CN1782124A - Porous low dielectric constant compositions and methods for making and using same - Google Patents
Porous low dielectric constant compositions and methods for making and using same Download PDFInfo
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- CN1782124A CN1782124A CN 200510129199 CN200510129199A CN1782124A CN 1782124 A CN1782124 A CN 1782124A CN 200510129199 CN200510129199 CN 200510129199 CN 200510129199 A CN200510129199 A CN 200510129199A CN 1782124 A CN1782124 A CN 1782124A
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Abstract
A porous organosilicate glass (OSG) film: Si v O w C x H y F z , where v+w+x+y+z = 100%, v is 10 to 35 atomic%, w is 10 to 65 atomic%, x is 5 to 30 atomic%, y is 10 to 50 atomic% and z is 0 to 15 atomic%, has a silicate network with carbon bonds as methyl groups (Si-CH 3 ) and contains pores with diameter less than 3nm equivalent spherical diameter and dielectric constant less than 2.7. A preliminary film is deposited by a chemical vapor deposition method from organosilane and/or organosiloxane precursors, and independent pore-forming precursors. Porogen precursors form pores within the preliminary film and are subsequently removed to provide the porous film. Compositions, film forming kits, include organosilane and/or organosiloxane compounds containing at least one Si-H bond and porogen precursors of hydrocarbons containing alcohol, ether, carbonyl, carboxylic acid, ester, nitro, primary amine, secondary amine, and/or tertiary amine functionality or combinations.
Description
The related application of cross-reference
The application requires the U.S. Provisional Application No.60/613 of submission on September 28th, 2004,937 right of priority.
Background of invention
Usually be used as the insulation layer of electron device by the advanced low-k materials of chemical vapor deposition (CVD) method production.In the electronic industry with insulating material as unicircuit (IC) and the circuit of corresponding electron device and the insulation layer between the element.In order to increase the speed and the device density of microelectronic device (for example computer chip), its linear dimension reduces just day by day.Along with reducing of linear dimension, also become more harsh for the insulating requirements of interlayer dielectic (ILD).Spacing is dwindled the lower specific inductivity of requirement, so that the RC time constant is minimized, wherein, R is the resistance of lead, and C is the electric capacity of layer insulation dielectric.C is inversely proportional to spacing and is directly proportional with the specific inductivity (k) of interlayer dielectic (ILD).
By SiH
4Or TEOS (Si (OCH
2CH
3)
4, positive tetraethyl orthosilicate) and O
2Traditional silicon-dioxide (the SiO that produces
2) the CVD dielectric film, its specific inductivity (k) is greater than 4.0.Industrial have some kinds of methods of attempting to produce the silicon-dioxide-Ji chemical vapor deposition (CVD) film with low-k, wherein successful method is that organic group is introduced in the insulation silica membrane the most, and its specific inductivity that provides is in the scope of 2.7-3.5.Remove oxygenant such as O
2Or N
2Outside the O, this organosilicate (OSG) glass is usually by containing silicon precursor, and as alkyl silane, organoalkoxysilane and/or siloxanes are with dense film (the about 1.5g/cm of density
3) form deposition.Because more and more higher device density and more and more littler device size require specific inductivity or " k " value to be reduced to below 2.7, therefore, the industrial various porous materials that improve insulating property that just turning to.Increase the total dielectric constant that porosity will reduce this material to OSG, wherein the free dielectric constant of void space is 1.0.Porous OSG material is considered to low-k materials, and this is less than the standard material that uses in the industry-silica glass that undopes traditionally because of its specific inductivity.These materials are formed by following method usually: in deposition process, add pore-forming material or pore former (porogen) precursor as reactant, and from deposited or the preliminary material remove pore former so that porous material is provided.Other material property such as mechanical hardness, modulus of elasticity, unrelieved stress, thermostability and the clinging power of various substrates is depended on the chemical ingredients and the structure of porous material or film.Regrettably, when increasing porosity to film, the performance of many these films will suffer harmful effect.
Summary of the invention
In invention, will describe by chemical formula Si
vO
wC
xH
yF
zPorous organic silicate glass (OSG) film that the monophase materials of expression is formed, v+w+x+y+z=100% wherein, v is the 10-35% atom, w is the 10-65% atom, x is the 5-30% atom, y is the 10-50% atom, and z is the 0-15% atom, and wherein said film has the hole and specific inductivity is 2.7 or littler.
What the present invention also will describe is the chemical gaseous phase depositing process that is used to produce the porous organic silicate glassy membrane, comprising: a base material is provided in treatment chamber; Introduce gaseous reagent, described reagent comprises and is selected from the organosilane that contains at least one Si-H key and at least a precursor and the porogen precursor of organo-siloxane; Gaseous reagent in the treatment chamber is applied energy with the reaction that causes gaseous reagent and the preliminary film is provided on base material, wherein, the preliminary film comprises pore former; Then, remove at least a portion pore former, comprise the hole and specific inductivity is lower than 2.7 porous membrane to provide from the preliminary film.
In addition, the present invention also will describe: comprise the pore former that is used for production porous OSG film and the composition of precursor.
Summary of drawings
Fig. 1 is provided for forming the process flow sheet of an embodiment of the method for porous organic silicate glass material of the present invention.
Fig. 2 provides: be used for by organosilane precursor diethoxymethyl silicomethane (DEMS) and pimelinketone (CHO) or 1,2 two kinds of stoichiometric specific refractory poweres of different porogen precursor of the sedimentary film of 4-trimethyl-cyclohexane (TMC) porogen precursor.
Fig. 3 provides: after deposition and be exposed to after the UV-light 5 minutes, by Fourier transform infrared (FT-IR) absorption spectrum of organosilane precursor DEMS and porogen precursor CHO or the sedimentary porous OSG film of TMC.
Fig. 4 provides: by the FT-IR absorption spectrum of the sedimentary film of precursor mixture that comprises DEMS and CHO (22/78 mol ratio).
Fig. 5 provides: by the FT-IR absorption spectrum of the sedimentary film of precursor mixture that comprises DEMS and DMHD (20/80 mol ratio).
Fig. 6 provides: by comprising α-terpinene (ATP), limonene (LIM), CHO, and cyclohexane oxide (CHO
x) the hardness and the specific inductivity of the sedimentary film of precursor mixture.
Detailed Description Of The Invention
The present invention will describe porous organic silicate material and film, its preparation method and the mixture that is used for preparing.With porous, inorganic SiO
2The material difference, porous OSG material of Miao Shuing and film are owing to the organic group that is wherein comprised demonstrates hydrophobicity in the present invention.Porous OSG material also demonstrates low specific inductivity, or 2.7 or lower specific inductivity, also have enough mechanical hardness simultaneously, Young's modulus, low unrelieved stress, high thermal stability, and make it be suitable for the high clinging power to various substrates of multiple application.The density of porous OSG material described here is 1.5g/ml or lower, or 1.25g/ml or lower, or 1.0g/ml or lower.In certain embodiments, porous OSG material can be made into film, with respect to other porous OSG glass material, described film has low-k, high-mechanical property and (oxygen for example in various environment, water, oxidation or reducing environment) high relatively heat and chemical stability.It is believed that some performance in described these performances may be owing to optionally introduce the result of carbon in film, preferred main the organic carbon ,-CH of introducing
x, wherein x is 1-3, perhaps to the small part organic carbon for being connected on the netted thing of silicate-CH as terminal methyl group by the Si-C key
3Form.In certain preferred aspects, be included in 50% in the OSG material of the present invention or more, or 75% or more, or 90% or more hydrogen and bond with carbon, perhaps, the minimum numberization of terminal Si-H key in final film.In certain embodiments, described material has at least 10 SiCH for each Si-H key
3Key more preferably, has 50 Si-CH for each Si-H key
3Key most preferably has 100 Si-CH for each Si-H key
3Key.
Fig. 1 be provided for forming porous OSG material film, at the process flow sheet of an embodiment of this disclosed method.Porous OSG material or film can deposit by comprising the reagent that contains silicon precursor and the mixture of porogen precursor.In this employed " containing-silicon precursor " is the reagent that comprises at least one Siliciumatom, as organic silane or organo-siloxane.In this employed " porogen precursor " is the reagent that produces void volume in the film that is used for forming.In first step, base material is introduced in the treatment chamber.During deposition step, will contain silicon precursor and porogen precursor and introduce in the treatment chamber and before introducing treatment chamber and/or activate by one or more energy afterwards.Described precursor may codeposition or copolymerization at least a portion substrate surface, thereby a preliminary film is provided.In next step, can be by applying one or more energy, for example but be not limited to heating, and illumination, electron beam, and be incorporated on the film and remove at least a portion porogen precursor from the preliminary film.Described processing can be in vacuum to one or more pressure of environmental stress, and carry out under inertia, oxidation or reductive condition.Removing of at least a portion pore former with the formation porous organic silicate material.In these embodiments, the porosity and/or the specific inductivity of final film may be subjected to influence of various factors, and described factor is including, but not limited to the ratio that contains silicon precursor and porogen precursor in precursor mixture.In certain embodiments, during forming or after film forms, can also be further processed to the small part film.These additional processing for example may improve some performance, as physical strength, and unrelieved stress, and/or clinging power.
In the present invention, term " precursor " is used for describing such reagent, and it comprises " organosilicon precursor " and " porogen precursor ", and forms the desirable any other reagent of film on base material, as " carrier gas ", or other " gas of interpolation ".Although term " gasiform " is used for describing described precursor in the present invention sometimes, but this term should not have any restrictedly comprising as gas and directly is delivered to reactor, be conveyed into reactor as evaporated liquid, Solid Conveying and Melting as distillation is gone into reactor, and/or is conveyed into the reagent of reactor by inert carrier gas.
In certain embodiments, contain silicon precursor and porogen precursor differs from one another on chemical property, and be not connected by any covalent linkage.In the embodiment of these and other, the concentration that contains silicon precursor and porogen precursor can be controlled by different mass flow controllers, and by in the different source of supply introducing reaction chambers, in reaction chamber, mix then, mix in the line of pipes before entering reaction chamber, and/or before entering reaction chamber, mix so that reaction mixture to be provided.In the latter's embodiment, can carry by the reaction mixture of single source of supply and contain the dispensable additive of silicon precursor and porogen precursor and other, wherein, its concentration in reaction chamber determines by the stoichiometry of mixture, and the flow velocity that enters reaction chamber is controlled with single mass flow controller.Can precursor be delivered in the reactive system by many methods, described method including, but not limited to: utilize the pressurisable stainless steel vessel of suitable valve and accessory is installed, so that liquid can be delivered in the reaction chamber.
In other embodiment, the molecule of single kind can be used as structure-formation agent and pore former simultaneously.That is the precursor that forms structure need not different molecules with the precursor that forms the hole, and in certain embodiments, pore former is for forming the part (for example covalently being connected on it) of structure precursor.Comprise the precursor that is connected to the pore former on it and be referred to as " pore-forming precursor " hereinafter sometimes.For example, might be with new basic TMCTS as one matter, the TMCTS of this molecule partly forms basic OSG structure thus, and the new base of huge alkyl substituent is the material in the formation hole that is removed during anneal.Having to be connected to net is become pore former on the Si class material of OSG structure, is favourable for more efficiently pore former being introduced in the film in deposition process.In addition, be connected with two pore formers on the silicon in precursor as in two-Xin hexyl-diethoxy silane, perhaps two silicon are connected on the pore former as 1, on 4-two (diethoxy silyl) hexanaphthene also is favourable, this is because the most keys that rupture in plasma body in deposition process all are silicon-pore former keys.In this mode, the reaction of a silicon-pore former key will make pore former introduce in the deposit film in plasma body.The other indefiniteness example of preferred pore-forming precursor comprises: 1-new hexyl-1,3,5,7-tetramethyl-ring tetrasiloxane, 1-neo-pentyl-1,3,5,7-tetramethyl-ring tetrasiloxane, neo-pentyl diethoxy silicomethane, new hexyl diethoxy silicomethane, new hexyl triethoxy-silicane, neo-pentyl triethoxy-silicane and neo-pentyl two tert.-butoxy silicomethanes.
Single or multiple pore former being connected in some embodiment of the material on the silicon, maybe advantageously design pore former like this, to cause, when film hardening forms the hole,, a part of pore former gives film on the silicon with hydrophobicity thereby still being connected to.Pore former in siliceous-porogen precursor can be selected like this, to cause when decomposing or solidify, keeps the terminal chemical group that is derived from pore former that is connected on the silicon, as-CH
3For example, if when selecting the pore former neo-pentyl, can be contemplated that the bond rupture of the C-C key at the β place that heating anneal under proper condition will cause at Si, promptly when heating, incite somebody to action the most favourable generation bond rupture at the key between the quaternary carbon of the secondary carbon(atom) that connects silicon and the tertiary butyl.Under suitable condition, this will stay end-CH
3Base, thus compensate silicon, and provide hydrophobicity and low-k to film.The example of precursor is neo-pentyl triethoxy-silicane, neo-pentyl diethoxy silicomethane and neo-pentyl diethoxymethyl silicomethane.
In certain embodiments, porous OSG film comprises: (a) silicon of about 35% atom of about 10-or about 30% atom of about 20-; (b) oxygen of about 65% atom of about 10-or about 45% atom of about 20-; (c) hydrogen of about 50% atom of about 10-or about 40% atom of about 15-; (d) carbon of about 30% atom of about 5-or about 20% atom of about 5-.Depend on employed precursor, OSG film described here can also comprise the fluorine of about 15% atom of about 0.1-or about 7.0% atom of about 0.5-, so that improve the performance that one or more plant material.In the embodiment of these and other, the OSG film can also comprise at least a column element down in addition: fluorine, boron, nitrogen, and phosphorus.
The unadulterated silica glass of being produced by plasma body enhanced (PE) CVD TEOS has the free volume aperture that inherent is determined by positron annihilation life spectroscopy (PALS) analysis, is about 0.6nm in its value of equivalent spherical diameter.Only the fine and close OSG film produced of the CVD that is produced by alkyl, alkoxyl group and/or silicon (oxygen) alkane precursor (not having the porogen precursor that forms the hole) has by PALS and analyzes the inherent free volume aperture of determining, is about 0.7-0.9nm in its value of equivalent spherical diameter.
The inherent free volume aperture that the porosity of deposit film has is that equivalent spherical diameter (about 0.6-0.9nm) with unadulterated silicate glass and fine and close organic silicate glass is more or less the same, determined by positron annihilation life spectroscopy (PALS) analysis.Because the pore former that exists in film is filled described void volume, therefore, in some cases, the aperture of deposit film even may be less than viewed aperture in undoped silicate glass or fine and close organic silicate glass.Aperture that determine by Small angle scattering of neutrons (SANS) or PALS, film of the present invention (" final film ") in equivalent spherical diameter less than 3.0nm, perhaps in equivalent spherical diameter less than 2.0nm.
Depend on the desirable final performance of treatment condition and film, the overall porosity of final film can be 5-75%.The density of porous membrane described herein is less than 1.5g/ml, perhaps less than 1.25g/ml or less than 1.00g/ml.In certain embodiments, the density of the similar OSG film that the density of OSG film described herein is produced than there not being pore former at least is low by 10%, or hangs down 20% at least.
To need not be uniform to the porosity of film in whole film.In certain embodiments, exist porosity gradient and/or have the multilayer of different aperture degree.For example, can pass through between depositional stage, to regulate the ratio of pore former and precursor, or, provide described film so that form the gradient of composition or density by after deposition, film being handled.
Porous OSG film described herein is compared with the fine and close OSG material of not controlling porosity, has lower specific inductivity.In certain embodiments, the specific inductivity of the similar OSG film that the specific inductivity of film described herein is produced than there not being pore former at least is low by 15%, more preferably hangs down 25% at least.
In certain embodiments, porous OSG film described herein is compared with common OSG material and is had excellent mechanical property.Utilize standard MTS rules to pass through the definite mechanical hardness of millimicro impression greater than 0.5GPa, or greater than 1.0GPa.
In certain embodiments, porous OSG film can comprise the fluorine that is inorganic fluorine (for example Si-F) form.When having fluorine, its content is the 0.5-7% atom.
Described film is heat-staple.Particularly preferred film after annealing, its 425 ℃ in nitrogen during constant temperature the weight in average loss less than 1.0% weight/hour.In addition preferably, 425 ℃ in air during constant temperature the loss of the weight in average of film less than 1.0% weight/hour.
Described film demonstrates for various chemical environment favorable chemical resistance.The appearance or the disappearance of vibrational band in change that can be by specific inductivity or the infrared spectra, perhaps chemical resistant properties is measured in the change formed of the film of measuring by the sub-spectroscopy of X-ray photoelectric (XPS).The typical chemical environment that these films demonstrate its excellent chemical stability is: common aqueous acidic or the alkaline environment that uses in the photoresist lift off prescription, the common oxidation plasma condition that in plasma ashing, uses, and other environment of high humidity (＞85% relative humidity,＞85 ℃) for example.
Described film can be compatible with isotropic etching with chemical-mechanical planarization (CMP), and can adhere on the various materials, as silicon, and silicon-dioxide, Si
3N
4, OSG, FSG, silicon carbide, hydrogenation silicon carbide, silicon nitride, hydrogenated silicon nitride, carbonitride of silicium, hydrogenated carbon silicon nitride, boron nitride, anti-reflection coating, photo-resist, organic polymer, organic and the inorganic materials of porous, metal such as copper and aluminium, and diffusion barrier is as (but being not limited to) TiN, Ti (C) N, TaN, Ta (C) N, Ta, W, WN or W (C) N.Preferably, described film can adhere on previous materials at least a, and is enough to by traditional tensile test, tests as ASTM D 3359-95a tensile force of belt.If there is not noticeable film to remove, so just think that specimen test is qualified.
