CN1782124B - Porous low dielectric constant composition, its preparation method and its use method - Google Patents

Abstract

Porous low dielectric constant composition, preparation method thereof, and use method thereof The present invention discloses a porous organosilicate glass (OSG) film: Si _v O _w C _x H _y F _z , wherein 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%. The film has a silicate network with carbon bonds, such as methyl (Si-CH ₃ ), pores with a diameter less than 3 nm equivalent spherical diameter, and a dielectric constant less than 2.7. The preliminary film is deposited by chemical vapor deposition from organosilane and/or organosiloxane precursors and a separate pore-forming precursor. The pore-forming precursor forms pores in the preliminary film and is subsequently removed to provide a porous film. The composition, i.e., the film-forming kit, includes: an organosilane and/or organosiloxane compound containing at least one Si-H bond, and a hydrocarbon porogen precursor containing alcohol, ether, carbonyl, carboxylic acid, ester, nitro, primary amine, secondary amine and/or tertiary amine functional groups or combinations thereof.

Description

Porous low dielectric constant composition, its preparation method and its use method

Cross-Referenced Related Applications

This application claims priority to US Provisional Application No. 60/613,937, filed September 28, 2004.

Background of the invention

Low dielectric constant materials produced by chemical vapor deposition (CVD) methods are commonly used as insulating layers for electronic devices. Insulating materials are used in the electronics industry as insulating layers between circuits and components of integrated circuits (ICs) and corresponding electronic devices. In order to increase the speed and device density of microelectronic devices, such as computer chips, their linear dimensions are increasingly reduced. As linear dimensions decrease, the insulation requirements for interlayer dielectrics (ILDs) become more stringent. Shrinking the pitch requires a lower dielectric constant in order to minimize the RC time constant, where R is the resistance of the wire and C is the capacitance of the interlayer dielectric. C is inversely proportional to the pitch and directly proportional to the dielectric constant (k) of the interlayer insulating material (ILD).

Traditional silicon dioxide (SiO ₂ ) CVD dielectric films produced from SiH ₄ or TEOS (Si(OCH ₂ CH ₃ ) ₄ , tetraethylorthosilicate) and O ₂ with a dielectric constant (k) greater than 4.0 . There are several industrial attempts to produce SiO2-based chemical vapor deposition (CVD) films with low dielectric constants, the most successful of which is the introduction of organic groups into insulating SiO2 films, which provide dielectric The electric constant is in the range of 2.7-3.5. In addition to oxidizing agents such as O ₂ or N ₂ O, the organosilicate (OSG) glass is usually formed from silicon-containing precursors, such as alkylsilanes, alkoxysilanes and/or siloxanes, in a dense film (density about 1.5 g/cm ³ ). As higher and higher device densities and smaller device sizes require dielectric constants or "k" values to be lowered below 2.7, the industry is turning to various porous materials with improved insulating properties. Adding porosity to OSG will lower the overall dielectric constant of the material, where the intrinsic dielectric constant of the void space is 1.0. Porous OSG materials are considered low-k materials because their dielectric constants are lower than standard materials traditionally used in industrial-undoped silica glass. These materials are generally formed by adding a porogen or porogen precursor as a reactant during deposition and removing the porogen from the deposited or prepared material to provide a porous material. Other material properties such as mechanical hardness, elastic modulus, residual stress, thermal stability, and adhesion to various substrates depend on the chemical composition and structure of the porous material or film. Unfortunately, the performance of many of these films suffers detrimental effects when porosity is added to the film.

Summary of the invention

In the invention, a porous organosilicate glass (OSG) film composed of a single-phase material represented by the chemical formula Si _v O _w C _{x Hy} F _z , where v+w+x+y+z=100%, will be described, 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 holes and intervening The electric constant is 2.7 or less.

Also described herein is a chemical vapor deposition method for producing porous organosilicate glass films comprising: providing a substrate within a processing chamber; introducing a gaseous reagent comprising a gaseous reagent selected from An organosilane and at least one precursor of an organosiloxane and a porogen precursor; applying energy to a gaseous reagent in a processing chamber to initiate a reaction of the gaseous reagent and provide a prepared film on a substrate, wherein the prepared The film comprises a porogen; then, at least a portion of the porogen is removed from the prepared film to provide a porous film comprising pores and having a dielectric constant below 2.7.

Additionally, the present invention will describe compositions comprising porogens and precursors for producing porous OSG films.

Figure overview

Figure 1 provides a process flow diagram of one embodiment of a method for forming the porous organosilicate glass material of the present invention.

Figure 2 provides: porogen precursors for organosilane precursor diethoxymethylsilane (DEMS) and cyclohexanone (CHO) or 1,2,4-trimethylcyclohexane (TMC) Refractive indices of the two different porogen precursor stoichiometries of the deposited films.

Figure 3 provides: Fourier transform infrared (FT-IR) absorption spectra of porous OSG films deposited from organosilane precursor DEMS and porogen precursor CHO or TMC after deposition and after 5 min exposure to UV light .

Figure 4 provides: FT-IR absorption spectra of films deposited from precursor mixtures comprising DEMS and CHO (22/78 molar ratio).

Figure 5 provides: FT-IR absorption spectra of films deposited from precursor mixtures comprising DEMS and DMHD (20/80 molar ratio).

Figure 6 provides: hardness versus dielectric constant of films deposited from precursor mixtures containing alpha-terpinene (ATP), limonene (LIM), CHO, and cyclohexane oxide (CHO _x ).

Detailed description of the invention

The present invention will describe porous organosilicate materials and films, methods of making them, and mixtures used for making them. Unlike porous inorganic _SiO2 materials, the porous OSG materials and films described in this invention exhibit hydrophobicity due to the organic groups contained therein. The porous OSG material also exhibits a low dielectric constant, or a dielectric constant of 2.7 or lower, while also possessing sufficient mechanical hardness, elastic modulus, low residual stress, high thermal stability, and making it suitable for a variety of applications High adhesion to various substrates. The porous OSG materials described herein have a density of 1.8 g/ml or less, or 1.25 g/ml or less, or 1.0 g/ml or less. In certain embodiments, porous OSG materials can be fabricated into thin films that exhibit low dielectric constants, high mechanical properties, and resistance to various environments (e.g., oxygen, water, oxidizing or Reducing environment) relatively high thermal and chemical stability. It is believed that some of these properties may be the result of the selective introduction of carbon into the film, preferably primarily organic carbon, -CH _x , where x is 1-3, or at least some of the organic carbon is The Si-C bond acts as a _-CH3 form where the terminal methyl group is attached to the silicate network. In certain preferred embodiments, 50% or more, or 75% or more, or 90% or more of the hydrogen contained in the OSG material of the present invention is bonded to carbon, or, in the final The number of terminal Si-H bonds in the film is minimized. In certain embodiments, the material has at least 10 SiCH ₃ bonds per Si-H bond, more preferably 50 Si-CH ₃ bonds per Si-H bond, most preferably For every Si-H bond there are 100 Si- _CH3 bonds.

Figure 1 provides a process flow diagram of one embodiment of the method disclosed herein for forming a thin film of porous OSG material. Porous OSG materials or films can be deposited from a mixture of reagents comprising silicon-containing precursors and porogen precursors. A "silicon-containing precursor" as used herein is a reagent comprising at least one silicon atom, such as an organosilane or organosiloxane. As used herein, a "porogen precursor" is an agent used to create void volume in the formed film. In a first step, the substrate is introduced into the treatment chamber. During the deposition step, the silicon-containing precursor and porogen precursor are introduced into the processing chamber and activated by one or more energy sources before and/or after introduction into the processing chamber. The precursors may be co-deposited or co-polymerized on at least a portion of the substrate surface to provide a prepared film. In a next step, at least a portion of the porogen precursor can be removed from the prepared film by applying one or more energy sources such as, but not limited to, heat, light, electron beam, and combinations thereof to the film. The treatment can be carried out under one or more pressures ranging from vacuum to ambient pressure, and under inert, oxidizing or reducing conditions. Removal of at least a portion of the porogen will result in a porous organosilicate material. In these embodiments, the porosity and/or dielectric constant of the final film may be affected by a variety of factors including, but not limited to, the ratio of the silicon-containing precursor to the porogen precursor in the precursor mixture. Compare. In certain embodiments, further processing may also be performed during at least part of the film formation or after film formation. These additional treatments may, for example, improve certain properties such as mechanical strength, residual stress, and/or adhesion.

In the present invention, the term "chemical precursor" is used to describe reagents, including "organosilicon precursors" and "porogen precursors", as well as any additional reagents desired to form a thin film on a substrate, Such as "carrier gas", or other "added gas". Although the term "gaseous" is sometimes used in this invention to describe the precursor, the term shall include, without any limitation, direct delivery to the reactor as a gas, delivery to a reactor as a vaporized liquid, delivery as a sublimated solid into the reactor, and/or the reagents delivered into the reactor by an inert carrier gas.

In certain embodiments, the silicon-containing precursor and the porogen precursor are chemically distinct from each other and are not linked by any covalent bond. In these and other embodiments, the concentrations of silicon-containing precursors and porogen precursors can be controlled by different mass flow controllers and introduced into the reaction chamber from different supply sources, and then mixed in the reaction chamber, Mixing in the transfer line prior to entering the reaction chamber, and/or prior to entering the reaction chamber to provide a reaction mixture. In the latter embodiment, the silicon-containing precursor and porogen precursor and other optional additives can be delivered from a single source reaction mixture, wherein their concentration in the reaction chamber is determined by the stoichiometric ratio of the mixture. to determine, and the flow rate into the reaction chamber is controlled with a single mass flow controller. Chemical precursors can be delivered to the reaction system by a number of methods including, but not limited to, the use of pressurizable stainless steel vessels fitted with appropriate valves and fittings to enable liquid delivery into the reaction chamber.

In other embodiments, a single species of molecule may be used as both a structure-forming agent and a porogen. That is, the structure-forming precursor and the pore-forming precursor need not be different molecules, and in certain embodiments, the porogen is part of (eg, covalently attached to) the structure-forming precursor. A precursor comprising a porogen attached thereto is sometimes referred to hereinafter as a "porogen". For example, it is possible to use neohexyl TMCTS as a single species, whereby the TMCTS portion of the molecule forms the base OSG structure, while the bulky alkyl substituent neohexyl is the pore-forming species that is removed during the annealing treatment. Having a porogen attached to the Si species that will network into the OSG structure would be beneficial for more efficient incorporation of the porogen into the film during deposition. Furthermore, there are two porogens attached to one silicon in a precursor such as in di-neohexyl-diethoxysilane, or two silicons attached to one porogen such as 1,4-bis( Diethoxysilyl)cyclohexane is also advantageous because the vast majority of bonds broken in the plasma during deposition are silicon-porogen bonds. In this way, the reaction of a silicon-porogen bond in the plasma will still introduce the porogen into the deposited film. Additional non-limiting examples of preferred pore-forming precursors include: 1-neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-neopentyl-1,3,5,7 -Tetramethylcyclotetrasiloxane, Neopentyldiethoxysilane, Neohexyldiethoxysilane, Neohexyltriethoxysilane, Neopentyltriethoxysilane and Neopentyl di-tert-butoxysilane.

