installation " or " circuit board " include, but not limited to silicon dioxide-base device, GaAs-base device, carborundum-base device, focal plane arrays, opto-electronic device, photovoltaic cell and optics.
The present invention needs porous dielectric material as initiation material.Be applicable to that typical HSQ-base dielectric material of the present invention comprises FOx HSQ-base dielectric material and can be from Dow CorningCorporation (Midland, the HSQ-that MI) obtains base XLK porous dielectric material.In addition, be applicable to that the typical ultralow dielectric porous MSQ-Ji dielectric material by spin coating method preparation of the present invention can be from Chemat Technology, and Inc (Northridge, CA) and JSRCorporation (Tokyo, Japan) acquisition.
The following method of preparation porous network coating is as the example of producing typical porous dielectric material.It is not inventor's intention for the MSQ-basement membrane only that invention is confined to.In fact method of the present invention is applicable to any porous dielectric material.
LKD (can be from JSR Corporation, Tokyo, Japan obtains) be coating composition (being called " coating composition " hereinafter) by at least a silicone compounds preparation of dissolving in organic solvent.Indication composition of the present invention (A) is a silicone compounds, is the compound (being called " compound (1) " hereinafter) that comprises with following formula (1) expression being selected from:
R
1 aSi (OR
2)
4-a(1) R wherein
1Expression hydrogen atom or any monovalent organic radical group; R
2Expression any monovalent organic radical group; With a be the integer of 0-2 and by at least a compound hydrolysis in the compound (being called " compound (2) " hereinafter) of following formula (2) expression and/or concentrate the product that obtains,
R
3 b(R
4O)
3-bSi (R
7)
dSi (OR
5)
3-cR
6 c(2) wherein, in the formula (2), R
3, R
4, R
5And R
6Can be identical or different and represent any monovalent organic radical group separately; B and c can be identical or different and the integer of the 0-2 that respectively does for oneself; R
7Expression oxygen atom or by-(CH
2)
nThe group of-expression, wherein n is the integer of 1-6; With d be integer 0 or 1.
R in the formula (1)
1And R
2The example of any monovalent organic radical group of expression comprises alkyl, aryl, pi-allyl and glycidyl.In formula (1), R
1Typically be any monovalent organic radical group, more be typically alkyl or phenyl.
Alkyl generally contains 1 to 5 carbon atom, and its example comprises methyl, ethyl, propyl group and butyl.These alkyl can be straight or brancheds, and wherein one or more hydrogen atoms can be replaced by for example fluorine atom.
In formula (1), the example of aryl comprises phenyl, naphthyl, aminomethyl phenyl, ethylphenyl, chlorphenyl, bromophenyl and fluorophenyl.
The instantiation of the compound of formula (1) expression comprises: trialkoxy silane, trimethoxy silane for example, triethoxysilane, three-just-propoxyl group silane, three isopropoxy silane, three-just-butoxy silane, three-second month in a season-butoxy silane, three-uncle-butoxy silane, triple phenoxyl silane, the fluoro trimethoxy silane, the fluoro triethoxysilane, fluoro three-just-propoxyl group silane, fluoro three isopropoxy silane, fluoro three-just-butoxy silane, three-second month in a season of fluoro-butoxy silane, fluoro three-uncle-butoxy silane and fluoro triple phenoxyl silane; Tetraalkoxysilane, tetramethoxy-silicane for example, tetraethoxysilane, four-just-propoxyl group silane, tetraisopropoxysilan, four-just-butoxy silane, four-second month in a season-butoxy silane, four-tert-butoxy silane and tetraphenoxy-silicane alkane; Alkyltrialkoxysilaneand is methyltrimethoxy silane for example, methyl triethoxysilane, methyl three-just-propoxyl group silane, methyl three isopropoxy silane, methyl three-just-butoxy silane, three-second month in a season of methyl-butoxy silane, methyl three-uncle-butoxy silane, methyl triple phenoxyl silane, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three-just-propoxyl group silane, ethyl three isopropoxy silane, ethyl three-just-butoxy silane, three-second month in a season of ethyl-butoxy silane, ethyl three-uncle-butoxy silane, ethyl triple phenoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three-just-propoxyl group silane, vinyl silane triisopropoxide, vinyl three-just-butoxy silane, three-second month in a season of vinyl-butoxy silane, vinyl-uncle-butoxy silane, vinyl triple phenoxyl silane, just-propyl trimethoxy silicane, just-propyl-triethoxysilicane, just-propyl group three-just-propoxyl group silane, just-propyl group three isopropoxy silane, just-propyl group three-just-butoxy silane, just-three-second month in a season of propyl group-butoxy silane, just-propyl group three-uncle-butoxy silane, just-propyl group triple phenoxyl silane, the isopropyl trimethoxy silane, the isopropyl triethoxysilane, isopropyl three-just-propoxyl group silane, isopropyl three isopropoxy silane, isopropyl three-just-butoxy silane, three-second month in a season of isopropyl-butoxy silane, isopropyl three-uncle-butoxy silane, isopropyl triple phenoxyl silane, just-butyl trimethoxy silane, just-the butyl triethoxysilane, just-butyl three-just-propoxyl group silane, just-butyl three isopropoxy silane, just-butyl three-just-butoxy silane, just-three-second month in a season of butyl-butoxy silane, just-butyl three-uncle-butoxy silane, just-butyl triple phenoxyl silane, the second month in a season-butyl trimethoxy silane, the second month in a season-the butyl triethoxysilane, the second month in a season-butyl three-just-propoxyl group silane, the second month in a season-butyl three isopropoxy silane, the second month in a season-butyl three-just-butoxy silane, three-second month in a season of the second month in a season-butyl-butoxy silane, the second month in a season-butyl three-uncle-butoxy silane, the second month