JP2011014925A - Porogen, porogenated precursor and method for using the same to provide porous organosilica glass film with low dielectric constant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a porous organosilica glass film having a low dielectric constant, an improved mechanical property, a thermal stability and a chemical resistance.SOLUTION: A porous organosilica glass film represented by the formula SiOCHFis manufactured in which v+w+x+y+z=100%, v is from 10 to 35 atom%, w is from 10 to 65 atom%, x is from 5 to 30 atom%, y is from 10 to 50 atom% and z is from 0 to 15 atom%. The method includes: introducing a gaseous reagent into a vacuum chamber, the gaseous reagent containing precursor selected from a group consisting of organosilane and organosiloxane and porogen; and applying energy to the gaseous reagent to induce reaction of the gaseous reagent to deposit a preliminary film on the substrate. The preliminary film contains fine pores and substantially all of porogen is removed to provide the porous film with a dielectric constant less than 2.6.

Description

  The present invention relates to the field of low dielectric constant materials manufactured by CVD as an insulating layer in electronic devices.

The electronics industry uses dielectric materials as insulating layers between circuits (ICs) and integrated circuits and related electronic devices. Line dimensions have been reduced to increase the speed and storage capability of microelectronic devices (eg, computer chips). As microchip dimensions are reduced, the dielectric requirements for interlayer dielectric (ILD) are becoming increasingly stringent. The reduction in spacing requires a low dielectric constant to minimize the RC time constant (where R is the resistance of the conductor and C is the capacitance of the insulating dielectric interlayer). C is inversely proportional to the distance and proportional to the dielectric constant (k) of the interlayer dielectric (ILD). Conventional silica (SiO ₂ ) CVD insulating films made from SiH ₄ or TEOS (Si (OCH ₂ CH ₃ ) ₄ , tetraethylorthosilicate) and O ₂ have a dielectric constant k greater than 4.0. There are several methods that the industry has tried to produce silica-based CVD films with relatively low dielectric constants, the most successful being insulating oxidation with organic groups that give a dielectric constant of 2.7-3.5 Doping a silicon film. Organosilica glass is a normal that is deposited as a dense film (density to 1.5 g / cm ³⁾ from methylsilane or organosilicon precursors such as siloxanes and O ₂ or N ₂ oxidants such as _O . The organic silica glass is referred to herein as OSG. Since the dielectric constant or “k” value drops below 2.7 with relatively high device density and relatively small dimensions, the industry has studied most suitable low k for dense films and has improved dielectric properties. Various porous materials have been investigated for improvement.

CVD method regions patents and applications are known in the area of the porous ILD by include the following: Patent Document 1 and 2, the reaction in the presence of the oxidant and optionally a peroxide, such as N 2 _O A method is described in which an OSG film is deposited from an organosilicon precursor having an active group, and then a reactive OS group is removed by thermal annealing to obtain a porous OSG film; Teaches removing essentially all organic groups from the deposited OSG to obtain porous inorganic SiO ₂ ; US Pat. describes obtaining an inorganic SiO _2; and Patent Document 6 and 7 and non-Patent Document 1, a co-deposition of a film from all the organosilicon precursor and an organic compound, and subsequent thermal annealing - Le multiphase OSG / Give organic film, It teaches that one part of the polymerized organic component is retained. In these latter documents, the final composition of the film exhibits residual porogen and high hydrocarbon film content (80-90 atomic%). It is preferred that the final film retain a SiO ₂ -like network in which one part of the oxygen atoms has been replaced with an organic group.

  All references are incorporated herein by reference in their entirety.

European Patent Publication No. 1,119,035 US Pat. No. 6,171,945 US Pat. No. 6,054,206 US Pat. No. 6,238,751 European Patent Publication No. 1037275 US Pat. No. 6,312,793 International Publication WO00 / 24050

Grill, A.M. Patel, V.W. Appl. Phys. Lett. (2001), 79 (6), pages 803-805.

  The present invention aims to provide a porous organosilica glass film having a low dielectric constant and improved mechanical properties, thermal stability and chemical resistance.

The present invention has the formula Si _v O _w C _x H _y F _z (where v + w + x + y + z = 100%, v is 10-35 atomic%, w is 10-65 atomic%, x is 5-30 atomic%, y is 10-50 atomic%, and z is 0-15 atomic%), wherein the film has pores and a dielectric constant of less than 2.6.

The present invention further provides a chemical vapor deposition method for producing the porous organosilica glass membrane of the present invention, which method comprises the following steps:
(A) providing a substrate in a vacuum chamber; (b) vacuuming at least one precursor selected from the group consisting of an organosilane and an organosiloxane and a gaseous reagent containing a porogen that can be distinguished from at least one precursor. Introducing into the chamber; (c) applying energy to the gaseous reagent in the vacuum chamber and causing the reaction of the gaseous reagent to deposit a preliminary film on the substrate, wherein the preliminary film is The preliminary film containing the porogen and deposited without the addition of oxidant; and (d) to obtain a porous film having pores and a dielectric constant of less than 2.6 Removing substantially all porogen from the membrane.

Furthermore, the present invention provides a chemical vapor deposition method for producing the porous organic silica glass membrane of the present invention, which method comprises the following steps:
(A) providing a substrate in a vacuum chamber; (b) introducing a gaseous reagent containing at least one precursor selected from the group consisting of an organosilane and an organosiloxane into the vacuum chamber, wherein at least one One precursor includes a porogen bound thereto; (c) applying energy to the gaseous reagent in the vacuum chamber to cause a reaction of the gaseous reagent to deposit a preliminary film on the substrate, wherein The preliminary membrane includes at least one porogen and a first amount of methyl groups bonded to silicon atoms; and (d) a porous membrane having pores and a dielectric constant of less than 2.6 Removing substantially all of the porogen from the preliminary membrane, wherein the porous membrane comprises a second amount of methyl groups bonded to silicon atoms, and the second amount Is the first More than 50% of the amount of.

  The present invention further provides a novel porogenized precursor for the production of porous organosilica glass membranes, which is porogenated but 1,3,5,7-tetramethylcyclo-tetrasiloxane, such as neohexyl. -1,3,5,7-tetramethylcyclo-tetrasiloxane and trimethylsilylethyl-1,3,5,7-tetramethylcyclo-tetrasiloxane.

  Still further, the present invention provides novel compositions of porogens and precursors (porogenated and / or not porogenized) for producing the films of the present invention.

The infrared spectrum of the film | membrane of this invention is shown. The infrared spectrum of the film | membrane of this invention is shown. The infrared spectrum of ATP used as a pore formation agent in the present invention is shown. 2 shows a thermogravimetric analysis of a membrane of the invention.

  Organic silicates are candidates for low-k materials, but their intrinsic dielectric constant is limited to as low as 2.7 unless porogen is added to impart porosity to these materials. Providing porosity (the void space has an intrinsic dielectric constant of 1.0) usually reduces the overall dielectric constant of the film at the expense of mechanical properties. Material properties depend on the chemical composition and structure of the film. The type of organosilicon precursor has a strong influence on the film structure and composition, thus ensuring that the addition of the amount of pores necessary to reach the desired dielectric constant does not result in a mechanically unhealthy film Thus, it is advantageous to use a precursor that provides the required film properties. Thus, the present invention provides a means for producing a porous OSG film having a desirable balance of electrical and mechanical properties. Other film properties often follow electrical or mechanical properties.

A preferred embodiment of the present invention is a thin film having a lower dielectric constant and improved mechanical properties, thermal stability and chemical resistance (oxygen, in an aqueous oxidizing environment, etc.) compared to other porous organosilica glass materials. Provide material. This is preferably in the form of carbon (preferably primarily in the form of organic carbon —CH _{x, where} x is 1-3), more preferably the majority of C in the form of —CH ₃ ) and inorganic fluorine (eg, Si—F bonds). Environment in which certain precursors or network-forming chemicals are free of oxidants (other than any additional / carrier gas CO ₂ up to the limit that would appear to act as oxidants) Used to deposit films. Furthermore, it is preferred that most of the hydrogen in the film is bonded to carbon.

Thus, preferred embodiments of the present invention are: (a) about 10 to about 35 atomic percent, more preferably about 20 to about 30 atomic percent silicon; (b) about 10 to about 65 atomic percent, more preferably About 20 to about 45 atomic percent oxygen; (c) about 10 to about 50 atomic percent, more preferably about 15 to about 40 atomic percent hydrogen; and (d) about 5 to about 30 atomic percent, more preferably about 5 to about 20 atomic percent carbon. In addition, the film may contain from about 0.1 to about 15 atomic percent, more preferably from about 0.5 to about 7.0 atomic percent fluorine to improve one or more material properties. A relatively small amount of other elements may also be present in the film of the present invention. OSG materials are considered low-k materials because they have a lower dielectric constant than the standard material traditionally used in the industry—silica glass. The material of the present invention adds a pore-forming species or porogen to the deposition process, blends the porogen into the as-deposited (ie, preliminary) OSG film, and removes substantially all of the porogen from the preliminary film. Can be provided by obtaining a product film while substantially retaining the terminal Si—CH ₃ groups of the preliminary film. The product film is a porous OSG and has a reduced dielectric constant compared to a preliminary film as well as a similar film deposited without porogen. It is important to identify the membrane of the present invention as porous OSG, whereas porous inorganic SiO ₂ lacks the hydrophobicity imparted by the organic groups of OSG.

  Silica produced with PE (plasma enhanced) -CVD TEOS (tetraethoxysilane) has an inherent free volume pore diameter measured by positron annihilation lifetime spectroscopy (PALS) analysis of about 0.6 nm spherical equivalent diameter. It is. The pore diameter of the membrane of the present invention measured by small angle neutron scattering (SANS) or PALS is preferably a sphere equivalent diameter of less than 5 nm, more preferably a sphere equivalent diameter of less than 2.5 nm.

  The total porosity of the membrane can be 5-75%, depending on the process conditions and the desired final membrane properties. Preferably, the membrane of the present invention has a density less than 2.0 g / cc, alternatively less than 1.5 g / cc, or less than 1.25 g / cc. Preferably, the films of the present invention have a density that is at least 10% less, more preferably at least 20% less than the density of similar OSG films made without porogen.

  The porosity of the membrane need not be uniform throughout the membrane. In certain embodiments, there are multiple layers of porosity gradients and / or various porosity. Such films can be obtained, for example, by adjusting the ratio of porogen to precursor during deposition.

  The film of the present invention has a dielectric constant lower than that of a general OSG material. Preferably, the films of the present invention have a dielectric constant that is at least 0.3 less, more preferably at least 0.5 less than the density of similar OSG films made without porogen. Preferably, the Fourier transform infrared (FTIR) spectrum of the porous membrane of the present invention is substantially the same as the control FTIR of the control membrane prepared by substantially the same method except for the absence of porogen.

  Preferably, the film of the present invention has superior mechanical properties compared to common OSG materials. Preferably, the basic OSG structure (eg, no porogen added film) of the film of the present invention is at least 10% larger than a similar OSG film having the same dielectric constant, more preferably measured in nanosteps Has a hardness or modulus that is at least 25% greater.