In certain embodiments of materials with single or multiple porogens attached to silicon, it may be advantageous to design the porogen such that, when the film cures to form pores, a portion of the porogen remains attached to the silicon. Silicon thus imparting hydrophobicity to the film. The porogen in the silicon-containing-porogen precursor can be selected such that upon decomposition or cure, the porogen-derived terminal chemical groups, such as —CH ₃ , attached to the silicon remain. For example, if the porogen neopentyl is selected, it can be expected that thermal annealing under appropriate conditions will cause the bond breaking of the CC bond at the β of Si, that is, at the secondary carbon atom connecting the silicon and the tert-butyl group Bonds between the quaternary carbons will most favorably be broken when heated. Under the right conditions, this leaves a terminal _-CH3 group that compensates for the silicon and imparts hydrophobicity and a low dielectric constant to the film. Examples of precursors are neopentyltriethoxysilane, neopentyldiethoxysilane and neopentyldiethoxymethylsilane.

In certain embodiments, the porous OSG film comprises: (a) about 10 to about 35 atomic percent, or about 20 to about 30 atomic percent silicon; (b) about 10 to about 65 atomic percent, or about 20 to about 45 percent atomic oxygen; (c) about 10 to about 50 atomic percent or about 15 to about 40 atomic percent hydrogen; (d) about 5 to about 30 atomic percent or about 5 to about 20 atomic percent carbon. Depending on the precursor used, the OSG films described herein may also contain from about 0.1 to about 15 atomic percent or from about 0.5 to about 7.0 atomic percent fluorine in order to improve one or more material properties. In these and other embodiments, the OSG film may additionally contain at least one of the following elements: fluorine, boron, nitrogen, and phosphorus.

Undoped silica glass produced by plasma-enhanced (PE)CVD TEOS has an intrinsic free-volume pore size determined by positron annihilation lifetime spectroscopy (pALS) analysis, which is approximately 0.6 nm in terms of equivalent spherical diameter. CVD-produced dense OSG films produced only from alkyl, alkoxy and/or sil(ox)ane precursors (in the absence of pore-forming porogen precursors) have intrinsic free-volume pore sizes determined by PALS analysis, Its value is about 0.7-0.9 nm in terms of equivalent spherical diameter.

The porosity of the deposited films has a porosity determined by positron annihilation lifetime spectroscopy (PALS) analysis comparable to the equivalent spherical diameter (approximately 0.6-0.9 nm) of undoped silicate glasses and dense organosilicate glasses. Inherent free volume pore size. Due to the presence of porogens present in the film to fill the void volume, in some cases the pore size of the deposited film may even be smaller than that observed in undoped silicate glass or dense organosilicate glass aperture. The film of the invention ("final film") has a pore size of less than 3.0 nm as an equivalent spherical diameter, or less than 2.0 nm as an equivalent spherical diameter, as determined by means of small angle neutron scattering (SANS) or PALS.

The total porosity of the final film can range from 5-75%, depending on the processing conditions and the desired final properties of the film. The porous films described herein have a density of less than 1.5 g/ml, alternatively less than 1.25 g/ml or less than 1.00 g/ml. In certain embodiments, the OSG films described herein have a density that is at least 10% lower, or at least 20% lower, than a similar OSG film produced without a porogen.

The porosity of the film need not be uniform throughout the film. In certain embodiments, there is a porosity gradient and/or multiple layers with different porosities. For example, the film may be provided by adjusting the ratio of porogen to precursor during deposition, or by manipulating the film after deposition to create a gradient in composition or density.

The porous OSG films described here have lower dielectric constants than dense OSG materials without porosity control. In certain embodiments, the dielectric constant of the films described herein is at least 15% lower, more preferably at least 25% lower, than the dielectric constant of a similar OSG film produced without the porogen.

In certain embodiments, the porous OSG films described herein have superior mechanical properties compared to common OSG materials. Mechanical hardness determined by nanoindentation using standard MTS procedures is greater than 0.5 GPa, or greater than 1.0 GPa.

In certain embodiments, the porous OSG film may contain fluorine in the form of inorganic fluorine (eg, Si—F). When fluorine is present, it is present in an amount of 0.5-7 atomic %.

The films are thermally stable. Particularly preferred films after annealing have an average weight loss of less than 1.0% weight/hour when thermostatted at 425°C in nitrogen. It is also preferred that the average weight loss of the film is less than 1.0% by weight/hour at a constant temperature of 425° C. in air.

The films exhibit good chemical resistance to various chemical environments. Chemical resistance can be measured by changes in dielectric constant or the appearance or disappearance of vibrational bands in infrared spectroscopy, or by changes in film composition as measured by X-ray photoelectron spectroscopy (XPS). Typical chemical environments in which these films exhibit their excellent chemical stability are: aqueous acidic or alkaline environments commonly used in photoresist stripping formulations, oxidizing plasma conditions commonly used in plasma ashing, and e.g. high humidity (>85% relative humidity,>85°C) other environments.

The films are compatible with chemical mechanical planarization (CMP) and isotropic etching, and can adhere to various materials such as silicon, silicon dioxide, Si ₃ N ₄ , OSG, FSG, corundum, hydrogenated corundum , silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boronitrides, anti-reflective coatings, photoresists, organic polymers, porous organic and inorganic materials, metals such as copper and Aluminum, and a diffusion barrier layer such as (but not limited to) TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, WN or W(C)N. Preferably, the film is capable of adhesion to at least one of the aforementioned materials sufficient to pass a conventional pull test, such as the ASTM D3359-95a tape pull test. If there is no appreciable film removal, the sample is considered to pass the test.

Thus, in certain embodiments, the thin film is an insulating layer, an interlayer dielectric, an intermetallic dielectric, a capping layer, a chemical mechanical planarization or etch stop layer, a barrier layer or an adhesion layer in an integrated circuit .

Utilizing these properties, the film is suitable for various uses. Said films are particularly suitable for deposition onto semiconductor substrates and for use as, for example, insulating layers, interlayer dielectric layers and/or intermetal dielectric layers. The film can form a conformal coating. The mechanical properties exhibited by the film make it particularly suitable for: aluminum removal technology and copper damascene or double damascene technology.

Although the products of the methods and mixtures described herein are largely described in the form of films, the present disclosure is not limited thereto. For example, porous OSG materials can be provided in any form that can be deposited by CVD, such as coatings, multilayer components, and other types of objects that do not require planarization or thinning, and many that do not require use in integrated circuits. In certain preferred embodiments, the substrate is a semiconductor.

In addition to the porous OSG materials and films described herein, methods of making the products, methods of using the products, and compounds and compositions used to make the products are also described herein.

The compositions described herein may also include, for example, at least one chamber filled with suitable valves and fillers to enable delivery of the porogen precursor, silicon-containing precursor, and/or mixture of porogen and silicon-containing precursor to the reaction chamber. Pressurizable container (preferably a stainless steel container). The contents of the container may be premixed. Additionally, the porogen and the silicon-containing precursor can be kept in separate containers or in a single container with an isolation mechanism to keep the porogen and precursor separate during storage. When desired, the container may also have a mechanism for mixing the porogen and precursor.

In certain embodiments, the silicon-containing precursor can be composed of a mixture of different organosilanes and/or organosiloxanes. It is also contemplated that the porogen precursor may consist of a mixture of different porogen precursors.

In certain embodiments, one or more chemical precursors other than silicon-containing precursors and porogen precursors may be delivered to the reaction chamber before, during, and/or after the film forming step. The additional chemical precursors may include, for example: inert gases (e.g. He, Ar, N2, Kr, Xe, etc.) and organic species (e.g. NH ₃ , H ₂ , CO ₂ , CO, H ₂ O, H ₂ O 2 , O ₂ , _{O 3 ,} CH ₄ , C ₂ H ₂ , C ₂ H ₄ , etc.), in substoichiometric amounts, stoichiometric It can be used in low or excessive concentration in order to promote the improvement of the film forming reaction and thus improve the performance of the film, and/or can be used as a post-treatment agent in order to improve the performance or stability of the final film.

Those skilled in the art will appreciate that helium is often used as a carrier gas to facilitate delivery of chemical precursors to the reaction chamber. It may be advantageous to use a carrier gas with an ionization energy different from that of helium. This can lower the temperature of the electrons in the plasma, which will change the film formation process, which in turn will change the structure and/or composition of the deposited film. Examples of gases with ionization energies lower than helium include: _CO2 , _NH3 , CO, _CH4 , Ne, Ar, Kr, and Xe.

For thin films formed on a single 200mm wafer, the flow rate of each gaseous chemical precursor is preferably 5-5000 sccm. Flow rates for other chambers may depend on the size of the substrate and chamber configuration, and are in no way limited to 200mm silicon wafers or chambers holding single substrates. In certain embodiments, the flow rates of the organosilicon and porogen precursors are selected to provide the desired amount of organosilicate and porogen in the deposited film to provide a dielectric constant between about 1.1 and about 2.7. final film.

Energy is applied to the chemical precursors to initiate the reaction and form a thin film on the substrate. The energy can be provided by, for example, heating, plasma, pulsed plasma, microwave plasma, helicon plasma, high density plasma, inductively coupled plasma, and remote plasma methods. In certain embodiments, two frequencies of radiation can be used in the same plasma and can be used to modify the properties of the plasma on the substrate surface. Preferably, the film is formed by plasma enhanced chemical vapor deposition. In these embodiments, a capacitively coupled plasma can be generated at a frequency of 13.56 MHz. The power of the plasma may be 0.02-7 W/cm2 or 0.3-3 W/cm2 based on the surface area of the substrate.

The pressure in the reaction chamber during deposition may be 0.01-600 Torr or 1-15 Torr.

Although the thickness of the film can vary as desired, it is preferred that the film is deposited to a thickness of 0.002-10 microns. Cover films deposited on unpatterned surfaces have excellent uniformity, except for appropriate edges, e.g. where the outermost 5 mm edge of the substrate is not included in the statistical calculation of uniformity, at 1 standard across the substrate On the deviation, its thickness changes less than 2%.

The deposited films consist of organosilicates and porogens. The total mass or volume of the film is such that the percent mass or volume of the organosilicate plus the percent mass or volume of the porogen equals the total mass or volume of the deposited film.

Without being bound by theory, the relative amounts of organosilicate and porogen in the deposited film may be influenced by one or more of the following parameters. The relative amounts of porogen precursors and silicon-containing precursors in the chemical precursor mixture, and the relative formation rates of organosilicate glasses and porogens on the substrate, where the relative amounts of organosilicates in the deposited films The amount is a function of the amount of silicon-containing precursor in the precursor mixture and the relative rate of organosilicate formation on the substrate. Likewise, the amount of porogen in the deposited film may be a function of the amount of porogen precursor in the precursor mixture and the relative formation rate of the porogen on the substrate. Thus, it is possible to individually influence the respective amounts, compositions and structures of organosilicates and porogens formed on the substrate during the thin film formation step by selecting organosilicon precursors and porogen precursors.

Porous OSG films having desired mechanical properties are prepared from chemical reagents or mixtures of precursors comprising one or more silicon-containing precursors and porogen precursors. The following are non-limiting examples of silicon-containing precursors suitable for use with different porogen precursors. In the formulas below, as well as in all formulas throughout the application document, the term "independently" should be understood to mean that the R group is not only independently selected with respect to other R groups with different superscripts, but also with respect to any other class of the same The R groups are independently selected. For example, in the chemical formula R ¹ _n (OR ² ) _p (O(O)CR ³ ) _4-(n+p) Si, when n=2 or 3, two or three R ¹ need not be the same as each other or Same for ^R2 .