in a season-butyl triple phenoxyl silane, the tert-butyl trimethoxy silane, the tert-butyl triethoxysilane, tert-butyl three-positive propoxy silane, tert-butyl three isopropoxy silane, tert-butyl three-just-butoxy silane, three-second month in a season of tert-butyl-butoxy silane and tert-butyl three-uncle-butoxy silane; Tert-butyl triple phenoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl three-positive propoxy silane, the phenyl tri isopropyl silane, phenyl three-just-butoxy silane, three-second month in a season of phenyl-butoxy silane, phenyl three-uncle-butoxy silane, phenyl triple phenoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-Huan Yangbingyangbingjisanjiayangjiguiwan, γ-epoxypropoxy triethoxysilane, γ-trifluoro propyl trimethoxy silane, and γ-trifluoro propyl triethoxysilane; And dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl two-just-propoxyl group silane, dimethyl diisopropoxy silane, dimethyl two-just-butoxy silane, two-second month in a season of dimethyl-butoxy silane, dimethyl two-uncle-butoxy silane, dimethyl hexichol TMOS, diethyl dimethoxy silane, the diethyl diethoxy silane, diethyl two-just-propoxyl group silane, diethyl diisopropoxy silane, diethyl two-just-butoxy silane, two-second month in a season of diethyl-butoxy silane, diethyl two-uncle-butoxy silane, diethyl hexichol TMOS, two-just-propyl group dimethoxy silane, two-just-propyl group diethoxy silane, two-just-propyl group two-just-propoxyl group silane, two-just-propyl group diisopropoxy silane, two-just-propyl group two-just-butoxy silane, two-second month in a season of two-just-propyl group-butoxy silane, two-just-propyl group, two-uncle-butoxy silane, two-just-propyl group hexichol TMOS, diisopropyl dimethoxy silane, the diisopropyl diethoxy silane, diisopropyl two-just-propoxyl group silane, diisopropyl diisopropoxy silane, diisopropyl two-just-butoxy silane, two-second month in a season of diisopropyl-butoxy silane, diisopropyl two-uncle-butoxy silane, diisopropyl hexichol TMOS, two-just-butyl dimethoxy silane, two-just-butyl diethoxy silane, two-just-butyl two-just-propoxyl group silane, two-just-butyl diisopropoxy silane, two-just-butyl two-just-butoxy silane, two-second month in a season of two-just-butyl-butoxy silane, two-just-butyl, two-uncle-butoxy silane, two-just-butyl hexichol TMOS, two-second month in a season-butyl dimethoxy silane, two-second month in a season-butyl diethoxy silane, two-second month in a season-butyl two-just-propoxyl group silane, two-second month in a season-butyl diisopropoxy silane, two-second month in a season-butyl two-just-butoxy silane, two-second month in a season of two-second month in a season-butyl-butoxy silane, two-second month in a season-butyl two-uncle-butoxy silane, two-second month in a season-butyl hexichol TMOS, two-tert-butyl dimethoxy silane, two-tert-butyl diethoxy silane, two-tert-butyl two-just-propoxyl group silane, two-tert-butyl diisopropoxy silane, two-tert-butyl two-just-butoxy silane, two-second month in a season of two-tert-butyl-butoxy silane, two-tert-butyl, two-uncle-butoxy silane, two-tert-butyl hexichol TMOS, dimethoxydiphenylsilane, the diphenyl diethoxy silane, diphenyl two-just-propoxyl group silane, diphenyl diisopropoxy silane, diphenyl two-just-butoxy silane, two-second month in a season of diphenyl-butoxy silane, diphenyl two-uncle-butoxy silane, diphenyl hexichol TMOS, divinyl trimethoxy silane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-Huan Yangbingyangbingjisanjiayangjiguiwan, γ-epoxypropoxy triethoxysilane, γ-trifluoro propyl trimethoxy silane, and γ-trifluoro propyl triethoxysilane.
Exemplary compounds (1) is a tetramethoxy-silicane, tetraethoxysilane, four-just-propoxyl group silane, tetraisopropoxysilan, tetraphenoxy-silicane alkane, methyltrimethoxy silane, methyl triethoxysilane, methyl three-just-and propoxyl group silane, methyl three isopropoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, the diethyl diethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, trimethyl one methoxy silane, trimethyl one Ethoxysilane, triethyl group one methoxy silane, triethyl group one Ethoxysilane, triphenyl one methoxy silane and triphenyl one Ethoxysilane.
In formula (2), the example of any monovalent organic radical group comprises with above-mentioned about identical those of formula (1) organic group that compound exemplified.
In the formula (2) by R
7The example of the divalent organic group of expression comprises the alkylidene that contains 2 to 6 carbon atoms, for example methylene.
R wherein
7For the examples of compounds by formula (2) expression of oxygen atom comprises the hexa methoxy disiloxane, six ethyoxyl disiloxane, six phenoxy group disiloxane, 1,1,1,3,3-pentamethoxyl-3-methyl disiloxane, 1,1,1,3,3-five ethyoxyls-3-methyl disiloxane, 1,1,1,3,3-pentamethoxyl-3-phenyl disiloxane, 1,1,1,3,3-five ethyoxyls-3-phenyl disiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyl disiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyl disiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyl disiloxane, 1,1,3,3-tetraethoxy-1,3 diphenyl disiloxane, 1,1,3 ,-trimethoxy-1,3,3-trimethyl disiloxane, 1,1,3-triethoxy-1,3,3-trimethyl disiloxane, 1,1,3-trimethoxy-1,3,3-triphenyl disiloxane, 1,1,3-triethoxy-1,3,3-triphenyl disiloxane, 1,3-dimethoxy-1,1,3, the 3-tetramethyl disiloxane, 1,3-diethoxy-1,1,3,3-tetramethyl disiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyl disiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyl disiloxane.Typically, can be the hexa methoxy disiloxane, six ethyoxyl disiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyl disiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyl disiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyl disiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyl disiloxane, 1,3-diethoxy-1,1,3, the 3-tetramethyl disiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyl disiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyl disiloxane, or the like.