The films of the present invention do not require the use of oxidants to deposit low k films. The absence of oxidants (eg, O ₂ , N ₂ O, ozone, hydrogen peroxide, NO, NO ₂ , N ₂ O ₄ or mixtures thereof) added to the gas phase is the precursor methyl group in the film. Making it easier to hold. Here, this oxidant is defined as a moiety capable of oxidizing an organic group. This allows for the incorporation of the minimum amount of carbon necessary to impart desirable properties such as reduced dielectric constant and hydrophobicity. Similarly, it is easy to retain the silica network to the maximum, with excellent mechanical properties, adhesion, and common etch stop materials (eg, silicon carbide, hydrogenated silicon carbide, silicon nitride, silicon hydronitride, Etc.) is provided with a film having etching selectivity. This is because the film retains characteristics more similar to the traditional dielectric insulator silica.

  Furthermore, the membrane of the present invention may contain fluorine in the form of inorganic fluorine (eg, Si—F). When present, fluorine is preferably included in an amount of 0.5 to 7 atomic percent.

The membranes of the present invention are thermally stable and have good chemical resistance. In particular, annealing - having suitable membrane 1.0 wt% / hr average weight loss of less than isothermal at 425 ° C. in _{N 2} after Le. In addition, the membrane preferably has an average weight loss of less than 1.0 wt% / hr in air at an isothermal temperature of 425 ° C.

  The membrane is suitable for various applications. In particular, the film is suitable for deposition on a semiconductor substrate and is particularly suitable for use as, for example, an insulating layer, an interlayer insulating film and / or an intermetallic insulating film. The membrane can form a compatible coating. The mechanical properties exhibited by these films make them particularly suitable for use in Al subtractive methods as well as Cu damascene or dual damascene methods.

The film is compatible with chemical mechanical planarization and anisotropic etching, and silicon, SiO ₂ , Si ₃ N ₄ , OSG, FSG (fluorinated silica glass), silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated Silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, hydrogenated boron nitride, anti-reflective coating, photoresist, organic polymer, porous organic and inorganic materials, metals such as copper and aluminum, and TiN, Ti It can adhere to various materials such as (C) N, TaN, Ta (C) N, Ta, W, WN or W (C) N diffusion barrier layers such as but not limited to. The membrane is preferably capable of adhering at least one of the aforementioned materials that sufficiently passes a conventional tensile test, such as the ASTM D3359-95a tape tensile test. The sample is judged to pass if there is no discernible removal of the membrane.

  The invention is particularly suitable for supplying membranes, and the products of the invention are described herein primarily as membranes, but the invention is not so limited.

  The invention is particularly suitable for supplying membranes, and the products of the invention are mainly described herein as membranes, but the invention is not limited thereto. The product of the present invention can be supplied in any form that can be deposited by CVD, such as coatings, multilayer assemblies, and other types of objects that do not necessarily have to be flat or thin, and even in integrated circuits. There can be many objects that are not necessarily used. Preferably, the substrate is a semiconductor.

  In addition to the OSG product of the present invention, the present invention includes methods by which the product is produced, methods of using the product, and compounds and compositions useful for producing the product.

  It is also within the scope of the present invention for a single species of molecule to function as both a structure former and a porogen. That is, the structure-forming precursor and the pore-forming precursor need not necessarily be different molecules, and in some embodiments the porogen is a part of the structure-forming precursor (eg, covalently linked). Precursors containing porogens attached to them may hereinafter be referred to as “pologated precursors”. For example, it is possible to use neohexyl TMCTS (tetramethylcyclotetrasiloxane) as a single species, whereby the TMCTS portion of the molecule forms the basic OSG structure, and the bulky alkyl locating group neohexyl forms pores. A seed that is removed during the annealing process. Having a porogen bonded to a Si species that forms a network in the OSG structure can be advantageous to achieve a relatively high porogen loading into the film during deposition. Further, two porogens bonded to one Si in the precursor (for example in di-neohexyl-diethoxysilane) or two Si bonded to one porogen (for example 1,4-bis (diethoxysilyl)) Having (in cyclohexane) is also advantageous because the most fragile bond in the plasma during deposition is the Si-porogen bond. Thus, the reaction of one Si-porogen bond in the plasma still results in porogen incorporation in the deposited film. Further non-limiting examples of suitable porogenated precursors include 1-neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-neopentyl-1,3,5,7-tetra Including methylcyclotetrasiloxane, neopentyldiethoxysilane, neohexyldiethoxysilane, neohexyltriethoxysilane, neopentyltriethoxysilane and neopentyl-di-t-butoxysilane.

In some embodiments of materials in which a single or multiple porogens are bonded to silicon, when the film hardens to form pores, so that a portion of the porogen remains bonded to the silicon and imparts hydrophobicity to the film. It is advantageous to design the porogen. The porogen in the precursor containing Si-palogen can be chosen such that decomposition or curing leaves terminal chemical groups from the porogen such as —CH ₃ attached to the Si. For example, if neopentyl, a porogen, is selected, thermal annealing under the appropriate conditions will cause Si to cleave at the C-C bond at the β-position, which is a secondary carbon adjacent to Si. It is a bond between the quaternary carbons of the t-butyl group and is the most advantageous bond for thermodynamic cleavage. Under appropriate conditions, this leaves a terminal —CH ₃ group to fill Si and gives the film hydrophobicity and low dielectric constant. Examples of precursors are neopentyltriethoxysilane, neopentyldiethoxysilane and neopentyldiethoxymethylsilane.

  The porogen in the deposited film may or may not be in the same form as the porogen introduced into the reaction chamber. Similarly, the porogen removal process can liberate the porogen or fragments thereof from the membrane. In essence, the porogen reagent (or porogen substituent attached to the precursor), the porogen in the preliminary membrane and the porogen to be removed may or may not be of the same species, but they are all Preferably derived from the group). Regardless of whether the porogen does not change over the process of the present invention, the term “porogen” as used herein refers to the pore-forming reagent (or pore-forming substituent) and its derivatives (the entire process of the present invention). In any form found throughout).

  Another aspect of the present invention is novel organosilanes and organosiloxanes. Novel porogen-containing (ie porogenated) materials synthesized for use as low dielectric constant precursors such as neohexyl TMCTS and trimethylsilylethyl TMCTS have potential applications in yet other areas sell. The novel organosilanes of the present invention can be easily prepared by hydrosilylation of olefin precursors using TMCTS or diethoxymethylsilane. For example, when diethoxymethylsilane or TMCTS is added dropwise to equimolar distilled 3,3-dimethylbutene in the presence of a chloroplatinic acid catalyst, neohexyldiethoxymethylsilane and neohexyl, which are neohexyl-substituted silanes. Xyltetramethylcyclotetrasiloxane is obtained in high yield.

  The term “gaseous reagent” may be used herein to describe a reagent, but the term is supplied directly to the reactor as a gas, as a vaporized liquid, as a sublimated solid, and And / or reagents transported to the reactor by an inert carrier gas.

  Furthermore, the reagents can be fed into the reactor separately from distinct sources or as a mixture. Reagents can be sent to the reaction system by any number of means, preferably using a pressurizable stainless steel vessel equipped with suitable valves and fittings that allow liquid delivery to the process reactor.

  In some embodiments, a mixture of different organosilanes and / or organosiloxanes are used together. Furthermore, the use of a number of different porogen combinations and the use of organosilanes and / or organosiloxanes in combination with organosilanes and / or organosiloxane species having bound porogens are within the scope of the present invention. is there. Such embodiments facilitate adjusting the ratio of pores in the final product to Si and / or improve one or more important properties of the basic OSG structure. For example, deposition using diethoxymethylsilane (DEMS) and porogen can use additional organosilicon such as tetraethoxysilane (TEOS) to improve the mechanical properties of the film. A similar example may be the use of DEMS added to a reaction with the organosilicon neohexyl-diethoxymethylsilane, where the neohexyl group is attached as a porogen to the precursor functional group. A further example is the addition of di-t-butoxy-diacetoxysilane to reactions using di-t-butoxymethylsilane and porogen. In some embodiments, a mixture of a first organosilicon precursor having 2 or less Si—O bonds and a second organosilicon precursor having 3 or more Si—O bonds adapts the chemical composition of the film of the present invention. Given to.

In addition to the structure-forming species and the pore-forming species, additional material can be charged into the vacuum chamber before, during, and / or after the deposition reaction. Such materials are, for example, inert gases (eg, He, Ar, N ₂ , Kr, Xe, etc., and can be used and / or deposited as a carrier gas for relatively volatile precursors. As well as reactive materials such as NH ₃ , H ₂ , CO ₂ or CO, which can promote the curing of the raw material and provide a more stable final film). CO ₂ is a suitable carrier gas.

Energy is applied to the gaseous reagent to react the gas and form a film on the substrate. Such energy can be supplied by, for example, heat, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, and remote plasma methods. A secondary rf frequency source can be used to modify the plasma properties at the substrate surface. Preferably, the film is formed by plasma enhanced chemical vapor deposition. It is particularly preferred to generate a capacitively coupled plasma at a frequency of 13.56 MHz. The plasma power is based on the surface area of the substrate, preferably 0.02~7W / cm ^2, it is more preferably 0.3 to 3 watts / cm ^2. It is free to use a carrier gas that has a low ionization energy to reduce the plasma electron temperature and reduces fragmentation in the OSG precursor and porogen. Type of example with low ionization _{energy, CO 2, NH 3, CO} , a CH 4, Ar, Xe, Kr .

  Each flow rate of the gaseous reagent is preferably 10 to 5000 sccm, more preferably 30 to 1000 sccm, for a single 200 mm wafer. The individual flow rates are selected to provide the desired amount of structure former and pore former in the membrane. The actual flow rate required may depend on the wafer size and chamber configuration and is in no way limited to a 200 mm wafer or a single wafer chamber.

  It is preferred to deposit the film at a deposition rate of at least 50 nm / min. The pressure in the vacuum chamber during deposition is preferably 0.01 to 600 torr, more preferably 1 to 15 torr.

  The film is preferably deposited to a thickness of 0.002 to 10 μm, although the thickness can be varied as required. Blanket films deposited on non-patterned surfaces have excellent uniformity and less than 2% thickness variation over one standard deviation for a substrate with moderate peripheral exclusion. Here, for example, the outermost periphery of 5 mm of the substrate is not included in the uniform statistical calculation.

  The porosity of the membrane can be increased with bulk density, correspondingly decreasing to further reduce the dielectric constant of the material, and expand the applicability of this material to the next generation (eg, k <2.0).

  Substantially all porogen removal is considered if there is no statistically meaningful measured difference in atomic composition between annealed porous OSG and a similar porogen without added porogen. It is. Both the inherent measurement error and process variability of analytical methods for composition (X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectroscopy / hydrogen forward scattering spectroscopy (RBS / HFS)) contributed to the range of data Become. The inherent measurement error for XPS is about ± 2 atom%, but for RBS / HFS is expected to be much larger, ranging from about ± 2 to 5 atom% depending on the species. Process variability contributes ± 2 atomic percent of the final range of data.

The following are non-limiting examples of Si-based precursors suitable for using distinguishable porogens. In the following chemical formulas, and in all chemical formulas in this specification, the term “independently” is not only selected independently with respect to other R groups with the subject R group having a different superscript, but also the same R It should be understood to indicate that the group is independently selected for additional species. For example, in the formula R ¹ _n (OR ² ) _{4 -n} Si, when n is 2 or 3, the R ¹ groups of 2 or 3 do not have to be the same as each other or R ² .