1) A chemical structure represented by the formula R ¹ _n (OR ² ) _p (O(O)CR ³ ) _4-(n+p) Si, wherein R ¹ is independently H or C ₁ -C ₄ straight chain or Branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 is independently _C1 - _C6 linear or branched, saturated, mono- or polyunsaturated Saturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, ^R3 independently H, _C1 - _C4 linear or branched, saturated, mono- or polyunsaturated, cyclic , aromatic, partially or fully fluorinated hydrocarbons, n is 1-3, and p is 0-3,

2) A chemical structure represented by the 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 , wherein, R ¹ and R ³ are independently H or C _1- C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; R ² and R ⁶ is independently C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R ⁴ and R ⁵ are independently is H, C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, n is 0-3, m is 0 -3, q is 0-3, and p is 0-3, n+m≥1, n+p≤3 and m+q≤3,

3) A chemical structure represented by the 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-mq , wherein , R ¹ and R ³ are independently H or C _1- C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, 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, partially or fully fluorinated hydrocarbons, R ^{and R} are independently H , C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, n is 0-3, m is 0-3 , q is 0-3, and p is 0-3, n+m≥1, n+p≤3 and m+q≤3,

4) The chemical represented by the 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-mq Structure, wherein, R ¹ and R ³ are independently H or C ₁ -C ₄ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; R ² and ^R6 are independently _C1 - _C6 linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, ^R4 and ^R5 are independently R is H, C ₁ -C ₆ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R ⁷ is C ₂ -C ₆ Linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons, n is 0-3, m is 0-3, q is 0-3, and p is 0-3, n+m≥1, n+p≤3 and m+q≤3,

5) A chemical structure represented by the formula (R ¹ _n (OR ² ) _p (O(O)CR ³ ) _4-(n+p) Si) _t CH _4-t , wherein R ¹ is independently H or C ₁ - _C4 linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 is independently _C1 - _C6 linear or branched, Saturated, mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, ^R3 is independently H, _C1 - _C6 linear or branched, saturated, mono- or Polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, n is 1-3, p is 0-3, t is 2-4, and n+p≤4,

6) A chemical structure represented by the formula (R ¹ _n (OR ² ) _p (O(O)CR ³ ) _4-(n+p) Si) _t NH _3-t , wherein R ¹ is independently H or C ₁ - _C4 linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 is independently _C1 - _C6 linear or branched, Saturated, mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, ^R3 is independently H, _C1 - _C6 linear or branched, saturated, mono- or Polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, n is 1-3, p is 0-3, t is 1-3, and n+p≤4,

7) A chemical structure represented by a cyclosilazane of the formula (NR ¹ SiR ² R ³ ) _x , wherein R1 and ^R3 are independently H, C ₁ -C ₄ linear or branched, saturated, mono or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons, and x can be an integer from 2 to 8,

8) A chemical structure represented by a cyclosilazane of the formula (C(R ¹ R ² )Si(R ³ R ⁴ )) _x , wherein R ¹ -R ⁴ are independently H, C ₁ -C ₄ straight chain or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons, and x can be an integer from 2 to 8,

Although reference is made throughout the specification to siloxanes, carbosilanes, and silazanes as precursors and porogenizing precursors, it should be understood that the methods and films of the present invention are not limited thereto, such as other Siloxanes such as trisiloxane, tetrasiloxane, and other even longer length linear siloxanes are also possible for use in the present invention.

The above-mentioned silicon-containing precursors may be mixed with the above-listed porogen precursors and/or any other silicon-containing precursors, including the described species except n and/or m is 0-3 Different silicon-containing precursors. Examples thereof include TEOS, triethoxysilane, di-tert-butoxysilane, monosilane, disilane, di-tert-butoxydiacetoxysilane and the like.

Such embodiments would facilitate control of the amount, structure and composition of the organosilicate moiety of the deposited film. These embodiments can also control the ratio of porogen to organosilicate in the deposited film, enhance one or more critical properties of the deposited film and/or the final film, or control the size of the porogen in the deposited film or the final film The size of the mesopores controls the distribution of porogens in the deposited film or the distribution of pores in the final film, and/or controls the connectivity of the pores in the final film. For example, films formed from the reaction of diethoxymethylsilane (DEMS) and porogen precursors may benefit from the use of additional silicon-containing precursors such as TEOS, thereby reducing the adhesion of organosilicate moieties to the films. The number of end groups, thereby increasing the silicate density in the deposited film and the final porous film, and improving one or more desired film properties of the deposited film and the final film, namely mechanical strength, or less of tensile stress. Another example is a film formed by the reaction of di-tert-butoxymethylsilane and a porogen precursor, which may also benefit from the addition of di-tert-butoxydiacetoxysilane to the reaction chamber. Thus, in certain embodiments, there is provided a mixture of a first silicon-containing precursor having two or fewer Si-O bonds and a second silicon-containing precursor having three or more Si-O bonds, In order to modify the chemical composition of the film of the present invention.

Without being bound by theory, controlled pores are formed in organosilicate glass films using a porogen, the size and shape of which essentially determines the size and shape of the pores formed upon its removal. Thus, the size, shape, connectivity, and number of pores in the final film are primarily determined by the size, shape, connectivity, and amount of porogens in the deposited film. Therefore, by controlling the structure, composition of the porogen precursor, the ratio of the organosilicate precursor to the porogen precursor introduced into the reaction chamber, and the conditions used to form the porogen on the substrate in the reaction chamber to affect the size, shape, connectivity, and number of pores in porous organosilicate materials. In addition, a certain composition and structure of porogen precursors in the deposited film may be beneficial for forming porogens that will impart preferred properties to the final film.

The porogen in the deposited film may be in the same or different form as the porogen precursor introduced into the reaction chamber. The porogen removal treatment will release or remove substantially all of the porogen or porogen fragments from the film. The porogen precursor, the porogen in the deposited film, and the removed porogen can be the same substance or different substances, but preferably, they all originate from the porogen precursor or the porogen precursor. body mixture. Regardless of whether the porogen composition is changed throughout the method of the present invention, the term "precursor of porogen" as used herein is meant to include: all porogens and derivatives thereof, including those used throughout the method of the present invention. any form found.

The composition of the porogen material in the deposited film consists of carbon and hydrogen and at least one element selected from the group consisting of oxygen, nitrogen, fluorine, boron, and phosphorus.

The structure and composition of the porogen in the deposited film can be measured using various analytical techniques. The porogen composition in the deposited film consists mainly of carbon, which can be detected by various techniques, including X-ray photoelectron scattering (XPS) and Rutherford backscattering/hydrogen forward scattering (RBS/HFS). The carbon content of the deposited film will be more than 10% higher or 20% higher than the comparative film deposited without the porogen precursor in the precursor mixture. In addition, the increased carbon content of the deposited film can also be measured by FT-IR by measuring the area of the peaks in the 2600 and 3100 cm ^-1 region related to the frequency of CH vibrational extension. In the case of predominantly hydrocarbon porogen species, the peak area within said region is at least 100% greater or 200% greater than the peak area of a comparative film deposited without the porogen precursor in the precursor mixture.

In certain embodiments, at least a portion or substantially all of the porogen in the deposited film can be substantially removed during the post-processing step. The post-processing step can also affect the chemical structure and/or composition of the porous organosilicate network that remains on the substrate to form the final porous film.

Desired gaseous, liquid, or solid chemical species for use as porogen precursors can be identified based on various criteria. For example, in order to form a porogen on a substrate, the porogen precursor should have sufficient volatility to be transported into the reaction chamber. Once in the reaction chamber, the porogen precursor is able to react in the gas or vapor phase, or on the surface of the substrate, thereby being incorporated into the film as a porogen. Methods that may be used to promote porogen formation from porogen precursors include: intramolecular and/or intermolecular reactions, including two-body impacts, three-body impacts, impacts with sidewalls, impacts with inert gases, and Reactions of metastable noble gases, reactions with oxidizing or reducing gases, reactions or collisions with silicate network-forming precursors, reactions or collisions with active electrons in plasmas, reactions with active neutrons in plasmas reaction or impact, ionization, oxidation reaction, reduction reaction, impact with ions in the plasma, photochemical reaction or rearrangement, thermally activated reaction or rearrangement, reaction with activated and/or neutral species on the substrate , or any other method capable of depositing a porogen precursor onto a substrate is considered a viable method for depositing a porogen in a thin film. Additionally, the porogen precursor may not undergo any other reaction other than condensation on the substrate to transform into the porogen.

The structure and composition of the porogen precursor may include functional groups that make it available to form the porogen on the substrate. Examples of functional groups that may be included in porogen precursors include: ether; epoxide; aldehyde; ketone; enone; acetoxy; ester; acrylate; acrolein; acrylic acid; acrylonitrile; carboxylic acid; primary, secondary or tertiary amine; nitro; cyano; isocyano; amide; imide; anhydride; partially fluorinated and/or perfluorinated groups; , phospites and/or phosphates and combinations thereof.

It is believed that the formation of porogens from porogen precursors using plasma-enhanced chemical vapor deposition techniques may depend on the electron impact cross-section of functional groups within the porogen precursors, which can induce secondary reactions to form porogens. Thus, in certain embodiments, in order to enhance the rate of formation of porogens from porogen precursors and the curing process, elemental, compositional, and/or structural, such as other atomic species such as _O2 , _N2 , B, or Ph May be desired.

Without being bound by theory, it is possible that the formation of porogens from porogen precursors does not seriously affect the formation of organosilicates from organosilicon precursors, and that under certain conditions, organosilicate films and pore-forming Covalent bonds between agents may be minimized. For example, the absence of a covalent bond between the porogen and the organosilicate region of the deposited film may make the porogen easier to remove from the deposited film with a post-processing step, which may limit the thermal budget of the post-processing. ) needs to be minimized. One of the major constraints on semiconductor processing is the thermal budget. The thermal budget for an individual processing step consists of the time and temperature required to perform the step. In some instances, it is desirable to minimize the thermal budget of any processing step. Therefore, a treatment that can be performed at a low temperature and/or a short time would be more desirable than a similar treatment requiring a high temperature and/or a long time. Thus, the porogen precursors and silicon-containing precursors described herein form porous organosilicate films using certain processing steps in which the thermal budget can be controlled or even minimized.

The porogen is removed from the deposited film by post-processing steps which may include: thermal annealing under inert atmosphere, thermal annealing under vacuum, thermal annealing under oxidizing atmosphere, thermal annealing under reducing atmosphere , exposure to oxidizing and/or reducing chemicals, exposure to electron beam irradiation, exposure to oxidizing plasma, exposure to reducing plasma, exposure to ultraviolet light under vacuum, exposure to ultraviolet light under an inert atmosphere, Exposure to UV light under oxidizing and/or reducing nitrogen, exposure to microwave radiation under vacuum, exposure to microwave radiation under inert atmosphere, exposure to microwave radiation under oxidizing and/or reducing atmosphere, exposure to laser radiation , exposure to any of the above treatments listed that are applied concurrently, or to any form of energy or chemical treatment that acts as an initiator to break down the structure and remove the porogen from the film. In addition, other in situ or post-deposition treatments can be used to improve material properties such as hardness, stability (relative to shrinkage, exposure to air, etching, wet etching, etc.), integrity, consistency, and adhesion. The treatment may be applied to the film before, during and/or after removal of the porogen by the same or different means as that used to remove the porogen. Accordingly, the term "post-treatment" as used herein generally refers to the treatment of thin films with energy (e.g., heat, plasma, photons, electrons, microwaves, etc.) or chemicals to remove porogens and possibly Unlimitedly improve the performance of the material.

The porogen precursor can be selected based on the structure, composition, or functional groups introduced to aid in the complete removal of the porogen from the deposited film. For example, porogen precursors that result in the introduction of thermally, photosensitive or chemically sensitive functional groups in the porogen on the substrate make it possible to effectively employ heat, light or chemical reactions to remove the porogen from the film. Thus, porogen precursors are utilized that form porogens in deposited films where activation of chemical groups or structures in the porogen enables efficient and potentially complete removal of the porogen.