Therefore, in certain embodiments, film is the insulation layer in the unicircuit, interlayer dielectric layer, intermetallic dielectric layer, capping layer, chemical-mechanical planarization or etching stopping layer, blocking layer or adhesion layer.
Utilize these performances, described film is applicable to various uses.Described film is particularly suitable for being deposited on the semiconductor chip, and is particularly suitable for as for example insulation layer, interlayer dielectric layer and/or metal intermetallic dielectric layer.Described film can form conformal coating.The mechanical property that is demonstrated by described film is specially adapted to it: aluminium is removed technology and copper ripple or dual damascene technology.
Although what the product of method described here and mixture was a large amount of is to describe with form of film, what the present invention was disclosed is not limited thereto.For example, porous OSG material can carry out sedimentary any form by CVD to be provided, as coating, and multilayer module, and need not to carry out complanation or the object of other type of attenuating, and the numerous objects that need not in unicircuit, to use.In certain preferred aspects, substrate is a semi-conductor.
Except that porous OSG material described herein and film, the method for preparing described product has also been described in the present invention, the using method of described product, and the compound and the composition that are used for preparing described product.
Composition described here also can comprise: for example be filled be suitable for valve and filler so as can be with porogen precursor, contain silicon precursor, and/or pore former and the mixture that contains silicon precursor are delivered at least one container that pressurizes (preferably stainless steel vessel) of reaction chamber.The inclusion of container can be pre-mixed.In addition, can with pore former and contain silicon precursor be kept at independently in the container or be kept at isolation mechanism so as storage period chien shih pore former and precursor keep in the isolating single container.When wishing, described container also can have the mechanism of mixing pore former and precursor.
In certain embodiments, containing silicon precursor can be made up of the mixture of different organosilanes and/or organo-siloxane.What it is also contemplated that in addition is that porogen precursor can be made up of the mixture of different porogen precursor.
In certain embodiments, one or more except that containing silicon precursor and porogen precursor are planted precursors can be before forming the film step, during, and/or be delivered in the reaction chamber afterwards.Described other precursor for example can comprise: rare gas element (for example He, Ar, N
2, Kr, Xe or the like) and can be used as the solid-state organic substance of carrier gas active substance such as gaseous state, liquid state or volatility (NH for example
3, H
2, CO
2, CO, H
2O, H
2O
2, O
2, O
3, CH
4, C
2H
2, C
2H
4Or the like), therefore it so that promote film to form the improvement of reaction, and improve the performance of film, and/or can be used as the post-treatment agent use, so that improve the performance or the stability of final film with inferior stoichiometric quantity, stoichiometric quantity or excessive concentrations use.
Those skilled in the art should be understood that helium is through being commonly used for carrier gas to promote the conveying of precursor to reaction chamber.Maybe advantageously, adopt carrier gas with the ionization energy that is different from helium.This can make the electronic temp in the plasma body descend, and this will change film formation process, and it will change the structure and/or the composition of deposit film successively again.The example that ionization energy is lower than the gas of helium comprises: CO
2, NH
3, CO, CH
4, Ne, Ar, Kr, and Xe.
For the film that forms on single 200mm disk, the flow velocity of every kind of gaseous chemical precursor is preferably 5-5000sccm.The flow velocity that is used for other reaction chamber can be depending on the size of substrate and the structure of reaction chamber, in any case and also be not limited to the silicon chip of 200mm or deposit the reaction chamber of single base material.In certain embodiments, select the flow velocity of organosilicon and porogen precursor,, thereby provide the final film of specific inductivity between about 1.1 and about 2.7 in deposit film so that the organosilicate and the pore former of desired amount are provided.
Energy is applied on the precursor, so that cause described reaction and on base material, form film.Described energy can heat by for example, plasma body, and pulsed plasma, microwave plasma, spiral (helicon) plasma body, high density plasma, inductively coupled plasma and remote plasma process provide.In certain embodiments, in identical plasma body, can use the width of cloth of two kinds of frequencies to penetrate, and can be used to improve the plasma characteristics on the substrate surface.Preferably, film forms by plasma body enhanced chemical vapour sedimentation method.In these embodiments, capacity coupled plasma body can produce in the frequency of 13.56MHz.The power of plasma body can be 0.02-7 watt/square centimeter in the surface-area of substrate, or is 0.3-3 watt/square centimeter.
Pressure between depositional stage in the reaction chamber can be 0.01-600 holder or 1-15 holder.
Although the thickness of film can change as required, preferably the thickness of thin film deposition is the 0.002-10 micron.Sedimentary coating film has excellent homogeneity on non-patterned surface, remove beyond the suitable edge, for example wherein the outermost edge of 5 millimeters of substrates is not included in the inhomogeneity statistical computation, and on 1 standard deviation of spanning substrate, its thickness changes and is lower than 2%.
Sedimentary film is made up of organosilicate and pore former.The total mass of film or cumulative volume are such, wherein the percentage quality of organosilicate or the volume percentage quality that adds pore former or the volume total mass or the volume that equal deposit film.
Be not bound by theory, one or more that the relative quantity of organosilicate and pore former may be subjected to following parameter in the deposit film influences.Porogen precursor and the relative quantity that contains silicon precursor in the precursor mixture, and organic silicate glass and the relative rate of formation of pore former on base material, wherein the relative quantity of organosilicate is the function that contains the amount of silicon precursor and the relative rate of formation of organosilicate on base material in the precursor mixture in deposit film.Similarly, the amount of pore former may be the function of the amount and the relative rate of formation of pore former on base material of porogen precursor in the precursor mixture in deposit film.Therefore, might form the organosilicate that on base material, forms during the step and amount separately, composition and the structure of pore former by selecting organosilicon precursor and porogen precursor to influence individually at film.
One or more kinds contain the chemical reagent of silicon precursor and porogen precursor or the mixture preparation of precursor has the porous OSG film of wishing mechanical property by comprising.Be to be suitable for the indefiniteness example that contains silicon precursor that uses together with different porogen precursor below.In all chemical formulas in chemical formula below and the whole application documents, term " independently " should be understood to: the R group is not only selected independently with respect to having different other R groups of target of going up, but also the R group identical with respect to any other class selected independently.For example, at chemical formula R
1 n(OR
2)
p(O (O) CR
3)
4-(n+p)Among the Si, when n=2 or 3, two or three R
1Need not mutually the same or and R
2Identical.
1) by formula R
1 n(OR
2)
p(O (O) CR
3)
4-(n+p)The chemical structure that Si represents, wherein, R
1Be H or C independently
1-C
4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2Be C independently
1-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R
3Be H independently, C
1-C
4Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, and p is 0-3,
2) by formula R
1 n(OR
2)
p(O (O) CR
4)
3-n-pSi-O-SiR
3 m(O (O) CR
5)
q(OR
6)
3-m-qThe chemical structure of expression, wherein, R
1And R
3Be H or C independently
1-C
4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2And R
6Be C independently
1-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R
4And R
5Be H independently, C
1-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is 0-3, and p is 0-3, n+m 〉=1, n+p≤3 and m+q≤3,
3) by formula R
1 n(OR
2)
p(O (O) CR
4)
3-n-pSi-SiR
3 m(O (O) CR
5)
q(OR
6)
3-m-qThe chemical structure of expression, wherein, R
1And R
3Be H or C independently
1-C
4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2And R
6Be C independently
1-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R
4And R
5Be H independently, C
1-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is 0-3, and p is 0-3, n+m 〉=1, n+p≤3 and m+q≤3,
4) by formula R
1 n(OR
2)
p(O (O) CR
4)
3-n-pSi-R
7-SiR
3 m(O (O) CR
5)
q(OR
6)
3-m-qThe chemical structure of expression, wherein, R
1And R
3Be H or C independently
1-C
4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2And R
6Be C independently
1-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R
4And R
5Be H independently, C
1-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R
7Be C
2-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is 0-3, and p is 0-3, n+m 〉=1, n+p≤3 and m+q≤3,
5) by formula (R
1 n(OR
2)
pO (O) CR
3)
4-(n+p)Si
tCH
4-tThe chemical structure of expression, wherein, R
1Be H or C independently
1-C
4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2Be C independently
1-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R
3Be H independently, C
1-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, and p is 0-3, and t is 2-4, and n+p≤4,
6) by formula (R
1 n(OR
2)
p(O (O) CR
3)
4-(n+p)Si)
tNH
3-tThe chemical structure of expression, wherein, R
1Be H or C independently
1-C
4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2Be C independently
1-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R
3Be H independently, C
1-C
6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, and p is 0-3, and t is 1-3, and n+p≤4,
7) by formula (NR
1SiR
2R
3)
xThe chemical structure represented of ring silazane, wherein, R
1And R
3Be H independently, C
1-C
4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon, and x can be the integers of 2-8,
8) by formula (C (R
1R
2) Si (R
3R
4))
xThe chemical structure represented of ring silazane, wherein, R
1-R
4Be H independently, C
1-C
4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon, and x can be the integers of 2-8,
Although in whole specification sheets all with reference to siloxanes, carbon silane, with the precursor of silazane as precursor and pore-formingization, but should be understood that, method of the present invention and film are not limited thereto, for example other siloxanes such as trisiloxanes, tetrasiloxane, and other even the longer linear siloxanes of length also may be used for the present invention.
The above-mentioned silicon precursor that contains can be contained silicon precursor with top listed porogen precursor and/or any other and mixes, the described silicon precursor that contains comprises and removes the different silicon precursors that contain that n and/or m are the described kind of 0-3.Its example has: TEOS, triethoxy-silicane, two tert.-butoxy silicomethanes, silicomethane, silicoethane, two tert.-butoxy diacetoxy silicomethanes or the like.
Described embodiment will help controlling amount, structure and the composition of deposit film organosilicate part.These embodiments can also be controlled the ratio of pore former and organosilicate in the deposit film, improve one or more critical properties of deposit film and/or final film, or the size of pore former or the size of final film mesopore in the control deposit film, the distribution of pore former or in the distribution of final film mesopore in the control deposit film, and/or control pore connectivity in the final film.For example, react the use that formed film may have benefited from containing in addition silicon precursor such as TEOS by diethoxymethyl silicomethane (DEMS) and porogen precursor, thereby reduced the quantity of the end group that is adhered to film organosilicate part, increased the density of deposit film and final porous membrane mesosilicic acid salt thus, and improved the film performance of one or more hope of deposit film and final film, be physical strength, or lower tensile stress.Other example is to react formed film by two tert.-butoxy methyl-silicanes and porogen precursor, and it may have benefited from having added two tert.-butoxy diacetoxy silicomethanes equally in reaction chamber.Therefore, in certain embodiments, provide have two or still less the Si-O key first contain silicon precursor and have the mixture that second of three or more Si-O keys contain silicon precursor so that the chemical constitution of film of the present invention is repaired.
Do not fettered by following theory: utilize pore former to form controlled hole in the organic silicate glass film, the size of pore former and shape have determined the size and the shape of formed pore when it is removed basically.Therefore, in size, the shape of final film mesopore, connectedness, and quantity is mainly by size, shape, the connectedness of pore former in the deposit film, and quantity decides.Therefore, ratio that can be by the organosilicate precursor in the structure, composition, introducing reaction chamber of control porogen precursor and porogen precursor and the condition of formation pore former on the base material of being used in reaction chamber influence the size of pore in the porous organic silicate material, shape, connectedness, and quantity.In addition, the porogen precursor of definite composition and structure may be favourable for forming pore former in deposit film, and it will give final film with preferred performance.
Pore former in the deposit film can be identical or different with the form of introducing the porogen precursor in the reaction chamber.Pore former is removed processing will discharge or remove all basically pore formers or pore former fragment from film.Porogen precursor, the pore former in the deposit film, and the pore former that is removed can be identical material or different materials, but preferably, they all are derived from the mixture of porogen precursor or porogen precursor.Whether form with pore former in the whole method of the present invention and to change irrelevantly, mean at this used term " porogen precursor " and to comprise: all pores form agent and derivatives thereof, are included in any form of being found in the entire method of the present invention.
The composition of pore former material is by carbon and hydrogen and be selected from following at least a elementary composition in the deposit film: oxygen, nitrogen, fluorine, boron, and phosphorus.
The structure of pore former in deposit film and composition can utilize various analytical technologies to measure.Pore former in deposit film is formed and mainly is made up of carbon, and it can detect by various technology, comprises the sub-scattering of X-ray photoelectric (XPS) and rutherford's backscattering/hydrogen forward scatter (RBS/HFS).The carbon content of deposit film will be than in precursor mixture, there not being porogen precursor sedimentary contrast film high more than 10% or high by 20%.In addition, the carbon content of deposit film increase also can be by 2600 relevant and the 3100cm of frequency that measures and the C-H vibration is extended
-1The area at the peak in the zone utilizes FT-IR to measure.Under the situation that mainly is hydrocarbon pore former material, the peak area in described zone is the peak area of sedimentary contrast film greatly at least 100% or big by 200% than there is not porogen precursor in precursor mixture at least.
In certain embodiments, during post-processing step, at least a portion or basically the pore former in all deposit films can be removed basically.Described post-processing step can also influence chemical structure and/or the composition that is retained on the base material with the porous organic silicate reticulation that forms final porous membrane.
Based on various judging criterions, can identify desirable gaseous state, liquid state or solid-state chemical substance as porogen precursor.For example, in order to form pore former on base material, porogen precursor should have the enough volatility that deliver into reaction chamber.In case enter reaction chamber, porogen precursor just can perhaps be reacted on the surface of base material in gas phase or vapor phase, thereby mixes in the film with the form of pore former.May be used for promoting that the method that is formed pore former by porogen precursor comprises: intramolecular reaction and/or intermolecular reaction, comprise two bodies bump, the trisome bump, bump with sidewall, bump with rare gas element, reaction with the inferior stable state rare gas element, reaction with oxidation or reducing gas, form the reaction or the bump of precursor with the netted thing of silicate, with the reaction or the bump of active electrons in the plasma body, with the reaction or the bump of active neutron in the plasma body, ionization, oxidizing reaction, reduction reaction is with the ionic bump in the plasma body, photochmeical reaction or rearrangement, hot activation reaction or rearrangement, with the reaction of activation and/or neutral substance on the base material, any other method that porogen precursor is deposited on the base material is all thought the feasible method of deposition pore former in film.In addition, except in condensation on the base material to change into the pore former, porogen precursor may be without any other reaction.
The structure of porogen precursor and composition can comprise: the functional group that makes it to can be used to form pore former on base material.The example that may be included in the functional group in the porogen precursor comprises: ether; Epoxide; Aldehyde; Ketone; Ketenes; Acetoxyl group; Ester; Acrylate; Propenal; Vinylformic acid; Vinyl cyanide; Carboxylic acid; The primary, the second month in a season or tertiary amine; Nitro; Cyano group; Isocyano-; Acid amides; Imide; Acid anhydrides; Partially fluorinated and/or fluoridized group; Boron nitride, boric acid, boric acid ester; Phosphoryl (phosphyl), phosphorous acid ester (phospite) and/or phosphoric acid ester and combination thereof.
It is believed that and utilize plasma body enhanced chemical vapour deposition technique, form the electron impact cross section that pore former may depend on functional group in the porogen precursor by porogen precursor, this can bring out the secondary reaction that forms pore former.Therefore, in certain embodiments, in order to improve speed and the solidification process that is formed pore former by porogen precursor, element is formed, and/or structure, as other atomic species such as O
2, N
2, B or Ph may be desirable.
Be not bound by theory, possible is, form pore former by porogen precursor and can not have a strong impact on by organosilicon precursor and form organosilicate, and under certain conditions, the covalent linkage between organosilicate film and the pore former may be minimized.For example, do not have covalent linkage between the organosilicate zone of pore former and deposit film, may make pore former be easier to remove from deposit film with post-processing step, this may make heat budget (thermal budget) demand of aftertreatment minimize.For one of major limitation of semiconductor machining is heat budget.Heat budget for the individual curing step is formed by carrying out required time of described step and temperature.In some example, desirable is that the heat budget of any treatment step is minimized.Therefore, compare, can will more wish in the processing that low temperature and/or short period of time carry out with requiring high temperature and/or long similar processing.Therefore, porogen precursor described herein and contain silicon precursor and utilize wherein heat budget to control and even minimized some treatment step forms porous organic silicate film.
Pore former is removed from deposit film by post-processing step, described treatment step can comprise: the thermal annealing under inert atmosphere, thermal annealing under vacuum, thermal annealing under oxidizing atmosphere, thermal annealing under reducing atmosphere, be exposed in oxidation and/or the reduction chemical reagent, be exposed in the electron beam irradiation, be exposed in the oxidation plasma, be exposed in the reduction plasma body, be exposed in the ultraviolet ray under the vacuum, be exposed in the ultraviolet ray under the inert atmosphere, be exposed in the ultraviolet ray under oxidation and/or the reduction nitrogen, be exposed in the microwave radiation under the vacuum, be exposed in the microwave radiation under the inert atmosphere, be exposed in the microwave radiation under oxidation and/or the reducing atmosphere, be exposed in the laser radiation, be exposed in simultaneously applied listed any above-mentioned processing, or be exposed to the initiator effect so that STRUCTURE DECOMPOSITION and from film, removing in any type of energy or chemical treatment of pore former.In addition can also with other on the spot or deposit post-treatment improve the performance of material, as hardness, stability (with respect to contraction, be exposed in the air, etching, wet etching, or the like), globality, consistence and tackiness.Described processing can be before the identical or different means that pore former is removed in utilization be removed pore former, during and/or be applied to described film afterwards.Therefore, at this used term " aftertreatment " ordinary representation: utilize energy (for example heating, plasma body, photon, electronics, microwave, or the like) or chemical substance to the processing of film, so that remove pore former, and not essential the performance that improves material.