-R ¹ _n (OR ² ) _3-n Si
Where R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; n Can be 1-3.
Example: Diethoxymethylsilane, dimethyldimethoxysilane

-R ¹ _n (OR ² ) _3-n Si-O-SiR ³ _m (OR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁴ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; n can be 1-3; and m can be 1-3.
Example: 1,3-dimethyl-1,3-diethoxydisiloxane

-R ¹ _n (OR ² ) _3-n Si-SiR ³ _m (OR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁴ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; n can be 1-3; and m can be 1-3.
Example: 1,2-dimethyl-1,1,2,2, -tetraethoxydisilane

-R ¹ _n (O (O) CR ² ) _4-n Si
Where R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently hydrogen or a C ₁ -C ₆ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon And n is 1-3.
Example: Dimethyldiacetoxysilane

—R ¹ _n (O (O) CR ² ) _3-n Si—O—SiR ³ _m (O (O) CR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbon; R ² and R ^{4 are} independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or wholly Can be fluorinated hydrocarbons; n can be 1-3; and t can be 1-3.
Example: 1,3-dimethyl-1,3-diacetoxysiloxane

—R ¹ _n (O (O) CR ² ) _3-n Si—SiR ³ _m (O (O) CR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁴ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or wholly Fluorinated hydrocarbons; n can be 1-3; and m can be 1-3.
Example: 1,2-dimethyl-1,1,2,2, -tetraacetoxydisilane

—R ¹ _n (O (O) CR ² ) _3-n Si—O—SiR ³ _m (OR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. A hydrocarbon; R ² is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ⁴ is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; n is 1-3 As well as m can be 1-3.
Example: 1,3-dimethyl-1-acetoxy-3-ethoxydisiloxane

-R ¹ _n (OR ² ) _3-n Si-SiR ³ _m (OR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbon; R ² is independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; R ⁴ is independently a C ₁ -C ₆ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; n can be 1-3; and m can be 1-3.
Example: 1,2-dimethyl-1-acetoxy-2-ethoxydisilane

^{_{-R 1 n (OR 2) p}} (O (O) R 4) 4- (n + p) Si
Where R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; ⁴ is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; n can be 1-3; and p can be 1-3.
Example: Methylacetoxy-t-butoxysilane

^{_{-R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-O-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Alternatively, all fluorinated hydrocarbons; n can be 1-3; m can be 1-3; p can be 1-3; and q can be 1-3.
Example: 1,3-dimethyl-1,3-diacetoxy-1,3-diethoxydisiloxane

^{_{-R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Alternatively, all fluorinated hydrocarbons; n can be 1-3; m can be 1-3; p can be 1-3; and q can be 1-3.
Example: 1,2-dimethyl-1,2-diacetoxy-1,2-diethoxydisilane

A cyclic siloxane of formula (OSiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic Or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8;
Example: 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane

All of the precursor groups discussed above have the following conditions: 1) the reaction environment is essentially free of non-oxidizing and / or the reaction mixture is added the oxidant (as much CO ₂ that are not considered oxidant 2) The porogen is added to the reaction mixture, and 3) the curing (eg annealing) step removes substantially all contained porogen from the deposited film to obtain k <2.6. Can be used to do.

The precursors described above can be mixed with porogens or have bound porogens and are of the same type, except for those types of other molecules, and / or where n and / or m is 0-3. Can be mixed with
Examples: TEOS, triethoxysilane, di-t-butoxysilane, silane, disilane, di-t-butoxydiacetoxysilane, etc.

  The following are additional formulas showing certain Si-based precursors that are suitable for using distinguishable porogens:

(A) Formula R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
Wherein R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; ³ is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; n is 1 to 3; and p is 0 to 3;

(B) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—O—SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _3-mq
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3) is there;

(C) formula _{^{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3) is there;

(D) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—R ⁷ —SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _{3-m— q}
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² , R ⁶ and R ⁷ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully Is a fluorinated hydrocarbon; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, Or partially or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3);

(E) formula _{^{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t CH 4-t
Where R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; ³ is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1 to 3; p is 0 to 3; and t is 2 to 4 (where n + p ≦ 4);

(F) formula _{^{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t NH 3-t
Where R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; ³ is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1 to 3; p is 0 to 3; and t is 1 to 3 (where n + p ≦ 4);

(G) Cyclic siloxane of formula (OSiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated Cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8;

(H) a cyclic silazane of the formula (NR ¹ SiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, single or double. Saturated, cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8; or

(I) a cyclic carbosilane of the formula (CR ¹ R ³ SiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, single or A polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; and x is an integer of 2-8.

  Reference has been made throughout the specification for siloxanes and disiloxanes as precursors and porogenated precursors, but the invention is not limited thereto and other such as trisiloxanes and larger length linear siloxanes. It should be understood that siloxanes are also within the scope of the present invention.

The following are non-limiting examples of Si-based porogenized precursors, where the porogen material is one or more of R ¹ , R ³ and R ⁷ :

-R ¹ _n (OR ² ) _3-n Si
Where R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; n Can be 1-3.
Example: Diethoxy-neo-hexylsilane

-R ¹ _n (OR ² ) _3-n Si-O-SiR ³ _m (OR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁴ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; n can be 1-3; and m can be 1-3.
Example: 1,3-diethoxy-1-neo-hexyldisiloxane

-R ¹ _n (OR ² ) _3-n Si-SiR ³ _m (OR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁴ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; n can be 1-3; and m can be 1-3.
Example: 1,2-diethoxy-1-neo-hexyldisilane

-R ¹ _n (OR ² ) _3-n Si-R ⁷ -SiR ³ _m (OR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁴ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated R ⁷ is independently a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; Cross-linking of two Si atoms; n can be 1-3; and m can be 1-3.
Example: 1,4-bis (dimethoxysilyl) cyclohexane

-R ¹ _n (OR ² ) _3-n Si-SiR ³ _m (OR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁴ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; n can be 1-3; and m can be 1-3.
Example: 1,2-diethoxy-1-neo-hexyldisilane

-R ¹ _n (O (O) CR ² ) _4-n Si
Where R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon As well as n can be 1-3.
Example: Diacetoxy-neo-hexylsilane

—R ¹ _n (O (O) CR ² ) _3-n Si—O—SiR ³ _m (O (O) CR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbon; R ² and R ^{4 are} independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or wholly Fluorinated hydrocarbons; n can be 1-3; and m can be 1-3.
Example: 1,3-diacetoxy-1-neo-hexyldisiloxane

—R ¹ _n (O (O) CR ² ) _3-n Si—SiR ³ _m (O (O) CR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁴ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or wholly Fluorinated hydrocarbons; n can be 1-3; and m can be 1-3.
Example: 1,2-diacetoxy-1-neo-hexyldisilane

—R ¹ _n (O (O) CR ² ) _3-n Si—O—SiR ³ _m (OR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbon; R ² is independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated R ⁴ is independently a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated. Hydrocarbons; n can be 1-3; and m can be 1-3.
Example: 1-acetoxy-3,3-di-t-butoxy-1-neohexyldisiloxane

—R ¹ _n (O (O) CR ² ) _3-n Si—SiR ³ _m (OR ⁴ ) _3-m
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbon; R ² is independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated R ⁴ is independently a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated. Hydrocarbons; n can be 1-3; and m can be 1-3.
Example: 1-acetoxy-2,2-di-t-butoxy-1-neohexyldisilane

-R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
Where R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; ³ is independently hydrogen or a C _{1 to} C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; n can be 1-3; and p can be 1-3.
Example: Acetoxy-t-butoxy-neo-hexylsilane

^{_{-R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-O-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Alternatively, all fluorinated hydrocarbons; n can be 1-3; m can be 1-3; p can be 1-3; and q can be 1-3.
Example: 1,3-diacetoxy-1,3-di-t-butoxy-1-neohexyldisiloxane

^{_{-R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Alternatively, all fluorinated hydrocarbons; n can be 1-3; m can be 1-3; p can be 1-3; and q can be 1-3.
Example: 1,2-diacetoxy-1,2-di-t-1-butoxy-1-neohexyldisilane

A cyclic siloxane of the formula (OSiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic Or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8;
Example: 1-Neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane

All of the precursor groups discussed above have the following conditions: 1) the reaction environment is essentially free of non-oxidizing and / or the reaction mixture is added the oxidant (as much CO ₂ that are not considered oxidant 2) At least one of R ¹ , R ³ and R ⁷ has a hydrocarbon of C ₃ or higher and preferably acts as a pore former, and 3) cure (eg Step) can be used to remove substantially all contained porogen from the deposited film to obtain k <2.6.

  The aforementioned precursors can be mixed with these same types of other molecules and / or with the same type of molecules except where n and / or m is 0-3.

  Alternatively, a non-limiting example of a suitable Si-based porogenated precursor is shown by the following formula:

(A) Formula R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
Where R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated carbonized. Hydrogen; n is 1 to 3; and p is 0 to 3; provided that at least one of R ¹ is substituted with a C ₃ or higher hydrocarbon as a porogen;

(B) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—O—SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _3-mq
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbon; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or moieties Or 0 to 3; m is 0 to 3; q is 0 to 3; and p is 0 to 3; provided that n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 And at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen;

(C) formula _{^{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbon; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or moieties Or 0 to 3; m is 0 to 3; q is 0 to 3; and p is 0 to 3; provided that n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 And at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen;

(D) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—R ⁷ —SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _{3-m— q}
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic Or partially or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3; provided that n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 and at least one of R ¹ , R ³ and R ⁷ is substituted with a C ₃ or higher hydrocarbon as a porogen;

(E) formula _{^{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t CH 4-t
Where R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated carbonized. Hydrogen; n is 1 to 3; p is 0 to 3; and t is 2 to 4; provided that n + p ≦ 4, and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen ;

(F) formula _{^{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t NH 3-t
Where R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated carbonized. N is 1 to 3; p is 0 to 3; and t is 1 to 3; provided that n + p ≦, and at least one of R ¹ is substituted as a porogen with a hydrocarbon of C ₃ or more;

(G) Cyclic siloxane of formula (OSiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated , Cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8 and at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen ing;

(H) a cyclic silazane of the formula (NR ¹ SiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, single or double. Saturated, cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8; and at least one of R ¹ and R ³ is a hydrocarbon of C ₃ or higher as a porogen Substituted; or

(I) a cyclic carbosilane of the formula (CR ¹ R ³ SiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, single or A polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; and x is an integer from 2 to 8; and at least one of R ¹ and R ³ is a carbon of ₃ or more as a porogen Replaced with hydrogen.

  The following are non-limiting examples of materials suitable for use as the porogen of the present invention:

(1) Cyclic hydrocarbons having the general formula C _n H _2n where n is 4-14, the cyclic structure has 4-10 carbon atoms, and many simple or branched hydrocarbons substituted in the cyclic structure May be included. Examples include cyclohexane, trimethylcyclohexane, 1-methyl-4 (1-methylethyl) cyclohexane, cyclooctane, methylcyclooctane and the like.