The conditions for post-processing may vary. For example, post-treatment can be carried out under high pressure, normal pressure or under vacuum. In addition, post-treatment can also be carried out at high temperature (400-500°C), low temperature (-100°C and above), or at a temperature between these two temperature points. Workup can also consist of a series of steps carried out at different pressure and/or temperature combinations.

Thermal annealing is carried out under the following conditions: the environment can be inert (such as nitrogen, CO ₂ , noble gases (He, Ar, Ne, Kr, Xe, etc.), oxidative (such as oxygen, air, dilute oxygen environment, Oxygen-enriched environment, ozone, nitrous oxide, etc.) or reducing (dilute or concentrated hydrogen, hydrocarbons (saturated, unsaturated linear or branched, aromatic hydrocarbons), etc.). The pressure is preferably from about 1 to about 1000 Torr, more preferably at atmospheric pressure. However, a vacuum environment is also possible for thermal annealing as well as any other post-processing means. The temperature is preferably 200-500°C, and the temperature slope is 0.1-100°C/min. The total annealing time is preferably from 0.01 minutes to 12 hours.

The chemical treatment of OSG film is carried out under the following conditions: using fluorination treatment (HF, SiF ₄ , NF ₃ , F ₂ , COF ₂ , CO ₂ F _{2 ,} etc.), oxidation treatment (H ₂ O ₂ , O _{3 ,} etc. ), chemical drying, methylation, or other chemical treatments that improve the properties of the final material. The chemicals used in the process can be in solid, liquid, gaseous and/or supercritical fluid state.

Supercritical fluid post-treatment for selective removal of porogens from organosilicate films can be performed under the following conditions: The fluid can be carbon dioxide, water, nitrous oxide, ethylene, _SF6 and/or other types of chemicals . Other chemicals can be added to the supercritical fluid to enhance the process. Chemicals can be inert (such as nitrogen, CO ₂ , noble gases (He, Ar, Ne, Kr, Xe, etc.), oxidizing (such as oxygen, ozone, nitrous oxide, etc.), or reducing (dilute or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably from ambient temperature to 500°C. In addition, the chemical substances may also include a large number of chemical substances, such as surfactants. The total exposure time is preferably from 0.01 minutes to 12 hours.

Plasma treatment for porogen removal and possible organosilicate chemical modification is performed under the following conditions: The environment can be inert (e.g. nitrogen, _CO2 , noble gases (He, Ar, Ne, Kr, Xe), etc. etc.), oxidative (such as oxygen, air, dilute oxygen environment, oxygen-enriched environment, ozone, nitrous oxide, etc.) or reductive (dilute or concentrated hydrogen, hydrocarbon (saturated, unsaturated linear or branched chain , aromatic hydrocarbons) etc.). The power of the plasma is preferably 0-5000W. The temperature is preferably from ambient to 500°C. The pressure is preferably from 10 mTorr to atmospheric pressure. The total curing time is preferably from 0.01 minutes to 12 hours. Disk size and method vary with conditions.

The photocuring treatment to remove the porogen is carried out under the following conditions: the environment can be inert (such as nitrogen, CO ₂ , rare gases (He, Ar, Ne, Kr, Xe, etc.), oxidative (such as oxygen, air, oxygen-diluted atmosphere, oxygen-enriched atmosphere, ozone, nitrous oxide, etc.) or reducing (dilute or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably from ambient to 500°C. The power is preferably 0.1-5000W per square inch. The wavelength is preferably IR, visible, UV or far UV (wavelength less than 200nm). The total curing time is preferably from 0.01 minutes to 12 hours.

Microwave post-treatment to remove porogens is performed under the following conditions: the environment can be inert (e.g. nitrogen, CO ₂ , noble gases (He, Ar, Ne, Kr, Xe, etc.), oxidative (e.g. oxygen, air, oxygen-diluted atmosphere, oxygen-enriched atmosphere, ozone, nitrous oxide, etc.) or reducing (dilute or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably from ambient to 500°C. Power and wavelength can be varied and tuned to specific values. The total curing time is preferably from 0.01 minutes to 12 hours.

E-beam post-treatment to remove porogens and/or improve film properties is performed under the following conditions: the environment can be vacuum, inert (e.g. nitrogen, _CO2 , noble gases (He, Ar, Ne, Kr, Xe), etc. ), oxidizing (e.g. oxygen, air, oxygen-diluted atmosphere, oxygen-enriched atmosphere, ozone, nitrous oxide, etc.), or reducing (dilute or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably from ambient to 500°C. Electron density and energy can be changed and tuned to specific values. The total curing time is preferably from 0.001 minutes to 12 hours and may be continuous or pulsed. Additional guidance on the general use of electron beams can be found in the following publications: S. Chattopadhyay et al., Journal of Materials Science, 36 (2001) 4323-4330; G. Kloster et al., Proceedings of IITC, June 3-5, 2002 , SF, CA; and US 6,207,555 B1, 6,204,201 B1 and 6,132,814 A1. E-beam treatment can remove porogens and improve the mechanical properties of the film.

With a corresponding decrease in bulk density, the porosity of the film can be increased, further reducing the dielectric constant of the material and extending the applicability of the material to future generations (eg, k < 2.0).

In embodiments wherein substantially all porogens are removed, if between the post-treated porous organosilicate and a similar organosilicate film formed in the reaction chamber in which no porogen precursor is present, In the absence of statistically significant measured differences in FT-IR absorption in the hydrocarbon region (also referred to as C-Hx, 2600-3100 cm ^-1 ), it was assumed that substantially all porogen was removed.

Non-limiting examples of materials suitable as porogen precursors include:

1) A hydrocarbon structure comprising one or more alcohol groups and having the general formula _{CnH2n +2-2x-2y-z} (OH) _z , wherein n=1-12, x is the number of rings in the structure and is between 0 - Between -4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of alcohol groups in the compound and is between 1 and 4, and where the alcohol functionality can be exocyclic and/or intracyclic of. Examples thereof are: propanol (n=3, x=0, y=0, z=1), ethylene glycol (n=2, x=0, y=0, z=2), hexanol (n= 6, x=0, y=0, z=1), cyclopentanol (n=5, x=1, y=0, z=1), 1,5-hexadiene-3,4-diol (n=6, x=0, y=2, z=2), cresol (n=7, x=1, y=3, z=1), and resorcinol (n=6, x= 1, y=3, z=2), and so on.

2) A hydrocarbon structure containing one or more ether groups and having the general formula _{CnH2n +2-2x-2yOz ,} wherein n=1-12, x is the number of rings in the structure and is between 0-4 , y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of ether linkages in the structure and is between 1 and 4, and wherein the ether linkages can be exocyclic and/or intracyclic. Its examples are: diethyl ether (n=4, x=0, y=0, z=1), 2-methyl-tetrahydrofuran (n=5, x=1, y=0, z=1), 2, 3 - Benzofuran (n=8, x=2, y=4, z=1), ethylene glycol divinyl ether (n=6, x=0, y=2, z=2), cineole ( Eucalyptol) (n=10, x=2, y=0, z=1), and so on.

3) A hydrocarbon structure comprising one or more epoxy groups and having the general formula C _n H _{2n+2-2x-2y-2z} O _z , wherein n=1-12, x is the number of rings in the structure and is between 0 - Between -4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of epoxy groups in the structure and is between 1 and 4, and where the epoxy groups can be attached to the ring on or in a straight line. Its examples are: 1,2-epoxy-3-methylbutane (n=5, x=0, y=0, z=1), 1,2-epoxy-5-hexene (n=5 , x=0, y=1, z=1), cyclohexene oxide (n=6, x=1, y=0, z=1), 9-oxabicyclo[6.1.0]nonane-4 -ene (n=8, x=1, y=1, z=1), and so on.

4) A hydrocarbon structure comprising one or more aldehyde groups and having the general formula C _n H _{2n+2-2x-2y-2z} O _z , wherein n=1-12, x is the number of rings in the structure and is between 0-4 , y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of aldehyde groups in the structure and is between 1 and 4. Examples thereof include cyclopentanecarbaldehyde (n=5, x=1, y=0, z=1) and the like.

5) A hydrocarbon structure comprising one or more ketone groups and having the general formula C _n H _{2n+2-2x-2y-2z} O _z , wherein n=1-12, x is the number of rings in the structure and is between 0-4 Between, y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of aldehyde groups in the structure and is between 1 and 4, and wherein the keto group can be exocyclic and/or intracyclic. Examples thereof are: 3,4-hexanedione (n=6, x=0, y=0, z=2), cyclopentanone (n=5, x=1, y=0, z=1), 2,4,6-trimethylphenyl oxide (n=6, x=0, y=1, z=1), and so on.

6) A hydrocarbon structure comprising one or more carboxylic acid groups and having the general formula _{CnH2n +2-2x-2y-3z} (OOH) _z , wherein n=1-12, x is the number of rings in the structure and in Between 0-4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of carboxylic acid groups in the structure and is between 1 and 4. Examples thereof are: cyclopentanecarboxylic acid (n=6, y=1, x=0, z=1), and the like.

7) A hydrocarbon structure comprising an even number of carboxylic acid groups and the acid functional group is dehydrated to form a cyclic anhydride group, wherein the general formula of the structure is C _n H _{2n+2-2x-2y-6z} (O ₃ ) _z , where n=1-12, x is the number of rings in the structure and is between 0-4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of anhydride groups in the structure and is 1 or 2. Examples thereof are: maleic anhydride (n=2, x=0, y=1, z=1), and the like.

8) A hydrocarbon structure containing an ester group and having the general formula C _n H _{2n+2-2x-2y-2z} (O ₂ ) _z , wherein n=1-12, x is the number of rings in the structure and is between 0-4 , y is the number of unsaturated bonds in the structure and no unsaturated bonds are conjugated to the carbonyl of the ester, z is the number of anhydride groups in the structure and is 1 or 2.

9) A hydrocarbon structure comprising an acrylate functional group having the general formula _{CnH2n +2-2x-2y-2z} ( _O2 ) _z , said functional group consisting of an ester group and at least one unsaturated group conjugated to the carbonyl of the ester group Bond composition, where n=1-12, x is the number of rings in the structure and is between 0-4, y is the number of unsaturated bonds in the structure and is greater than or equal to 1, wherein at least the unsaturated bonds are conjugated to the carbonyl of the ester , z is the number of ester groups in the structure and is 1 or 2. Examples thereof are: ethyl methacrylate (n=6, x=0, y=1, z=1), and the like.

10) A hydrocarbon structure comprising ether and carbonyl functional groups and having the general formula _{CnH2n +2-2w-2x-2y} (O) _y (O) _z , wherein n=1-12, w is the number of rings in the structure and Between 0 and 4, x is the number of unsaturated bonds in the structure and between 0 and n, y is the number of carbonyl groups in the structure, where carbonyl groups can be ketones and/or aldehydes, z is the number of ether groups in the structure and is 1 or 2, and the ether group may be exocyclic and/or intracyclic. Examples thereof are: ethoxymethacryl (n=6, w=0, x=1, y=1, z=1), and the like.

11) A hydrocarbon structure comprising ether and alcohol functional groups and having the general formula _{CnH2n +2-2w-2x-y} (OH) _y (O) _z , wherein n=1-12, w is the number of rings in the structure and in Between 0 and 4, x is the number of unsaturated bonds in the structure and between 0 and n, y is the number of alcohol groups in the structure, z is the number of ether groups in the structure and is 1 or 2, and the ether group Can be external or internal. Examples thereof are: 3-hydroxytetrahydrofuran, and the like.