Wherein the examples of compounds of being represented by formula (2) when d is integer 0 comprises the hexa methoxy disilane, six ethyoxyl disilane, six phenoxy group disilane, 1,1,1,2,2-pentamethoxyl-2-methyl disilane, 1,1,1,2,2-five ethyoxyls-2-methyl disilane, 1,1,1,2,2-pentamethoxyl-2-phenyl disilane, 1,1,1,2,2-five ethyoxyls-2-phenyl disilane, 1,1,2,2-tetramethoxy-1,2-dimethyl disilane, 1,1,2,2-tetraethoxy-1,2-dimethyl disilane, 1,1,2,2-tetramethoxy-1,2-diphenyl disilane, 1,1,2,2-tetraethoxy-1,2-diphenyl disilane, 1,1,2-trimethoxy-1,2,2-trimethyl disilane, 1,1,2-triethoxy-1,2,2-trimethyl disilane, 1,1,2-trimethoxy-1,2,2-triphenyl disilane, 1,1,2-triethoxy-1,2,2-triphenyl disilane, 1,2-dimethoxy-1,1,2,2-tetramethyl disilane, 1,2-diethoxy-1,1,2,2-tetramethyl disilane, 1,2-dimethoxy-1,1,2,2-tetraphenyl disilane and 1,2-diethoxy-1,1,2,2-tetraphenyl disilane.
Wherein work as R
7For-(CH
2The examples of compounds of formula (2) expression the during group of)-expression comprises two (hexa methoxy silicyl) methane, two (six (ethoxymethyl) silylation) methane, two (six phenoxy group silicyls) methane, two (dimethoxy-methyl silicyl) methane, two (diethoxymethyl silicyl) methane, two (Dimethoxyphenyl silicyl) methane, two (diethoxy phenyl silicyl) methane, two (methoxyl group dimetylsilyl) methane, two (ethyoxyl dimetylsilyl) methane, two (methoxyl group diphenylmethyl silylation) methane, two (ethoxy diphenyl base silicyl) methane, two (hexa methoxy silicyl) ethane, two (six (ethoxymethyl) silylation) ethane, two (six phenoxy group silicyls) ethane, two (dimethoxy-methyl silicyl) ethane, two (diethoxymethyl silicyl) ethane, two (Dimethoxyphenyl silicyl) ethane, two (diethoxy phenyl silicyl) ethane, two (methoxyl group dimetylsilyl) ethane, two (ethyoxyl dimetylsilyl) ethane, two (methoxyl group diphenylmethyl silylation) ethane, two (ethoxy diphenyl base silicyl) ethane, 1, two (hexa methoxy silicyl) propane of 3-, 1, two (the six (ethoxymethyl) silylation) propane of 3-, 1, two (the six phenoxy group silicyls) propane of 3-, 1, two (dimethoxy-methyl silicyl) propane of 3-, 1, two (diethoxymethyl silicyl) propane of 3-, 1, two (Dimethoxyphenyl silicyl) propane of 3-, 1, two (the diethoxy phenyl silicyl) propane of 3-, 1, two (methoxyl group dimetylsilyl) propane of 3-, 1, two (ethyoxyl dimetylsilyl) propane of 3-, 1, two (the methoxyl group diphenylmethyl silylation) propane and 1 of 3-, two (the ethoxy diphenyl base silicyl) propane of 3-.Typically, can be the hexa methoxy disilane, six ethyoxyl disilane, six phenoxy group disilane, 1,1,2,2-tetramethoxy-1,2-dimethyl disilane, 1,1,2,2-tetraethoxy-1,2-dimethyl disilane, 1,1,2,2-tetramethoxy-1,2-diphenyl disilane, 1,1,2,2-tetraethoxy-1,2-diphenyl disilane, 1,2-dimethoxy-1,1,2,2-tetramethyl disilane, 1,2-diethoxy-1,1,2,2-tetramethyl disilane, 1,2-dimethoxy-1,1,2,2-tetraphenyl disilane, 1,2-diethoxy-1,1,2,2-tetraphenyl disilane, two (hexa methoxy silicyl) methane, two (six (ethoxymethyl) silylation) methane, two (dimethoxy-methyl silicyl) methane, two (diethoxymethyl silicyl) methane, two (Dimethoxyphenyl silicyl) methane, two (diethoxy phenyl silicyl) methane, two (methoxyl group dimetylsilyl) methane, two (ethyoxyl dimetylsilyl) methane, two (methoxyl group diphenylmethyl silylation) methane and two (ethoxy diphenyl base silicyl) methane.
In the present invention, generally use the alkyltrialkoxysilaneand in the above-mentioned compound that exemplifies (1) and (2) and the combination of tetraalkoxysilane.In this case, the tetraalkoxysilane proportion is generally calculates by weight about 5 to about 75%, be typically and calculate by weight about 10 to about 70%, more be typically and calculate by weight about 15 to about 70%, the ratio of alkyltrialkoxysilaneand is generally calculates by weight about 25 to about 95%, be typically and calculate by weight about 30, more be typically and calculate by weight about 30, calculate according to complete hydrolysis and the amount that concentrates the product that obtains to about 85% to about 90%.When tetraalkoxysilane and trialkoxy silane use in the ratio in the above-mentioned scope, resulting coated film has high modulus of elasticity and low-down dielectric constant.
The term of Shi Yonging " complete hydrolysis and the concentrated product that obtains " implication is all R in compound (1) and (2) herein
2O-, R
4O-and R
5O-group hydrolysis becoming SiOH group and quilt concentrate and the resulting product of formation siloxane structure fully.
Compound (1) and (2) are hydrolyzed in organic solvent and concentrate.In hydrolysis and concentrating, water generally with formula (1) and the middle R of formula (2)
2O-, R
4O-and R
5The group that O-represents uses to about 10 moles every mole amount according to about 0.3.