Porogen precursor can form, or functional group be selected according to help to remove fully the structure that pore former is introduced from deposit film.For example, cause introducing in the pore former on base material temperature-sensitive, porogen precursor photosensitive or chemical-sensitive functional group makes it to adopt heat, light or chemical reaction effectively, so that remove pore former from film.Therefore, utilize the porogen precursor that forms pore former in deposit film, wherein the activation by chemical group in the pore former or structure can effectively and potentially be removed described pore former fully.
The condition of carrying out aftertreatment can be varied.For example, aftertreatment can or be carried out under vacuum at high pressure, normal pressure.In addition, aftertreatment is at high temperature (400-500 ℃) also, low temperature (100 ℃ and more than), or under the temperature between these two temperature spots, carry out.Aftertreatment also can be made up of the series of steps of carrying out under different pressures and/or temperature combination.
Carry out thermal annealing under following condition: environment can be inert (for example nitrogen, CO
2, rare gas (He, Ar, Ne, Kr, Xe) or the like), (for example oxygen, air, rare oxygen environment, oxygen-enriched environment, ozone, nitrous oxide or the like) or (the rare or dense hydrogen of reductibility of oxidisability, hydrocarbon is (saturated, unsaturated straight or branched, arene), or the like).Pressure is preferably in about 1000 holders of about 1-, more preferably under barometric point.Yet for thermal annealing and any other aftertreatment means, vacuum environment also is possible.Temperature is preferably 200-500 ℃, and temperature slope is 0.1-100 ℃/minute.Total annealing time is preferably from 0.01 minute to 12 hours.
The chemical treatment of OSG film is carried out under following condition: utilize fluoridation (HF, SiF
4, NF
3, F
2, COF
2, CO
2F
2Or the like), oxide treatment (H
2O
2, O
3Or the like), chemical seasoning, other chemical treatment of methylating or improving final material property.The chemical substance of using in described processing can be a solid, liquid, gas and/or supercutical fluid state.
The supercutical fluid aftertreatment that selectivity is removed pore former from the organosilicate film can be carried out under following condition: fluid can be carbonic acid gas, water, nitrous oxide, ethene, SF
6And/or the chemical substance of other type.Other chemical substance can be added in the supercutical fluid to strengthen this processing.Chemical substance can be inert (for example nitrogen, CO
2, rare gas (He, Ar, Ne, Kr, Xe) or the like), (for example oxygen, ozone, nitrous oxide or the like) or (rare or dense hydrocarbon, hydrogen or the like) of reductibility of oxidisability.Temperature is preferably from envrionment temperature to 500 ℃.Chemical substance also can comprise a large amount of chemical substances in addition, as tensio-active agent.Total exposure duration is preferably 0.01 minute to 12 hours.
Remove the Cement Composite Treated by Plasma of pore former and possible organosilicate chemical modification under following condition: environment can be inert (for example nitrogen, CO
2, rare gas (He, Ar, Ne, Kr, Xe) or the like), (for example oxygen, air, rare oxygen environment, oxygen-enriched environment, ozone, nitrous oxide or the like) or (the rare or dense hydrogen of reductibility of oxidisability, hydrocarbon is (saturated, unsaturated straight or branched, arene) or the like).The power of plasma body is preferably 0-5000W.Temperature is preferably envrionment temperature to 500 ℃.Pressure is preferably 10 millitorrs to barometric point.Be preferably 0.01 minute to 12 hours total set time.Disk size and method change with condition.
Removing the photocuring of pore former under following condition handles: environment can be inert (for example nitrogen, CO
2, rare gas (He, Ar, Ne, Kr, Xe) or the like), (alkene or the dense hydrocarbon, hydrogen, or the like) of (for example oxygen, air, rare oxygen environment, oxygen-enriched environment, ozone, nitrous oxide, or the like) of oxidisability or reductibility.Temperature is preferably envrionment temperature to 500 ℃.Power is preferably 0.1-5000W per square inch.Wavelength is preferably IR, visible light, UV or UV (wavelength is less than 200nm) far away.Be preferably 0.01 minute to 12 hours total set time.
Remove the microwave aftertreatment of pore former under following condition: environment can be inert (for example nitrogen, CO
2, rare gas (He, Ar, Ne, Kr, Xe) or the like), (the rare or dense hydrocarbon, hydrogen, or the like) of oxidisability (for example oxygen, air, rare oxygen environment, oxygen-enriched environment, ozone, nitrous oxide or the like) or reductibility.Temperature is preferably envrionment temperature to 500 ℃.Power and wavelength can change, and can transfer to particular value.Be preferably 0.01 minute to 12 hours total set time.
Remove pore former and/or improve the electron beam aftertreatment of film performance under following condition: environment can be vacuum, inert (for example nitrogen, CO
2, rare gas (He, Ar, Ne, Kr, Xe) or the like), (the rare or dense hydrocarbon, hydrogen, or the like) of (for example oxygen, air, rare oxygen environment, oxygen-enriched environment, ozone, nitrous oxide, or the like) of oxidisability or reductibility.Temperature is preferably envrionment temperature to 500 ℃.Electron density and energy can change and can transfer to particular value.Be preferably 0.001 minute to 12 hours total set time, and can be continuous or pulse.Other the guidance that electron beam is general to be used can be with reference to following publication: people's such as S.Chattopadhyay, Journal of Materials Science, 36 (2001) 4323-4330; People's such as G.Kloster, Proceedings of IITC, June 3-5,2002, SF, CA; And US6,207,555 B1,6,204,201 B1 and 6,132,814 A1.Utilize electron beam treatment can remove pore former and improve the mechanical property of film.
Along with bulk density correspondingly reduces, can increase the porosity of film, thereby further reduce the specific inductivity of material, and make the suitability of this material extend to offspring (for example k＜2.0).
Therein in the embodiment that all pore formers are removed basically, if between the similar organosilicate film that forms in the porous organic silicate of aftertreatment and the reaction chamber that do not having porogen precursor to exist, (be also referred to as C-Hx, 2600-3100cm in the hydrocarbon zone
-1) FT-IR do not have tangible statistical significance to measure difference in absorbing, just assert that all pore formers are removed basically.
The indefiniteness example that is suitable for the material of making porogen precursor comprises:
1) comprising one or more alcohol radical and general formula is C
nH
2n+2-2x-2y-z(OH)
zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of alcohol radical in the compound and between 1 and 4, and the alcohol functional group outer and/or intra-annular of ring wherein.Its example has: and propyl alcohol (n=3, x=0, y=0, z=1), ethylene glycol (n=2, x=0, y=0, z=2), hexanol (n=6, x=0, y=0, z=1), and cyclopentanol (n=5, x=1, y=0, z=1), 1,5-hexadiene-3,4-glycol (n=6, x=0, y=2, z=2), and cresols (n=7, x=1, y=3, z=1), and Resorcinol (n=6, x=1, y=3, z=2), or the like.
2) comprising one or more ether and general formula is C
nH
2n+2-2x-2yO
zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of ehter bond in the structure and between 1 and 4, and the ehter bond outer and/or intra-annular of ring wherein.Its example has: and ether (n=4, x=0, y=0, z=1), the 2-methyltetrahydrofuran (n=5, x=1, y=0, z=1), 2,3-cumarone (n=8, x=2, y=4, z=1), ethylene glycol bisthioglycolate vinyl ether (n=6, x=0, y=2, z=2), Terpane (eucalyptol) (n=10, x=2, y=0, z=1), or the like.
3) comprising one or more epoxide group and general formula is C
nH
2n+2-2x-2y-2zO
zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of epoxide group in the structure and between 1 and 4, and wherein epoxide group can be connected to that ring is gone up or straight chain on.Its example has: 1,2-epoxy-3-methylbutane (n=5, x=0, y=0, z=1), and 1,2-epoxy-5-hexene (n=5, x=0, y=1, z=1), cyclohexene oxide (n=6, x=1, y=0, z=1), 9-oxabicyclo [6.1.0] ninth of the ten Heavenly Stems-4-alkene (n=8, x=1, y=1, z=1), or the like.
4) comprising one or more aldehyde radical and general formula is C
nH
2n+2-2x-2y-2zO
zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of aldehyde radical in the structure and between 1 and 4.Its example has: pentamethylene formaldehyde (n=5, x=1, y=0, z=1) or the like.
5) comprising one or more ketone group and general formula is C
nH
2n+2-2x-2y-2zO
zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of aldehyde radical in the structure and between 1 and 4, and the ketone group outer and/or intra-annular of ring wherein.Its example has: 3, the 4-hexanedione (n=6, x=0, y=0, z=2), cyclopentanone (n=5, x=1, y=0, z=1), the mesityl oxide compound (n=6, x=0, y=1, z=1), or the like.
6) comprising one or more carboxylic acid group and general formula is C
nH
2n+2-2x-2y-3z(OOH)
zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of carboxylic acid group in the structure and between 1 and 4.Its example has: cyclopentane-carboxylic acid (n=6, y=1, x=0, z=1), or the like.
7) comprise the dehydrated hydrocarbon structure with formation cyclic acid anhydride group of even number carboxylic acid group and acid functional group, wherein, the general formula of described structure is C
nH
2n+2-2x-2y-6z(O
3)
z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of anhydride group in the structure and is 1 or 2.Its example has: maleic anhydride (n=2, x=0, y=1, z=1), or the like.
8) comprising ester group and general formula is C
nH
2n+2-2x-2y-2z(O
2)
zHydrocarbon structure, n=1-12 wherein, x are the quantity of encircling in the structure and between 0-4, y is the quantity of unsaturated link(age) in the structure and does not have unsaturated link(age) and the carbonyl conjugation of ester that z is the quantity of anhydride group in the structure and is 1 or 2.
9) comprising acrylate-functional groups and general formula is C
nH
2n+2-2x-2y-2z(O
2)
zHydrocarbon structure, described functional group is made up of the carbonyl conjugated unsaturated link(age) of ester group and at least one and ester group, n=1-12 wherein, x is the quantity encircled in the structure and between 0-4, y is the quantity of unsaturated link(age) in the structure and more than or equal to 1, the carbonyl conjugation of unsaturated link(age) and ester at least wherein, z is the quantity of ester group in the structure and is 1 or 2.Its example has: Jia Jibingxisuanyizhi (n=6, x=0, y=1, z=1), or the like.
10) comprising ether and carbonyl functional group and general formula is C
nH
2n+2-2w-2x-2y(O)
y(O)
zHydrocarbon structure, n=1-12 wherein, w is the quantity encircled in the structure and between 0 and 4, x be unsaturated link(age) in the structure quantity and 0 and n between, y is the quantity of carbonyl in the structure, wherein carbonyl can be ketone and/or aldehyde, and z is the quantity of ether in the structure and is 1 or 2, and ether encircles outer and/or intra-annular.Its example has: the oxyethyl group methacrylaldehyde (n=6, w=0, x=1, y=1, z=1), or the like.
11) comprising ether and alcohol functional group and general formula is C
nH
2n+2-2w-2x-y(OH)
y(O)
zHydrocarbon structure, n=1-12 wherein, w are the quantity encircled in the structure and between 0 and 4, x be unsaturated link(age) in the structure quantity and 0 and n between, y is the quantity of alcohol radical in the structure, and z is the quantity of ether in the structure and is 1 or 2, and wherein ether to can be ring outer or interior ring.Its example has: the 3-hydroxyl tetrahydrofuran, or the like.
12) comprising any combination and the general formula that are selected from following functional group is C
nH
2n+2-2u-2v-w-2y-3z(OH)
w(O)
x(O)
y(OOH)
zHydrocarbon structure, described functional group is: alcohol, ether, carbonyl and carboxylic acid, n=1-12 wherein, u is the quantity encircled in the structure and between 0 and 4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of alcohol radical in the general formula and between 0 and 4, x is the quantity of ether in the structure and ether outside the ring or intra-annular between 0 and 4 and wherein, y is the quantity of carbonyl in the structure and between 0 and 3, wherein said carbonyl can be ketone and/or aldehyde, and z is between the quantity and 0 and 2 of carboxylic acid group in the structure.
13) comprising one or more primary amine groups and general formula is C
nH
2n+2-2x-2y-z(NH
2)
zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of amido in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein.Its example has: cyclopentamine (n=5, x=1, y=0, z=1), or the like.
14) comprising one or more secondary amine and general formula is C
nH
2n+2-2x-2y-2z(NH)
zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of secondary amine group in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein.Its example has: Diisopropylamine (n=6, x=0, y=0, z=1), piperidines (n=5, x=1, y=0, z=1), pyridine (pyride) (n=5, x=1, y=3, z=1), or the like.
15) comprising one or more tertiary amine groups and general formula is C
nH
2n+2-2x-2y-3z(N)
zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of tertiary amine groups in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein.Its example has: triethylamine (n=6, x=0, y=0, z=1), the N-crassitude (n=5, x=1, y=0, z=1), the N-methylpyrrole (n=5, x=1, y=2, z=1), or the like.
16) comprising one or more nitro and general formula is C
nH
2n+2-2x-2y-z(NO
2)
zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of nitro in the compound and between 1 and 4, and the nitro functions outer and/or intra-annular of ring wherein.Its example has: the nitro pentamethylene (n=5, x=1, y=0, z=1), oil of mirbane (n=6, x=1, y=3, z=1), or the like.
17) comprising amine and ether functional group and general formula is C
nH
2n+2-2u-2v-w-2x-3y-z(NH
2)
w(NH)
x(N)
y(OH)
zHydrocarbon structure, n=1-12 wherein, u is the quantity encircled in the structure and between 0 and 4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of primary amine groups, x is the quantity of secondary amine, y is the quantity of tertiary amine groups, and 1＜w+x+y＜4, z is the quantity of alcohol radical in the compound and between 1 and 4, and alcohol radical and/or the amido outer and/or intra-annular of ring.Its example has: 2-(2-aminoethylamino) ethanol (n=4, u=0, v=0, w=1 x=1, y=0, z=1), N-methylmorpholine (n=5, u=1, v=0, w=0, x=0, y=1, z=1), or the like.
18) comprising amine and alcohol functional group and general formula is C
nH
2n+2-2u-2v-w-2x-3y-z(NH
2)
w(NH)
x(N)
y(OH)
zHydrocarbon structure, n=1-12 wherein, u is the quantity encircled in the structure and between 0 and 4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of primary amine groups, x is the quantity of secondary amine, y is the quantity of tertiary amine groups, and 1＜w+x+y＜4 wherein, z is the quantity of ether in the compound and between 1 and 4, and ether and/or the amido outer and/or intra-annular of ring.Its example has: tetrahydrofurfuryl amine (n=5, u=1, v=0, w=1, x=0, y=0, z=1), or the like.
19) comprising amine and carbonyl functional group and general formula is C
nH
2N+2-2u-w-2x-3y-2z(NH
2)
w(NH)
x(N)
y(O)
zHydrocarbon structure, n=1-12 wherein, u is the quantity encircled in the structure and between 0 and 4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of primary amine groups, x is the quantity of secondary amine, y is the quantity of tertiary amine groups, and 1＜w+x+y＜4, and z is the quantity of carbonyl in the compound and between 1 and 4, wherein carbonyl can be aldehyde and/or ketone, and carbonyl and/or amido be the outer and/or intra-annular of ring.Its example has: N, the N-diethylformamide (n=5, u=0, v=0, w=0, x=0, y=1, z=1), (dimethylamine) acetone (n=5, u=0, v=0, w=0, x=0, y=1, z=1), N-Methyl pyrrolidone (n=5, u=1, v=1, w=0, x=0, y=1, z=1), or the like.
In certain embodiments, precursor mixture also comprises the pore-forming precursor.Be the indefiniteness example of the precursor of silica-based pore-formingization below, wherein, the pore former material is R
1, R
3Or R
7In one or more:
-R
1 n(OR
2)
3-nSi, wherein, R
1Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2Can be C independently
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, part or fluoridized alkyl, n is 1-3.
-example: diethoxy-Xin hexyl silicomethane
-R
1 n(OR
2)
3-nSi-O-SiR
3 m(OR
4)
3-m, wherein, R
1And R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2And R
4Can be C independently
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, part or fluoridized alkyl, n is 1-3, m is 1-3.
Example: 1, the new hexyl sily oxide of 3-diethoxy-1-
-R
1 n(OR
2)
3-nSi-SiR
3 m(OR
4)
3-m, wherein, R
1And R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2And R
4Can be C independently
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, part or fluoridized alkyl, n is 1-3, m is 1-3.
Example: 1, the new hexyl silicoethane of 2-diethoxy-1-
-R
1 n(OR
2)
3-nSi-R
7-SiR
3 m(OR
4)
3-m, wherein, R
1And R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2And R
4Can be C independently
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, part or fluoridized alkyl, R
7Be C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, two Siliciumatoms of partially or completely fluorizated, and bridge joint, n is 1-3, m is 1-3.
-example: 1,4-two (dimethoxy silyl) hexanaphthene
-R
1 n(OR
2)
3-nSi-SiR
3 m(OR
4)
3-m, wherein, R
1And R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2And R
4Can be C independently
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, part or fluoridized alkyl, n is 1-3, m is 1-3.
Example: 1, the new hexyl silicoethane of 2-diethoxy-1-
-R
1 n(O (O) (CR
2)
4-nSi, wherein, R
1Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R
2Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, part or fluoridized alkyl, n is 1-3.
The basic silicomethane of-example: diacetoxy-Xin
-R
1 n(O (O) (CR
2)
3-nSi-O-SiR
3 m(O (O) CR
4)
3-m, wherein, R
1And R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl; R
2And R
4Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, part or fluoridized alkyl, n is 1-3, and m is 1-3.
-example: 1, the newly basic sily oxide of 3-diacetoxy-1-
-R
1 n(O (O) (CR
2)
3-nSi-SiR
3 m(O (O) CR
4)
3-m, wherein, R
1And R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl; R
2And R
4Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, part or fluoridized alkyl, n is 1-3, and m is 1-3.