12) A hydrocarbon structure comprising any combination of functional groups selected from the group consisting of the general formula _{CnH2n +2-2u-2v-w-2y-3z} (OH) _w ( _Ox (O) _y (OOH) _z , The functional groups are: alcohol, ether, carbonyl and carboxylic acid, wherein n=1-12, u is the number of rings in the structure and is between 0 and 4, v is the number of unsaturated bonds in the structure and is between 0 and n Among them, w is the number of alcohol groups in the general formula and is between 0 and 4, x is the number of ether groups in the structure and is between 0 and 4 and wherein the ether groups can be exocyclic or intracyclic, y is the structure The number of carbonyl groups is between 0 and 3, wherein the carbonyl groups can be ketones and/or aldehydes, and z is the number of carboxylic acid groups in the structure and is between 0 and 2.

13) A hydrocarbon structure comprising one or more primary amino groups and having the general formula C _n H _2n+2-2x-2y-z (NH ₂ ) _z , wherein n=1-12, x is the number of rings in the structure and Between 0-4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of amine groups in the compound and is between 1 and 4, and where the amine functionality can be exocyclic and/or within the ring. Examples thereof are: cyclopentylamine (n=5, x=1, y=0, z=1), and the like.

14) A hydrocarbon structure comprising one or more secondary amino groups and having the general formula _{CnH2n +2-2x-2y-2z} (NH) _z , wherein n=1-12, x is the number of rings in the structure and in Between 0-4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of secondary amine groups in the compound and is between 1 and 4, and where the amine functionality can be exocyclic and/ or within the ring. Its example has: diisopropylamine (n=6, x=0, y=0, z=1), piperidine (n=5, x=1, y=0, z=1), pyridine (pyride) ( n=5, x=1, y=3, z=1), and so on.

15) A hydrocarbon structure comprising one or more tertiary amine groups and having the general formula C _n H _{2n+2-2x-2y-3z} (N) _z , wherein n=1-12, x is the number of rings in the structure and in between 0-4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of tertiary amine groups in the compound and is between 1 and 4, and where the amine functionality can be exocyclic and/or within the ring. Examples thereof are: triethylamine (n=6, x=0, y=0, z=1), N-methylpyrrolidine (n=5, x=1, y=0, z=1), N - methylpyrrole (n=5, x=1, y=2, z=1), etc.

16) A hydrocarbon structure containing one or more nitro groups and having the general formula C _n H _2n+2-2x-2y-z (NO ₂ ) _z , wherein n=1-12, x is the number of rings in the structure and in between 0 and 4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of nitro groups in the compound and is between 1 and 4, and where the nitro functionality can be exocyclic and/or within the ring. Examples thereof are: nitrocyclopentane (n=5, x=1, y=0, z=1), nitrobenzene (n=6, x=1, y=3, z=1), etc. .

17) Hydrocarbon structures comprising amine and ether functional groups and having the general formula _{CnH2n +2-2u-2v-w-2x-3y-z} ( _NH2 ) _w (NH) _x (N) _y (OH) _z , where n=1-12, u is the number of rings in the structure and is between 0 and 4, v is the number of unsaturated bonds in the structure and is between 0 and n, w is the number of primary amino groups, x is the secondary amine The number of groups, y is the number of tertiary amino groups, and 1<w+x+y<4, z is the number of alcohol groups in the compound and is between 1 and 4, and the alcohol groups and/or amine groups can be extracyclic and/or within the ring. Examples thereof are: 2-(2-aminoethylamino)ethanol (n=4, u=0, v=0, w=1x=1, y=0, z=1), N-methylmorpholine ( n=5, u=1, v=0, w=0, x=0, y=1, z=1), and so on.

18) Hydrocarbon structures comprising amine and alcohol functional groups and having the general formula _{CnH2n +2-2u-2v-w-2x-3y-z} ( _NH2 ) _w (NH) _x (N) _y (OH) _z , where n=1-12, u is the number of rings in the structure and is between 0 and 4, v is the number of unsaturated bonds in the structure and is between 0 and n, w is the number of primary amino groups, x is the secondary amine The number of groups, y is the number of tertiary amino groups, and wherein 1<w+x+y<4, z is the number of ether groups in the compound and is between 1 and 4, and the ether groups and/or amine groups can be cyclic outside and/or inside the ring. Examples thereof include tetrahydrofurfurylamine (n=5, u=1, v=0, w=1, x=0, y=0, z=1), and the like.

19) Hydrocarbon structures comprising amine and carbonyl functional groups and having the general formula _{CnH2n +2-2u-2v-w-2x-3y-2z} ( _NH2 ) _w (NH) _x (N) _y (O) _z , where n=1-12, u is the number of rings in the structure and is between 0 and 4, v is the number of unsaturated bonds in the structure and is between 0 and n, w is the number of primary amine groups, x is the secondary amine The number of groups, y is the number of tertiary amino groups, and 1<w+x+y<4, z is the number of carbonyl groups in the compound and is between 1 and 4, wherein carbonyl can be aldehyde and/or ketone, carbonyl and and/or amine groups may be exocyclic and/or intracyclic. Examples thereof are: N,N-diethylformamide (n=5, u=0, v=0, w=0, x=0, y=1, z=1), (dimethylamine) acetone ( n=5, u=0, v=0, w=0, x=0, y=1, z=1), N-methylpyrrolidone (n=5, u=1, v=1, w=0 , x=0, y=1, z=1), and so on.

In certain embodiments, the precursor mixture also includes a porogen. The following are non-limiting examples of precursors for silicon-based porogenization, wherein the porogen material is one or more of ^R1 , ^R3 or ^R7 :

-R ¹ _n (OR ² ) _3-n Si, wherein, R ¹ can be independently H, C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 can be independently _C1 - _C12 linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or perfluorinated hydrocarbon groups , n is 1-3.

- Example: Diethoxy-Neohexylsilane

-R ¹ _n (OR ² ) _3-n Si-O-SiR ³ _m (OR ⁴ ) _3-m , wherein, R ¹ and R ³ can be independently H, C ₁ -C ₁₂ straight chain or branched , saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; R ² and R ⁴ can be independently C ₁ -C ₁₂ linear or branched, saturated, mono- or poly Unsaturated, cyclic, aromatic, partially or perfluorinated hydrocarbon groups, n is 1-3, m is 1-3.

Example: 1,3-diethoxy-1-neohexyldisiloxane

-R ¹ _n (OR ² ) _3-n Si-SiR ³ _m (OR ⁴ ) _3-m , wherein, R ¹ and R ³ can be independently H, C ₁ -C ₁₂ linear or branched, saturated , mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 and ^R4 can be independently _C1 - _C12 linear or branched, saturated, mono- or polyunsaturated cyclic, aromatic, partially or perfluorinated hydrocarbon groups, n is 1-3, and m is 1-3.

Example: 1,2-diethoxy-1-neohexyldisilane

-R ¹ _n (OR ² ) _3-n Si-R ⁷ -SiR ³ _m (OR ⁴ ) _3-m , wherein, R ¹ and R ³ can be independently H, C ₁ -C ₁₂ straight chain or branched , saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 and ^R4 can be independently _C1 - _C12 linear or branched, saturated, mono- or Polyunsaturated, cyclic, aromatic, partially or perfluorinated hydrocarbyl, R ⁷ is C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, Partially or fully fluorinated, and bridging two silicon atoms, n is 1-3, m is 1-3.

- Example: 1,4-bis(dimethoxysilyl)cyclohexane

-R ¹ _n (OR ² ) _3-n Si-SiR ³ _m (OR ⁴ ) _3-m , wherein, R ¹ and R ³ can be independently H, C ₁ -C ₁₂ linear or branched, saturated , mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 and ^R4 can be independently _C1 - _C12 linear or branched, saturated, mono- or polyunsaturated cyclic, aromatic, partially or perfluorinated hydrocarbon groups, n is 1-3, and m is 1-3.

Example: 1,2-diethoxy-1-neohexyldisilane

-R ¹ _n (O(O)(CR ² ) _4-n Si, wherein, R ¹ can be independently H, C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, Cyclic, partially or fully fluorinated hydrocarbons; ^R2 can be independently H, _C1 - _C12 linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, Partially or perfluorinated hydrocarbyl, n is 1-3.

- Example: Diacetoxy-Neohexylsilane

-R ¹ _n (O(O)(CR ² ) _3-n Si-O-SiR ³ _m (O(O)CR ⁴ ) _3-m , wherein, R ¹ and R ³ can be independently H, C ₁ -C ₁₂ straight chain or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbon group; R ² and R ⁴ can be independently H, C ₁ -C ₁₂ straight chain or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or perfluorinated hydrocarbon groups, n is 1-3, and m is 1-3.

- Example: 1,3-diacetoxy-1-neohexyldisiloxane

-R ¹ _n (O(O)(CR ² ) _3-n Si-SiR ³ _m (O(O)CR ⁴ ) _3-m , wherein, R ¹ and R ³ can be independently H, C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbon groups; R ² and R ⁴ can be independently H, C ₁ -C ₁₂ linear or branched Chain, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or perfluorinated hydrocarbyl, n is 1-3, and m is 1-3.

Example: 1,2-diacetoxy-1-neohexyldisilane

-R ¹ _n (O(O)CR ² ) _3-n Si-O-SiR ³ _m (OR ⁴ ) _3-m , wherein, R ¹ and R ³ can be independently H, C ₁ -C ₁₂ straight chain or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbyl; ^R2 can be independently H, _C1 - _C12 linear or branched, saturated, Mono- or polyunsaturated, cyclic, aromatic, partially or perfluorinated hydrocarbyl, ^R4 can be independently _C1 - _C12 linear or branched, saturated, mono- or polyunsaturated , a cyclic, aromatic, partially or fully fluorinated hydrocarbon group, n is 1-3, and m is 1-3.

- Example: 1-acetoxy-3,3-di-tert-butoxy-1-neohexyldisiloxane

-R ¹ _n (O(O)(CR ² ) _3-n Si-SiR ³ _m (OR ⁴ ) _3-m , wherein, R ¹ and R ³ can be independently H, C ₁ -C ₁₂ straight chain or Branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbyl; ^R2 can be independently H, _C1 - _C12 linear or branched, saturated, mono or polyunsaturated, cyclic, aromatic, partially or perfluorinated hydrocarbyl, ^R4 can be independently _C1 - _C12 linear or branched, saturated, mono- or polyunsaturated, Cyclic, aromatic, partially or fully fluorinated hydrocarbon groups, n is 1-3, m is 1-3.

- Example: 1-acetoxy-2,2-di-tert-butoxy-1-neohexyldisilane

-R ¹ _n (OR ² ) _p (O(O)CR ³ ) _4-(n+p) Si, wherein, R ¹ can be independently H, C ₁ -C ₁₂ linear or branched, saturated , mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbon group; R ² is independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic , aromatic, partially or perfluorinated hydrocarbyl, ^R3 can be independently H, _C1 - _C12 linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic , a partially or fully fluorinated hydrocarbon group, n is 1-3, and p is 1-3.

-Example: Acetoxy-tert-butoxyneohexylsilane

-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 can be independently H, C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbon groups; R ² and R ⁶ can be independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon groups, R ⁴ , R ⁵ can be independently H, C ₁ - _C12 linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbyl, n is 1-3, m is 1-3, p is 1-3, and q is 1-3.

