TW200306282A - New porogens for porous silica dielectric for integral circuit applications - Google Patents

Abstract

The invention relates to the production of nanoporous silica dielectric films and to semiconductor devices and integrated circuits comprising these improved films. The nanoporous films of the invention are prepared using silicon containing pre-polymers and are prepared by a process that allows crosslinking at lowered gel temperatures by means of a metal-ion-free onium or nucleophile catalyst.

Description

200306282 发明, Description of the invention: TECHNICAL FIELD The present invention relates to the manufacture of nanoporous silica dielectric thin films, and to semiconductor devices and integrated circuits including such improved thin films. The nanoporous film of the present invention is prepared using a silicon-containing prepolymer, and is prepared by a double-ended pore-forming agent to avoid chemical contact between the pore-forming agent and the Si-network. Therefore, almost all of the silanol (Si-OH) groups used can be cross-linked to obtain a hard network before removing the pore-forming agent. Therefore, nanoporous films having a few silanol groups are manufactured. In the future, the size of the integrated circuit will be reduced to less than 0.15 micrometers, which will make the problems caused by the loss of the RC delay ’power and the interaction of signals more easily solved. The solution to overcome these difficulties is to develop materials with a dielectric constant of ^ 2 · 5 for the application of interspace dielectrics and intermetal dielectrics (IMD). Although previous efforts have been made to provide low dielectrics for integrated circuits, there is still a long-term need in the art to further improve the processing method and make the product: the dielectric and mechanical properties of the material used in manufacturing the best. The material with a low dielectric constant is a nanoporous silica film made of "3 silicon < prepolymer by spin sol-gel technique. The number of air hangs is ^ and when air enters In the suitable stone material with a nano-sized pore structure, a thin / cut stone material with a relative dielectric constant (, v) is prepared because the similar precursors include organically substituted silanes. For example, if the organic compound is used as a base matrix, tetraethyl 1 gas-based sintering (TAS) / methyl triethyl alkoxide 200306282 附 (attached double-cut polymer is used as the basic matrix, and it is currently used ... Xi Shi (SlO〆 Spin coating on glass (" S O.G ") and the substance has proven high mechanical strength, such as modulus; =: Taken: f. Mechanical properties can be controlled by controlling the gap of the porous film Γ .Namito purchased stone materials because its holes = inches can be controlled, and therefore can be controlled The obtained film and the dielectric constant. In addition to low k, the thermal stability of the mechanical accuracy of the rice picker is high; paste 2 =: ^ at least than the micro-electricity of the integrated circuit, that is, the size of the use of cut D Low-grade characteristics of the heart; can be prepared from, for example, the most widely used semiconductors, such as tetraethoxy sulfonium disulfide; it can make nano-porous stone Yuji II: using the "adjustment" in the range of ΓΓ and nano-porous film Shen ', ^ S.〇.G. Processing is achieved by similar equipment. The high porosity of the same material in Shi Xishi material, the other-stop ...:' Portrait-phase porous film H " Use another combination Materials and methods for preparing nanometers require the relative density of all pores = variable materials. Other material requirements include dimensions that are smaller than the characteristics of the circuit, and need to be processed due to the surface chemical use of the pores. 'And its dielectric constant and environment The related stability table is (the porosity) is the main 100 of the nanometer film that controls the dielectric constant of the material. The properties of the film can be easily changed on a continuous map, and when the porosity is increased by ° 1 = Dense stone slab with clearance to pore age of 0%. When porosity is built # 太 Y% The number and mechanical strength will increase, but the porosity will decrease, etc. Dielectric = The density range of the porous film needs to be optimally balanced between the low range and mechanical properties required for the desired application. 200306282 Nanoporous g-stone film It has been previously manufactured in many ways. For example, nanoporous membranes have been prepared using a mixture of a solvent and a silica precursor, which is deposited on a suitable substrate. Usually, for example, spin-coated forms on glass The precursor is added to the substrate, and then polymerized in the form of a dielectric film including nanopores. When the nanoporous film is formed by, for example, spin coating, the film coating is generally acidic or alkaline. Sexual catalyst and water catalyze, cause polymerization / gelation (,, aging,,) during the initial heating process. Maximum strength is not obtained by choosing pore size, so low molecular weight pore formers are used. US E1 Patent No. 5,895,263 describes heating the combination by coating a composition including a decomposable polymer and an organic polyoxygenated fragment (ie, containing a condensation or polymerization (Shiyu polymer) on a substrate such as a wafer) The polyisocyanate can be reduced to form a porous dielectric layer to form a porous dielectric layer to form a nanoporous precious stone dielectric film. This method is similar to many previous materials in forming a nanoporous layer on a semiconductor. The method of the thin film is μ, which has the disadvantages of f