Compound (1) and (2) hydrolysis in organic solvent and concentrate in to use catalyst usually.
The example of catalyst comprises organic acid, inorganic acid, organic base, inorganic base, and metallo-chelate.
The organic acid example comprises acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, decanedioic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2 ethyl hexanoic acid, oleic acid, stearic acid, linoleic acid, leukotrienes, salicylic acid, benzoic acid, p-aminobenzoic acid, p-methyl benzenesulfonic acid, benzene sulfonic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.
Representative examples of mineral pigments comprises hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
The example of inorganic base comprises ammonia, NaOH, potassium hydroxide, barium hydroxide, and calcium hydroxide.
The example of organic base comprises carbinolamine, monoethanolamine, Propanolamine, butanolamine, N-carbinol methine amine, N-ethyl carbinol amine, N-propyl carbinol amine, N-butyl carbinol amine, N-methylethanolamine, the N-ehtylethanolamine, N-propyl group monoethanolamine, N-butylethanolamine, N-methyl-prop hydramine, N-ethylpropanolamine, N-propyl group Propanolamine, N-butyl Propanolamine, N-methyl butanol amine, N-ethyl butanol amine, N-propyl group butanolamine, N-butyl butanolamine, N, N-dimethyl methyl hydramine, N, N-diethyl carbinol amine, N, N-dipropyl carbinolamine, N, N-dibutyl carbinolamine, N, N-dimethylethanolamine, N, N-diethyl ethylene diamine, N, N-dipropyl monoethanolamine, N, N-dibutyl monoethanolamine, N, the N-dimethyl propanol amine, N, N-diethylpropanolamine, N, N-dipropyl Propanolamine, N, N-dibutyl Propanolamine, N, N-dimethyl butyrate hydramine, N, N-diethyl butanolamine, N, N-dipropyl butanolamine, N, N-dibutyl butanolamine, N-methyl dimethoxy hydramine, N-ethyl dimethanolamine, N-propyl group dimethanolamine, N-butyl dimethanolamine, N methyldiethanol amine, the N-ethyldiethanolamine, N-propyl group diethanol amine, N butyl diethanol amine, N-methyl dipropanolamine, N-ethyl dipropanolamine, N-propyl group dipropanolamine, N-butyl dipropanolamine, N-methyl two butanolamines, N-ethyl two butanolamines, N-propyl group two butanolamines, N-butyl two butanolamines, N-(amino methyl) carbinolamine, N-(amino methyl) monoethanolamine, N-(amino methyl) Propanolamine, N-(amino methyl) butanolamine, N-(amino-ethyl) carbinolamine, N-(amino-ethyl) monoethanolamine, N-(amino-ethyl) Propanolamine, N-(amino-ethyl) butanolamine, N-(aminopropyl) carbinolamine, N-(aminopropyl) monoethanolamine, N-(aminopropyl) Propanolamine, N-(aminopropyl) butanolamine, N-(amino butyl) carbinolamine, N-(amino butyl) monoethanolamine, N-(amino butyl) Propanolamine, N-(amino butyl) butanolamine, methoxy amine, methoxy ethyl amine, METHOXY PROPYL AMINE, methoxyl group butylamine, ethoxyl methyl amine, ethoxyethyl group amine, ethoxycarbonyl propyl amine, ethyoxyl butylamine, the propoxyl group methyl amine, the propoxyl group ethylamine, propoxyl group propyl group amine, propoxyl group butylamine, butoxymethyl amine, butoxyethylamine, butoxy propyl group amine, butoxy butylamine, methyl amine, ethylamine, propyl group amine, butylamine, N, the N-dimethyl amine, N, N-diethylamide, N, the N-dipropylamine, N, N-dibutylamine, Trimethylamine, triethylamine, tripropylamine, tri-butylamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropyl ethylenediamine, tetrabutyl ethylenediamine, the methylamino methyl amine, the methylamino ethylamine, methylamino propyl group amine, methylamino butylamine, the ethylamino methyl amine, the ethylamino ethylamine, ethylamino propyl group amine, ethylamino butylamine, propyl group amino methyl amine, the propyl group amino ethyl amine, propyl group aminopropyl amine, the amino butylamine of propyl group, butyl amino methyl amine, the butyl amino ethyl amine, butyl aminopropyl amine, the amino butylamine of butyl, pyridine, the pyrroles, piperazine, pyrrolidines, piperidines, picoline, morpholine, methyl morpholine, the diazabicyclo octane, the diazabicyclo nonane, diazabicyclo endecatylene, and urea.