- Example: 1,3-diacetoxy-1,3-di-tert-butoxy-1-neohexyldisiloxane

-R ¹ _n (OR ² ) _p (O(O)CR ⁴ ) _3-np Si-SiR ³ _m (O(O)CR ⁵ ) _q (OR ⁶ ) _{-mq called} , where R ¹ and R ³ can be independently H, C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbon groups; R ² , R ⁶ can be independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon group, R ⁴ , R ⁵ can be independently H, C ₁ - _C12 linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbyl, n is 1-3, m is 1-3, p is 1 -3, and q is 1-3.

- Example: 1,2-diacetoxy-1,2-di-tert-butoxy-1-neohexyldisilane

- Cyclic siloxanes of formula (OSiR ¹ R ³ )x, wherein R ¹ and R ³ can be independently H, C ₁ -C ₁₂ straight or branched, saturated, mono- or polyunsaturated, Cyclic, partially or fully fluorinated hydrocarbon groups, and x can be an integer of 2-8.

- Example: eg 1-neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane.

Example

All experiments were performed on an Applied Materials Precision-5000 system using undoped TEOS processing equipment in a 200mn D×Z chamber equipped with an Advance Energy2000 RF generator. The method includes the basic steps of initial setup and stabilization of gas flow, deposition, and purging/evacuation of the chamber prior to wafer removal.

The post-treatment step with thermal annealing was carried out in a tube furnace at 425° C. for at least 1 hour under nitrogen atmosphere. Exposure to UV light was accomplished by a Fusion UV equipped with H+ bulbs using a 6000 W broadband UV lamp. The atmosphere was controlled by placing the film in a process chamber equipped with a 12.52 mm thick synthetic silica wafer so that the film could be illuminated with light. The pressure in the chamber was maintained between 0.3 and 760 Torr.

The porogen to DEMS ratio is the relative molar concentration of porogen precursor to silicon-containing precursor introduced into the reaction chamber. As the ratio is increased, the amount of porogen precursor will increase relative to the silicon-containing precursor. Since it is a molar ratio, relative concentrations are on a per-molecule basis; for example, porogen:DEMS of 4 means that 4 molecules of porogen precursor are introduced into the reaction chamber for every molecule of silicon-containing precursor.

The deposition rate is: the rate at which the deposited film is formed on the substrate in the reaction chamber. It is determined by measuring the film thickness of the deposited film and dividing by the time required for the deposition to complete. The deposition rate relates to the efficiency with which the porogen precursor and the silicon-containing precursor react in the deposition chamber to form the porogen and organosilicate, respectively, on the substrate surface.

Thickness and refractive index were measured using a SCI Filmtek 2000 reflectometer. The refractive index of a material is defined as:

RI=c/v

In the formula, c is the speed of light in vacuum, and υ is the speed of light passing through the film. The refractive index is measured using light at 632nm. The speed at which light travels through a film depends on the film's electron density, which in this study was moderately related to the dielectric constant in order to compare and contrast the properties of the deposited and final films. Therefore, films with higher refractive indices generally have higher dielectric constant values. Typically, the film after post-treatment has a lower refractive index than the deposited film. This is because the porogen in the deposited film has been replaced by void volume and the refractive index of air is about 1.00029 compared to about 1.400-1.600 for the porogen.

The dielectric constant of the material, k is defined as:

k=C/C ₀

In the formula, C is the capacitance of the dielectric, and C ₀ is the capacitance of the vacuum. The capacitance of the deposited film and/or the final porous organosilicate film deposited on a low resistance p-type silicon wafer (<0.02 ohm-cm) was measured using the mercury probe technique.

Mechanical properties (nanoindent hardness, Young's modulus) were measured with an MTS Nano Indenter using standard protocols.

Thermal stability and off-gas products were measured by thermogravimetric analysis using a Thermo TA Instruments 2050 TGA. Composition data were obtained by X-ray photoelectron spectroscopy (XPS) using a Physical Electronics 5000LS. The % atomic values listed in the tables do not include hydrogen.

In some of the tables below, "n/a" indicates that data were not available.

The present invention relates to the following technical solutions:

1. A chemical vapor deposition method forming an organosilicate glass porous film on a substrate, said method comprising the following steps:

Introducing a gaseous reactant comprising a precursor mixture comprising dimethoxymethylsilane, diethoxymethylsilane, diisopropoxymethylsilane, di-t-butoxy Methylmethylsilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane and, tri-tert-butoxy At least one organosilane and/or organosiloxane precursor of silane and mixtures thereof and porogen precursors having a radical structure selected from: propanol; ethylene glycol; hexanol; cyclopentanol; 1,5-hexadiene-3,4-diol; cresol; resorcinol; diethyl ether; 2-methyl-tetrahydrofuran; 2,3-benzofuran; ethylene glycol divinyl ether; cineole ; Cyclopentaneformaldehyde; Cyclopentanecarboxylic acid; Maleic anhydride; Ethyl methacrylate; Cyclopentylamine; Diisopropylamine; Triethylamine; N-Methylpyrrolidine; N-Methylpyrrole; Nitrocyclopentylamine nitrobenzene; 2-(2-aminoethylamino)ethanol; N-methylmorpholine; tetrahydrofurfurylamine; cyclohexanone; contains one or more epoxy groups and has the general formula C _n Hydrocarbon structure of H _{2n+2-2x-2y-2z Oz} , where n=1-12, x is the number of rings in the structure and is between 0-4, y is the number of unsaturated bonds in the structure and is between 0 and Between n, z is the number of epoxy groups in the structure and is between 1 and 4, and wherein the epoxy groups can be attached to rings or straight chains; contain one or more keto groups and have the general formula The hydrocarbon structure of C _n H _{2n+2-2x-2y-2z} O _z , wherein n=1-12, x is the number of rings in the structure and between 0-4, y is the number of unsaturated bonds in the structure and in Between 0 and n, z is the number of aldehyde groups in the structure and is between 1 and 4, and wherein the keto group can be exocyclic and/or intracyclic; and mixtures thereof;

applying energy to the gaseous reactant to initiate a reaction of the gaseous reactant to provide a prepared film, wherein the prepared film comprises a porogen formed from said porogen precursor; and

At least a portion of the porogen is removed from the prepared film to provide a porous organosilicate glass film, wherein the porous organosilicate glass film has a dielectric constant of less than 2.7.

2. The method of technical solution 1, wherein the dielectric constant is less than 1.9.

3. The method of technical scheme 1, wherein the porous organic silicate glass film comprises the compound of formula _SivOwCxHyFz , wherein _{v + w} +x+y+ _z =100% atom, v is 20- 30% atomic, w is 20-45% atomic, x is 5-20% atomic, y is 15-40% atomic, and z is 0-15% atomic.

4. The method of technical scheme 1, wherein the removing step involves treating the prepared film with at least one fluorinating agent selected from SiF ₄ , NF ₃ , F ₂ , COF ₂ , CO ₂ F ₂ and HF, and It is used to introduce F to the porous organosilicate glass film, and basically all the F in the porous film is bonded to Si in the form of Si-F group.

5. The method of claim 1, wherein 50% or more of hydrogen in the porous organosilicate glass thin film is bonded to carbon.

6. The method of technical solution 1, wherein the density of the porous organosilicate glass film is less than 1.5 g/ml.

7. The method of technical solution 1, wherein the porous organosilicate glass film includes pores with an equivalent sphere diameter less than or equal to 3 nm.

8. The method of embodiment 1, wherein the Fourier Transform Infrared (FTIP) spectrum of the porous film is substantially the same as the reference FTIR of a reference film prepared in substantially the same manner except that there is no porogen precursor in the gaseous reagent same.

9. The method of claim 8, wherein the dielectric constant of the porous film is at least 0.3 less than a reference film prepared by substantially the same method except without any porogen precursor in the gas reagent.

10. The method of claim 8, wherein the dielectric constant of the porous film is at least 10% lower than a reference film prepared by substantially the same method except without any porogen precursor in the gas reagent.

11. The method of technical solution 1, wherein the average weight loss of the porous film at a constant temperature of 425°C under a nitrogen atmosphere is less than 1.0 wt%/hr.

12. The method of technical solution 1, wherein the average weight loss of the porous film in air at a constant temperature of 425° C. is less than 1.0 wt%/hr.

13. The method of claim 1, wherein the porogen precursor is different from at least one organosilane and/or organosiloxane precursor.

14. The method of technical scheme 1, wherein, the porogen precursor is selected from 1,2-epoxy-3-methylbutane, 1,2-epoxy-5-hexene, cyclohexene oxide or 9-Oxabicyclo[6.1.0]non-4-ene.

15. The method of technical solution 1, wherein the pore-forming agent precursor is selected from 3,4-hexanedione, cyclopentanone or 2,4,6-trimethylphenyl oxide.

16. The method of technical solution 1, wherein the precursor mixture further comprises a pore-forming precursor.

17. The method of technical scheme 16, wherein the pore-forming precursor is selected from: 1-neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-neopentyl-1,3, 5,7-Tetramethylcyclotetrasiloxane, Neopentyldiethoxysilane, Neohexyldiethoxysilane, Neohexyltriethoxysilane, Neopentyltriethoxy Silane and Neopentyldi-tert-Butoxysilane.

18. The method of technical solution 1, further comprising: treating the prepared film with at least one post-treatment agent selected from heat energy, plasma energy, photon energy, electron energy, microwave energy and chemical substances.

19. The method of claim 18, wherein at least one post-treatment agent improves the properties of the resulting porous silicone glass film before, during and/or after removing substantially all of the porogen from the prepared film.

20. The method of claim 18, wherein the additional post-treatment removes at least a portion of the porogen from the prepared film.

21. The method of technical claim 18, wherein at least one post-treatment agent is photon energy in the range of 200-8000 nanometers.

22. The method of claim 18, wherein at least one post-treatment agent is electron energy provided by an electron beam.

23. The method of technical solution 18, wherein at least one post-treatment agent is a supercritical fluid.

24. An organosilicate glass porous film produced by the method of technical scheme 1, said organosilicate glass porous film is made up of the material represented by chemical formula Si _v O _w C _{x Hy} F _z , wherein 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 less than 2.6.

25. The organosilicate glass porous film of technical solution 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.

26. The organosilicate glass porous film of claim 24, wherein z is 0.5-7 atomic %, and wherein substantially all of F in the porous film is bonded to Si in the form of Si-F groups.

27. The organosilicate glass porous film of claim 24, wherein 50% or more of hydrogen contained in the film is bonded to carbon.

28. A composition comprising:

(a) has a compound selected from dimethoxymethylsilane, diethoxymethylsilane, diisopropoxymethylsilane, di-tert-butoxymethylsilane, trimethoxysilane, At least one organosilane and / or organosiloxane precursors;

(b) having a porogen different from said at least one organosilane and/or organosiloxane precursor selected from: propanol; ethylene glycol; hexanol; cyclopentanol; ene-3,4-diol; cresol; resorcinol; diethyl ether; 2-methyl-tetrahydrofuran; 2,3-benzofuran; ethylene glycol divinyl ether; eucalyptol; cyclopentanecarbaldehyde; Cyclopentanecarboxylic acid; maleic anhydride; ethyl methacrylate; cyclopentylamine; diisopropylamine; triethylamine; N-methylpyrrolidine; N-methylpyrrole; nitrocyclopentane; nitrobenzene; 2-(2-aminoethylamino)ethanol; N-methylmorpholine; tetrahydrofurfurylamine; cyclohexanone; contains one or more epoxy groups and has the general formula _{CnH2n +2-2x} - Hydrocarbon structure of _2y-2z O _z , where n=1-12, x is the number of rings in the structure and between 0-4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is The number of epoxy groups in the structure and is between 1 and 4, and where the epoxy groups can be attached to a ring or a straight chain; contains one or more keto groups and has the general formula C _n H _2n+2 - the hydrocarbon structure of _2x-2y-2z O _z , wherein n=1-12, x is the number of rings in the structure and is between 0-4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of aldehyde groups in the structure and is between 1 and 4, and wherein the keto groups can be exocyclic and/or intracyclic; and mixtures thereof.