(2) A linear or branched, saturated, mono- or polyunsaturated hydrocarbon of the general formula C _n H _{(2n + 2) -2y} , where n is 2-20 and y = 0-n is there. Examples include ethylene, propylene, acetylene, neohexane, and the like.

(3) a mono- or polyunsaturated cyclic hydrocarbon having the general formula C _n H _2n-2x ,
Where x is the number of sites of unsaturation in the molecule, n is 4-14, the carbon number of the cyclic structure is 4-10, and mono- or polyunsaturated cyclic hydrocarbons are replaced by many simple or Branched hydrocarbon substituents may be included. Unsaturation may be located in the ring or one of the hydrocarbon substituents to the ring structure. Examples include cyclohexene, vinylcyclohexene, dimethylcyclohexene, t-butylcyclohexene, alpha-terpinene, pinene, 1,5-dimethyl-1,5-cyclooctadiene, and the like.

(4) A bicyclic hydrocarbon having the general formula C _n H _2n-2 , where n is 4-14, the number of carbons in the bicyclic structure is 4-12, and many simple substituted with a bicyclic structure Alternatively, it may contain a branched hydrocarbon. Examples include norbornane, spirononan, decahydronaphthalene, and the like.

(5) a formula _{C n H 2n- (2 + 2x} ) 2 -cyclic hydrocarbon multiply unsaturated with carbon atoms of where x is the number of unsaturated sites in the molecule, n represents 4～14,2 ring structure May contain many simple or branched hydrocarbon substituents substituted with 4-12 bicyclic structures. Unsaturation may be located in the ring or one of the hydrocarbon substituents to the ring structure. Examples include camphene, norbornene, norbornadiene, and the like.

(6) a general formula _C n _{H 2n-4} 3 cyclic hydrocarbon with, where n is the number of carbon atoms of 4～14,3 ring structures 4-12, and many simply substituted the tricyclic structure Alternatively, it may contain a branched hydrocarbon. Examples include adamantane.

  The present invention further provides a composition for carrying out the method of the present invention. The composition of the present invention preferably comprises the following formula:

  (A) at least one porogenized precursor represented by the following formula:

(1) Formula R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
Wherein R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated carbonized. Hydrogen; n is 1 to 3; and p is 0 to 3; provided that n + p ≦ 4 and at least one of R ¹ is substituted with a C ₃ or higher hydrocarbon as a porogen;

(2) _{^{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-O-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbon; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or moieties Or 0 to 3; m is 0 to 3; q is 0 to 3; and p is 0 to 3; provided that n + m ≧ 1, n + p ≦ 3m + q ≦ 3, And at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen;

(3) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si-SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _3-m-q
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbon; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or moieties Or 0 to 3; m is 0 to 3; q is 0 to 3; and p is 0 to 3; provided that n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 And at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen;

(4) _{^{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-R 7 -SiR 3 m (O (O) CR 5) q (OR 6) 3-m- _q
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic Or partially or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3; provided that n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 and at least one of R ¹ , R ³ and R ⁷ is substituted with a C ₃ or higher hydrocarbon as a porogen;

(5) Formula (R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si) _t CH _4-t
Where R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated carbonized. Hydrogen; n is 1 to 3; p is 0 to 3; and t is 2 to 4; provided that n + p ≦ 4, and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen ;

(6) _{^{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t NH 3-t
Where R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated carbonized. N is 1 to 3; p is 0 to 3; and t is 1 to 3; provided that n + p ≦, and at least one of R ¹ is substituted as a porogen with a hydrocarbon of C ₃ or more;

(7) Cyclic siloxane of formula (OSiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated , Cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8, and at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen ing;

(8) Cyclic silazane of formula (NR ¹ SiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, single or double. Saturated, cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8; and at least one of R ¹ and R ³ is a hydrocarbon of C ₃ or higher as a porogen Is substituted; or

(9) Cyclic carbosilane of formula (CR ¹ R ³ SiR ¹ R ³ ) _x wherein R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, single or A polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; and x is an integer from 2 to 8; and at least one of R ¹ and R ³ is a carbon of ₃ or more as a porogen Substituted with hydrogen; or

  (B) (1) At least one precursor selected from the group consisting of:

(A) Formula R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
Wherein R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; ³ is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; n is 1 to 3; and p is 0 to 3;

(B) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—O—SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _3-mq
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3) is there;

(C) formula _{^{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated Hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3) is there;

(D) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—R ⁷ —SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _{3-m— q}
Where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; R ² , R ⁶ and R ⁷ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully Is a fluorinated hydrocarbon; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, Or partially or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3);

(E) formula _{^{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t CH 4-t
Where R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; ³ is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1 to 3; p is 0 to 3; and t is 2 to 4 (where n + p ≦ 4);

(F) formula _{^{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t NH 3-t
Where R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; ³ is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1 to 3; p is 0 to 3; and t is 1 to 3 (where n + p ≦ 4);

(G) Cyclic siloxane of formula (OSiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated Cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8;

(H) a cyclic silazane of the formula (NR ¹ SiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, single or double. Saturated, cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8; or

(I) a cyclic carbosilane of formula (CR ¹ R ³ SiR ¹ R ³ ) _x wherein R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, single or A polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; and x is an integer from 2 to 8; and

  (B) (2) A porogen that can be distinguished from at least one precursor, the porogen being at least one of the following:

(A) at least one cyclic hydrocarbon having a cyclic structure and the formula C _n H _2n , where n is 4-14, the carbon number of the cyclic structure is 4-10, and at least one cyclic hydrocarbon is May contain many simple or branched hydrocarbons substituted with a cyclic structure;

(B) at least one linear or branched, saturated, mono- or polyunsaturated hydrocarbon of the general formula C _n H _{(2n + 2) -2y} , where n is 2-20 and y = 0 -N;

(C) at least one mono- or polyunsaturated cyclic hydrocarbon having a cyclic structure and the formula C _n H _2n-2x , where x is the number of unsaturated sites, n is 4-14, The number of carbon atoms is 4 to 10, and the at least one mono- or polyunsaturated cyclic hydrocarbon may contain many simple or branched hydrocarbon substituents substituted with a cyclic structure, One of the hydrocarbon substituents may contain unsaturation;

(D) 2 ring structures and at least one bicyclic hydrocarbon having the formula _C n _{H 2n-2,} where n is the number of carbon atoms of 4～14,2 ring structures 4-12, and at least one 2 Cyclic hydrocarbons may include many simple or branched hydrocarbons substituted with a bicyclic structure;

(E) at least one bicyclic hydrocarbon multiply unsaturated with 2 ring structures and formulas _{C n H 2n- (2 + 2x} ), where x is the number of unsaturated sites, n represents 4～14,2 ring The structure has 4 to 12 carbon atoms, and the at least one polyunsaturated bicyclic hydrocarbon may contain many simple or branched hydrocarbon substituents substituted with a bicyclic structure, and further includes an endocyclic May be unsaturated or may include unsaturation in one of its hydrocarbon substituents; and

(F) at least one tricyclic hydrocarbon having a tricyclic structure and the formula C _n H _2n-4 , where n is 4 to 14, the carbon number of the tricyclic structure is 4 to 12, and at least one 3 Cyclic hydrocarbons may include many simple or branched hydrocarbons substituted with a tricyclic structure.

  In certain embodiments of the composition comprising a porogenated precursor, preferably the composition is neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane and trimethylsilylethyl-1,3,5,7-tetra. At least one porogenized precursor selected from the group consisting of methylcyclotetrasiloxane.

  In certain embodiments of the composition comprising a porogen-free precursor, preferably the composition comprises:

  (A) (i) diethoxymethylsilane, dimethoxymethylsilane, diisopropoxymethylsilane, di-t-butoxymethylsilane, methyltriethoxysilane, methyltrimethoxysilane, methyltriisopropoxysilane, methyltri-t- Consists of butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldi-t-butoxysilane, 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and tetraethoxysilane At least one precursor selected from the group, and (ii) a porogen that can be distinguished from at least one precursor, said porogen being alpha-terpinene, limonene, cyclohexane, 1,2,4-trimethylcyclo Hexane, 1,5-dimethyl-1,5-cyclooctadiene, camphene, adamantane, 1,3-butadiene is at least one selected from the group consisting of substituted dienes and decahydronaphthalene; and / or

  (B) (i) Trimethylsilane, tetramethylsilane, diethoxymethylsilane, dimethoxymethylsilane, di-t-butoxymethylsilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltriacetoxysilane, methyl Consists of diacetoxysilane, methylethoxydisiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, dimethyldiacetoxysilane, bis (trimethoxysilyl) methane, bis (dimethoxysilyl) methane, tetraethoxysilane and triethoxysilane At least one precursor selected from the group, and (ii) a porogen that is distinguishable from at least one precursor, said porogen being alpha-terpinene, gamma-terpinene, limo Emissions, dimethylhexadiene, ethylbenzene, decahydronaphthalene, 2-carene, 3-carene, which is one selected from the group consisting of cyclohexene and dimethyl cyclooctadiene to vinylcyclohexane.

  The composition of the present invention comprises, for example, a vessel (preferably made of stainless steel) with suitable valves and fittings, which can be pressurized, and the process reactor contains porogen, non-porogenated precursor and / or porogenation. Enable to supply precursor. The contents of the container can be premixed. Alternatively, the porogen and precursor can be held in separate containers or in a single container with means to hold the porogen and precursor separately during storage. Such containers may also have means for mixing the porogen and precursor when desired.

  The porogen is removed from the preliminary (ie, as-deposited) film by the curing step, which may include thermal annealing, chemical processing, in situ or remote plasma processing, photocuring and / or microwaves. . Other in-situ or post-deposition treatment materials such as hardness, stability (for shrinkage, exposure to air, etching, wet etching, etc.), integrity, uniformity and adhesion Can be used to improve properties. Such a treatment can be applied to the membrane before, during and / or after porogen removal using the same or different means as used for porogen removal. Thus, as used herein, the term “post-treating” refers to the treatment of membranes with energy (eg, heat, plasma, photons, electrons, microwaves, etc.) or chemical agents to remove porogens. , And optionally show improved material properties. The conditions under which post-processing is performed can vary greatly. For example, the post-treatment can be performed under high pressure or under vacuum.

Annealing is carried out under the following conditions. Environment is inert (eg, nitrogen, CO ₂ , noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidation (eg, oxygen, air, diluted oxygen environment, enriched oxygen environment, ozone, nitrous oxide) Etc.) or reduction (diluted or concentrated hydrogen, hydrocarbons (saturated, unsaturated, linear or branched, aromatic), etc.). The pressure is preferably about 1 Torr to about 1000 Torr, more preferably atmospheric pressure. However, a vacuum atmosphere is possible for thermal annealing as well as other post-treatment means. The temperature is preferably 200-500 ° C. and the temperature gradient is 0.1-100 ° C./min. The total annealing time is preferably 0.01 minutes to 12 hours. The chemical treatment of the OSG film is performed under the following conditions. Fluorinated _{(HF, SIF 4, NF 3} , F 2, COF 2, CO 2 F 2, etc.), oxidizing _{(H 2 O 2, O 3} , etc.), chemical drying, methylating, or the properties of the final material Other chemical treatments that improve can be used. The chemical agent used for such processing can be in a solid, liquid, gaseous, and / or supercritical fluid state.