The example of metallo-chelate comprises the titanium chelate compound, triethoxy one (acetylacetone,2,4-pentanedione (acetyIacetonato)) titanium for example, three-just-propoxyl group one (acetylacetone,2,4-pentanedione) titanium, three different third oxygen one (acetylacetone,2,4-pentanedione) titaniums, three-just-butoxy one (acetylacetone,2,4-pentanedione) titanium, three-second month in a season-butoxy one (acetylacetone,2,4-pentanedione) titanium, three-uncle-butoxy one (acetylacetone,2,4-pentanedione) titanium, two (acetylacetone,2,4-pentanedione) titaniums of diethoxy, two (acetylacetone,2,4-pentanedione) titaniums of two-just-third oxygen, two (acetylacetone,2,4-pentanedione) titaniums of diisopropoxy, two (acetylacetone,2,4-pentanedione) titaniums of two-just-butoxy, two (acetylacetone,2,4-pentanedione) titaniums of two-second month in a season-butoxy, two (acetylacetone,2,4-pentanedione) titaniums of two-uncle-butoxy, one ethyoxyl tri acetylacetonato titanium, one-just-propoxyl group tri acetylacetonato titanium, one isopropoxy tri acetylacetonato titanium, one-just-butoxy tri acetylacetonato titanium, one-second month in a season-butoxy tri acetylacetonato titanium, one-uncle-butoxy tri acetylacetonato titanium, four (acetylacetone,2,4-pentanedione) titanium, triethoxy one (oacetic acid base) titanium, three-just-propoxyl group one (oacetic acid base) titanium, three isopropoxies one (oacetic acid base) titanium, three-just-butoxy one (oacetic acid base) titanium, three-second month in a season-butoxy one (oacetic acid base) titanium, three-uncle-butoxy one (oacetic acid base) titanium, two (oacetic acid base) titaniums of diethoxy, two (oacetic acid base) titaniums of two-just-propoxyl group, two (oacetic acid base) titaniums of diisopropoxy, two (oacetic acid base) titaniums of two-just-butoxy, two (oacetic acid base) titaniums of two-second month in a season-butoxy, two (oacetic acid base) titaniums of two-uncle-butoxy, one ethyoxyl three (oacetic acid base) titanium, one-just-propoxyl group three (oacetic acid base) titanium, one isopropoxy three (oacetic acid base) titanium, one-just-butoxy three (oacetic acid base) titanium, one-second month in a season-butoxy three (oacetic acid base) titanium, one-uncle-butoxy three (oacetic acid base) titanium, four (oacetic acid base) titanium, one (acetylacetone,2,4-pentanedione) three (oacetic acid base) titanium, two (acetylacetone,2,4-pentanediones) two (oacetic acid base) titaniums and tri acetylacetonato one (oacetic acid base) titanium; The zirconium chelate compound, triethoxy one (acetylacetone,2,4-pentanedione) zirconium for example, three-just-propoxyl group one (acetylacetone,2,4-pentanedione) zirconium, three isopropoxy one (acetylacetone,2,4-pentanedione) zirconiums, three-just-butoxy one (acetylacetone,2,4-pentanedione) zirconium, three-second month in a season-butoxy one (acetylacetone,2,4-pentanedione) zirconium, three-uncle-butoxy one (acetylacetone,2,4-pentanedione) zirconium, two (acetylacetone,2,4-pentanedione) zirconiums of diethoxy, two (acetylacetone,2,4-pentanedione) zirconiums of two-just-propoxyl group, two (acetylacetone,2,4-pentanedione) zirconiums of diisopropoxy, two (acetylacetone,2,4-pentanedione) zirconiums of two-just-butoxy, two (acetylacetone,2,4-pentanedione) zirconiums of two-second month in a season-butoxy, two (acetylacetone,2,4-pentanedione) zirconiums of two-uncle-butoxy, one ethyoxyl tri acetylacetonato zirconium, one-just-propoxyl group tri acetylacetonato zirconium, one isopropoxy tri acetylacetonato zirconium, one-just-butoxy tri acetylacetonato zirconium, one-second month in a season-butoxy tri acetylacetonato zirconium, one-uncle-butoxy tri acetylacetonato zirconium, four (acetylacetone,2,4-pentanedione) zirconium, triethoxy one (oacetic acid base) zirconium, three-just-propoxyl group one (oacetic acid base) zirconium, three isopropoxies one (oacetic acid base) zirconium, three-just-butoxy one (oacetic acid base) zirconium, three-second month in a season-butoxy one (oacetic acid base) zirconium, three-uncle-butoxy one (oacetic acid base) zirconium, two (oacetic acid base) zirconiums of diethoxy, two (oacetic acid base) zirconiums of two-just-propoxyl group, two (oacetic acid base) zirconiums of diisopropoxy, two (oacetic acid base) zirconiums of two-just-butoxy, two (oacetic acid base) zirconiums of two-second month in a season-butoxy, two (oacetic acid base) zirconiums of two-uncle-butoxy, one ethyoxyl three (oacetic acid base) zirconium, one-just-propoxyl group three (oacetic acid base) zirconium, one isopropoxy three (oacetic acid base) zirconium, one-just-butoxy three (oacetic acid base) zirconium, one-second month in a season-butoxy three (oacetic acid base) zirconium, one-uncle-butoxy three (oacetic acid base) zirconium, four (oacetic acid base) zirconium, one (acetylacetone,2,4-pentanedione) three (oacetic acid base) zirconium, two (acetylacetone,2,4-pentanediones) two (oacetic acid base) zirconiums and tri acetylacetonato one (oacetic acid base) zirconium; With the aluminium chelate compound, aluminium tris(acetylacetonate) and three (oacetic acid base) aluminium for example.
Catalyst consumption is generally about 0.0001 to about 1 mole, is typically about 0.001 to about 0.1 mole, the total amount of every mole compound (1) and (2).
At silicone compounds is under the situation of polymer, and it generally has about 500 to about 100,000 weight average molecular weight, calculates with polystyrene standard.
In the present invention, silicone compounds is dissolved in usually and is used as coating composition in the organic solvent.