29. The composition of technical scheme 28, wherein said composition also comprises:

(c) a porogen having a structure selected from the formula:

1) Formula R ¹ _n (OR ² ) _p (O(O)CR ³ ) _4-(n+p) Si, wherein, R ¹ is independently H or C ₁ -C ₁₂ linear or branched, saturated , mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 and ^R3 are independently _C1 - _C12 linear or branched, saturated, mono- or polyunsaturated , cyclic, aromatic, partially or fully fluorinated hydrocarbons, n is 1-3, and p is 0-3, provided that n + p ≤ 4, and at least one R ¹ is used as porogen C ₃ or greater hydrocarbon substitution;

2) 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 , wherein, R ¹ and r ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; R ² , R ⁴ , R ⁵ and R are ^{independently} C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, 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 and R ³ - substituted by a _C3 or greater 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-mq , wherein, R ¹ and R ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, 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 R1 and ^R3 is used as _C3 or greater hydrocarbon substitution of the porogen;

4) 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-mq , wherein, R ¹ and R ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; 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, partially or fully fluorinated hydrocarbons, n is 0-3, m is 0-3, q is 0-3 and p is 0-3, the prerequisite is that n+m≥1, n+p≤3, m+q≤3, and R ¹ , R ³ and at least one of ^R is substituted with a C _or greater hydrocarbon as a porogen;

5) Formula (R ¹ _n (OR ² ) _p (O(O)CR ³ ) _4-(n+p) Si) _t CH _4-t , wherein, R ¹ is independently H or C ₁ -C ₁₂ straight Chain or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 and ^R3 are independently _C1 - _C12 straight-chain or branched, saturated , mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, n is 1-3, p is 0-3, and t is 2-4, provided that n+p ≤ 4, and at least one R ¹ is substituted by a C ₃ or larger hydrocarbon as a porogen;

6) Formula (R ¹ _n (OR ² ) _p (O(O)CR ³ ) _4-(n+p) Si) _t NH _3-t , wherein, R1 is independently H or C ₁ -C ₁₂ straight chain or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 and ^R3 are independently _C1 - _C12 linear or branched, saturated, Mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, n is 1-3, p is 0-3, and t is 1-3, provided that n+p≤ 4, and at least one R ¹ is substituted by a C ₃ or larger hydrocarbon as a porogen;

7) Cyclosiloxanes of the formula (OSiR ¹ R ³ ) _x , wherein R ¹ and R ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, Cyclic, partially or fully fluorinated hydrocarbon groups, and x can be an integer from 2 to 8, with the proviso that at least one of R ^{and R} is substituted by a C _or greater hydrocarbon as a porogen;

8) Cyclosilazanes of formula (NR ¹ SiR ¹ R ³ ) _x , wherein R ¹ and R ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated , cyclic, partially or fully fluorinated hydrocarbon groups, and x can be an integer from 2 to 8, provided that at least one of ^R1 and ^R3 is used as a porogen _C3 or greater hydrocarbon replace;

9) Cyclosilanes of the formula (CR ¹ R ³ SiR ¹ R ³ ) _x , wherein R ¹ and R ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or poly Unsaturated, cyclic, partially or fully fluorinated hydrocarbon groups, and x can be an integer of 2-8, provided that at least one of ^R1 and ^R3 is used as a porogen of _C3 or greater Hydrocarbon substitution;

10) and mixtures thereof.

Example 1

Changes in stoichiometric amounts of porogen precursors relative to silicon-containing precursors

Composite thin films were deposited from a mixture of cyclohexanone (CHO) and diethoxymethylsilane (DEMS). The deposition conditions were as follows: plasma power of 450 watts, chamber pressure of 8 torr, electrode distance of 350 mils, carrier gas of helium at a flow rate of 210 sccm, and substrate temperature of 225°C. The flow rates of CHO and DEMS were varied to control the ratio of CHO and DEMS introduced into the reaction chamber while keeping the total flow rate of chemicals into the reaction chamber constant. The films were post-treated by exposing them to broadband UV light (λ = 200-400 nm) under vacuum for 5 minutes.

Tables 1a and 1b. Properties of deposited and final films for films deposited using cyclohexanone and DEMS,

The data in Tables 1a and 2a show that changes in the precursor stoichiometry will lead to changes in the final properties of the films. This is because the amount of porogen precursor and silicon-containing precursor in the chemical feed to the reaction chamber essentially determines the amount of porogen and organosilicate deposited onto the substrate. For example, the lowest final film dielectric constant will be achieved at the highest CHO:DEMS ratio. When the ratio of CHO:DEMS is decreased, both the dielectric constant and mechanical hardness of the film will increase. Thus, film properties can be controlled by the amount of porogen precursor and the amount of organosilicon precursor in the reaction chamber.

Example 2

Functional groups of porogen precursors

Additionally, the structure and/or composition of the porogen precursor can also be used to control film properties. Composite thin films were deposited from CHO or 1,2,4-trimethylcyclohexane (TMC). Table 2 compares the pure liquid properties of these precursors. The CHO precursor consists of a 6-carbon ring with a ketone functional group, while the TMC precursor has a 6-carbon ring with three methyl groups attached at the 1, 2 and 4-positions.

Table 2. Properties of pure liquid porogen precursors.

Table 3 details the deposition conditions of the composite thin films deposited from TMC and DEMS, or from CHO and DEMS. The films deposited using the CHO precursor had a higher deposition rate and deposited refractive index compared to the deposited TMC films, thus implying a higher porogen concentration in the deposited CHO films. This higher amount of porogen in the CHO film can be easily observed by examining the FT-IR spectrum of the deposited film as shown in FIG. 2 . The spectra in Figure 2 have been normalized to a film thickness of 1 μm. The porogen concentration in the deposited film is best observed when the CH _x vibrational stretch between 2700-3100 cm ⁻¹ increases. The data in Table 3 shows that the peak area in the CHO-1 film is 5.25, while the peak area in the TMC-1 film is 3.27. Therefore, under the same processing conditions, the CHO porogen precursor was more effective in increasing the CH _bond concentration of the deposited composite films.

Table 3. Deposition conditions, deposition rates, and refractive indices for depositing composite thin films in Example 2.

Figure 3 shows the FT-IR spectra of CHO-1 and TMC-1 films after exposure to broadband UV light for 5 minutes under vacuum. The spectra show that the CH _x peak areas of the two films are reduced to about 0.9 and 0.6, respectively. The difference between the CH _peak intensities after porogen removal can be attributed to the higher amount of Si-CH groups in the CHO- ₁ film, which would contribute to some absorption in this region.

Table 4 lists the final properties of the films for TMC-1 and CHO-1 after exposure to broadband UV light for 5 minutes under vacuum. This data indicates that the CHO-1 film has a lower dielectric constant than the TMC-1 film. This is due to the higher porogen concentration and thus higher porosity achieved with the CHO precursor. Therefore, for some applications it is advantageous to select porogen precursors with ketone or other functional groups relative to porogen precursors with a purely organic composition in order to enhance one or more of the porous organosilicate films. Multiple properties.

Table 4. Properties of the final porous film for the film in Comparative Example 2.

Example 3

Composite thin films were deposited from a 22/78 mole percent mixture of cyclohexanone (CHO) and diethoxymethylsilane (DEMS). The deposition conditions are as follows: the plasma power is 600 watts, the reaction chamber pressure is 8 torr, the electrode distance is 350 mils, the carrier gas is CO ₂ with a flow rate of 200 sccm, the additional gas is O ₂ with a flow rate of 10 sccm, and the deposition rate is 450 nanometers (nm)/minute, and the substrate temperature is 250°C. The flow rates of CHO and DEMS were varied to control the ratio of CHO and DEMS introduced into the reaction chamber while keeping the total flow rate of chemicals into the reaction chamber constant. The film was post-treated by exposing it to broadband UV light (λ = 200-400 nm) under vacuum for 5 minutes and had a shrinkage percentage of 30%. Table 5 provides various properties of the deposited and final films after exposure to UV light treatment.

Figure 4 shows the FT-IR spectra of DEMS/CHO thin films before deposition or after deposition and after 5 min exposure to broadband UV light under vacuum. The spectrum shows that the _CHx peak area of the UV-treated film is reduced by about 84% relative to the as-deposited film.

Table 5. Individual properties of the deposited and final films for films deposited using DEMS/CHO (22/78)

performance deposited film final film Refractive index 1.486 1.340 Dielectric constant n/a 2.3

Example 4

Composite thin films were deposited from a 20/80 mole percent mixture of DMHD and diethoxymethylsilane (DEMS). The deposition conditions are as follows: the plasma power is 600 watts, the reaction chamber pressure is 8 torr, the electrode distance is 350 mils, the carrier gas is CO ₂ with a flow rate of 200 sccm, the additional gas is O ₂ with a flow rate of 10 sccm, and the substrate The temperature is 300°C. The flow rates of DMHD and DEMS were varied to control the ratio of DMHD and DEMS introduced into the reaction chamber while keeping the total flow rate of chemicals into the reaction chamber constant. The film was post-treated by exposing it to broadband UV light (λ = 200-400 nm) under vacuum for 5 minutes and had a shrinkage percentage of 30%. Table 6 provides various properties of the deposited and final films after exposure to UV light treatment.

Figure 5 shows the FT-IR spectra of DEMS/DMHD films before or during deposition and after 5 min exposure to broadband UV light under vacuum.

Table 6. Individual properties of the deposited and final films for films deposited using DEMS/DMHD (22/78)

performance deposited film final film Refractive index 1.48 1.35 Dielectric constant n/a 2.47 hardness n/a 0.9 Elastic Modulus n/a 6.2

Example 5

DEMS-containing films were deposited using the following porogen precursors: ATP, LIM, CHO, _CHOx . The deposition conditions for each film are provided in Tables 7a-7d. The properties of the final films after exposure to UV curing for 5 minutes are provided in Tables 8a-8d. Figure 6 shows the relationship between hardness and dielectric constant of these films.