The supercritical fluid post-treatment for selectively removing porogen from the organic silicate membrane is performed under the following conditions. Fluid carbon dioxide, water, nitrous oxide, ethylene, may be SF _6, and / or other types of chemical agents. Other chemical agents are inert (eg, nitrogen, CO ₂ , noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidized (eg, oxygen, ozone, nitrous oxide, etc.) or reduced (diluted) Or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably from atmospheric to 500 ° C. Further, the chemical agent can include relatively large chemical species such as surfactants. The total exposure time is preferably 0.01 minutes to 12 hours. Plasma treatment for selective removal of reactive active groups and possible chemical modification of the OSG film is performed under the following conditions. Environment is inert (eg, nitrogen, CO ₂ , noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidation (eg, oxygen, air, diluted oxygen environment, enriched oxygen environment, ozone, sub-oxidation) Nitrogen, etc.), or reduction (diluted or concentrated hydrogen, hydrocarbons (saturated, unsaturated, linear or branched, aromatic), etc.). The plasma power is preferably 0 to 5000 W. The temperature is preferably from atmospheric to 500 ° C. The pressure is preferably about 10 mtorr to atmospheric pressure. The total curing time is preferably 0.01 minutes to 12 hours.

Photocuring for selective removal of porogen from the organosilicate film is performed under the following conditions. Environment is inert (eg, nitrogen, CO ₂ , noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidation (eg, oxygen, air, diluted oxygen environment, enriched oxygen environment, ozone, sub-oxidation) Nitrogen, etc.), or reduction (diluted or concentrated hydrogen, hydrocarbons (saturated, unsaturated, linear or branched, aromatic), etc.). The temperature is preferably from atmospheric to 500 ° C. The power is preferably 0 to 5000W. The wavelength is preferably IR, visible, UV, or deep UV (wavelength <200 nm). The total curing time is preferably 0.01 minutes to 12 hours.

Microwave post-treatment for selective removal of porogen from the organosilicate membrane is carried out under the following conditions. Environment is inert (eg, nitrogen, CO ₂ , noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidation (eg, oxygen, air, diluted oxygen environment, enriched oxygen environment, ozone, sub-oxidation) Nitrogen, etc.), or reduction (diluted or concentrated hydrogen, hydrocarbons (saturated, unsaturated, linear or branched, aromatic), etc.). The temperature is preferably from atmospheric to 500 ° C. The power and wavelength will vary and can be adapted depending on the particular coupling. The total curing time is preferably 0.01 minutes to 12 hours.

Electron beam post-treatment for selective removal of porogens or specific chemical species from organic silicate films and / or improvement of film properties is carried out under the following conditions. Environment is inert (eg, nitrogen, CO ₂ , noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidation (eg, oxygen, air, diluted oxygen environment, enriched oxygen environment, ozone, sub-oxidation) Nitrogen, etc.), or reduction (diluted or concentrated hydrogen, hydrocarbons (saturated, unsaturated, linear or branched, aromatic), etc.). The temperature is preferably from atmospheric to 500 ° C. The total curing time is preferably from 0.01 min to 12 hours and may be continuous or pulsating. Additional guidance on the general use of electron beams is available in the publication: Chattopadhyay et al., Journal of Materials Science, 36 (2001) 4323-4330; Kloster et al., Proceedings of IITC, June 3-5, 2002, SF, CA; and US Pat. Nos. 6,207,555B1; 6,204, 201B1; The use of electron beam treatment can provide porogen removal and improved mechanical properties of the film due to the bond formation process in the matrix.

  While the present invention will be described in further detail with reference to the following examples, it is to be understood that the invention is not limited thereto.

All experiments were performed with an Applied Materials Precision-5000 system in a 200 mm DxZ chamber fitted with an Advance Energy 2000rf generator using an undoped TEOS process kit. The recipe included the following basic steps: initial setup and stabilization for chamber purge / evacuation prior to gas flow, deposition, and wafer removal. The membrane was annealed under N ₂ at 425 ° C. for 4 hours in a tube furnace.

  Thickness and refractive index were measured with a SCI Filmtek 2000 Reflectometer. The dielectric constant was measured using a Hg probe method on a low resistivity P-type wafer (<0.02 ohm-cm). Mechanical properties were measured using a MTS Nano Indenter. Thermal stability and off-gas products were measured by thermogravimetric analysis using a Thermo TA Instruments 2050 TGA. The composition data was obtained by X-ray photoelectron spectroscopy (XPS) using Physical Electronics 5000LS. The atomic% shown in the table does not contain hydrogen.

  Three routes were chosen to introduce pores into the OSG membrane. The first route investigated to produce low-k films with k <2.6 is the co-deposition of thermally reactive organic oligomers as porogens with OSG by plasma enhanced chemical vapor deposition (RECVD), followed by The oligomer was removed in the thermal annealing step.

<Example 1A>
Alpha-terpinene (ATP) was co-deposited with diethoxymethylsilane (DEMS) on a silicon wafer by PECVD in an oxidant-free environment. The process conditions were 700 mg / min (mgm) with a 39.4 vol% ATP mixture flow in DEMS. A carrier gas flow of 500 sccm CO ₂ was used to entrain the chemical into the deposition chamber. Additional process conditions were as follows: chamber pressure 5 Torr; wafer chuck temperature 150 ° C .; showerhead-wafer spacing 0.26 inches (about 0.6 cm); and plasma power 300 W, 180 seconds. The as-deposited film had a thickness of 650 nm and a dielectric constant of 2.8. The membrane was annealed at 425 ° C. for 4 hours under nitrogen to remove substantially all of the formulated ATP as confirmed by XPS. FIG. 1 shows the infrared spectrum of the film before annealing (light solid line) and after (dark solid line), and the disappearance of the porogen is observed. The annealed film had a thickness of 492 nm and a dielectric constant of 2.4 (see Table 2 bottom). FIG. 4 shows a thermogravimetric analysis of the film, showing the weight loss during heat treatment.

<Example 1B>
ATP was co-deposited with DEMS on a silicon wafer by PECVD in an oxidant-free environment. Process conditions were 1300 mg / min (mgm) of 70 vol% ATP mixture flow in DEMS. A carrier gas flow of 500 sccm CO ₂ was used to entrain the chemical into the deposition chamber. Additional process conditions were as follows: chamber pressure 8 Torr; wafer chuck temperature 200 ° C .; showerhead-wafer spacing 0.30 inch (about 0.8 cm); and plasma power 600 W, 120 seconds. The as-deposited film had a thickness of 414 nm and a dielectric constant of 2.59. The membrane was annealed at 425 ° C. for 4 hours under nitrogen to remove substantially all of the formulated ATP. The annealed film had a thickness of 349 nm and a dielectric constant of 2.14 (see Table 2 bottom).

<Example 1C>
The membrane was prepared and annealed substantially according to Example 1A except that the anneal was performed at a reduction temperature of 400 ° C. The infrared spectrum of the obtained film is shown in FIG. The infrared spectra of porogen and ATP are shown in FIG. 3 for comparison.

<Example 1D (comparison)>
A membrane was prepared and annealed substantially according to Example 1A except that no porogen was used. The film had a dielectric constant of 2.8 and had substantially the same composition as the annealed film of Example 1A (see Tables 1 and 2).

<Example 1E (comparison)>
The membrane was prepared and annealed substantially according to Example 1D except that the plasma power was 400W. The film had a dielectric constant of 2.8 and had substantially the same composition as the annealed film of Example 1A (see Tables 1 and 2).

<Example 1F>
The membrane was prepared substantially according to Example 1A, except that the process conditions were 1000 vol / min (mgm) of 75 vol% ATP mixture flow in di-t-butoxymethylsilane (DtBOMS) and annealed. It was done. A carrier gas flow of 500 sccm CO ₂ was used to entrain the chemical into the deposition chamber. Additional process conditions were as follows: chamber pressure 7 Torr; wafer chuck temperature 215 ° C .; showerhead-wafer spacing 0.30 inch (about 0.8 cm); and plasma power 400 W, 240 seconds. The as-deposited film had a thickness of 540 nm and a dielectric constant of 2.8. The membrane was annealed at 425 ° C. for 4 hours under nitrogen to remove substantially all of the formulated ATP as confirmed by XPS. The annealed film had a thickness of 474 nm and a dielectric constant of 2.10. The modulus and hardness were 2.23 and 0.18 GPa, respectively.

<Example 1G>
ATP was co-deposited with DtBOMS on a silicon wafer by PECVD in an oxidant-free environment. The process conditions were 700 vol / min (mgm) of 75 vol% ATP mixture flow in DtBOMS. A carrier gas flow of 500 sccm CO ₂ was used to entrain the chemical into the deposition chamber. Additional process conditions were as follows: chamber pressure 9 Torr; wafer chuck temperature 275 ° C .; showerhead-wafer spacing 0.30 inch (about 0.8 cm); and plasma power 600 W, 240 seconds. The as-deposited film had a thickness of 670 nm and a dielectric constant of 2.64. The membrane was annealed at 425 ° C. for 4 hours under nitrogen to remove substantially all of the formulated ATP. The annealed film had a thickness of 633 nm and a dielectric constant of 2.19. The modulus and hardness were 3.40 and 0.44 GPa, respectively.

<Example 2>
A second route investigated to produce low-k films with k <2.6 uses a single source organosilane precursor containing a thermally reactive organic functional group as part of the molecular structure did. A potential advantage of attaching thermally reactive groups to the silica precursor is an improved introduction of thermally reactive groups into the membrane. To study this route, neo-hexyl-tetramethylcyclotetrasiloxane (neo-hexyl-TMCTS) was synthesized and the neo-hexyl group was grafted to the TMCTS framework. The process used for this test was: Neo-Hexyl-TMCTS 500 mgm flow and 500 sccm CO ₂ carrier gas flow; chamber pressure 6 Torr; wafer chuck temperature 150 ° C .; showerhead-wafer spacing 0.32 inch. 8 cm); and a plasma power of 300 W for 90 seconds. The as-deposited film had a thickness of 1120 nm and a dielectric constant of 2.7. The membrane was annealed at 425 ° C. for 4 hours under nitrogen. The film thickness was reduced to 710 nm and the dielectric constant was 2.5. The film deposited from TMCTS at 150 ° C. was as deposited and had a dielectric constant of 2.8, but did not change after annealing at 425 ° C. for 4 hours.

<Example 3>
A third route that has been considered to produce low-k films with k <2.6 was to physically mix the organosilicon precursor with thermally reactive large groups attached to it. It was. To show the effect of this pathway, a potential advantage of attaching thermally reactive groups to the silica precursor is an improved introduction of thermally reactive groups into the membrane. To study this route, flufuroxydimethylsilane was co-deposited with TMCTS under the following conditions: 1000 mgm flow of 11% flufroxydimethylsilane mixture in TMCTS and 500 sccm He carrier gas flow; chamber pressure 6 Torr; Wafer chuck temperature 150 ° C .; showerhead-wafer spacing 0.26 inch (about 0.6 cm); and plasma power 300 W, 40 seconds. The as-deposited film had a thickness of 1220 nm and a dielectric constant of 3.0. The content of furfuroxy was indicated by FTIR in the as-deposited film. After a thermal post-treatment at 400 ° C. for 4 hours under nitrogen, k was 2.73. In this case, it is believed that a significant portion of the introduced furfuroxy remained even after thermal annealing.