heating in aging or condensation, and removing the polymer to form a nanoporous film.: The second disadvantage is that the organic polymer contained in the precursor solution is prepared: The L increases the amount of knives'. Therefore, during the storage process, the solubility of the precursor is increased, and the thickness of the film that is inhibited by the storage solution will be dissolved along with shorter storage time, cooling and storage ... And precisely adjust the coating parameters to achieve consistent thin-touch properties during the bulk circuit manufacturing process. The formation of the porous structure is better than that of the United States. ≪ The parts are removed by the porogen. Temperature, soil mm (or gel temperature) ). It is found that the anodic / anionic porous structure with a pore size of less than 10Mr 200306282 can not be manufactured at a concentration of less than 200-300 ppb when the positive ion ions such as sodium are rotated in solution. There is an urgent need for low metal concentration in 1C applications. The general practice is that the metal concentration rotating on the solution is less than 50 ppb. Therefore, there is a need to develop a sustainable supply that has a dielectric constant below 2.5 and a pore size with a diameter below 10 nm nano-porous silica thin film. In the past, without selecting the pore size to obtain the maximum strength, low molecular weight polyethylene glycol monomethyl ether was selected as the pore-forming agent. The conditions that depend on the formation of a stable porous structure The temperature at which the pore-forming agent is removed is higher than the cross-linking temperature (or gelation temperature) of the matrix material. It was found that the pore-forming agent can chemically react with the Si-network to cover the free silane contained in the cross reaction in the process Alcohol groups. This species will decompose after the final hardening stage that occurs at higher temperatures, resulting in unnecessarily isolated Si-OH groups. The change in hydrophilicity is due to the fact that silanol groups can greatly affect the dielectric properties. Therefore, in order to obtain a low-k stable dielectric material, it is necessary to minimize the amount of silanol present in the final film. Furthermore, having a free silanol group will also cause unnecessary external aeration in the 1C compact. The strict requirements of low external inflation and stable k need to meet the application of 1C. The general practice is to obtain a hydrophobic film. Therefore, it is necessary to develop a suspicious hydrophobicity that provides a dielectric constant below 2.2 and absorbs as little water vapor as possible. Nanoporous silica films. Furthermore, it is widely assumed that pores are caused by the chemical adhesion of pore-forming agents to the silica network. It has now been found that chemical adhesion is not necessary for the formation of porous silica. The capped polyethylene oxide pore-forming agent can be obtained through the porous silica formed by the physical blending of the pore-forming agent and the prepolymer through a lower k value of 5 between the fat film under the surrounding and after heating. More hydrophobic film. Double 200306282 capping into pores I / π, (ethylene glycol) dimethyl ether can avoid any chemical adhesion of pore-forming agent and% 罔, so it will not produce free, Outer foot silanol, and the existing silanol group will be fully cross-linked as much as possible, so i produces _ |? U «/, ^ (existed on the right) of the Shixiyan alcohol-based nano porous film. 4 Another 4 ions or nucleophiles can be used to help form a porous silica network in low metal spin compounds at low, 4π r 丄 々 weeks, and low M. Samarium ion or nucleophilicity: It is used to lower the gelling temperature, so it can be hardened before removing the pore-forming agent, thus producing nano-porous films without alkaline ions. Pore formation d < forces control the pore size and decompose immediately after the formation of stable pores. The side reactions which can avoid cross-linking of gluten can be minimized. SUMMARY OF THE INVENTION The present invention provides a method for manufacturing a nanoporous crushed stone dielectric film, comprising: preparing a metal ion-free catalyst composition comprising a group containing a silicon-containing prepolymer; And nucleophile composition and pores not bonded to the silicon-containing prepolymer (b) coating the substrate with the composition to form a thin film; (c) cross-linking the composition to produce a gel film, and remove the substance The above mentioned causes the gelling film to be heated with the pore-forming agent at a temperature and during an effective period. Mao Ming also provides an eight-dimensional pancreas (Wanfa) and semiconductor devices, such as integrated circuits including nano-polyelectric thin films, on the substrate by the above method. The present invention also provides no bond with silicon-containing prepolymer. The pore-forming agent, these 200306282 agents are selected from the group consisting of poly (alkylene) diethers, poly (arylene) diethers, poly (cyclic diol) diethers, crown: 豳, completely capped Polyalkylene oxide, a group consisting of fully-terminated polyarylene oxide, polynorbene, and combinations thereof. The present invention also provides a composition including a silicon-containing prepolymer, which is not bonded to the silicon-containing prepolymer, and is selected from the group consisting of poly (alkylene) diether, poly (alkylene) diether, and poly ( Cyclic glycols) diethers, crown ethers, fully terminated polyalkylene oxides. A group of porogens consisting of fully capped polyarylene oxides, polynorbene, and combinations thereof.