Example: 1, the new hexyl silicoethane of 2-diacetoxy-1-
-R
1 n(O (O) CR
2)
3-nSi-O-SiR
3 m(OR
4)
3-m, wherein, R
1And R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl; R
2Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, part or fluoridized alkyl, R
4Can be C independently
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated alkyl partially or completely, n is 1-3, and m is 1-3.
-example: 1-acetoxyl group 3, the new hexyl sily oxide of 3-two tert.-butoxy 1-
-R
1 n(O (O) (CR
2)
3-nSi-SiR
3 m(OR
4)
3-m, wherein, R
1And R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl; R
2Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, part or fluoridized alkyl, R
4Can be C independently
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated alkyl partially or completely, n is 1-3, m is 1-3.
-example: 1-acetoxyl group-2, the new hexyl silicoethane of 2-two tert.-butoxies-1-
-R
1 n(OR
2)
p(O (O) CR
3)
4-(n+p)Si, wherein, R
1Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl; R
2Be C independently
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, part or fluoridized alkyl, R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated alkyl partially or completely, n is 1-3, and p is 1-3.
-example; The new hexyl silicomethane of acetoxyl group-tert.-butoxy
-R
1 n(OR
2)
p(O (O) CR
4)
3-n-pSi-O-SiR
3 m(O (O) CR
5)
q(OR
6)
3-m-q, wherein, R
1And R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl; R
2, R
6Can be C independently
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated alkyl partially or completely, R
4, R
5Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated alkyl partially or completely, n is 1-3, and m is 1-3, and p is 1-3, and q is 1-3.
-example: 1,3-diacetoxy-1, the new hexyl sily oxide of 3-two tert.-butoxy 1-
-R
1 n(OR
2)
p(O (O) CR
4)
3-n-pSi-SiR
3 m(O (O) CR
5)
q(OR
6)
3-m-q, wherein, R
1And R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl; R
2, R
6Can be C independently
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated alkyl partially or completely, R
4, R
5Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated alkyl partially or completely, n is 1-3, and m is 1-3, and p is 1-3, and q is 1-3.
-example: 1,2-diacetoxy-1, the new hexyl silicoethane of 2-two tert.-butoxies-1-
-Shi (OSiR
1R
3)
xCyclosiloxane, wherein, R
1And R
3Can be H independently, C
1-C
12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl, and x can be the integers of 2-8.
-example: as 1-new hexyl-1,3,5,7-tetramethyl-ring tetrasiloxane.
Embodiment
All tests all utilize unadulterated TEOS to handle equipment, in the chamber of the 200mm D * Z that is equipped with Advance Energy 2000 radio frequency generatorss, finish in Applied Materials Precision-5000 system.This method comprises following basic step: the stabilization of initial setting up and air-flow, and deposition, and before removing disk, the chamber is cleaned/found time.
Utilize the post-processing step of thermal annealing under nitrogen atmosphere, in 425 ℃ tube furnace, to carry out at least 1 hour.Utilize the ultraviolet lamp in 6000 watts of broadbands, finish by the Fusion UV that is equipped with the H+ bulb and be exposed in the UV light.By film being placed the treatment chamber that is equipped with the thick synthetic silica sheet of 12.52mm come controlled atmosphere, can shine with light to cause described film.Pressure in the described chamber remains between 0.3 and 760 holders.
Pore former is porogen precursor and the relative volumetric molar concentration that contains silicon precursor of introducing reaction chamber with the ratio of DEMS.When described ratio increases, with respect to containing silicon precursor, the amount of porogen precursor will increase.Because it is a mol ratio, therefore, relative concentration is benchmark with the per molecule; For example, pore former: DEMS 4 means that each molecule contains silicon precursor and has 4 molecules to introduce the porogen precursor of reaction chamber.
Sedimentation rate is: the speed that deposit film forms on the base material of reaction chamber.It is determined by the film thickness of measurement deposit film and divided by depositing the required time of end.Sedimentation rate relates to: porogen precursor and contain the efficient that silicon precursor reacts in the sediment chamber, so that form pore former and organosilicate respectively at substrate surface.
Utilize SCI Filmtek 2000 reflectometry thickness and specific refractory poweres.The specific refractory power of material is defined as:
RI＝c/υ
In the formula, c is a light speed in a vacuum, and υ is the speed of light by film.Utilize the light of 632nm to measure specific refractory power.Light depends on the electron density of film by the speed of film, in this research, for relatively and the performance of contrast deposit film and final film, makes electron density moderately relevant with specific inductivity.Therefore, the film with high index has the higher dielectric constant value usually.Usually, the film after aftertreatment has the specific refractory power that is lower than deposit film.This be because, the pore former in the deposit film is substituted by void volume, and compares with the specific refractory power of about 1.400-1.600 of pore former, the specific refractory power of air is about 1.00029.
The specific inductivity of material, k is defined as:
k＝C/C
0
In the formula, C is dielectric electric capacity, C
0Electric capacity for vacuum.Utilize the mercury probe technologies, measure being deposited on the deposit film on the low-resistance p-type silicon chip (＜0.02 ohm-cm) and/or the electric capacity of final porous organic silicate film.
Utilize Standards Code, utilize MTS Nano Indenter measure mechanical properties (millimicro scratch hardness, Young's modulus).
Utilize Thermo TA Instruments 2050 TGA, measure thermostability and tail gas product by thermogravimetric analysis.Utilize Physical Electronics 5000 LS, obtain to form data by the sub-spectroscopy of X-ray photoelectric (XPS).The % value of atom of listing in table does not comprise hydrogen.
In some tables of tabulation down, " n/a " expression data do not obtain.
Porogen precursor contains the change of silicon precursor stoichiometric quantity relatively
Mixture deposition laminated film by pimelinketone (CHO) and diethoxymethyl silicomethane (DEMS).Mode of deposition is as follows: plasma power is 450 watts, and chamber pressure is 8 holders, and spread of electrodes is 350 mils, and carrier gas is a helium, and its flow velocity is 210sccm, and base material temperature is 225 ℃.The flow velocity that changes CHO and DEMS is introduced the CHO of reaction chamber and the ratio of DEMS with control, and the overall flow rate that keeps entering the chemical substance in the reaction chamber simultaneously is constant.By being exposed to (following 5 minutes of the λ=200-400nm) and film is carried out aftertreatment of UV light in broadband under the vacuum.
Show 1a and 1b. for utilizing the sedimentary film of pimelinketone and DEMS, the performance of deposit film and final film,
| CHO flow velocity (mg/min) | DEMS flow velocity (mg/min) | Overall flow rate (mg/min) | CHO: DEMS ratio | Sedimentation rate (nm/min) | Specific refractory power (deposit film) |
| 450 400 350 | 150 200 250 | 600 600 600 | 4.10 2.74 1.91 | 200 230 260 | 1.480 1.470 1.460 |
| CHO: DEMS ratio | UV cure shrinkage (%) | Specific refractory power (finally) | Specific inductivity (finally) | Young modulus (GPa) | Hardness (GPa) |
| 4.16 2.78 1.94 | 28 17 16 | 1.340 1.350 1.370 | 2.49 2.56 2.67 | 8.0 8.3 9.7 | 1.2 1.3 1.6 |
Data among table 1a and the 2a show: the change of precursor stoichiometric quantity will cause the change of the final performance of film.This is because porogen precursor in the chemical charging of input reaction chamber and the amount that contains silicon precursor have determined to be deposited into the amount of pore former and organosilicate on the base material basically.For example, at the highest CHO: during the DEMS ratio, will realize minimum final thin-film dielectric constant.As CHO: when the DEMS ratio reduces, the specific inductivity of film and mechanical hardness all will increase.Therefore, film performance can be controlled by the amount of porogen precursor in the reaction chamber and the amount of organosilicon precursor.
Embodiment 2
The functional group of porogen precursor
In addition, can also be used as the structure of hole agent precursor and/or form and to control film performance.Laminated film is by CHO or 1,2, and 4-trimethyl-cyclohexane (TMC) deposits.Table 2 will compare the neat liquid performance of these precursors.The CHO precursor is made up of 6 carbocyclic rings with ketone, and the TMC precursor have have be connected 1,2 and the 4-position on 6 carbocyclic rings of three methyl.
The performance of table 2. neat liquid porogen precursor.
| Porogen precursor | Chemical formula | The H/C ratio | Molecular weight | Density (g/mL) | Specific refractory power | Boiling point (℃) |
| Pimelinketone (CHO) 1,2,4-trimethyl-cyclohexane (TMC) | C 6H 10O C 9H 18 | 1.67 2.0 | 98.15 126.24 | 0.947 0.786 | 1.450 1.433 | 155 141-143 |
Listed in detail by TMC and DEMS in the table 3, or deposited the mode of deposition of the laminated film that obtains by CHO and DEMS.Compare with sedimentary TMC film, utilize the film of CHO precursor deposition to have higher sedimentation rate and deposition specific refractory power, therefore hint has higher pore former concentration in the deposition CHO film.As shown in Figure 2, can easily observe the described more a large amount of pore former in the CHO film by the FT-IR spectrum that detects deposit film.Spectrum among Fig. 2 has been normalized to 1 micron film thickness.When at 2700-3100cm
-1Between C-H
xVibration is stretched when increasing, and can observe the pore former concentration in the deposit film best.Data in the table 3 show: the peak area in the CHO-1 film is 5.25, and the peak area in the TMC-1 film is 3.27.Therefore, under same treatment condition, the CHO porogen precursor is at the C-H that increases the deposition laminated film
xKey concentration aspect is more effective.
The mode of deposition of deposition laminated film among table 3. embodiment 2, sedimentation rate, and specific refractory power.
| Treatment variable | TMC-1 | CHO-1 |
| Gas ions power (watt) chamber pressure (holder) electrode spacing (in the least-inch) base material temperature (℃) pore former flow velocity (mg/min) DEMS flow velocity (mg/min) pore former: DEMS mol ratio carrier gas flow rate of carrier gas (sccm) additional gas additional gas flow velocity (sccm) sedimentation rate (nm/min) refractive index FT-IR C-HxPeak area | 600 8 350 300 435 120 3.86 CO 2 200 O 2 10 150 1.452 3.27 | 600 8 350 300 450 150 4.10 He 200 O 2 10 290 1.515 5.25 |
Fig. 3 has showed the FT-IR spectrum that is exposed to CHO-1 film and TMC-1 film after the broadband UV light 5 minutes under vacuum.This spectrum shows: the C-H of two films
xPeak area is reduced to about 0.9 and 0.6 respectively.C-H after pore former is removed
xDifference between the peak intensity is attributable in the CHO-1 film the more Si-CH of a large amount
3Group, this will help some absorption in this zone.
Listed in the table 4 and under vacuum, be exposed to after the broadband UV light 5 minutes the final performance of film for TMC-1 and CHO-1.These data show: the CHO-1 film has the specific inductivity lower than TMC-1 film.This owing to: utilize the obtained higher pore former concentration of CHO precursor, and therefore higher porosity.Therefore, use advantageously, in porogen precursor, select to have the porogen precursor of ketone group or other functional group, so that improve one or more performance of porous organic silicate film with pure organic composition for some.
Table 4. is for the film in the Comparative Examples 2, the performance of its final porous membrane.
| Film | Specific refractory power | Specific inductivity | UV cure shrinkage (%) | Young's modulus (GPa) | Hardness (GPa) | FT-IR C-Hx area |
| TMC-1 CHC-1 | 1.410 1.370 | 2.61 2.77 | 7 6 | 4.8 10.8 | 0.6 1.5 | 0.6 0.9 |
Embodiment 3
By molar percentage is the mixture deposition laminated film of 22/78 pimelinketone (CHO) and diethoxymethyl silicomethane (DEMS).Mode of deposition is as follows: plasma power is 600 watts, and chamber pressure is 8 holders, and spread of electrodes is 350 mils, and carrier gas is CO
2, its flow velocity is 200sccm, additional gas is O
2, its flow velocity is 10sccm, sedimentation rate be 450 nanometers (nm)/minute, and base material temperature is 250 ℃.The flow velocity that changes CHO and DEMS is introduced the CHO of reaction chamber and the ratio of DEMS with control, and the overall flow rate that keeps entering the chemical substance in the reaction chamber simultaneously is constant.By being exposed to (following 5 minutes of the λ=200-400nm) and film is carried out aftertreatment, and shrinking percentage is 30% of UV light in broadband under the vacuum.Table 5 provides at the various characteristics that is exposed to deposit film and final film after the UV optical processing.
Fig. 4 has shown: before the deposition or after being exposed to broadband UV light 5 minutes after the deposition and under vacuum, and the FT-IR spectrum of DEMS/CHO film.This spectrum shows: the C-H of the film after handling with respect to deposit film, UV
xPeak area reduces about 84%.
Table 5. for utilizing the sedimentary film of DEMS/CHO (22/78), deposit film and final film performance separately
| Performance | Deposit film | Final film |
| Specific refractory power | 1.486 | 1.340 |
| Specific inductivity | n/a | 2.3 |
Embodiment 4
By molar percentage is the mixture deposition laminated film of 20/80 DMHD and diethoxymethyl silicomethane (DEMS).Mode of deposition is as follows: plasma power is 600 watts, and chamber pressure is 8 holders, and spread of electrodes is 350 mils, and carrier gas is CO
2, its flow velocity is 200sccm, additional gas is O
2, its flow velocity is 10sccm, and base material temperature is 300 ℃.The flow velocity that changes DMHD and DEMS is introduced the DMHD of reaction chamber and the ratio of DEMS with control, and the overall flow rate that keeps entering the chemical substance in the reaction chamber simultaneously is constant.By being exposed to (following 5 minutes of the λ=200-400nm) and film is carried out aftertreatment, and shrinking percentage is 30% of UV light in broadband under the vacuum.Table 6 provides at the various characteristics that is exposed to deposit film and final film after the UV optical processing.
Fig. 5 has shown: before the deposition or in when deposition and after under vacuum, being exposed to broadband UV light 5 minutes, and the FT-IR spectrum of DEMS/DMHD film.
Table 6. for utilizing the sedimentary film of DEMS/DMHD (22/78), deposit film and final film performance separately
| Performance | Deposit film | Final film |
| Specific refractory power | 1.48 | 1.35 |
| Specific inductivity | n/a | 2.47 |
| Hardness | n/a | 0.9 |
| Young's modulus | n/a | 6.2 |
Embodiment 5
Utilize following porogen precursor deposition to contain the film of DEMS: ATP, LIM, CHO, CHO
xBe provided among the table 7a-7d for every kind of depositing of thin film condition.Be exposed to UV solidify 5 minutes after the characteristic of final film be provided at and show among the 8a-8d.Fig. 6 has shown the hardness of these films and the relation between the specific inductivity.