Can be used for examples of solvents of the present invention and comprise aliphatic solvent, for example just-pentane, isopentane, just-and hexane, isohexane, just-and heptane, isoheptane, 2,2, the 4-trimethylpentane, just-and octane, isooctane, cyclohexane, and hexahydrotoluene; Aromatic hydrocarbon solvent, benzene for example, toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, ethyl methyl benzene, just-and propylbenzene, cumene, diethylbenzene, isobutyl-benzene, triethylbenzene, diisopropyl benzene, just-amyl naphthalene, and trimethylbenzene; MHA, methyl alcohol for example, ethanol, just-and propyl alcohol, isopropyl alcohol, just-and butanols, isobutanol, the second month in a season-butanols, uncle-butanols, just-and amylalcohol, isoamyl alcohol, 2-methyl butanol, the second month in a season-amylalcohol, uncle-amylalcohol, the 3-methoxybutanol, just-and hexanol, the 2-methyl anyl alcohol, the second month in a season-hexanol, 2-ethyl butanol, the second month in a season-enanthol, enanthol-3, just-and octanol, 2-Ethylhexyl Alcohol, the second month in a season-octanol, just-nonyl alcohol, 2,6-dimethyl enanthol-4, just-and decyl alcohol, the second month in a season-undecyl alcohol, Exxal 12, the second month in a season-tetradecyl alchohol, the second month in a season-pentadecanol, phenol, cyclohexanol, methyl cyclohexanol, 3,3, the 5-cyclonol, phenmethylol, phenylmethylcarbinol diacetone alcohol, and cresols; Polyhydroxy-alcohol, ethylene glycol for example, 1,2-propylene glycol, 1,3-butanediol, pentanediol-2,4,2 hexylene glycol-2,4, hexylene glycol-2,5, heptandiol-2,4,2-ethohexadiol-1,3, diethylene glycol (DEG), dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol; Ketone solvent, acetone for example, methyl ethyl ketone, methyl just-acetone, methyl just-butanone, diethyl ketone, methylisobutylketone, methyl just-pentanone, ethyl just-butanone, methyl just-hexanone, diisobutyl ketone, the trimethyl nonanone, cyclohexanone, methyl cyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, acetophenone, and fenchone; Ether solvents, ether for example, isopropyl ether, just-butyl ether, just-hexyl ether, 2-ethyl hexyl ether, oxirane, 1,2 epoxy prapane, dioxolanes, 4-methyl dioxolanes, dioxane, the dimethyl dioxane, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the ethylene glycol bisthioglycolate ethylether, glycol monomethyl-just-and butyl ether, glycol monomethyl-n-hexyl ether, the glycol monomethyl phenyl ether, glycol monomethyl-2-ethyl-butyl ether, ethylene glycol bisthioglycolate butyl ether, the diglycol monotertiary methyl ether, carbiphene, diethylene glycol diethyl ether, diglycol monotertiary-just-butyl ether, diethylene glycol (DEG) two-just-and butyl ether, diethylene glycol (DEG)-list-n-hexyl ether, the ethyoxyl triethylene glycol, tetraethylene glycol two-just-and butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol single-butyl ether, DPGME, dihydroxypropane single-ethyl ether, the tripropylene glycol monomethyl ether, oxolane and 2-methyltetrahydrofuran; Ester solvent, for example, diethyl carbonate, methyl acetate, ethyl acetate, gamma-butyrolacton, gamma-valerolactone, acetate just-propyl ester, isopropyl acetate, acetate just-butyl ester, isobutyl acetate, the acetate second month in a season-butyl ester, acetate just-pentyl ester, the acetate second month in a season-pentyl ester, acetate 3-methoxyl group butyl ester, methyl amyl acetate, acetate 2-ethyl butyl ester, acetate 2-Octyl Nitrite, phenylmethyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, acetate just-ninth of the ten Heavenly Stems ester, methyl acetoacetate, oacetic acid base, the glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, the diethylene glycol monoethyl ether acetate, diglycol monotertiary-just-monobutyl ether acetate, propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetate, the propylene glycol monopropyl ether acetate, the propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, DPG list ethyl ether acetate ester, ethylene acetate, methoxyl group triethylene glycol acetic acid esters, ethyl propionate, propionic acid just-butyl ester, isoamyl propionate, diethy-aceto oxalate, oxalic acid two-just-and butyl ester, methyl lactate, ethyl lactate, lactic acid just-butyl ester, lactic acid just-pentyl ester, diethyl malonate, repefral, and diethyl phthalate; Nitrogen-containing solvent, N-methylformamide for example, N, dinethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetylamide, N-methyl propanamide and N-methyl pyrrolidone; The sulfur-bearing solvent, dimethyl sulfide for example, diethyl sulfide, thiophene, thiophane, dimethyl sulfoxide (DMSO), sulfolane and 1,3-propyl group sultane.These solvents can use separately or two or more are mixed use.
The used organic solvent of the present invention has usually and is lower than about 250 ℃ boiling point.Example wherein comprises alcohol, methyl alcohol for example, ethanol, and isopropyl alcohol; Polyhydroxy-alcohol, for example ethylene glycol and glycerol; Glycol ether solvent, glycol monoethyl ether for example, ethylene glycol monobutyl ether, diethyl ethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monopropyl ether and DPG list ether; Ethylene glycol ethyl ethers acid esters/ether solvents, glycol monoethyl ether acetate for example, diethylene glycol monobutyl ether acetate, ethylene diacetate, and 1-Methoxy-2-propyl acetate; Amide solvent, N for example, N-dimethylacetylamide, N, dinethylformamide and N-N-methyl-2-2-pyrrolidone N-; Ketone solvent, acetone for example, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetylacetone,2,4-pentanedione, and methyl amyl ketone; With the carboxylate solvent, ethyl lactate for example, propionic acid methoxyl group methyl esters, and ethoxyethyl propionate.These solvents can use separately or two or more are mixed use.
Among the present invention the consumption of organic solvent be generally silicone compounds (in complete hydrolysis and concentrate the product obtain) amount about 0.3 to about 25 times (calculating by weight).The used coating composition of the present invention can prepare by silicone compounds and organic solvent and other compositions of adding are as required mixed.
Although it is desirable having the porous dielectric material of low-k, obtaining to have more, the porous dielectric material of high elastic modulus and material hardness will be favourable.
In order to improve the modulus of elasticity of porous dielectric material, be with its plasma curing.According to the present invention, this process is utilized fluorine-free plasma gas.Described " free-floride " refers to not fluorine-containing plasma gas.For example, fluorine-free plasma gas can be CH
4And N
2Mixing, or CH
4And N
2With H
2Or the mixing of inert gas, inert gas such as He, Ar, Ne or its mixing.