Table 7A. Deposition conditions of DEMS+ATRP

Table 7A. Deposition conditions for DEMS+ATRP (continued)

Table 7B. Deposition conditions of DEMS+LIMO

Table 7B. Deposition conditions of DEMS+LIMO (continued)

Table 7B. Deposition conditions of DEMS+LIMO (continued)

Table 7C. Deposition conditions of DEMS+CHO

Table 7D. Deposition conditions of DEMS+CHOx

Table 8A. Thin film properties of DEMS+ATRP

Table 8A. Thin film properties of DEMS+ATRP (continued)

Table 8B. Thin film properties of DEMS+LIMO

Table 8B. Thin film properties of DEMS+LIMO (continued)

Table 8B. Thin film properties of DEMS+LIMO (continued)

Table 8C. Thin film properties of DEMS+CHO

Table 8D. Thin film properties of DEMS+CHOx

Claims (1)

1. A chemical vapor deposition method forming an organosilicate glass porous film on a substrate, said method comprising the following steps: Introducing a gaseous reactant comprising a precursor mixture comprising dimethoxymethylsilane, diethoxymethylsilane, diisopropoxymethylsilane, di-t-butoxy Methylmethylsilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane and, tri-tert-butoxy At least one organosilane and/or organosiloxane precursor of silane and mixtures thereof and porogen precursors having a radical structure selected from: propanol; ethylene glycol; hexanol; cyclopentanol; 1,5-Hexadiene-3,4-diol; Cresol; Resorcinol; Diethyl ether; 2-Methyl-tetrahydrofuran; 2,3-Benzofuran; Ethylene glycol divinyl ether; Cineole ; Cyclopentaneformaldehyde; Cyclopentanecarboxylic acid; Maleic anhydride; Ethyl methacrylate; Cyclopentylamine; Diisopropylamine; Triethylamine; N-Methylpyrrolidine; N-Methylpyrrole; Nitrocyclopentylamine nitrobenzene; 2-(2-aminoethylamino)ethanol; N-methylmorpholine; tetrahydrofurfurylamine; cyclohexanone; contains one or more epoxy groups and has the general formula C _n Hydrocarbon structure of H _{2n+2-2x-2y-2z Oz} , where n=1-12, x is the number of rings in the structure and between 0-4, y is the number of unsaturated bonds in the structure and is between 0 and Between n, z is the number of epoxy groups in the structure and is between 1 and 4, and wherein the epoxy groups can be attached to rings or straight chains; contain one or more keto groups and have the general formula The hydrocarbon structure of C _n H _{2n+2-2x-2y-2z} O _z , where n=1-12, x is the number of rings in the structure and between 0-4, y is the number of unsaturated bonds in the structure and in Between 0 and n, z is the number of aldehyde groups in the structure and is between 1 and 4, and wherein the keto group can be exocyclic and/or intracyclic; and mixtures thereof; applying energy to the gaseous reactant to initiate a reaction of the gaseous reactant to provide a prepared film, wherein the prepared film comprises a porogen formed from said porogen precursor; and At least a portion of the porogen is removed from the prepared film to provide a porous organosilicate glass film, wherein the porous organosilicate glass film has a dielectric constant of less than 2.7. 2. The method of claim 1, wherein the dielectric constant is less than 1.9. 3. The method of claim 1, wherein the porous organosilicate glass film comprises a compound of the formula _SivOwCxHyFz , wherein _v + _w +x+ _y + _z =100% atoms, and v is 20- 30% atomic, w is 20-45% atomic, x is 5-20% atomic, y is 15-40% atomic, and z is 0-15% atomic. 4. The method of claim 1, wherein said removing step involves treating said prepared film with at least one fluorinating agent selected from the group consisting of _SiF4 , _NF3 , _F2 , _COF2 , _{CO2F2 ,} and HF, and It is used to introduce F to the porous organosilicate glass film, and basically all the F in the porous film is bonded to Si in the form of Si-F group. 5. The method of claim 1, wherein 50% or more of the hydrogen in the porous organosilicate glass film is bonded to carbon. 6. The method of claim 1, wherein the porous organosilicate glass film has a density of less than 1.5 g/ml. 7. The method of claim 1 , wherein the porous organosilicate glass film comprises pores having an equivalent spherical diameter of less than or equal to 3 nm. 8. The method of claim 1, wherein the Fourier Transform Infrared (FTIR) spectrum of the porous film is substantially the same as the reference FTIR of a reference film prepared in substantially the same manner except without any porogen precursor in the gaseous reagent same. 9. The method of claim 8, wherein the porous film has a dielectric constant that is at least 0.3 less than a reference film prepared in substantially the same manner except without any porogen precursor in the gas reagent. 10. The method of claim 8, wherein the dielectric constant of the porous film is at least 10% lower than a reference film prepared by substantially the same method except without any porogen precursor in the gas reagent. 11. The method of claim 1, wherein the average weight loss of the porous film at a constant temperature of 425° C. under a nitrogen atmosphere is less than 1.0 wt%/hr. 12. The method of claim 1, wherein the average weight loss of the porous film at a constant temperature of 425° C. in air is less than 1.0 wt%/hr. 13. The method of claim 1, wherein the porogen precursor is different from at least one organosilane and/or organosiloxane precursor. 14. The method of claim 1, wherein the porogen precursor is selected from 1,2-epoxy-3-methylbutane, 1,2-epoxy-5-hexene, cyclohexene oxide or 9-Oxabicyclo[6.1.0]non-4-ene. 15. The method of claim 1, wherein the porogen precursor is selected from 3,4-hexanedione, cyclopentanone or 2,4,6-trimethylphenyl oxide. 16. The method of claim 1, wherein the precursor mixture further comprises a porogen. 17. The method of claim 16, wherein the pore-forming precursor is selected from the group consisting of: 1-neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-neopentyl-1,3, 5,7-Tetramethylcyclotetrasiloxane, Neopentyldiethoxysilane, Neohexyldiethoxysilane, Neohexyltriethoxysilane, Neopentyltriethoxy Silane and neopentyl di-tert-butoxysilane. 18. The method of claim 1, further comprising: treating the prepared film with at least one post-treatment agent selected from the group consisting of thermal energy, plasma energy, photon energy, electronic energy, microwave energy, and chemical substances. 19. The method of claim 18, wherein the at least one post-treatment agent improves the properties of the resulting porous silicone glass film before, during and/or after removing substantially all of the porogen from the prepared film. 20. The method of claim 18, wherein the additional post-treatment removes at least a portion of the porogen from the prepared film. 21. The method of claim 18, wherein the at least one post-treatment agent is a photon energy in the range of 200-8000 nanometers. 22. The method of claim 18, wherein the at least one post-treatment agent is electron energy provided by an electron beam. 23. The method of claim 18, wherein at least one post-treatment agent is a supercritical fluid. 24. A porous organosilicate glass film produced by the method of claim 1, said porous organosilicate glass film is made up of a material represented by the chemical formula Si _v O _w C _{x Hy} F _z , wherein v+w +x+y+z=100%, v is 10-35% atoms, w is 10-65% atoms, x is 5-30% atoms, y is 10-50% atoms, and z is 0-15% atoms , wherein the film has pores and a dielectric constant less than 2.6. 25. The organosilicate glass porous film of claim 24, wherein v is 20-30% atoms, w is 20-45% atoms, x is 5-25% atoms, y is 15-40% atoms, and z is 0. 26. The organosilicate glass porous film of claim 24, wherein z is 0.5-7 atomic %, and wherein substantially all of the F in the porous film is bonded to Si in the form of Si-F groups. 27. The organosilicate glass porous film of claim 24, wherein 50% or more of the hydrogen contained in the film is bonded to carbon. 28. A composition comprising: (a) has a compound selected from dimethoxymethylsilane, diethoxymethylsilane, diisopropoxymethylsilane, di-tert-butoxymethylsilane, trimethoxysilane, At least one organosilane and / or organosiloxane precursors; (b) having a porogen different from said at least one organosilane and/or organosiloxane precursor selected from: propanol; ethylene glycol; hexanol; cyclopentanol; ene-3,4-diol; cresol; resorcinol; diethyl ether; 2-methyl-tetrahydrofuran; 2,3-benzofuran; ethylene glycol divinyl ether; eucalyptol; cyclopentanecarbaldehyde; Cyclopentanecarboxylic acid; maleic anhydride; ethyl methacrylate; cyclopentylamine; diisopropylamine; triethylamine; N-methylpyrrolidine; N-methylpyrrole; nitrocyclopentane; nitrobenzene; 2-(2-aminoethylamino)ethanol; N-methylmorpholine; tetrahydrofurfurylamine; cyclohexanone; contains one or more epoxy groups and has the general formula _{CnH2n +2-2x} - The hydrocarbon structure of _2y-2z O _z , where n=1-12, x is the number of rings in the structure and between 0-4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is The number of epoxy groups in the structure and is between 1 and 4, and where the epoxy groups can be attached to a ring or a straight chain; contains one or more keto groups and has the general formula C _n H _2n+2 - the hydrocarbon structure of _{2x-2y-2z Oz} , where n=1-12, x is the number of rings in the structure and is between 0-4, y is the number of unsaturated bonds in the structure and is between 0 and n, z is the number of aldehyde groups in the structure and is between 1 and 4, and wherein the keto groups can be exocyclic and/or intracyclic; and mixtures thereof. 29. The composition of claim 28, wherein said composition further comprises: (c) a porogen having a structure selected from the following formulae: 1) Formula R ¹ _n (OR ² ) _p (O(O)CR ³ ) _4-(n+p) Si, wherein, R ¹ is independently H or C ₁ -C ₁₂ linear or branched, saturated , mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 and ^R3 are independently _C1 - _C12 linear or branched, saturated, mono- or polyunsaturated , cyclic, aromatic, partially or fully fluorinated hydrocarbons, n is 1-3, and p is 0-3, provided that n + p ≤ 4, and at least one R ¹ is used as porogen C ₃ or greater hydrocarbon substitution; 2) 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 , wherein, R ¹ and R ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; R ² , R ⁴ , R ⁵ and R are ^{independently} C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, 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 and R ³ - substituted by a _C3 or greater 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-mq , wherein, R ¹ and R ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; R ² , R ⁴ , R ⁵ and R ⁶ are independently C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, aromatic, 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 and R ³ is used as C _or greater hydrocarbon substitution of porogens; 4) 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-mq , wherein, R ¹ and R ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; 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, partially or fully fluorinated hydrocarbons, n is 0-3, m is 0-3, q is 0-3 and p is 0-3, the prerequisite is that n+m≥1, n+p≤3, m+q≤3, and R ¹ , R ³ and at least one of ^R is substituted with a C _or greater hydrocarbon as a porogen; 5) Formula (R ¹ _n (OR ² ) _p (O(O)CR ³ ) _4-(n+p) Si) _t CH _4-t , wherein, R ¹ is independently H or C ₁ -C ₁₂ straight Chain or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 and ^R3 are independently _C1 - _C12 straight-chain or branched, saturated , mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, n is 1-3, p is 0-3, and t is 2-4, provided that n+p ≤ 4, and at least one R ¹ is substituted by a C ₃ or larger hydrocarbon as a porogen; 6) Formula (R ¹ _n (OR ² ) _p (O(O)CR ³ ) _4-(n+p) Si) _t NH _3-t , wherein, R ¹ is independently H or C ₁ -C ₁₂ straight Chain or branched, saturated, mono- or polyunsaturated, cyclic, partially or fully fluorinated hydrocarbons; ^R2 and ^R3 are independently _C1 - _C12 straight-chain or branched, saturated , mono- or polyunsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbons, n is 1-3, p is 0-3, and t is 1-3, provided that n+p ≤ 4, and at least one R ¹ is substituted by a C ₃ or larger hydrocarbon as a porogen; 7) Cyclosiloxanes of the formula (OSiR ¹ R ³ ) _x , wherein R ¹ and R ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated, Cyclic, partially or fully fluorinated hydrocarbon groups, and x can be an integer from 2 to 8, with the proviso that at least one of R ^{and R} is substituted by a C _or greater hydrocarbon as a porogen; 8) Cyclosilazanes of formula (NR ¹ SiR ¹ R ³ ) _x , wherein R ¹ and R ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or polyunsaturated , cyclic, partially or fully fluorinated hydrocarbon groups, and x can be an integer from 2 to 8, provided that at least one of ^R1 and ^R3 is used as a porogen _C3 or greater hydrocarbon replace; 9) Cyclosilanes of the formula (CR ¹ R ³ SiR ¹ R ³ ) _x , wherein R ¹ and R ³ are independently H or C ₁ -C ₁₂ linear or branched, saturated, mono- or poly Unsaturated, cyclic, partially or fully fluorinated hydrocarbon groups, and x can be an integer of 2-8, provided that at least one of ^R1 and ^R3 is used as a porogen of _C3 or greater Hydrocarbon substitution; 10) and mixtures thereof.

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