The mode of deposition of table 7A.DEMS+ATRP
| Operation sequence number # | Power (watt) | Pressure (holder) | Spread of electrodes (mil) | Temperature (℃) | ATRP flow velocity (mg/min) | DEMS flow velocity mg/min) | Carrier gas | Carrier gas (sccm) | Additional gas | Additional gas (sccm) | Additional gas 2 | Additional gas 2 (ssm) | The ATRP/DEMS ratio |
| 1 | 450 | 8 | 300 | 225 | 800 | 200 | He | 500 | O2 | 50 | - | 0 | 4.0 |
| 2 | 450 | 8 | 300 | 225 | 800 | 200 | He | 500 | O2 | 50 | - | 0 | 4.0 |
| 3 | 450 | 8 | 300 | 225 | 720 | 180 | He | 500 | O2 | 50 | - | 0 | 4.0 |
| 4 | 450 | 8 | 300 | 225 | 800 | 200 | He | 750 | O2 | 50 | - | 0 | 4.0 |
| 5 | 450 | 8 | 300 | 225 | 800 | 200 | He | 450 | O2 | 50 | Ar | 300 | 4.0 |
| 6 | 450 | 8 | 300 | 225 | 800 | 200 | He | 750 | O2 | 50 | - | 0 | 4.0 |
| 7 | 450 | 8 | 300 | 225 | 880 | 220 | He | 500 | O2 | 50 | - | 0 | 4.0 |
| 8 | 750 | 8 | 350 | 300 | 660 | 165 | CO2 | 200 | O2 | 10 | - | 0 | 4.0 |
| 9 | 750 | 8 | 350 | 300 | 490 | 210 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 10 | 750 | 8 | 350 | 300 | 580 | 145 | CO2 | 200 | O2 | 10 | - | 0 | 4.0 |
| 11 | 600 | 6 | 350 | 300 | 580 | 145 | CO2 | 200 | O2 | 10 | - | 0 | 4.0 |
| 12 | 600 | 8 | 350 | 300 | 580 | 145 | CO2 | 200 | O2 | 10 | - | 0 | 4.0 |
| 13 | 450 | 8 | 300 | 225 | 800 | 200 | He | 450 | O2 | 50 | CO2 | 300 | 4.0 |
| 14 | 750 | 8 | 350 | 300 | 760 | 190 | CO2 | 200 | O2 | 25 | - | 0 | 4.0 |
| 15 | 750 | 8 | 350 | 300 | 760 | 190 | CO2 | 200 | O2 | 25 | - | 0 | 4.0 |
| 16 | 750 | 8 | 350 | 300 | 490 | 210 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 17 | 750 | 8 | 350 | 300 | 760 | 190 | CO2 | 200 | O2 | 10 | - | 0 | 4.0 |
| 18 | 750 | 8 | 350 | 300 | 760 | 190 | CO2 | 200 | O2 | 10 | - | 0 | 4.0 |
| 19 | 600 | 6 | 350 | 300 | 490 | 210 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 20 | 600 | 8 | 350 | 300 | 420 | 105 | CO2 | 220 | O2 | 25 | - | 0 | 4.0 |
| 21 | 750 | 10 | 350 | 300 | 490 | 210 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 22 | 600 | 8 | 550 | 300 | 580 | 145 | CO2 | 600 | O2 | 10 | - | 0 | 4.0 |
| 23 | 600 | 8 | 550 | 300 | 580 | 145 | CO2 | 600 | O2 | 10 | - | 0 | 4.0 |
| 24 | 750 | 8 | 350 | 330 | 420 | 105 | CO2 | 200 | O2 | 50 | - | 0 | 4.0 |
| 25 | 750 | 8 | 350 | 330 | 420 | 105 | CO2 | 200 | O2 | 50 | - | 0 | 4.0 |
| 26 | 750 | 8 | 350 | 350 | 420 | 105 | CO2 | 200 | O2 | 25 | - | 0 | 4.0 |
| 27 | 750 | 8 | 350 | 300 | 560 | 240 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 28 | 750 | 8 | 350 | 330 | 380 | 90 | CO2 | 200 | O2 | 50 | - | 0 | 4.0 |
| 29 | 600 | 8 | 350 | 300 | 490 | 210 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 30 | 600 | 8 | 550 | 300 | 580 | 145 | CO2 | 400 | O2 | 10 | - | 0 | 4.0 |
The mode of deposition (continuing) of table 7A.DEMS+ATRP
| Operation sequence number # | Power (watt) | Pressure (holder) | Spread of electrodes (mil) | Temperature (℃) | ATRP flow velocity (mg/min) | DEMS flow velocity (mg/min) | Carrier gas | Carrier gas (sccm) | Additional gas | Additional gas (sccm) | Additional gas 2 | Additional gas 2 (ssm) | The ATRP/DEMS ratio |
| 31 | 600 | 8 | 450 | 300 | 580 | 145 | CO2 | 200 | O2 | 10 | - | 0 | 4.0 |
| 32 | 750 | 8 | 400 | 300 | 490 | 210 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 33 | 600 | 6 | 350 | 300 | 490 | 210 | CO2 | 200 | - | 0 | - | 0 | 2.3 |
| 34 | 600 | 10 | 350 | 300 | 580 | 145 | CO2 | 200 | O2 | 10 | - | 0 | 4.0 |
| 35 | 750 | 8 | 350 | 350 | 420 | 105 | CO2 | 200 | O2 | 50 | - | 0 | 4.0 |
| 36 | 750 | 8 | 350 | 350 | 420 | 105 | CO2 | 200 | O2 | 50 | - | 0 | 4.0 |
| 37 | 750 | 8 | 350 | 330 | 420 | 105 | CO2 | 200 | O2 | 75 | - | 0 | 4.0 |
| 38 | 600 | 8 | 350 | 330 | 420 | 105 | CO2 | 220 | O2 | 25 | - | 0 | 4.0 |
| 39 | 750 | 8 | 350 | 350 | 360 | 90 | CO2 | 200 | O2 | 50 | - | 0 | 4.0 |
| 40 | 450 | 6 | 350 | 300 | 490 | 210 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 41 | 750 | 8 | 350 | 330 | 480 | 120 | CO2 | 200 | O2 | 50 | - | 0 | 4.0 |
| 42 | 450 | 6 | 350 | 300 | 490 | 210 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 43 | 750 | 8 | 350 | 300 | 490 | 210 | CO2 | 200 | O2 | 35 | - | 0 | 2.3 |
| 44 | 750 | 10 | 350 | 325 | 490 | 210 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 45 | 750 | 8 | 350 | 300 | 420 | 180 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 46 | 750 | 8 | 300 | 300 | 490 | 210 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 47 | 600 | 8 | 550 | 300 | 580 | 145 | CO2 | 200 | O2 | 10 | - | 0 | 4.0 |
| 48 | 750 | 8 | 350 | 350 | 480 | 120 | CO2 | 200 | O2 | 50 | - | 0 | 4.0 |
The mode of deposition of table 7B.DEMS+LIMO
| Operation sequence number # | Power (watt) | Pressure (holder) | Spread of electrodes (mil) | Temperature (℃) | LIMO flow velocity (mg/min) | DEMS flow velocity (mg/min) | Carrier gas | Carrier gas (sccm) | Additional gas | Additional gas (sccm) | Additional gas 2 | Additional gas 2 (ssm) | The LIMO/DEMS ratio |
| 1 | 750 | 8 | 350 | 300 | 850 | 150 | CO2 | 200 | O2 | 25 | - | 0 | 5.7 |
| 2 | 750 | 8 | 350 | 300 | 723 | 127.5 | CO2 | 200 | O2 | 25 | - | 0 | 5.7 |
| 3 | 600 | 8 | 400 | 250 | 568 | 142 | CO2 | 250 | - | 0 | - | 0 | 4.0 |
| 4 | 750 | 8 | 350 | 300 | 808 | 142.5 | CO2 | 200 | O2 | 25 | - | 0 | 5.7 |
| 5 | 750 | 8 | 350 | 300 | 680 | 120 | CO2 | 200 | O2 | 25 | - | 0 | 5.7 |
| 6 | 600 | 8 | 400 | 200 | 500 | 200 | CO2 | 300 | - | 0 | - | 0 | 2.5 |
| 7 | 750 | 8 | 350 | 300 | 659 | 116.25 | CO2 | 200 | O2 | 25 | - | 0 | 5.7 |
| 8 | 750 | 8 | 350 | 300 | 560 | 240 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 9 | 600 | 8 | 350 | 250 | 450 | 150 | CO2 | 200 | O2 | 10 | - | 0 | 3.0 |
| 10 | 600 | 8 | 350 | 250 | 450 | 150 | CO2 | 200 | O2 | 10 | - | 0 | 3.0 |
| 11 | 600 | 8 | 400 | 250 | 456 | 114 | CO2 | 250 | - | 0 | - | 0 | 4.0 |
| 12 | 750 | 8 | 350 | 300 | 765 | 135 | CO2 | 200 | O2 | 25 | - | 0 | 5.7 |
| 13 | 450 | 8 | 300 | 225 | 720 | 180 | He | 750 | O2 | 50 | - | 0 | 4.0 |
| 14 | 750 | 8 | 350 | 300 | 638 | 112.5 | CO2 | 200 | O2 | 25 | - | 0 | 5.7 |
| 15 | 750 | 8 | 350 | 300 | 350 | 150 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 16 | 750 | 8 | 350 | 300 | 490 | 210 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 17 | 700 | 8 | 350 | 300 | 210 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 1.0 |
| 18 | 600 | 8 | 350 | 300 | 210 | 195 | CO2 | 200 | O2 | 10 | - | 0 | 1.1 |
| 19 | 750 | 8 | 350 | 300 | 333 | 142.5 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 20 | 600 | 8 | 400 | 250 | 680 | 170 | CO2 | 250 | - | 0 | - | 0 | 4.0 |
| 21 | 500 | 6 | 350 | 300 | 210 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 1.0 |
| 22 | 600 | 8 | 350 | 300 | 450 | 150 | CO2 | 200 | O2 | 10 | - | 0 | 3.0 |
| 23 | 600 | 8 | 350 | 300 | 450 | 150 | CO2 | 200 | O2 | 10 | - | 0 | 3.0 |
| 24 | 750 | 8 | 350 | 300 | 595 | 105 | CO2 | 200 | O2 | 25 | - | 0 | 5.7 |
| 25 | 450 | 8 | 300 | 225 | 800 | 200 | He | 450 | O2 | 50 | Ar | 300 | 4.0 |
| 26 | 450 | 8 | 300 | 225 | 800 | 200 | He | 750 | O2 | 50 | - | 0 | 4.0 |
| 27 | 450 | 8 | 300 | 225 | 800 | 200 | He | 750 | O2 | 50 | - | 0 | 4.0 |
| 28 | 750 | 8 | 350 | 300 | 507.5 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 29 | 750 | 8 | 350 | 300 | 368 | 157.5 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 30 | 750 | 8 | 350 | 300 | 385 | 165 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
The mode of deposition (continuing) of table 7B.DEMS+LIMO
| Operation sequence number # | Power (watt) | Pressure (holder) | Spread of electrodes (mil) | Temperature (℃) | LIMO flow velocity (mg/min) | DEMS flow velocity (mg/min) | Carrier gas | Carrier gas (sccm) | Additional gas | Additional gas (sccm) | Additional gas 2 | Additional gas 2 (ssm) | The LIMO/DEMS ratio |
| 31 | 750 | 8 | 350 | 300 | 553 | 97.5 | CO2 | 200 | O2 | 25 | - | 0 | 5.7 |
| 32 | 600 | 8 | 350 | 300 | 210 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 1.0 |
| 33 | 500 | 6 | 350 | 300 | 210 | 195 | CO2 | 200 | O2 | 10 | - | 0 | 1.1 |
| 34 | 700 | 10 | 350 | 300 | 210 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 1.0 |
| 35 | 750 | 8 | 350 | 300 | 315 | 135 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 36 | 750 | 8 | 350 | 300 | 315 | 135 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 37 | 450 | 8 | 300 | 225 | 800 | 200 | He | 450 | O2 | 50 | CO2 | 300 | 4.0 |
| 38 | 750 | 8 | 350 | 300 | 490 | 210 | CO2 | 200 | - | 0 | - | 0 | 2.3 |
| 39 | 600 | 6 | 350 | 300 | 210 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 1.0 |
| 40 | 700 | 8 | 350 | 300 | 630 | 270 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 41 | 450 | 8 | 300 | 225 | 880 | 220 | He | 750 | O2 | 50 | - | 0 | 4.0 |
| 42 | 750 | 8 | 350 | 300 | 420 | 180 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 43 | 750 | 8 | 350 | 300 | 420 | 180 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 44 | 600 | 8 | 350 | 300 | 630 | 270 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 45 | 750 | 8 | 350 | 300 | 510 | 90 | CO2 | 200 | O2 | 25 | - | 0 | 5.7 |
| 46 | 600 | 8 | 350 | 300 | 507.5 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 47 | 450 | 6 | 300 | 300 | 507.5 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 48 | 500 | 6 | 350 | 300 | 210 | 232.5 | CO2 | 200 | O2 | 10 | - | 0 | 0.9 |
| 49 | 700 | 8 | 350 | 300 | 630 | 270 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 50 | 750 | 8 | 350 | 325 | 490 | 210 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 51 | 750 | 8 | 350 | 300 | 455 | 195 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 52 | 750 | 8 | 350 | 325 | 490 | 210 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 53 | 750 | 8 | 350 | 325 | 560 | 240 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 54 | 600 | 8 | 350 | 300 | 507.5 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 55 | 750 | 8 | 350 | 325 | 560 | 240 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 56 | 750 | 8 | 350 | 325 | 630 | 270 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 57 | 750 | 8 | 350 | 300 | 280 | 120 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 58 | 650 | 8 | 350 | 300 | 630 | 270 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 59 | 600 | 8 | 350 | 300 | 507.5 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 60 | 750 | 8 | 350 | 300 | 630 | 270 | CO2 | 200 | - | 0 | - | 0 | 2.3 |
The mode of deposition (continuing) of table 7B.DEMS+LIMO
| Operation sequence number # | Power (watt) | Pressure (holder) | Spread of electrodes (mil) | Temperature (℃) | LIMO flow velocity (mg/min) | DEMS flow velocity (mg/min) | Carrier gas | Carrier gas (sccm) | Additional gas | Additional gas (sccm) | Additional gas 2 | Additional gas 2 (ssm) | The LIMO/DEMS ratio |
| 61 | 600 | 8 | 350 | 300 | 210 | 232.5 | CO2 | 200 | O2 | 10 | - | 0 | 0.9 |
| 62 | 650 | 8 | 350 | 300 | 630 | 270 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 63 | 500 | 7 | 300 | 325 | 507.5 | 217.5 | CO2 | 140 | O2 | 15 | - | 0 | 2.3 |
| 64 | 600 | 8 | 325 | 320 | 507.5 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 65 | 750 | 8 | 350 | 325 | 700 | 300 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 66 | 750 | 8 | 450 | 325 | 577.5 | 247.5 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 67 | 450 | 6 | 300 | 320 | 620 | 155 | CO2 | 200 | O2 | 10 | - | 0 | 4.0 |
| 68 | 750 | 8 | 350 | 300 | 420 | 180 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 69 | 750 | 8 | 350 | 300 | 420 | 180 | CO2 | 200 | - | 0 | - | 0 | 2.3 |
| 70 | 600 | 8 | 350 | 300 | 630 | 270 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 71 | 750 | 8 | 350 | 325 | 630 | 270 | CO2 | 200 | O2 | 25 | - | 0 | 2.3 |
| 72 | 600 | 8 | 400 | 300 | 507.5 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 73 | 450 | 6 | 325 | 320 | 507.5 | 217.5 | CO2 | 200 | O2 | 10 | - | 0 | 2.3 |
| 74 | 750 | 8 | 450 | 320 | 620 | 155 | CO2 | 200 | O2 | 25 | - | 0 | 4.0 |
The mode of deposition of table 7C.DEMS+CHO
| Operation sequence number # | Power (watt) | Pressure (holder) | Spread of electrodes (mil) | Temperature (℃) | CHO flow velocity (mg/min) | DEMS flow velocity (mg/min) | Carrier gas | Carrier gas (sccm) | Additional gas | Additional gas (sccm) | Additional gas 2 | Additional gas 2 (ssm) | CHO/DEMS is additional |
| 1 | 600 | 8 | 350 | 250 | 45O | 150 | CO2 | 200 | O2 | 10 | - | 0 | 3.0 |
| 2 | 600 | 8 | 350 | 250 | 450 | 150 | CO2 | 200 | O2 | 10 | - | 0 | 3.0 |
| 3 | 350 | 8 | 350 | 225 | 450 | 150 | He | 190 | O2 | 20 | - | 0 | 3.0 |
| 4 | 600 | 8 | 350 | 225 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
| 5 | 600 | 8 | 350 | 225 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
| 6 | 450 | 8 | 350 | 225 | 450 | 150 | He | 200 | O2 | 10 | - | 0 | 3.0 |
| 7 | 450 | 8 | 350 | 225 | 450 | 150 | He | 200 | O2 | 10 | - | 0 | 3.0 |
| 8 | 450 | 10 | 350 | 225 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
| 9 | 450 | 8 | 350 | 225 | 450 | 150 | He | 210 | - | 0 | Ar | 200 | 3.0 |
| 10 | 770 | 8 | 350 | 225 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
| 11 | 450 | 8 | 350 | 225 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
| 12 | 450 | 8 | 350 | 225 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
| 13 | 600 | 8 | 350 | 225 | 450 | 150 | He | 420 | - | 0 | - | 0 | 3.0 |
| 14 | 450 | 8 | 350 | 225 | 575 | 200 | He | 210 | - | 0 | - | 0 | 2.9 |
| 15 | 450 | 6 | 350 | 225 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
| 16 | 450 | 8 | 350 | 225 | 450 | 150 | He | 420 | - | 0 | - | 0 | 3.0 |
| 17 | 450 | 8 | 350 | 225 | 450 | 150 | He | 420 | - | 0 | - | 0 | 3.0 |
| 18 | 450 | 8 | 350 | 225 | 400 | 200 | He | 210 | 0 | - | 0 | 2.0 | |
| 19 | 450 | 8 | 350 | 225 | 700 | 250 | He | 210 | - | 0 | - | 0 | 2.8 |
| 20 | 600 | 8 | 350 | 300 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
| 21 | 600 | 8 | 350 | 300 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
The mode of deposition of table 7D.DEMS+CHOx
| Operation sequence number # | Power (watt) | Pressure (holder) | Spread of electrodes (mil) | Temperature (℃) | CHOx flow velocity (mg/min) | DEMS flow velocity (mg/min) | Carrier gas | Carrier gas (sccm) | Additional gas | Additional gas (sccm) | Additional gas 2 | Additional gas 2 (ssm) | The CHOx/ |
| 1 | 450 | 8 | 350 | 225 | 450 | 150 | He | 190 | O2 | 20 | - | 0 | 3.0 |
| 2 | 450 | 8 | 350 | 225 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
| 3 | 450 | 8 | 350 | 225 | 400 | 130 | He | 210 | - | 0 | - | 0 | 3.1 |
| 4 | 450 | 10 | 350 | 225 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
| 5 | 450 | 6 | 350 | 225 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
| 6 | 450 | 8 | 350 | 225 | 500 | 170 | He | 210 | - | 0 | - | 0 | 2.9 |
| 7 | 450 | 8 | 350 | 225 | 450 | 150 | He | 420 | - | 0 | - | 0 | 3.0 |
| 8 | 450 | 8 | 350 | 225 | 350 | 250 | He | 210 | - | 0 | - | 0 | 1.4 |