  The above examples show the ability to introduce various functional groups into the as-deposited film, and more importantly, the proper choice of porogen to allow materials with k <2.6. Show importance. A variety of other porogens can also function using these pathways. Providing a low dielectric constant material with k <2.6 requires a network-forming organosilane / organosiloxane precursor so that the appropriate type and amount of organic groups can be introduced into the OSG network. It is preferred to use a network forming precursor that does not require the addition of an oxidant to produce an OSG film. This is particularly important when using oxidation-sensitive hydrocarbon-based pore-forming precursors. Oxidation can cause significant denaturation of the pore former during deposition and can interfere with the ability to be removed during the annealing process.

Comparison of the IR spectra of as-deposited and N ₂ thermal post-treated DEMS / ATP films shows that thermal post-treatment in an inert atmosphere was successful for selective removal of porogen and retention of the OSG lattice. There is no substantial change in Si—CH ₃ absorption at 1275 cm ⁻¹ after thermal annealing (Si—CH ₃ is associated with the OSG network). However, there was a dramatic decrease in C—H absorption near 3000 cm ⁻¹ , indicating that essentially all the carbon associated with ATP has been removed. The IR spectrum for ATP is shown as a control in FIG. A further advantage of this anneal appears to be a significant reduction in Si-H absorption at 2240 and 2170 cm ^-1 which makes the membrane more hydrophobic. Thus, in certain embodiments of the invention, the core Si atoms of the film are bonded to 1 or less H atoms. However, in other embodiments, the number of H atoms bonded to Si atoms is not so limited. Elemental analysis showed that a DEMS-ATP film (Example 1A) after annealing at 425 ° C. for 4 hours was deposited in a similar manner and had essentially the same composition as the annealed DEMS film (Example 1D). Was. The pre-anneal DEMS-ATP film shows a substantially higher amount of carbon-based material in the film (IR analysis supports that this carbon-based material is very similar to ATP, see FIG. 3). This supports the explanation that the porogen material introduced into the DEMS film when co-deposited with ATP is essentially fully removed in the thermal aftertreatment process. Furthermore, thermogravimetric analysis (FIG. 4) shows that a significant weight loss of as-deposited material is experienced when heated to temperatures above 350 ° C., which indicates the removal of porogen during annealing. It becomes additional proof. The observed membrane shrinkage appears to have been caused by the collapse of some parts of the OSG network upon porogen removal. However, there is almost no loss of organic groups from the OSG network, that is, most of the terminal methyl groups in the DEMS are retained (see XPS data before and after heat treatment for the DEMS film shown in Table 1). This is supported by the equivalent Si—CH ₃ band at ˜1275 wavenumbers in the IR spectrum. The hydrophobicity of this material is demonstrated by the deletion of the Si-OH group in the IR spectrum. The decrease in the refractive index and dielectric constant of the post-treatment film suggests that it is less dense than the film before annealing despite the decrease in film thickness. Positron annihilation lifetime spectroscopy (PALS) indicates that the pores of the 1A, 1B, and 1F samples are in the range of ~ 1.5 nm sphere equivalent diameter. Furthermore, unlike the previously described work by Grill et al., The decrease in thickness associated with composition change (Example 1A) indicates that the OSG network is retained during annealing and is hardly degraded.

  While the invention has been described in terms of several preferred embodiments, the scope of the invention is not limited to these embodiments and should be ascertained from the claims.

  According to the present invention, a porous organic silica glass film having a low dielectric constant and improved mechanical properties, thermal stability and chemical resistance can be provided.

Claims (67)