By utilizing fluorine-free plasma gas, will not exist fluorine and porous low dielectric constant material to react or penetrate into the chance of porous low-k material.Fluorine is subside the spaceization that may cause dielectric material in porous network, corrosion and other forms of infringement, and these will cause containing the direct fault of the device of these materials, and influence equipment yield and/or significantly reduce useful life of equipment.And, the residual compounds reaction that free fluorine can be absorbed by dielectric and with other or subside, or arrive on the other materials at the interface in the dielectric and cause severe impairment.Therefore, the present invention significantly reduces by the curing that utilizes fluorine-free plasma gas to carry out porous dielectric material or has eliminated the fluorine in the film.
Fluorine-free plasma curing can pass through radio frequency (RF), inductance coupling high, and the RF capacitive coupling, helical resonator (resinator), microwave following current and microwave electron cyclotron resonance (ESR) plasma carries out.The fluorine-free plasma curing process has improved the mechanical performance of porous low-k dielectric material, is keeping the dielectric hole, and structure has improved material hardness in the time of density and electric property.
In typical fluorine-free plasma curing technology, wafer is being heated to desired temperature in the heating step of slope fast, and wafer CH
4And N
2Mist carry out plasma curing, this has produced the curing plasma chemistry.Plasma gas does not contain any plasma fluorine.
The accurate condition of fluorine-free plasma curing depends on the type of the plasma curing of use.Typically, porous dielectric material carries out plasma curing at about 1.0Torr to the tonnage of about 5.0Torr.The example of the typical microwave plasma condition of cure of 200 millimeters wafers is as shown in table 1 below.
The typical fluorine-free plasma curing condition of table 1200 millimeter wafer
| Microwave plasma power | 1000-2000W |
| Chip temperature | 250-450℃ |
| Tonnage | 1.0-5.0Torr |
| The plasma curing time | ＜180 seconds |
| Plasma gas | CH 4/N 2Or CH 4/N 2/H 2 |
| CH 4/N 2Flow rate | 2000-3000sccm |
| CH 4∶N 2Gas ratio | 0.01 to 0.05 |
Compare with material hardness with the modulus of elasticity of (heat) curing porous dielectric material in those stoves, the modulus of elasticity of the porous dielectric material that fluorine-free plasma curing of the present invention obtains and material hardness are quite or higher.The modulus of elasticity of cured porous dielectric material when dielectric constant is 1.6～2.4 is generally about 0.5GPa to about 5GPa in the stove.The modulus of elasticity of the porous dielectric material of fluorine-free plasma curing of the present invention generally greater than or be about 3GPa, more typically about 3GPa is to about 10GPa.The material hardness of rigidized porous foam is about 0.1 to about 0.8GPa in the stove.Typically, the material hardness of the porous dielectric material of fluorine-free plasma curing of the present invention for greater than or be about 0.3GPa, more be typically about 0.5GPa to 1.0GPa.
The contrast of the process conditions of hot curing and material character is as following table 2 in the fluorine-free plasma curing of the present invention, fluorine-based plasma cure and vertical heater.
Process conditions and material character under the different conditions of cure of table 2
| Fluorine-free plasma curing | Fluorine-based plasma cure | The vertical heater hot curing | |
| Instrument | Plasma curing | Plasma curing | Vertical heater |
| Atmosphere | CH 4/N 2 | CF 4+H 2/N 2 | LP STD |
| Pressure (Torr) | 3.50 | 3.50 | 0.15 |
| Curing temperature (℃) | 420 | 420 | 420 |
| Curing time (branch) | 2 | 1.5 | 60 |
| Plasma power | 2000W | 2000W | n/a |
| R.I. | 1.2458 | 1.2580 | 1.2514 |
| Th/A | 6036 | 6252 | 5972 |
| 3σ(％) | 1.5 | 1.45 | 1.5 |
| Wafer shrinks (%) | -1.9 | -2.8 | -2.7 |
| Dielectric constant (k) | 2.32 | 2.23 | 2.22 |
| 200 ℃ of following dielectric constants | 2.15 | 2.13 | 2.12 |
| Δk | 0.17 | 0.10 | 0.10 |
| Modulus of elasticity (GPa) | 3.82at 0.20 st.dev. | 3.95at 0.16 st.dev. | 3.82at 0.13 st.dev. |
| Material hardness (GPa) | 0.62at 0.02 st.dev. | 0.62at 0.05 st.dev. | 0.63at 0.03 st.dev. |
Table 2 illustrates that fluorine-free plasma curing causes the thermal budget that reduces.Process time 60 minutes of hot curing in the vertical heater taper to 2 minutes of fluorine-free plasma curing, and temperature is suitable (420 ℃).The material that the porous dielectric material that fluorine-free plasma curing of the present invention obtains and stove solidify is compared, the spatial stability that has a suitable chemical stability and improved.Described chemical stability, we refer to that floride-free porous dielectric material can resist chemical substance, such as the erosion of washing agent and chemical polishing agent, and the plasma damage in photoetching polishing and deep dry etch process.
Fluorine-free plasma curing is compared with the low-k film of heating furnace or hot curing, significantly reduces or eliminated oligomerisation (oliomeric) silicon dioxide to outgas from perforated membrane with other materials.In addition, different with the based plasma cure processes of using fluorine-containing plasma gas, fluorine-free plasma curing technology of the present invention can not produce a large amount of polar components in film.Usually, utilize this fluorine-based plasma cure processes, the initial plasma of film solidifies the variation that will cause on chemistry and the electricity, and these variations can utilize replys or repair the second back curing plasma treatment of film.Yet by utilizing fluorine-free plasma gas, based plasma cure processes of the present invention defines and does not cause the above variation of not expecting and the one-step process of cured film.Therefore, the additional back cured of film has not just needed.
Though, for a person skilled in the art, obviously on composition that is disclosed in this and method, all can do various variations and not exceed scope of the present invention in order to illustrate that the present invention has provided some representational embodiment and details.Therefore, the invention is not restricted to described embodiment, scope dictates is in following claim.