| 9 | 600 | 8 | 350 | 300 | 450 | 150 | He | 210 | - | 0 | - | 0 | 3.0 |
The film performance of table 8A.DEMS+ATRP
| Operation sequence number # | RI (deposit film) | RI (UV handles the back) | The change of RI | D (nm, deposit film) | D (nm, VU handle the back) | The % shrinking percentage | K (UV handles the back) | Mod (GPa, UV handle the back) | H (GPa, UV handle the back) |
| 1 | 1.505 | 1.308 | -0.197 | 1046 | 699 | 33 | 2.04 | 1.71 | 0.09 |
| 2 | 1.511 | 1.308 | -0.203 | 1046 | 699 | 33 | 2.04 | 1.71 | 0.18 |
| 3 | 1.516 | 1.347 | -0.169 | 756 | 480 | 37 | 2.14 | 2.99 | 0.32 |
| 4 | 1.516 | 1.364 | -0.152 | 667 | 422 | 37 | 2.15 | 3.70 | 0.42 |
| 5 | 1.514 | 1.343 | -0.171 | 703 | 448 | 36 | 2.15 | 3.54 | 0.41 |
| 6 | 1.517 | 1.364 | -0.153 | 667 | 422 | 37 | 2.15 | 3.70 | 0.21 |
| 7 | 1.504 | 1.330 | -0.174 | 651 | 459 | 29 | 2.17 | 2.47 | 0.25 |
| 8 | 1.479 | 1.351 | -0.128 | 941 | 784 | 17 | 2.18 | 4.09 | 0.50 |
| 9 | 1.477 | 1.343 | -0.134 | 1003 | 884 | 12 | 2.21 | 4.32 | 0.62 |
| 10 | 1.510 | 1.374 | -0.136 | 1157 | 955 | 17 | 2.22 | 2.51 | 0.25 |
| 11 | 1.506 | 1.363 | -0.143 | 1151 | 919 | 20 | 2.25 | 3.30 | 0.40 |
| 12 | 1.492 | 1.350 | -0.142 | 848 | 719 | 15 | 2.25 | 5.64 | 0.76 |
| 13 | 1.505 | 1.356 | -0.149 | 654 | 423 | 35 | 2.26 | 3.50 | 0.40 |
| 14 | 1.456 | 1.324 | -0.132 | 727 | 613 | 16 | 2.29 | 5.44 | 0.69 |
| 15 | 1.478 | 1.349 | -0.129 | 1187 | 1037 | 13 | 2.29 | 6.53 | 0.95 |
| 16 | 1.482 | 1.345 | -0.137 | 1723 | 1529 | 11 | 2.29 | 3.74 | 0.57 |
| 17 | 1.503 | 1.351 | -0.152 | 499 | 414 | 17 | 2.30 | ||
| 18 | 1.466 | 1.363 | -0.103 | 946 | 767 | 19 | 2.30 | 9.37 | 1.32 |
| 19 | 1.483 | 1.344 | -0.139 | 1007 | 910 | 10 | 2.30 | 3.64 | 0.48 |
| 20 | 1.479 | 1.333 | -0.146 | 797 | 732 | 8 | 2.30 | 6.13 | 0.91 |
| 21 | 1.463 | 1.345 | -0.118 | 993 | 899 | 9 | 2.34 | 4.32 | 0.61 |
| 22 | 1.494 | 1.369 | -0.125 | 608 | 515 | 15 | 2.34 | 6.89 | 0.86 |
| 23 | 1.495 | 1.338 | -0.157 | 385 | 346 | 10 | 2.34 | ||
| 24 | 1.493 | 1.347 | -0.146 | 867 | 810 | 7 | 2.39 | 4.91 | 0.65 |
| 25 | 1.493 | 1.348 | -0.145 | 868 | 821 | 5 | 2.39 | 4.91 | 0.65 |
| 26 | 1.468 | 1.352 | -0.116 | 825 | 791 | 4 | 2.42 | 4.76 | 0.62 |
| 27 | 1.469 | 1.355 | -0.114 | 1081 | 1022 | 5 | 2.43 | 4.26 | 0.61 |
| 28 | 1.509 | 1.365 | -0.144 | 1035 | 925 | 11 | 2.44 | 3.90 | 0.47 |
| 29 | 1.458 | 1.338 | -0.120 | 783 | 748 | 4 | 2.44 | 5.87 | 0.90 |
| 30 | 1.467 | 1.328 | -0.139 | 418 | 385 | 8 | 2.46 |
The film performance (continuing) of table 8A.DEMS+ATRP
| Operation sequence number # | RI (deposit film) | RI (UV handles the back) | The change of RI | D (nm, deposit film) | D (nm, UV handle the back) | The % shrinking percentage | K (UV handles the back) | Mod (GPa, UV handle the back) | H (GPa, UV handle the back) |
| 31 | 1.452 | 1.338 | -0.114 | 463 | 435 | 6 | 2.46 | ||
| 32 | 1.476 | 1.364 | -0.112 | 1041 | 987 | 5 | 2.47 | 4.28 | 0.54 |
| 33 | 1.479 | 1.362 | -0.117 | 487 | 402 | 17 | 2.48 | 6.90 | 0.95 |
| 34 | 1.444 | 1.341 | -0.103 | 557 | 503 | 10 | 2.50 | 10.30 | 1.51 |
| 35 | 1.492 | 1.378 | -0.114 | 899 | 842 | 6 | 2.50 | 6.10 | 0.84 |
| 36 | 1.492 | 1.378 | -0.114 | 824 | 786 | 5 | 2.50 | 6.10 | 0.84 |
| 37 | 1.488 | 1.367 | -0.121 | 947 | 888 | 6 | 2.50 | 4.90 | 0.58 |
| 38 | 1.467 | 1.369 | -0.098 | 899 | 858 | 5 | 2.51 | 7.55 | 1.15 |
| 39 | 1.494 | 1.400 | -0.094 | 1048 | 954 | 9 | 2.53 | 4.16 | 0.48 |
| 40 | 1.450 | 1.357 | -0.093 | 1013 | 993 | 2 | 2.54 | 5.85 | 0.85 |
| 41 | 1.467 | 1.371 | -0.096 | 755 | 694 | 8 | 2.55 | 9.25 | 1.34 |
| 42 | 1.447 | 1.339 | -0.108 | 696 | 676 | 3 | 2.56 | 7.43 | 1.12 |
| 43 | 1.485 | 1.392 | -0.093 | 1214 | 1174 | 3 | 2.56 | 4.08 | 0.47 |
| 44 | 1.434 | 1.346 | -0.088 | 743 | 734 | 1 | 2.56 | 7.19 | 1.11 |
| 45 | 1.502 | 1.381 | -0.121 | 1313 | 1223 | 7 | 2.57 | 3.46 | 0.36 |
| 46 | 1.490 | 1.390 | -0.100 | 1300 | 1245 | 4 | 2.58 | 3.64 | 0.40 |
| 47 | 1.423 | 1.366 | -0.057 | 359 | 330 | 8 | 2.60 | ||
| 48 | 1.467 | 1.366 | -0.101 | 706 | 683 | 3 | 2.60 | 7.38 | 1.04 |
The film performance of table 8B.DEMS+LIMO
| Operation sequence number # | RI (deposit film) | RI (UV handles the back) | The change of RI | D (nm, deposit film) | D (nm, UV handle the back) | The % shrinking percentage | K (UV handles the back) | Mod (GPa, UV handle the back) | H (GPa, UV handle the back) |
| 1 | 1.504 | 1.318 | -0.186 | 898 | 741 | 17 | 2.12 | 3.26 | 0.41 |
| 2 | 1.511 | 1.335 | -0.176 | 902 | 712 | 21 | 2.12 | 1.98 | 0.14 |
| 3 | 1.517 | 1.338 | -0.179 | 465 | 346 | 26 | 2.13 | 6.40 | 0.74 |
| 4 | 1.510 | 1.332 | -0.178 | 859 | 724 | 16 | 2.14 | 2.58 | 0.28 |
| 5 | 1.516 | 1.361 | -0.155 | 916 | 712 | 22 | 2.15 | 2.50 | 0.25 |
| 6 | 1.471 | 1.318 | -0.153 | 494 | 408 | 17 | 2.19 | 2.75 | 0.28 |
| 7 | 1.512 | 1.362 | -0.150 | 949 | 726 | 23 | 2.20 | 2.49 | 0.24 |
| 8 | 1.514 | 1.371 | -0.143 | 817 | 597 | 27 | 2.22 | 2.62 | 0.24 |
| 9 | 1.506 | 1.337 | -0.169 | 1305 | 869 | 33 | 2.23 | ||
| 10 | 1.500 | 1.317 | -0.183 | 1445 | 1000 | 31 | 2.23 | 2.60 | 0.32 |
| 11 | 1.524 | 1.386 | -0.138 | 560 | 315 | 44 | 2.26 | 4.10 | 0.43 |
| 12 | 1.516 | 1.351 | -0.165 | 885 | 750 | 15 | 2.26 | 2.48 | 0.22 |
| 13 | 1.480 | 1.309 | -0.171 | 1703 | 1289 | 25 | 2.29 | 3.61 | 0.55 |
| 14 | 1.511 | 1.410 | -0.101 | 1011 | 769 | 24 | 2.29 | 2.63 | 0.28 |
| 15 | 1.484 | 1.355 | -0.129 | 1396 | 1251 | 10 | 2.31 | 3.15 | 0.55 |
| 16 | 1.523 | 1.388 | -0.135 | 963 | 610 | 37 | 2.32 | 2.72 | 0.25 |
| 17 | 1.485 | 1.366 | -0.119 | 1112 | 917 | 18 | 2.33 | 4.35 | 0.61 |
| 18 | 1.478 | 1.332 | -0.146 | 811 | 669 | 18 | 2.33 | 4.44 | 0.58 |
| 19 | 1.494 | 1.363 | -0.131 | 1454 | 1300 | 11 | 2.33 | 3.30 | 0.44 |
| 20 | 1.502 | 1.298 | -0.204 | 420 | 349 | 17 | 2.34 | 7.70 | 0.92 |
| 21 | 1.479 | 1.378 | -0.101 | 1044 | 855 | 18 | 2.34 | 2.34 | 0.91 |
| 22 | 1.500 | 1.353 | -0.147 | 986 | 821 | 17 | 2.34 | ||
| 23 | 1.503 | 1.330 | -0.173 | 1316 | 1131 | 14 | 2.34 | 3.20 | 0.44 |
| 24 | 1.527 | 1.410 | -0.117 | 1080 | 774 | 28 | 2.35 | 2.66 | 0.20 |
| 25 | 1.467 | 1.302 | -0.165 | 1117 | 848 | 24 | 2.36 | 5.30 | 0.83 |
| 26 | 1.471 | 1.315 | -0.156 | 966 | 741 | 23 | 2.36 | 4.40 | 0.69 |
| 27 | 1.471 | 1.315 | -0.156 | 966 | 741 | 23 | 2.36 | 3.40 | 0.51 |
| 28 | 1.362 | 1.362 | 1500 | 1235 | 18 | 2.36 | 5.09 | 0.75 | |
| 29 | 1.478 | 1.356 | -0.122 | 1297 | 1181 | 9 | 2.37 | 3.94 | 0.57 |
| 30 | 1.475 | 1.343 | -0.132 | 1301 | 1179 | 9 | 2.37 | 4.45 | 0.66 |
The film performance (continuing) of table 8B.DEMS+LIMO
| Operation sequence number # | RI (deposit film) | RI (UV handles the back) | The change of RI | D (nm, deposit film) | D (nm, UV handle the back) | The % shrinking percentage | K (UV handles the back) | Mod (GPa, UV handle the back) | H (GPa, UV handle the back) |
| 31 | 1.541 | 1.422 | -0.119 | 1171 | 764 | 35 | 2.38 | 3.00 | 0.28 |
| 32 | 1.469 | 1.334 | -0.135 | 962 | 849 | 12 | 2.38 | 4.71 | 0.68 |
| 33 | 1.483 | 1.355 | -0.128 | 824 | 662 | 20 | 2.38 | 5.70 | 0.78 |
| 34 | 1.485 | 1.335 | -0.130 | 1014 | 900 | 11 | 2.39 | 4.48 | 0.65 |
| 35 | 1.490 | 1.358 | -0.132 | 1569 | 1379 | 12 | 2.40 | 3.38 | 0.44 |
| 36 | 1.501 | 1.351 | -0.150 | 1479 | 1318 | 11 | 2.40 | 3.38 | 0.44 |
| 37 | 1.464 | 1.299 | -0.165 | 1076 | 856 | 20 | 2.40 | 4.50 | 0.72 |
| 38 | 1.514 | 1.414 | -0.100 | 665 | 478 | 28 | 2.40 | 3.65 | 0.34 |
| 39 | 1.497 | 1.410 | -0.087 | 1164 | 951 | 18 | 2.41 | 4.34 | 0.59 |
| 40 | 1.450 | 1.341 | -0.109 | 1194 | 1104 | 8 | 2.42 | 4.13 | 0.56 |
| 41 | 1.465 | 1.321 | -0.144 | 976 | 796 | 18 | 2.43 | 4.00 | 0.61 |
| 42 | 1.461 | 1.338 | -0.123 | 1223 | 1149 | 6 | 2.43 | 4.45 | 0.65 |
| 43 | 1.475 | 1.342 | -0.133 | 1172 | 1085 | 7 | 2.43 | 4.45 | 0.65 |
| 44 | 1.445 | 1.323 | -0.122 | 1018 | 937 | 8 | 2.44 | 5.32 | 0.87 |
| 45 | 1.543 | 1.449 | -0.094 | 1287 | 779 | 39 | 2.44 | 3.74 | 0.41 |
| 46 | 1.351 | 1.351 | 851 | 733 | 14 | 2.45 | 7.42 | 1.11 | |
| 47 | 1.351 | 1.351 | 640 | 524 | 18 | 2.45 | 9.01 | 1.22 | |
| 48 | 1.479 | 1.337 | -0.142 | 878 | 714 | 19 | 2.45 | 7.98 | 1.16 |
| 49 | 1.454 | 1.341 | -0.113 | 920 | 839 | 9 | 2.45 | 5.55 | 0.87 |
| 50 | 1.482 | 1.356 | -0.126 | 1479 | 1371 | 7 | 2.46 | 3.70 | 0.54 |
| 51 | 1.464 | 1.349 | -0.115 | 1188 | 1113 | 6 | 2.46 | 5.64 | 0.88 |
| 52 | 1.490 | 1.355 | -0.135 | 1253 | 1149 | 8 | 2.46 | 3.80 | 0.55 |
| 53 | 1.464 | 1.349 | -0.115 | 1043 | 996 | 5 | 2.49 | 5.26 | 0.83 |
| 54 | 1.348 | 1.348 | 1117 | 976 | 13 | 2.49 | 7.05 | 1.13 | |
| 55 | 1.460 | 1.345 | -0.115 | 1303 | 1227 | 6 | 2.50 | 4.87 | 0.74 |
| 56 | 1.448 | 1.360 | -0.088 | 955 | 896 | 6 | 2.52 | 6.74 | 1.07 |
| 57 | 1.509 | 1.389 | -0.120 | 1689 | 1468 | 13 | 2.52 | 3.13 | 0.36 |
| 58 | 1.443 | 1.330 | -0.113 | 1058 | 1009 | 5 | 2.52 | 4.94 | 0.74 |
| 59 | 1.396 | 1.396 | 1031 | 862 | 16 | 2.52 | 9.65 | 1.41 | |
| 60 | 1.495 | 1.407 | -0.088 | 596 | 476 | 20 | 2.53 | 3.95 | 0.40 |
The film performance (continuing) of table 8B.DEMS+LIMO
| Operation sequence number # | RI (deposit film) | RI (UV handles the back) | The change of RI | D (nm, deposit film) | D (nm, UV handle the back) | The % shrinking percentage | K (UV handles the back) | Mod (GPa, UV handle the back) | H (GPa, UV handle the back) |
| 61 | 1.459 | 1.306 | -0.153 | 830 | 690 | 17 | 2.53 | 8.69 | 1.28 |
| 62 | 1.435 | 1.331 | -0.104 | 741 | 702 | 5 | 2.54 | 6.88 | 1.11 |
| 63 | 1.355 | 1.355 | 852 | 727 | 15 | 2.55 | 12.50 | 1.10 | |
| 64 | 1.366 | 1.366 | 1055 | 901 | 15 | 2.55 | 10.45 | 1.61 | |
| 65 | 1.445 | 1.362 | -0.083 | 1143 | 1085 | 5 | 2.55 | 7.31 | 1.19 |
| 66 | 1.375 | 1.375 | 1075 | 983 | 9 | 2.56 | 12.46 | 1.61 | |
| 67 | 1.355 | 1.355 | 773 | 677 | 12 | 2.56 | 10.99 | 1.65 | |
| 68 | 1.535 | 1.488 | 0.047 | 1114 | 660 | 41 | 2.58 | 3.32 | 0.25 |
| 69 | 1.540 | 1.461 | -0.079 | 807 | 536 | 34 | 2.58 | 3.84 | |
| 70 | 1.438 | 1.343 | -0.095 | 654 | 629 | 4 | 2.59 | 7.16 | 1.13 |
| 71 | 1.454 | 1.348 | -0.106 | 1200 | 1138 | 5 | 2.59 | 6.13 | 0.98 |
| 72 | 1.336 | 1.336 | 864 | 785 | 9 | 2.59 | 8.61 | 1.35 | |
| 73 | 1.374 | 1.374 | 734 | 641 | 13 | 2.60 | 11.53 | 1.71 | |
| 74 | 1.367 | 1.367 | 966 | 892 | 8 | 2.60 | 8.94 | 1.42 |
The film performance of table 8C.DEMS+CHO
| Operation sequence number # | RI (deposit film) | RI (UV handles the back) | The change of RI | D (nm deposits very thin) | D (nm, UV handle the back) | The % shrinking percentage | K (UV handles the back) | Mod (GPa, UV handle the back) | H (GPa, UV handle the back) |
| 1 | 1.485 | 1.339 | -0.146 | 1538 | 1237 | 20 | 2.30 | ||
| 2 | 1.487 | 1.340 | -0.147 | 1568 | 1264 | 19 | 2.30 | ||
| 3 | 1.456 | 1.322 | -0.134 | 1008 | 764 | 24 | 2.30 | 3.52 | 0.36 |
| 4 | 1.502 | 1.350 | -0.152 | 1018 | 760 | 25 | 2.36 | 5.48 | 0.83 |
| 5 | 1.504 | 1.388 | -0.116 | 1364 | 1018 | 25 | 2.36 | 5.48 | 0.83 |
| 6 | 1.472 | 1.342 | -0.130 | 947 | 689 | 27 | 2.37 | 6.34 | 0.95 |
| 7 | 1.476 | 1.355 | -0.121 | 1233 | 890 | 28 | 2.37 | 6.34 | 0.95 |
| 8 | 1.464 | 1.320 | -0.144 | 807 | 625 | 23 | 2.40 | 5.69 | 0.92 |
| 9 | 1.489 | 1.352 | -0.137 | 814 | 641 | 21 | 2.44 | 5.79 | 0.81 |
| 10 | 1.533 | 1.385 | -0.148 | 1158 | 923 | 20 | 2.47 | 4.22 | 0.60 |
| 11 | 1.478 | 1.347 | -0.131 | 676 | 486 | 28 | 2.49 | 9.01 | 1.33 |
| 12 | 1.475 | 1.360 | -0.115 | 914 | 654 | 28 | 2.49 | 9.01 | 1.33 |
| 13 | 1.494 | 1.375 | -0.119 | 829 | 672 | 19 | 2.51 | 6.26 | 0.94 |
| 14 | 1.457 | 1.328 | -0.129 | 825 | 659 | 20 | 2.52 | 7.83 | 1.24 |
| 15 | 1.474 | 1.368 | -0.106 | 548 | 431 | 21 | 2.52 | 7.12 | 1.02 |
| 16 | 1.465 | 1.346 | -0.119 | 535 | 420 | 21 | 2.56 | 8.50 | 1.26 |
| 17 | 1.477 | 1.387 | -0.090 | 801 | 607 | 24 | 2.56 | 8.50 | 1.26 |
| 18 | 1.459 | 1.350 | -0.109 | 682 | 563 | 17 | 2.56 | 8.30 | 1.27 |
| 19 | 1.447 | 1.348 | -0.099 | 918 | 755 | 18 | 2.60 | 8.13 | 1.34 |
| 20 | 1.514 | 1.396 | -0.118 | 1131 | 1061 | 6 | 2.60 | 4.91 | 0.64 |
| 21 | 1.507 | 1.436 | -0.071 | 1291 | 1155 | 11 | 2.60 | 4.91 | 0.64 |
The film performance of table 8D.DEMS+CHOx
| Operation sequence number # | RI (deposit film) | RI (UV handles the back) | The change of RI | D (nm, deposit film) | D (nm, UV handle the back) | The % shrinking percentage | K (UV handles the back) | Mod (GPa, UV handle the back) | H (GPa, UV handle the back) |
| 1 | 1.481 | 1.334 | -0.147 | 1548 | 1048 | 32 | 2.21 | 3.60 | 0.48 |
| 2 | 1.499 | 1.327 | -0.172 | 1086 | 690 | 36 | 2.29 | 4.20 | 0.61 |
| 3 | 1.505 | 1.338 | -0.167 | 1033 | 649 | 37 | 2.29 | 2.60 | 0.24 |
| 4 | 1.493 | 1.325 | -0.168 | 1236 | 756 | 39 | 2.31 | 3.70 | 0.54 |
| 5 | 1.495 | 1.366 | -0.129 | 881 | 612 | 31 | 2.31 | 5.10 | 0.71 |
| 6 | 1.490 | 1.336 | -0.154 | 1438 | 958 | 33 | 2.35 | 3.20 | 0.39 |
| 7 | 1.497 | 1.331 | -0.166 | 891 | 624 | 30 | 2.40 | 5.20 | 0.77 |
| 8 | 1.471 | 1.357 | -0.114 | 1234 | 935 | 24 | 2.48 | 6.10 | 0.97 |
| 9 | 1.522 | 1.404 | -0.118 | 1411 | 1253 | 11 | 2.50 | 3.90 | 0.55 |
Claims (55)