Formula _{Si v O w C x H y} F z (v + w + x + y + z = 100%, v is from 10 to 35 atomic%, w is from 10 to 65 atomic%, x is from 5 to 30 atomic%, y is from 10 to 50 atomic%, and z is a chemical vapor deposition method for producing a porous organic silica glass film represented by 0 to 15 atomic%, and includes the following steps:
Providing a substrate in a vacuum chamber;
Introducing a gaseous reagent comprising at least one precursor selected from the group consisting of an organosilane and an organosiloxane and a porogen into a vacuum chamber;
Applying energy to the gaseous reagent in the vacuum chamber to cause a reaction of the gaseous reagent to deposit a preliminary film on the substrate, wherein the preliminary film comprises a porogen and the preliminary film Is deposited without the addition of an oxidant when the porogen is distinguishable from at least one precursor);
Removing substantially all of the porogen from the preliminary membrane to obtain a porous membrane having pores and a dielectric constant of less than 2.6.   The method of claim 1, wherein the dielectric constant is less than 1.9.   The method of claim 1, wherein v is 20-30 atomic%, w is 20-45 atomic%, x is 5-20 atomic%, y is 15-40 atomic%, and z is 0. z is 0.5-7 atomic%, and the at least one fluorinating agent is selected from the group consisting of SiF ₄ , NF ₃ , F ₂ , COF ₂ , CO ₂ F ₂ , and HF; The method according to claim 1, wherein substantially all of the F in the porous membrane is bonded to Si of the Si—F group.   The method of claim 1, wherein most of the hydrogen in the porous membrane is bonded to carbon.   The method of claim 1, wherein the porous membrane has a density of less than 1.5 g / mL.   The method according to claim 1, wherein the pores have a sphere equivalent diameter of 5 nm or less.   The method of claim 1, wherein the Fourier transform infrared (FTIR) spectrum of the porous membrane is substantially the same as the control FTIR of the control membrane prepared by substantially the same method except for the absence of the porogen.   9. The method of claim 8, wherein the porous film has a dielectric constant that is at least 0.3 less than the control dielectric constant of the control film.   The method of claim 8, wherein the porous membrane has a density that is at least 10% less than the control density of the control membrane. The method of claim 8, wherein the porous membrane has an average weight loss of less than 1.0 wt% / hour at 425 ° C. isothermal in N ₂ .   The method of claim 8, wherein the porous membrane has an average weight loss of less than 1.0 wt% / hour at 425 ° C. isothermal in air.   The method of claim 1, wherein the porogen is distinguishable from the at least one precursor. 14. The method of claim 13, wherein the at least one precursor is represented by the formula:
(A) Formula R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; n is 1-3; and p is 0-3);
(B) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—O—SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _3-mq
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated. R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3)) ;
(C) formula ^{_{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated. R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3)) ;
(D) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—R ⁷ —SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _{3-m— q}
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁶ and R ⁷ are independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully Fluorinated hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, Or a partially or fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3));
(E) formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t CH 4-t
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1-3; p is 0-3; and t is 2-4 (where n + p ≦ 4));
(F) formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t NH 3-t
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1-3; p is 0-3; and t is 1-3 (where n + p ≦ 4));
(G) a cyclic siloxane of the formula (OSiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, Cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8);
(H) a cyclic silazane of the formula (NR ¹ SiR ¹ R ³ ) _x (R ¹ and R ³ are independently hydrogen, or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated Cyclic or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8); or (i) a cyclic carbosilane of formula (CR ¹ R ³ SiR ¹ R ³ ) _x (R ¹ And R ³ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; and x is an integer of 2 to 8).   At least one precursor is diethoxymethylsilane, dimethoxymethylsilane, diisopropoxymethylmethylsilane, di-t-butoxymethylsilane, methyltriethoxysilane, methyltrimethoxysilane, methyltriisopropoxysilane, methyltri-t. -From butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldi-t-butoxysilane, 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and tetraethoxysilane 14. The method of claim 13, wherein the method is selected from the group consisting of:   The at least one precursor is a mixture of a first organosilicon precursor having 2 or less Si-O bonds and a second organosilicon precursor having 3 or more Si-O bonds, and The method of claim 1, wherein the mixture is provided to match the chemical composition of the porous membrane. The method of claim 1, wherein the porogen is selected from the group consisting of:
(A) at least one cyclic hydrocarbon of the formula C _n H _2n having a cyclic structure (n is 4-14, the number of carbons in the cyclic structure is 4-10, and the at least one cyclic hydrocarbon is cyclic May have a plurality of simple or branched hydrocarbons substituted on the structure);
(B) at least one linear or branched, saturated, mono- or polyunsaturated hydrocarbon of the general formula C _n H _{(2n + 2) -2y} , where n is 2 to 20 and y = 0 to n;
(C) At least one mono- or polyunsaturated cyclic hydrocarbon of the formula C _n H _2n-2x having a cyclic structure (where x is the number of unsaturated sites, n is 4 to 14, and the number of carbons in the cyclic structure is 4-10, and the at least one mono- or polyunsaturated cyclic hydrocarbon may have a plurality of simple or branched hydrocarbon substituents substituted on the cyclic structure, and the hydrocarbon substitution One of the groups may have unsaturation or endocyclic unsaturation);
(D) at least one bicyclic hydrocarbon of the formula C _n H _2n-2 having a bicyclic structure (wherein n is 4-14, the number of carbons in the bicyclic structure is 4-12, and this at least one bicyclic carbon Hydrogen may have multiple simple or branched hydrocarbons substituted on the bicyclic structure);
(E) wherein _{C n H 2n- (2 + 2x} ) of at least one bicyclic hydrocarbon (x is the number of unsaturated sites in multiply unsaturated with two ring structure, n represents carbon in 4～14,2 ring structure The number is 4 to 12, and the at least one polyunsaturated bicyclic hydrocarbon may have a plurality of simple or branched hydrocarbon substituents substituted on the bicyclic structure, and the carbon One of the hydrogen substituents may have unsaturation or endocyclic unsaturation); and
(F) at least one tricyclic hydrocarbon of the formula C _n H _2n-4 having a tricyclic structure (wherein n is 4 to 14, the number of carbons in the tricyclic structure is 4 to 12, and the at least one tricyclic carbon Hydrogen may have multiple simple or branched hydrocarbons substituted on the tricyclic structure).   Porogen is alpha-terpinene, limonene, cyclohexane, 1,2,4-trimethylcyclohexane, 1,5-dimethyl-1,5-cyclooctadiene, camphene, adamantane, 1,3-butadiene, substituted diene And at least one selected from the group consisting of decahydronaphthalene.   The method of claim 1, wherein the at least one precursor comprises at least one porogen bound thereto.   20. The method of claim 19, wherein the gaseous reagent further comprises at least one porogen-free precursor selected from the group consisting of organosilanes and organosiloxanes.   20. The method of claim 19, wherein the removing step leaves the methyl group attached to the Si to which the porogen has been previously attached. 20. The method of claim 19, wherein the at least one precursor is represented by the formula:
(A) Formula R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; and p is 0 to 3 (where n + p ≦ 4 and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen));
(B) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—O—SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _3-mq
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3m + q ≦ 3, and At least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen)));
(C) formula ^{_{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 And at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen));
(D) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—R ⁷ —SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _{3-m— q}
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, Or partially or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 and at least one of R ¹ , R ³ and R ⁷ is substituted with a C ₃ or higher hydrocarbon as a porogen));
(E Formula (R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si) _t CH _4-t
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; p is 0 to 3; and t is 2 to 4 (where n + p ≦ 4, and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen); ));
(F) formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t NH 3-t
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; p is 0 to 3; and t is 1 to 3 (where n + p ≦ and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen) );
(G) a cyclic siloxane of the formula (OSiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, Cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8 (provided that at least one of R ¹ and R ³ is substituted with a hydrocarbon of C ₃ or more as a porogen) There));
(H) a cyclic silazane of formula (NR ¹ SiR ¹ R ³ ) _x (R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated Cyclic or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8 (provided that at least one of R ¹ and R ³ is substituted with a hydrocarbon of C ₃ or more as a porogen) Or)); or
(I) a cyclic carbosilane of formula (CR ¹ R ³ SiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, single or double Unsaturated, cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer of 2-8 (wherein at least one of R ¹ and R ³ is a hydrocarbon of C ₃ or more as a porogen) ))).   At least one precursor is 1-neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-neopentyl-1,3,5,7-tetramethylcyclotetrasiloxane, neopentyldiethoxysilane 20. The method of claim 19, wherein the method is selected from the group consisting of:, neohexyldiethoxysilane, neohexyltriethoxysilane, neopentyltriethoxysilane, and neopentyl-di-t-butoxysilane. A porous organic silica glass membrane produced by the method according to claim 1, wherein the formula Si _v O _w C _x H _y F _z (v + w + x + y + z = 100%, v is 10 to 35 atomic%, w is 10 to 65 Atom%, x is 5 to 30 atom%, y is 10 to 50 atom%, and z is 0 to 15 atom%), has pores, and has a dielectric constant of 2 A porous organic silica glass membrane that is less than .6.   25. The film of claim 24, wherein v is 20-30 atomic%, w is 20-45 atomic%, x is 5-25 atomic%, y is 15-40 atomic%, and z is 0.   25. The membrane of claim 24, wherein z is 0.5-7 atomic% and substantially all of the F in the porous membrane is bonded to Si of the Si-F group.   25. The membrane of claim 24, wherein a majority of hydrogen is bonded to carbon.   Neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane.   Trimethylsilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane.   A composition comprising 1,3,5,7-tetramethylcyclotetrasiloxane substituted with a porogen. (A) at least one porogenized precursor represented by the following formula:
(1) Formula R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; and p is 0 to 3 (where n + p ≦ 4 and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen));
(2) ^{_{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-O-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 And at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen));
(3) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si-SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _3-m-q
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 And at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen));
(4) ^{_{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-R 7 -SiR 3 m (O (O) CR 5) q (OR 6) 3-m- _q
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, Or partially or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 and at least one of R ¹ , R ³ and R ⁷ is substituted with a C ₃ or higher hydrocarbon as a porogen));
(5) Formula (R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si) _t CH _4-t
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; p is 0 to 3; and t is 2 to 4 (where n + p ≦ 4, and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen); ));
(6) ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t NH 3-t
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; p is 0 to 3; and t is 1 to 3 (where n + p ≦ and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen) );
(7) Cyclic siloxane of formula (OSiR ¹ R ³ ) _x (R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, Cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8 (provided that at least one of R ¹ and R ³ is substituted with a hydrocarbon of C ₃ or more as a porogen) There));
(8) Cyclic silazane of formula (NR ¹ SiR ¹ R ³ ) _x (R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated Cyclic or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8 (provided that at least one of R ¹ and R ³ is substituted with a hydrocarbon of C ₃ or more as a porogen) Or;
(9) Cyclic carbosilanes of formula (CR ¹ R ³ SiR ¹ R ³ ) _x (R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, single or double Unsaturated, cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer of 2-8 (wherein at least one of R ¹ and R ³ is a hydrocarbon of C ₃ or more as a porogen) Substituted with); or
(B) (1) At least one precursor selected from the group consisting of:
(A) Formula R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; n is 1-3; and p is 0-3);
(B) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—O—SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _3-mq
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated. R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3)) ;
(C) formula ^{_{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated. R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3)) ;
(D) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—R ⁷ —SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _{3-m— q}
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁶ and R ⁷ are independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully Fluorinated hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, Or a partially or fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3));
(E) formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t CH 4-t
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1-3; p is 0-3; and t is 2-4 (where n + p ≦ 4));
(F) formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t NH 3-t
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1-3; p is 0-3; and t is 1-3 (where n + p ≦ 4));
(G) a cyclic siloxane of the formula (OSiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, Cyclic, or partially or fully fluorinated hydrocarbons; and x may be an integer from 2 to 8);
(H) a cyclic silazane of the formula (NR ¹ SiR ¹ R ³ ) _x (R ¹ and R ³ are independently hydrogen, or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated Cyclic or partially or fully fluorinated hydrocarbons; and x may be an integer from 2 to 8); or (i) cyclic of formula (CR ¹ R ³ SiR ¹ R ³ ) _x Carbosilane (R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; and x may be an integer from 2 to 8);
(B) (2) A porogen that can be distinguished from at least one precursor, the porogen being at least one of the following:
(A) at least one cyclic hydrocarbon of the formula C _n H _2n having a cyclic structure (n is 4-14, the number of carbons in the cyclic structure is 4-10, and the at least one cyclic hydrocarbon is cyclic May have a plurality of simple or branched hydrocarbons substituted on the structure);
(B) at least one linear or branched, saturated, mono- or polyunsaturated hydrocarbon of the general formula C _n H _{(2n + 2) -2y} , where n is 2 to 20 and y = 0 to n;
(C) At least one mono- or polyunsaturated cyclic hydrocarbon of the formula C _n H _2n-2x having a cyclic structure (where x is the number of unsaturated sites, n is 4 to 14, and the number of carbons in the cyclic structure is 4-10, and the at least one mono- or polyunsaturated cyclic hydrocarbon may have a plurality of simple or branched hydrocarbon substituents substituted on the cyclic structure, and the hydrocarbon substitution One of the groups may have unsaturation or endocyclic unsaturation);
(D) at least one bicyclic hydrocarbon of the formula C _n H _2n-2 having a bicyclic structure (wherein n is 4-14, the number of carbons in the bicyclic structure is 4-12, and this at least one bicyclic carbon Hydrogen may have multiple simple or branched hydrocarbons substituted on the bicyclic structure);
(E) wherein _{C n H 2n- (2 + 2x} ) of at least one bicyclic hydrocarbon (x is the number of unsaturated sites in multiply unsaturated with two ring structure, n represents carbon in 4～14,2 ring structure The number is 4 to 12, and the at least one polyunsaturated bicyclic hydrocarbon may have a plurality of simple or branched hydrocarbon substituents substituted on the bicyclic structure, and the carbon One of the hydrogen substituents may have unsaturation or endocyclic unsaturation); and
(F) at least one tricyclic hydrocarbon of the formula C _n H _2n-4 having a tricyclic structure (wherein n is 4 to 14, the carbon number in the tricyclic structure is 4 to 12, and the at least one tricyclic carbon Hydrogen may have multiple simple or branched hydrocarbons substituted on the tricyclic structure);
A composition comprising A composition comprising at least one porogenized precursor represented by the formula:
(A) Formula R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; and p is 0 to 3 (where n + p ≦ 4 and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen));