Claims (26)
1. prepare the method for fluorine-free plasma curing material, comprising:
Provide to have first dielectric constant porous dielectric material of first modulus of elasticity and first material hardness; With
Have with preparation with fluorine-free plasma gas plasma curing porous dielectric material and to compare second dielectric constant less or that approximately equate with first dielectric constant, bigger second modulus of elasticity than first modulus of elasticity, with the fluorine-free plasma curing porous dielectric material of second material hardness bigger than first material hardness, wherein fluorine-free plasma gas comprises CH
4Plasma gas and N
2The mixing of plasma gas.
2. the process of claim 1 wherein that porous dielectric material is selected from organic dielectric materials, Inorganic Dielectric Material, or their combination.
3. the method for claim 2, wherein organic dielectric materials is selected from the hydrogen silsesquioxane dielectric material, methyl silsesquioxane dielectric material, or their combination.
4. the process of claim 1 wherein porous dielectric material be by use spin coating proceeding or chemical vapor deposition method that dielectric coat is deposited on the matrix and
Forming the hole in coating prepares.
5. the process of claim 1 wherein that porous dielectric material is selected from the porous dielectric material of pore former-generation, the porous dielectric material of solvent-formation, the porous dielectric material of molecular engineering, or their combination.
6. the process of claim 1 wherein that porous dielectric material is being lower than or is being about under 450 ℃ the temperature by plasma curing.
7. the process of claim 1 wherein porous dielectric material about 250 ℃ to about 450 ℃ of temperature by plasma curing.
8. the process of claim 1 wherein porous dielectric material about 1.0Torr to the tonnage of about 5.0Torr by plasma curing.
9. the process of claim 1 wherein that porous dielectric material is being less than or is being about in time of 180 seconds by plasma curing.
10. the process of claim 1 wherein that fluorine-free plasma gas further comprises H
2Plasma gas.
11. the process of claim 1 wherein that fluorine-free plasma gas further comprises inert gas.
12. the method for claim 11, wherein inert gas is selected from He, Ar, Ne, or their combination.
13. the process of claim 1 wherein that fluorine-free plasma gas limits CH
4And N
2Gas ratio, and this gas ratio is about 0.01 to about 0.05.
14. the process of claim 1 wherein modulus of elasticity between second modulus of elasticity of porous dielectric material of first modulus of elasticity of porous dielectric material and fluorine-free plasma curing increase greater than or be about 50%.
15. the process of claim 1 wherein modulus of elasticity between second modulus of elasticity of porous dielectric material of first modulus of elasticity of porous dielectric material and fluorine-free plasma curing increase greater than or be about 100%.
16. the process of claim 1 wherein fluorine-free plasma curing porous dielectric material second modulus of elasticity greater than or be about 3GPa.
17. the process of claim 1 wherein that second modulus of elasticity of porous dielectric material of fluorine-free plasma curing is about 3GPa about 10GPa extremely.
18. the process of claim 1 wherein material hardness between second material hardness of porous dielectric material of first material hardness of porous dielectric material and fluorine-free plasma curing increase greater than or be about 50%.
19. the process of claim 1 wherein fluorine-free plasma curing porous dielectric material second material hardness greater than or be about 0.3GPa.
20. the process of claim 1 wherein that second material hardness of porous dielectric material of fluorine-free plasma curing is about 0.5GPa about 1.0GPa extremely.
21. the process of claim 1 wherein that the fluorine-free plasma curing porous dielectric material compares with the hot curing porous dielectric material, degassing level is greatly reduced or eliminates.
22. the porous dielectric material of the fluorine-free plasma curing of the method for claim 1 preparation.
23. contain the electronic device of porous dielectric material of fluorine-free plasma curing of the method preparation of claim 1.
24. contain the matrix of porous dielectric material of fluorine-free plasma curing of the method preparation of claim 1.
25. dielectric constant be about 1.1 to about 2.7 and modulus of elasticity be about 3GPa porous dielectric material of the fluorine-free plasma curing of about 10GPa extremely.
26. dielectric constant be about 1.5 to about 2.3 and modulus of elasticity be about 3GPa porous dielectric material of the fluorine-free plasma curing of about 10GPa extremely.
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|---|---|---|---|
| US10/346,560 US20030157267A1 (en) | 2000-03-20 | 2003-01-17 | Fluorine-free plasma curing process for porous low-k materials |
| US10/346,560 | 2003-01-17 | ||
| US10/627,894 | 2003-07-24 |
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|---|---|
| CN1739190A true CN1739190A (en) | 2006-02-22 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103397307A (en) * | 2010-02-04 | 2013-11-20 | 气体产品与化学公司 | Method to prepare silicon-containing film |
| CN104157552A (en) * | 2014-08-15 | 2014-11-19 | 上海华力微电子有限公司 | Method of improving vertical uniformity of porous low-dielectric constant material |
-
2004
- 2004-01-16 CN CN 200480002329 patent/CN1739190A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103397307A (en) * | 2010-02-04 | 2013-11-20 | 气体产品与化学公司 | Method to prepare silicon-containing film |
| US9502234B2 (en) | 2010-02-04 | 2016-11-22 | Air Products And Chemicals, Inc. | Methods to prepare silicon-containing films |
| CN103397307B (en) * | 2010-02-04 | 2017-07-07 | 弗萨姆材料美国有限责任公司 | Method for preparing silicon-containing films |
| CN104157552A (en) * | 2014-08-15 | 2014-11-19 | 上海华力微电子有限公司 | Method of improving vertical uniformity of porous low-dielectric constant material |
| CN104157552B (en) * | 2014-08-15 | 2017-04-12 | 上海华力微电子有限公司 | Method of improving vertical uniformity of porous low-dielectric constant material |
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