- One kind have hole and specific inductivity be 2.7 or littler base material on form the chemical gaseous phase depositing process of organic silicate glass porous membrane, described method comprises: the precursor mixture that comprises at least a organosilane and/or organo-siloxane precursor and be selected from following porogen precursor is reacted:A) comprising one or more alcohol radical and general formula is C nH 2n+2-2x-2y-z(OH) zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of alcohol radical in the compound and between 1 and 4, and the alcohol functional group outer and/or intra-annular of ring wherein;B) comprising one or more ether and general formula is C nH 2n+2-2x-2yO zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of ehter bond in the structure and between 1 and 4, and the ehter bond outer and/or intra-annular of ring wherein;C) comprising one or more epoxide group and general formula is C nH 2n+2-2x-2y-2zO zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of epoxide group in the structure and between 1 and 4, and wherein epoxide group can be connected to that ring is gone up or straight chain on;D) comprising one or more aldehyde radical and general formula is C nH 2n+2-2x-2y-2zO zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of aldehyde radical in the structure and between 1 and 4;E) comprising one or more ketone group and general formula is C nH 2n+2-2x-2y-2zO zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of aldehyde radical in the structure and between 1 and 4, and the ketone group outer and/or intra-annular of ring wherein;F) comprising one or more carboxylic acid group and general formula is C nH 2n+2-2x-2y-3z(OOH) zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of carboxylic acid group in the structure and between 1 and 4;(g) comprise the dehydrated hydrocarbon structure with formation cyclic acid anhydride group of even number carboxylic acid group and acid functional group, wherein, the general formula of described structure is C nH 2n+2-2x-2y-6z(O 3) z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of anhydride group in the structure and is 1 or 2;(h) comprising ester group and general formula is C nH 2n+2-2x-2y-2z(O 2) zHydrocarbon structure, n=1-12 wherein, x are the quantity of encircling in the structure and between 0-4, y is the quantity of unsaturated link(age) in the structure and does not have unsaturated link(age) and the carbonyl conjugation of ester that z is the quantity of anhydride group in the structure and is 1 or 2;(i) comprising acrylate-functional groups and general formula is C nH 2n+2-2x-2y-2z(O 2) zHydrocarbon structure, described functional group is made up of the carbonyl conjugated unsaturated link(age) of ester group and at least one and ester group, n=1-12 wherein, x is the quantity encircled in the structure and between 0-4, y is the quantity of unsaturated link(age) in the structure and more than or equal to 1, the carbonyl conjugation of unsaturated link(age) and ester at least wherein, z is the quantity of ester group in the structure and is 1 or 2;(j) comprising ether and carbonyl functional group and general formula is C nH 2n+2-2w-2x-2y(O) y(O) zHydrocarbon structure, n=1-12 wherein, w is the quantity encircled in the general formula and between 0 and 4, x be unsaturated link(age) in the structure quantity and 0 and n between, y is the quantity of carbonyl in the structure, wherein carbonyl can be ketone and/or aldehyde, and z is the quantity of ether in the structure and is 1 or 2, and ether encircles outer or intra-annular;(k) comprising ether and alcohol functional group and general formula is C nH 2n+2-2w-2x-2y(OH) y(O) zHydrocarbon structure, n=1-12 wherein, w are the quantity encircled in the structure and between 0 and 4, x is the quantity of unsaturated link(age) in the structure and between 0-n, y is the quantity of alcohol radical in the structure, and z is the quantity of ether in the structure and is 1 or 2, and wherein ether encircles outer or intra-annular;(l) arbitrary combination and the general formula that comprises the functional group that is selected from alcohol, ether, carbonyl and carboxylic acid is C nH 2n+2+2u-2v-w-2y-3z(OH) w(O) x(O) y(OOH) zHydrocarbon structure, n=1-12 wherein, u is the quantity encircled in the structure and between 0 and 4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of alcohol radical in the general formula and between 0 and 4, and x is the quantity of ether in the structure and between 0 and 4 and this ether outside the ring or intra-annular, and y is the quantity of carbonyl in the structure and between 0 and 3, wherein carbonyl can be ketone and/or aldehyde, and z is the quantity of carboxylic acid group in the structure and between 0 and 2;(m) comprising one or more primary amine groups and general formula is C nH 2n+2-2x-2y-z(NH 2) zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of amido in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein;(n) comprising one or more secondary amine and general formula is C nH 2n+2-2x-2y-2z(NH) zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of secondary amine in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein;(o) comprising one or more tertiary amine groups and general formula is C nH 2n+2-2x-2y-3z(N) zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of tertiary amine groups in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein;(p) comprising one or more nitro and general formula is C nH 2n+2-2x-2y-z(NO 2) zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of nitro in the compound and between 1 and 4, and the nitro functions outer and/or intra-annular of ring wherein;(q) comprising amine and ether functional group and general formula is C nH 2n+2-2u-2v-w-2x-3y-z(NH 2) w(NH) x(N) y(OH) zHydrocarbon structure, n=1-12 wherein, u is the quantity encircled in the structure and between 0 and 4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of primary amine groups, x is the quantity of secondary amine, y is the quantity of tertiary amine groups, and 1＜w+x+y＜4, and wherein z is the quantity of alcohol radical in the compound and between 1 and 4, and alcohol radical and/or the amido outer and/or intra-annular of ring;(r) containing amine and alcohol functional group and general formula is C nH 2n+2-2u-2v-w-2x-3y-z(NH 2) w(NH) x(N) y(OH) zHydrocarbon structure, n=1-12 wherein, u is the quantity encircled in the structure and between 0 and 4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of primary amine groups, x is the quantity of secondary amine, y is the quantity of tertiary amine groups, and 1＜w+x+y＜4, z is the quantity of ether in the compound and between 1 and 4, and ether and/or the amido outer and/or intra-annular of ring;(s) and composition thereof.
- 2. the process of claim 1 wherein that specific inductivity is less than 1.9.
- 3. the process of claim 1 wherein that porous membrane comprises Si vO wC xH yF z, v+w+x+y+z=100% atom wherein, v is the 20-30% atom, and w is the 20-45% atom, and x is the 5-20% atom, and y is the 15-40% atom, and z is 0.
- 4. the process of claim 1 wherein that z is the 0.5-7% atom, at least a fluorizating agent is selected from SiF 4NF 3, F 2, CCF 2, CO 2F 2And HF, and be used for F is caused on the porous membrane, the F in all porous membranes all is bonded on the Si with the formal bond of Si-F group basically.
- 5. the process of claim 1 wherein, in the film 50% or more hydrogen bonding to carbon.
- 6. the process of claim 1 wherein that the density of porous membrane is less than 1.5 grams per milliliters.
- 7. the process of claim 1 wherein that the equivalent spherical diameter in hole is less than or equal to 3nm.
- 8. the process of claim 1 wherein, the Fourier transform infrared of porous membrane (FTIR) spectrum with use except reference FTIR in gaseous reagent without any the reference thin film of method substantially the same porogen precursor preparation basic identical.
- 9. the method for claim 8, wherein, the permittivity ratio of porous membrane use except in gaseous reagent without any the reference thin film little at least 0.3 of method preparation substantially the same the porogen precursor.
- 10. the method for claim 8, wherein, the permittivity ratio of porous membrane use except in gaseous reagent without any the reference thin film little at least 10% of method preparation substantially the same the porogen precursor.
- 11. the process of claim 1 wherein that porous membrane loses less than 1.0wt%/hr in 425 ℃ of homothermic weight in averages under nitrogen atmosphere.
- 12. the process of claim 1 wherein that porous membrane loses less than 1.0wt%/hr in 425 ℃ of homothermic weight in averages in air.
- 13. the process of claim 1 wherein that porogen precursor is different with at least a organosilane and/or organo-siloxane precursor.
- 14. the method for claim 13, wherein, at least a organosilane and/or organo-siloxane precursor are by formula SiR 1 n(OR 2) p(O (O) CR 3) 4-(n+p), wherein, R 1Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 3Be H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, and p is 0-3.
- 15. the method for claim 13, wherein, at least a organosilane and/or organo-siloxane are by formula R 1 n(OR 2) P(O (O) CR 4) 3-n-pSi-O-SiR 3 m(O (O) CR 5) q(OR 6) 3-m-qExpression, wherein, R 1And R 3Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2And R 6Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 4And R 5Be H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is 0-3, and p is 0-3, n+m 〉=1, n+p≤3 and m+q≤3.
- 16. the method for claim 13, wherein, at least a organosilane and/or organo-siloxane are by formula R 1 n(OR 2) p(O (O) CR 4) 3-n-pSi-SiR 3 m(O (O) CR 5) q(OR 6) 3 -m-qExpression, wherein, R 1And R 3Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2And R 6Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 4And R 5Be H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is 0-3, and p is 0-3, n+m 〉=1, n+p≤3 and m+q≤3.
- 17. the method for claim 13, wherein, at least a organosilane and/or organo-siloxane are by formula R 1 n(OR 2) p(O (O) CR 4) 3-n-pSi-R 7-SiR 3 m(O (O) CR 5) q(OR 6) 3-m-qExpression, wherein, R 1And R 3Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2And R 6Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 4And R 5Be H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 7Be C 2-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is 0-3, and p is 0-3, n+m 〉=1, n+p≤3 and m+q≤3.
- 18. the method for claim 13, wherein, at least a organosilane and/or organo-siloxane precursor are by formula (R 1 n(OR 2) p(O (O) CR 3) 4-(n+p)Si) tCH 4-tExpression, wherein, R 1Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 3Be H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, p is 0-3, and t is 2-4, n+p≤4.
- 19. the method for claim 13, wherein, at least a organosilane and/or organo-siloxane precursor are by formula (R 1 n(OR 2) p(O (O) CR 3) 4-(n+p)Si) tNH 3-tExpression, wherein, R 1Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 3Be H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, p is 0-3, and t is 1-3, n+p≤4.
- 20. the method for claim 13, wherein, at least a organosilane and/or organo-siloxane precursor are by formula (N (R 1) Si (R 1R 2)) xThe ring silazane represent, wherein, R 1And R 2Be H independently, C 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon, and x are the integers of 2-8.
- 21. the method for claim 13, wherein, at least a organosilane and/or organo-siloxane precursor are by formula (C (R 1R 2) Si (R 1R 2)) xRing silicon-carbon alkane represent, wherein, R 1And R 2Be H independently, C 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon, and x are the integers of 2-8, precondition is to have a Si-H key in molecule at least.
- 22. the method for claim 13, wherein, at least a organosilane and/or organo-siloxane precursor are selected from: dimethoxy-methyl silicomethane, diethoxymethyl silicomethane, diisopropoxy methyl-silicane, two tert.-butoxy methyl-silicanes, trimethoxy silicomethane, triethoxy-silicane, three isopropoxy silicomethanes, methyl trimethoxy oxygen base silicomethane, methyl-triethoxysilane and three tert.-butoxy silicomethanes.
- 23. the method for claim 1, wherein, described at least a organosilane and/or organo-siloxane precursor are to have two or first the containing silicon precursor and have a mixture that second of three or more Si-O keys contain silicon precursor of S-O key still less, and this mixture is used for adjusting the chemical constitution of porous membrane, precondition is that described precursor comprises at least one Si-O key.
- 24. the method for claim 13, wherein, described porogen precursor is C by comprising one or more alcohol radical and general formula nH 2n+2-2x-2y-z(OH) zHydrocarbon structure represent, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of alcohol radical in the compound and between 1 and 4, and the alcohol functional group outer and/or intra-annular of ring wherein.
- 25. the method for claim 13, wherein, described porogen precursor is C by comprising one or more ether and general formula nH 2n+2-2x-2yO zHydrocarbon structure represent, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of ehter bond in the structure and between 1 and 4, and the ehter bond outer and/or intra-annular of ring wherein.
- 26. the method for claim 13, wherein, described porogen precursor is C by comprising one or more epoxide group and general formula nH 2n+2-2x-2y-2zO zHydrocarbon structure represent, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of epoxide group in the structure and between 1 and 4, and wherein epoxide group can be connected to that ring is gone up or straight chain on.
- 27. the method for claim 13, wherein, described porogen precursor is C by comprising one or more aldehyde radical and general formula nH 2n+2-2x-2y-2zO zHydrocarbon structure represent that n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of aldehyde radical in the structure and between 1 and 4.
- 28. the method for claim 13, wherein, described porogen precursor is C by comprising one or more ketone group and general formula nH 2n+2-2x-2y-2zO zHydrocarbon structure represent, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of aldehyde radical in the structure and between 1 and 4, and the ketone group outer and/or intra-annular of ring wherein.
- 29. the method for claim 13, wherein, described porogen precursor is C by comprising one or more carboxylic acid group and general formula nH 2n+2-2x-2y-3z(OOH) zHydrocarbon structure, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of carboxylic acid group in the structure and between 1 and 4.
- 30. the method for claim 13, wherein, even number carboxylic acid group and acid functional group are dehydrated to be represented with the hydrocarbon structure that forms the cyclic acid anhydride group described porogen precursor by comprising, and wherein, the general formula of described structure is C nH 2n+2-2x-2y-6z(O 3) z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of anhydride group in the structure and is 1 or 2.
- 31. the method for claim 13, wherein, described porogen precursor is C by comprising ester group and general formula nH 2n+2-2x-2y-2z(O 2) zHydrocarbon structure represent that n=1-12 wherein, x are the quantity of encircling in the structure and between 0-4, y is the quantity of unsaturated link(age) in the structure and does not have unsaturated link(age) and the carbonyl conjugation of ester that z is the quantity of anhydride group in the structure and is 1 or 2.
- 32. the method for claim 13, wherein, described porogen precursor is C by comprising acrylate-functional groups and general formula nH 2n+2-2x-2y-2z(O 2) zHydrocarbon structure represent, described functional group is made up of the carbonyl conjugated unsaturated link(age) of ester group and at least one and ester group, n=1-12 wherein, x is the quantity encircled in the structure and between 0-4, y is the quantity of unsaturated link(age) in the structure and more than or equal to 1, the carbonyl conjugation of unsaturated link(age) and ester at least wherein, z is the quantity of ester group in the structure and is 1 or 2.
- 33. the method for claim 13, wherein, described porogen precursor is C by comprising ether and carbonyl functional group and general formula nH 2n+2-2w-2x-2y(O) y(O) zHydrocarbon structure represent, n=1-12 wherein, w is the quantity encircled in the general formula and between 0 and 4, x be unsaturated link(age) in the structure quantity and 0 and n between, y is the quantity of carbonyl in the structure, wherein carbonyl can be ketone and/or aldehyde, and z is the quantity of ether in the structure and is 1 or 2, and ether encircles outer or intra-annular.