(B) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—O—SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _3-mq
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 And at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen));
(C) formula ^{_{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 And at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen);
(D) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—R ⁷ —SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _{3-m— q}
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, Or partially or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 and at least one of R ¹ , R ³ and R ⁷ is substituted with a C ₃ or higher hydrocarbon as a porogen));
(E) formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t CH 4-t
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; p is 0 to 3; and t is 2 to 4 (where n + p ≦ 4, and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen); ));
(F) formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t NH 3-t
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; p is 0 to 3; and t is 1 to 3 (where n + p ≦ and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen) );
(G) a cyclic siloxane of the formula (OSiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, Cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8 (at least one of R ¹ and R ³ is substituted with a hydrocarbon of C ₃ or more as a porogen) );
(H) a cyclic silazane of formula (NR ¹ SiR ¹ R ³ ) _x (R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated Cyclic, partially or fully fluorinated hydrocarbons; and x is an integer from 2 to 8 (provided that at least one of R ¹ and R ³ is substituted with a C ₃ or higher hydrocarbon as a porogen) Or)); or
(I) a cyclic carbosilane of formula (CR ¹ R ³ SiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, single or double Unsaturated, cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer of 2-8 (wherein at least one of R ¹ and R ³ is a hydrocarbon of C ₃ or more as a porogen) ))). 33. The composition of claim 32, comprising at least one porogenized precursor represented by the formula:
Formula R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; and p is 0 to 3 (where n + p ≦ 4, and at least one of R ¹ is substituted with a C ₃ or more hydrocarbon as a porogen). 33. The composition of claim 32, comprising at least one porogenized precursor represented by the formula:
Wherein ^{_{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-O-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 And at least one of R ¹ and R ³ is substituted with a hydrocarbon of C ₃ or more as a porogen)). 33. The composition of claim 32, comprising at least one porogenized precursor represented by the formula:
Wherein ^{_{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or a fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 And at least one of R ¹ and R ³ is substituted with a hydrocarbon of C ₃ or more as a porogen)). 33. The composition of claim 32, comprising at least one porogenized precursor represented by the formula:
Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—R ⁷ —SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _3-m-q
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, Or partially or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3, m + q ≦ 3 and at least one of R ¹ , R ³ and R ⁷ is substituted with a C ₃ or higher hydrocarbon as a porogen)). 33. The composition of claim 32, comprising at least one porogenized precursor represented by the formula:
Formula (R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si) _t CH _4-t
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; p is 0 to 3; and t is 2 to 4 (where n + p ≦ 4, and at least one of R ¹ is substituted with a hydrocarbon of C ₃ or more as a porogen )). 33. The composition of claim 32, comprising at least one porogenized precursor represented by the formula:
Formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t NH 3-t
(R ¹ is independently hydrogen or a C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² and R ³ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbons. N is 1 to 3; p is 0 to 3; and t is 1 to 3 (where n + p ≦ and at least one of R ¹ is substituted with a C ₃ or more hydrocarbon as a porogen) ). 33. The composition of claim 32, comprising at least one porogenized precursor represented by the formula:
A cyclic siloxane of formula (OSiR ¹ R ³ ) _{x wherein} R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, cyclic, Or a partially or fully fluorinated hydrocarbon; and x is an integer of 2 to 8 (wherein at least one of R ¹ and R ³ is substituted with a hydrocarbon of C ₃ or more as a porogen)) . 33. The composition of claim 32, comprising at least one porogenized precursor represented by the formula:
A cyclic silazane of the formula (NR ¹ SiR ¹ R ³ ) _x (R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic Or a partially or fully fluorinated hydrocarbon; and x is an integer of 2-8, provided that at least one of R ¹ and R ³ is substituted with a hydrocarbon of C ₃ or more as a porogen )). 33. The composition of claim 32, comprising at least one porogenized precursor represented by the formula:
Cyclic carbosilanes of formula (CR ¹ R ³ SiR ¹ R ³ ) _x (R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated , Cyclic, or partially or fully fluorinated hydrocarbons; and x is an integer of 2-8 (wherein at least one of R ¹ and R ³ is substituted with a hydrocarbon of C ₃ or more as a porogen) ing)). A composition comprising at least one precursor and a porogen that is distinguishable from the precursor, wherein the precursor is selected from the group consisting of:
(A) Formula R ¹ _n (OR ² ) _p (O (O) CR ³ ) _{4- (n + p)} Si
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; n is 1-3; and p is 0-3);
(B) R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—O—SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _3-mq
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated. R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3)) ;
(C) formula ^{_{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m-q
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated. R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3)) ;
(D) Formula R ¹ _n (OR ² ) _p (O (O) CR ⁴ ) _3-np Si—R ⁷ —SiR ³ _m (O (O) CR ⁵ ) _q (OR ⁶ ) _{3-m— q}
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁶ and R ⁷ are independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully Fluorinated hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, Or a partially or fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3));
(E) formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t CH 4-t
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1-3; p is 0-3; and t is 2-4 (where n + p ≦ 4));
(F) formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) t NH 3-t
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1-3; p is 0-3; and t is 1-3 (where n + p ≦ 4));
(G) a cyclic siloxane of the formula (OSiR ¹ R ³ ) _x where R ¹ and R ³ are independently hydrogen or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, Cyclic, or partially or fully fluorinated hydrocarbons; and x may be an integer from 2 to 8);
(H) a cyclic silazane of the formula (NR ¹ SiR ¹ R ³ ) _x (R ¹ and R ³ are independently hydrogen, or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated Cyclic or partially or fully fluorinated hydrocarbons; and x may be an integer from 2 to 8); or (i) cyclic of formula (CR ¹ R ³ SiR ¹ R ³ ) _x Carbosilane (R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated. Hydrocarbons; and x may be an integer from 2 to 8). Porogen comprises at least one cyclic hydrocarbon of the formula C _n H _2n having a cyclic structure, according to claim 42, wherein the composition:
(N is 4-14, the carbon number in the cyclic structure is 4-10, and the at least one cyclic hydrocarbon has a plurality of simple or branched hydrocarbons substituted on the cyclic structure, May be good). Porogen, the general formula C _{n H (2n + 2)} of at least one linear or branched _-2Y, saturated, singly or multiply unsaturated, including hydrocarbons, according to claim 42, wherein the composition:
(N = 2-20 and y = 0-n). Porogen, at least one of the formula C _{n H 2n-2x} having a cyclic structure, including cyclic hydrocarbon singly or multiply unsaturated, claim 42 of the composition:
(X is the number of unsaturated sites, n is 4 to 14, the number of carbons in the cyclic structure is 4 to 10, and the at least one mono- or polyunsaturated cyclic hydrocarbon is substituted on the cyclic structure. And may have unsaturation or endocyclic unsaturation in one of the hydrocarbon substituents). Porogen comprises at least one bicyclic hydrocarbon of the formula _C n _{H 2n-2} having a bicyclic structure, according to claim 42, wherein the composition:
(N is 4-14, the number of carbons in the bicyclic structure is 4-12, and the at least one bicyclic hydrocarbon has a plurality of simple or branched hydrocarbons substituted on the bicyclic structure. May be). Porogen, including bicyclic hydrocarbon of at least one multiply unsaturated of formula _{C n H 2n- (2 + 2x} ) with 2 ring structure, according to claim 42, wherein the composition:
(X is the number of unsaturated sites, n is 4 to 14, the carbon number in the bicyclic structure is 4 to 12, and the at least one polyunsaturated bicyclic hydrocarbon is substituted on the bicyclic structure. A plurality of simple or branched hydrocarbon substituents, and one of the hydrocarbon substituents may have unsaturation or endocyclic unsaturation). Porogen comprises at least one tricyclic hydrocarbon of formula _C n _{H 2n-4} having a tricyclic structure, according to claim 42, wherein the composition:
(Wherein n is 4-14, the number of carbons in the tricyclic structure is 4-12, and the at least one tricyclic hydrocarbon has a plurality of simple or branched hydrocarbons substituted on the tricyclic structure. May be). A composition comprising at least one precursor and a porogen distinguishable from the precursor, wherein the porogen is at least one of the following:
(A) at least one cyclic hydrocarbon of the formula C _n H _2n having a cyclic structure (n is 4-14, the number of carbons in the cyclic structure is 4-10, and the at least one cyclic hydrocarbon is May have a plurality of simple or branched hydrocarbons substituted with
(B) at least one linear or branched, saturated, mono- or polyunsaturated hydrocarbon of the general formula C _n H _{(2n + 2) -2y} :
(N is 2 to 20 and y = 0 to n);
(C) at least one mono- or polyunsaturated cyclic hydrocarbon of the formula C _n H _2n-2x having a cyclic structure:
(X is the number of unsaturated sites, n is 4 to 14, the number of carbons in the cyclic structure is 4 to 10, and the at least one mono- or polyunsaturated cyclic hydrocarbon is substituted on the cyclic structure. A simple or branched hydrocarbon substituent, and one of the hydrocarbon substituents may have unsaturation or endocyclic unsaturation);
(D) at least one bicyclic hydrocarbon of formula C _n H _2n-2 having a bicyclic structure:
(N is 4-14, the number of carbons in the bicyclic structure is 4-12, and the at least one bicyclic hydrocarbon has a plurality of simple or branched hydrocarbons substituted on the bicyclic structure. May be);
(E) at least one polyunsaturated bicyclic hydrocarbon of formula C _n H _{2n- (2 + 2x)} having a bicyclic structure:
(X is the number of unsaturated sites, n is 4 to 14, the carbon number in the bicyclic structure is 4 to 12, and the at least one polyunsaturated bicyclic hydrocarbon is substituted on the bicyclic structure. A plurality of simple or branched hydrocarbon substituents, and one of the hydrocarbon substituents may have unsaturation or endocyclic unsaturation); and / or
(F) at least one tricyclic hydrocarbon of the formula C _n H _2n-4 having a tricyclic structure:
(Wherein n is 4-14, the number of carbons in the tricyclic structure is 4-12, and the at least one tricyclic hydrocarbon has a plurality of simple or branched hydrocarbons substituted on the tricyclic structure. May be). At least one precursor is represented by the formula ^{_{R 1 n (OR 2) p}} (O (O) CR 3) 4- (n + p) is represented by Si, it claims 49 of the composition:
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; n is 1 to 3; and p is 0 to 3). At least one ^{_{precursor, R 1 n (OR 2)}} p (O (O) CR 4) 3-n-p Si-O-SiR 3 m (O (O) CR 5) q (OR 6) 3- _50. The composition of claim 49, represented by _m-q :
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated. R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3)) . At least one precursor is represented by the formula ^{_{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-SiR 3 m (O (O) CR 5) q (OR 6) 3-m _50. The composition of claim 49, represented by _-q :
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² and R ⁶ are independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated. R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partial Or fully fluorinated hydrocarbons; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3)) . At least one precursor is represented by the formula ^{_{R 1 n (OR 2) p}} (O (O) CR 4) 3-n-p Si-R 7 -SiR 3 m (O (O) CR 5) q (OR 6) 50. The composition of claim 49, represented by _3-mq :
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; R ² , R ⁶ and R ⁷ are independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully Fluorinated hydrocarbons; R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, Or a partially or fully fluorinated hydrocarbon; n is 0-3; m is 0-3; q is 0-3; and p is 0-3 (where n + m ≧ 1, n + p ≦ 3 and m + q ≦ 3)). At least one precursor is represented by the formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) is represented by t _{CH 4-t,} claim 49 of the composition:
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1 to 3; p is 0 to 3; and t is 2 to 4 (where n + p ≦ 4). At least one precursor is represented by the formula ^{_{(R 1 n (OR 2)}} p (O (O) CR 3) 4- (n + p) Si) is represented by t _{NH 3-t,} claim 49 of the composition:
(R ¹ is independently hydrogen or a C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated hydrocarbon; R ² is independently a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon; R ³ Is independently hydrogen or a C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, or partially or fully fluorinated hydrocarbon N is 1 to 3; p is 0 to 3; and t is 1 to 3 (where n + p ≦ 4). 50. The composition of claim 49, wherein the at least one precursor is represented by a cyclic siloxane of formula (OSiR _< ¹ > R _< ³ >) _x :
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; and x may be an integer from 2 to 8). At least one precursor is represented by the formula ^{(NR 1} SiR ¹ R ₃₎ is represented by cyclic silazane of _x, claim 49 of the composition:
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; and x may be an integer from 2 to 8). At least one precursor is represented by the formula ^{(CR 1 R 3 SiR 1 R} 3) is represented by _x cyclic carbosilane claim 49, wherein the composition:
(R ¹ and R ³ are independently hydrogen or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, or partially or fully fluorinated carbonization. Hydrogen; and x may be an integer from 2 to 8).   At least one porogenized precursor selected from the group consisting of neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane and trimethylsilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane; A composition comprising. (A) (i) diethoxymethylsilane, dimethoxymethylsilane, diisopropoxymethylsilane, di-t-butoxymethylsilane, methyltriethoxysilane, methyltrimethoxysilane, methyltriisopropoxysilane, methyltri-t- Consists of butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldi-t-butoxysilane, 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and tetraethoxysilane At least one precursor selected from the group, and (ii) a porogen that can be distinguished from at least one precursor, alpha-terpinene, limonene, cyclohexane, 1,2,4-trimethylcyclohexane, At least one porogen selected from the group consisting of 5-dimethyl-1,5-cyclooctadiene, camphene, adamantane, 1,3-butadiene, substituted dienes and decahydronaphthalene); and / or (b) (i) trimethyl Silane, tetramethylsilane, diethoxymethylsilane, dimethoxymethylsilane, di-t-butoxymethylsilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltriacetoxysilane, methyldiacetoxysilane, methylethoxydi Siloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, dimethyldiacetoxysilane, bis (trimethoxysilyl) methane, bis (dimethoxysilyl) methane, tetraethoxysilane and tri At least one precursor selected from the group consisting of toxisilane, and (ii) a porogen that is distinguishable from at least one precursor comprising alpha-terpinene, gamma-terpinene, limonene, dimethylhexadiene, ethylbenzene, decahydronaphthalene, One porogen selected from the group consisting of 2-carene, 3-carene, vinylcyclohexene and dimethylcyclooctadiene);
A composition comprising:   Further comprising treating the preliminary film with at least one post-treatment agent selected from the group consisting of thermal energy, plasma energy, photon energy, electron energy, microwave and chemical agent, and at least one post-treatment thereof The method of claim 1, wherein the agent removes substantially all of the porogen from the preliminary film to obtain a porous organosilica glass film having pores and a dielectric constant of less than 2.6. .   62. The at least one post-treatment agent improves the properties of the resulting porous organosilica glass membrane before, during and / or after removal of substantially all porogen from the preliminary membrane. Method.   The additional post-treatment agent improves the properties of the resulting porous organosilica glass membrane before, during and / or after the at least one post-treatment agent removes substantially all of the porogen from the preliminary membrane. 63. The method of claim 62.   62. The method of claim 61, wherein the at least one aftertreatment agent is electron energy supplied by an electron beam.   64. The method of claim 62, wherein the at least one aftertreatment agent is electron energy provided by an electron beam.   64. The method of claim 63, wherein the at least one aftertreatment agent is electron energy provided by an electron beam.   62. The method of claim 61, wherein the at least one aftertreatment agent is a supercritical fluid.

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