- 34. the method for claim 13, wherein, described porogen precursor is C by comprising ether and alcohol radical functional group and general formula nH 2n+2-2w-2x-y(OH) y(O) zHydrocarbon structure represent that n=1-12 wherein, w are the quantity encircled in the general formula and between 0 and 4, x be unsaturated link(age) in the structure quantity and 0 and n between, y is the quantity of alcohol radical in the structure, and z is the quantity of ether in the structure and is 1 or 2, and ether encircles outer or intra-annular.
- 35. the method for claim 13, wherein, described porogen precursor is C by arbitrary combination that comprises the functional group that is selected from alcohol, ether, carbonyl and carboxylic acid group and general formula nH 2n+2-2u-2v-w-2y-3z(OH) w(O) x(O) y(OOH) zHydrocarbon structure represent, n=1-12 wherein, u is the quantity encircled in the structure and between 0 and 4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of alcohol radical in the general formula and between 0 and 4, x is the quantity of ether in the structure and between 0 and 4, and ether is the outer or intra-annular of ring, y is the quantity of carbonyl in the structure and between 0 and 3, wherein carbonyl can be ketone and/or aldehyde, and z is the quantity of carboxylic acid group in the structure and between 0 and 2.
- 36. the method for claim 13, wherein, described porogen precursor is C by comprising one or more primary amine and general formula nH 2n+2-2x-2y-z(NH 2) zHydrocarbon structure represent, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of amido in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein.
- 37. the method for claim 13, wherein, described porogen precursor is C by comprising one or more secondary amine and general formula nH 2n+2-2x-2y-2z(NH) zHydrocarbon structure represent, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of secondary amine in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein.
- 38. the method for claim 13, wherein, described porogen precursor is C by comprising one or more tertiary amine groups and general formula nH 2n+2-2x-2y-3z(N) zHydrocarbon structure represent, wherein=1-12, x is the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of tertiary amine groups in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein.
- 39. the method for claim 13, wherein, described porogen precursor is C by comprising one or more nitro and general formula nH 2n+2-2x-2y-z(NO) zHydrocarbon structure represent, wherein=1-12, x is the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of nitro in the compound and between 1 and 4, and the nitro functions outer and/or intra-annular of ring wherein.
- 40. the method for claim 13, wherein, described porogen precursor is C by having amine and ether functional group and general formula nH 2n+2-2u-2v-w-2x-3y-z(NH 2) w(NH) x(N) y(OH) zHydrocarbon structure represent, n=1-12 wherein, u is the quantity encircled in the structure and between 0 and 4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of primary amine groups, x is the quantity of secondary amine, y is the quantity of tertiary amine groups, and, 1＜w+x+y＜4, and wherein z is the quantity of alcohol radical in the compound and between 1 and 4, and alcohol radical and/or amido be the outer and/or intra-annular of ring.
- 41. the method for claim 13, wherein, described porogen precursor is C by having amine and alcohol functional group and general formula nH 2n+2-2u-2v-w-2x-3y-z(NH 2) w(NH) x(N) y(OH) zHydrocarbon structure represent, n=1-12 wherein, u is the quantity encircled in the structure and between 0 and 4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of primary amine groups, x is the quantity of secondary amine, y is the quantity of tertiary amine groups, and 1＜w+x+y＜4, and z is the quantity of ether in the compound and between 1 and 4, wherein ether and/or the amido outer and/or intra-annular of ring.
- 42. the process of claim 1 wherein that precursor mixture also comprises the pore-forming precursor.
- 43. the method for claim 19, wherein, the pore-forming precursor is selected from: 1-new hexyl-1,3,5,7-tetramethyl-ring tetrasiloxane, 1-neo-pentyl-1,3,5,7-tetramethyl-ring tetrasiloxane, neo-pentyl diethoxy silicomethane, new hexyl diethoxy silicomethane, new hexyl triethoxy-silicane, neo-pentyl triethoxy-silicane and neo-pentyl two tert.-butoxy silicomethanes.
- 44. an organic silicate glass porous membrane of being produced by the method for claim 1, described film is by chemical formula Si vO wC xH yF zThe material of expression is formed, v+w+x+y+z=100% wherein, and v is the 10-35% atom, and w is the 10-65% atom, and x is the 5-30% atom, and y is the 10-50% atom, and z is the 0-15% atom, wherein said film has hole and specific inductivity less than 2.6.
- 45. the film of claim 42, wherein, v is the 20-30% atom, and w is the 20-45% atom, and x is the 5-25% atom, and y is the 15+40% atom, and z is 0.
- 46. the film of claim 42, wherein, z is the 0.5-7% atom, and wherein in the porous membrane basically all F all be bonded on the Si with the formal bond of Si-F group.
- 47. the film of claim 42 wherein, is included in 50% in film or more hydrogen bonding to carbon.
- 48. a composition comprises:(a) be selected from following at least a organosilane and/or organo-siloxane precursor:1) formula SiR 1 n(OR 2) p(O) CR 3) 4-(n+p), wherein, R 1Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 3Be H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, and p is 0-3, precondition is to have a Si-H key in the molecule at least;2) formula R 1 n(OR 2) p(O (O) CR 4) 3-n-pSi-O-SiR 3 m(O (O) CR 5) q(OR 6) 3-m-q, wherein, R 1And R 3Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2And R 6Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R4 Hes R5 is H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is 0-3, and p is 0-3, n+m 〉=1, n+p≤3 and m+q≤3, precondition is to have a Si-H key in the molecule at least;3) formula R 1 n(OR 2) p(O (O) CR 4) 3-n-pSi-SiR 3 m(O (O) CR 5) q(OR 6) 3-m-q, wherein, R 1And R 3Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2And R 6Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 4And R 5Be H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is that 0-3 and p are 0-3, n+m 〉=1, n+p≤3, and m+q≤3, precondition is to have a Si-H key in the molecule at least;4) formula R 1 n(OR 2) p(O (O) CR 4) 3-n-pSi-R 7-SiR 3 m(O (O) CR 5) q(OR 6) 3-m-q, wherein, R 1And R 3Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2And R 6Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 4And R 5Be H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 7Be C 2-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is 0-3, and p is 0-3, n+m 〉=1, n+p≤3 and m+q≤3, precondition is to have a Si-H key in the molecule at least;5) formula (R 1 n(OR 2) p(O (O) CR 3) 4-(n+p)Si) tCH 4-t, wherein, R 1Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 3Be H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, p is 0-3, and t is 2-4, n+p≤4, precondition is to have a Si-H key in the molecule at least;6) formula (R 1 n(OR 2) p(O (O) CR 3) 4-(n+p)Si) tNH 3-t, wherein, R 1Be H or C independently 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2Be C independently 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, R 3Be H independently, C 1-C 6Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, p is 0-3, and t is 1-3, n+p≤4, precondition is to have a Si-H key in the molecule at least;7) formula (N (R 1) Si (R 1R 2)) x, wherein, R 1And R 2Be H independently, C 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl, and x can be the integers of 2-8;8) formula (C (R 1) Si (R 1R 2)) x, wherein, R 1And R 2Be H independently, C 1-C 4Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon, and x are the integers of 2-8, precondition is to have a Si-H key in the molecule at least;9) and composition thereof;(b) be selected from following, with described at least a organosilane and/or the different pore former of organo-siloxane precursor:1) formula C nH 2n+2-2x-2y-z(OH) z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of alcohol radical in the structure and between 1 and 4, and described the alcohol functional group outer and/or intra-annular of ring;2) formula C nH 2n+2-2x-2yO z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of ehter bond in the structure and between 1 and 4, and the ehter bond outer and/or intra-annular of ring;3) formula C nH 2n+2-2x-2y-2zO z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of epoxy group(ing) in the structure and between 1 and 4, and described epoxy group(ing) can be connected to that ring is gone up or straight chain on;4) formula C nH 2n+2-2x-2y-2zO z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of aldehyde radical in the structure and between 1 and 4;5) formula C nH 2n+2-2x-2y-2zO z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of aldehyde radical in the structure and between 1 and 4, and the ketone group outer and/or intra-annular of ring;6) formula C nH 2n+2-2x-2y-3z(OOH) z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of carboxylic acid group in the structure and between 1 and 4;7) formula C nH 2n+2-2x-2y-6z(O 3) z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of anhydride group in the structure and is 1 or 2;8) formula C nH 2n+2-2x-2y-2z(O 2) z, n=1-12 wherein, x are the quantity of encircling in the structure and between 0-4, y is the quantity of unsaturated link(age) in the structure and does not have unsaturated link(age) and the carbonyl conjugation of ester that z is the quantity of anhydride group in the structure and is 1 or 2;9) formula C nH 2n+2-2x-2y-2z(O 2) z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, and y is the quantity of unsaturated link(age) in the structure and more than or equal to 1, and the carbonyl conjugation of at least one unsaturated link(age) and ester, and z is the quantity of ester group in the structure and is 1 or 2;10) formula C nH 2n+2-2w-2x-2y(O) y(O) zN=1-12 wherein, w is the quantity encircled in the structure and between 0-4, x is the quantity of unsaturated link(age) in the structure and between 0-n, but y is quantity and the carbonyl ketone and/or the aldehyde of carbonyl in the structure, z is the quantity of ether in the compound and is 1 or 2, and wherein ether encircles outer or intra-annular.11) formula C nH 2n+2-2w-2x-y(OH) y(O) z, n=1-12 wherein, w are the quantity encircled in the structure and between 0-4, x be unsaturated link(age) in the structure quantity and 0 and n between, y is the quantity of alcohol radical in the structure, and z is the quantity of ether in the structure and is 1 or 2, and wherein ether encircles outer or intra-annular;12) formula C nH 2n+2-2u-2v-w-2y-3z(OH) w(O) x(O) y(OOH) zN=1-12 wherein, u is the quantity encircled in the structure and between 0-4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of alcohol radical in the structure and between 0 and 4, x is the quantity of ether in the structure and between 0 and 4, and this ether can be the outer or intra-annular of ring, y is the quantity of carbonyl in the structure and between 0 and 3, but wherein carbonyl ketone and/or aldehyde, and z is the quantity of carboxylic acid group in the structure and between 0 and 2;13) formula C nH 2n+2-2x-2y-z(NH 2) z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of amido in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein;14) formula C nH 2n+2-2x-2y-2z(NH) z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of secondary amine in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein;15) formula C nH 2n+2-2x-2y-3z(N) z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of tertiary amine groups in the compound and between 1 and 4, and the amine functional group outer and/or intra-annular of ring wherein;16) formula C nH 2n+2-2x-2y-z(NO 2) z, n=1-12 wherein, x are the quantity encircled in the structure and between 0-4, y be unsaturated link(age) in the structure quantity and 0 and n between, z is the quantity of nitro in the compound and between 1 and 4, and the nitro functions outer and/or intra-annular of ring wherein;17) formula C nH 2n+2-2u-2v-w-2x-3y-z(NH 2) w(NH) x(N) y(OH) zN=1-12 wherein, u is the quantity encircled in the structure and between 0-4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of primary amine groups, x is the quantity of secondary amine, y is the quantity of tertiary amine groups, and 1＜w+x+y＜4, z is the quantity of alcohol radical in the compound and between 1 and 4, and alcohol and/or the amido outer and/or intra-annular of ring wherein;18) formula C nH 2n+2-2u-2v-w-2x-3y-z(NH 2) w(NH) x(N) y(OH) zN=1-12 wherein, u is the quantity encircled in the structural formula and between 0 and 4, v be unsaturated link(age) in the structure quantity and 0 and n between, w is the quantity of primary amine groups, x is the quantity of secondary amine, y is the quantity of tertiary amine groups, and 1＜w+x+y＜4, z is the quantity of ether in the compound and between 1 and 4, and ether and/or the amido outer and/or intra-annular of ring;(19) and composition thereof.
- 49. the composition of claim 48, wherein said composition also comprises:(c) be selected from following pore-forming precursor:1) formula R 1 n(OR 2) p(O (O) CR 3) 4-(n+p)Si, wherein, R 1Be H or C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2And R 3Be C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, and p is 0-3, precondition is n+p≤4, and at least one R 1Be used as the C of pore former 3Or bigger hydrocarbon replaces;2) formula R 1 n(OR 2) p(O (O) CR 4) 3-n-pSi-O-SiR 3 m(O (O) CR 5) q(OR 6) 3-m-q, wherein, R 1And R 3Be H or C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2, R 4, R 5And R 6Be C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is 0-3, and p is 0-3, and precondition is n+m 〉=1, n+p≤3, m+q≤3, and R 1And R 3In be used as one of at least the C of pore former 3Or bigger hydrocarbon replaces;3) formula R 1 n(OR 2) p(O (O) CR 4) 3-n-pSi-SiR 3 m(O (O) CR 5) q(OR 6) 3-m-q, wherein, R 1And R 3Be H or C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2, R 4, R 5And R 6Be C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is that 0-3 and p are 0-3, and precondition is n+m 〉=1, n+p≤3, m+q≤3, and R 1And R 3In be used as one of at least the C of pore former 3Or bigger hydrocarbon replaces;4) formula R 1 n(OR 2) p(O (O) CR 4) 3-n-pSi-R 7-SiR 3 m(O (O) CR 5) q(OR 6) 3-m-q, wherein, R 1And R 3Be H or C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2, R 4, R 5, R 6And R 7Be C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 0-3, and m is 0-3, and q is that 0-3 and p are 0-3, and precondition is n+m 〉=1, n+p≤3, m+q≤3, and R 1, R 3With ROne of at least be used as the C of pore former in 7 3Or bigger hydrocarbon replaces;5) formula (R 1 n(OR 2) p(O (O) CR 3) 4-(n+p)Si) tCH 4-t, wherein, R 1Be H or C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2And R 3Be C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, and p is 0-3, and t is 2-4, and precondition is n+p≤4, and at least one R 1Be used as the C of pore former 3Or bigger hydrocarbon replaces;6) formula (R 1 n(OR 2) p(O (O) CR 3) 4-(n+p)Si) tNH 3-t, wherein, R 1Be H or C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated hydrocarbon; R 2And R 3Be C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, aromatics, fluorizated hydrocarbon partially or completely, n is 1-3, and p is 0-3, and t is 1-3, and precondition is n+p≤4, and at least one R 1Be used as the C of pore former 3Or bigger hydrocarbon replaces;7) formula (OSiR 1R 3) xCyclosiloxane, wherein, R 1And R 3Be H or C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl, and x can be the integers of 2-8, precondition is R 1And R 3In be used as one of at least the C of pore former 3Or bigger hydrocarbon replaces;8) formula (NR 1SiR 1R 3) xThe ring silazane, wherein, R 1And R 3Be H or C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl, and x can be the integers of 2-8, precondition is R 1And R 3In be used as one of at least the C of pore former 3Or bigger hydrocarbon replaces;9) formula (CR 1R 3SiR 1R 3) xRing silicon-carbon alkane, wherein, R 1And R 3Be H or C independently 1-C 12Straight or branched, saturated, single or polyunsaturated, cyclic, partially or completely fluorizated alkyl, and x can be the integers of 2-8, precondition is R 1And R 3In be used as one of at least the C of pore former 3Or bigger hydrocarbon replaces;10) and composition thereof.
- 50. the method for claim 1, described method also comprises: with at least a post-treatment agent that is selected from heat energy, plasma energy, photon energy, electron energy, micro-wave energy and chemical substance the preliminary film is handled.
- 51. the method for claim 50, wherein, remove basically all pore formers the film from preparation before, during and/or afterwards, at least a post-treatment agent improves the performance of the porous organic glass film that obtains.
- 52. the method for claim 50, wherein, additional post-treatment agent is removed at least a portion pore former from the preparation film.
- 53. the method for claim 50, wherein, at least a post-treatment agent is the photon energy in the 200-8000 nanometer range.
- 54. the method for claim 50, wherein, at least a post-treatment agent is the electron energy that is provided by electron beam.
- 55. the method for claim 50, wherein, at least a post-treatment agent is a supercutical fluid.
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| US11/228,223 | 2005-09-19 | ||
| US11/228,223 US7332445B2 (en) | 2004-09-28 | 2005-09-19 | Porous low dielectric constant compositions and methods for making and using same |
| US11/228223 | 2005-09-19 |
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|---|---|---|---|---|
| CN102162091A (en) * | 2009-12-23 | 2011-08-24 | 气体产品与化学公司 | Low k precursors providing superior integration attributes |
| CN103397307A (en) * | 2010-02-04 | 2013-11-20 | 气体产品与化学公司 | Method to prepare silicon-containing film |
| CN104136657A (en) * | 2012-03-07 | 2014-11-05 | 东丽工程株式会社 | Chemical vapor deposited film formed by plasma chemical vapor deposition method |
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| US7404990B2 (en) * | 2002-11-14 | 2008-07-29 | Air Products And Chemicals, Inc. | Non-thermal process for forming porous low dielectric constant films |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102162091A (en) * | 2009-12-23 | 2011-08-24 | 气体产品与化学公司 | Low k precursors providing superior integration attributes |
| US8753986B2 (en) | 2009-12-23 | 2014-06-17 | Air Products And Chemicals, Inc. | Low k precursors providing superior integration attributes |
| US9018107B2 (en) | 2009-12-23 | 2015-04-28 | Air Products And Chemicals, Inc. | Low K precursors providing superior integration attributes |
| 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 |
| CN104136657A (en) * | 2012-03-07 | 2014-11-05 | 东丽工程株式会社 | Chemical vapor deposited film formed by plasma chemical vapor deposition method |
| CN104136657B (en) * | 2012-03-07 | 2017-03-08 | 东丽工程株式会社 | The chemical deposited film being formed by plasma CVD method |
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