The present invention further provides a method for controlling the pore size of a porous silica film, comprising the preparation of a silicon prepolymer, a metal-free catalyst selected from the group consisting of a europium compound and a nucleophile, and a pore former. The composition; (b) coating the substrate with the composition to form a film; (C) crosslinking the composition to produce a gel film, and (d) heating and removing the gel film at a temperature and during the effective period Substantially all of the pore-forming agent; the method includes using a pore-forming agent that is not bonded to the silicon-containing prepolymer. Embodiments Accordingly, nanoporous silica dielectric thin films having a dielectric constant or k value of about 3 or less, preferably about 2.5 or less, can be prepared by the method of the present invention. Generally, silicon-based dielectric films (including nanoporous silica dielectric films) are composed of a pore-forming agent that is not bonded to a silicon-containing prepolymer, and may be a hafnium compound or a nucleophile. Preparation of suitable silicon-containing prepolymers without metal ion catalyst blend. It may also contain one or more selected solvents, other pore-forming agents-11-200306282, and / or other precursors of dielectric ^ dielectric precursors, J fine from any antagonism φ p know "Methods, coating on the applicable base On the material, for example, a substrate for a two-layer circuit (τ ′) is formed, and a thin film is formed by cross-linking the compound to form a gel film. Then heat the gelatin === to substantially remove all pore formers. The same temperature of H car is based on: Invention: The film prepared by the method has many advantages over the Prophet "advantages 'includes manufacturing with a small (if any) cutting base, more = base, improving my mechanical strength', which can be manufactured Can withstand the treated and stable dielectric constant. The production of a fixed-step k film 'and a low 2 form a nano-porous material as required by the method of the dielectric thin film-y surface modification step are advantageously achieved. In addition, the monolithic dielectric film produced by the method of the present invention can be sufficiently hydrophobic as it was originally formed. The method of this hairy month & the pore size for nanometer diameter diameter, its size is equal to the dielectric constant of the nanoporous yoshinolite film of the household weight-generally about 3 t: the next 'more usually about It is U to about 3.0, and most usually about 1.7 to about 2.5.莼 月 吴 < The average pore diameter is usually from about 1 to about 100%, more preferably from about 1 nm to about 10 nm, and usually from about 5 nm to about 5 nm. The pore volume of the film is based on the thin Wang Deng volume, which is generally about 5% to about 800/0. It should be understood that nano-porous dielectric films-the word refers to the method of the present invention, which is composed of organic or inorganic glass matrix materials (for example, any suitable material based on Shi Xi: Debei Di dielectric film. In addition "Aging" refers to the gelation, condensation, or polymerization of the combined precursor-based precursor composition on the substrate after deposition. "Hardening" refers to the removal of residual silanol (Si-OH). Base, remove the residual water, • 12- 200306282 and subsequent addition in the microelectronics method. Hardening the furnace, the more stable film of the female, the modification of the α is performed after gelling, and κ can be used any other technique猎 Hunting is carried out by heating, and the energy is in the form of electron beam, ultraviolet radiation, etc., such as by applying a dielectric film such as a spaced dielectric coating system. Preparation. Coated dielectric precursor composition = The above method includes (but is not limited to) spin coating, dip coating, known cloth and / or chemical gas, and redundant. / Person soil brush Coating, roll coating, spraying and rolling. Before coating these materials, the surface of the substrate may be The coating is prepared by the standard method of cleaning electricity: thin film. The coating is processed to achieve the known dielectric coating phase # in the core, and the processing in the choice of two and two and the :: object and expectations The final product. Other details of the method and composition: As used herein, the "substrate" is included in the composition or in combination, and is coated with silicon dioxide and silicon dioxide. < Applicable composition that can be formed. For example, the substrate is generally a Shi Xi wafer suitable for manufacturing integrated circuits, and the basic material for forming a porous Shi Xi Shi film is by a general method: (Unlimited) Spin coating, dip coating, brush coating, roll coating, earth material or spray coating. Before coating the base material to form a nanoporous silica film, the surface of the material can be cleaned according to standard conditions and known in the art according to the circumstances. The preparation method is as follows. The substrate expected in this article may include any required solid solid material. In particular: the required substrate layer includes film, glass; ceramic, plastic, metal or coated metal, or composite metal .In the preferred embodiment, Arsenic fossil or kunhua gallium die mouth or wafer surface, package surface as seen in II, =, nickel 13 200306282 or gold plating lead wire frame, copper surface as seen in circuit board or package connection wire ^ Interfaces of perforated walls or reinforcements ("copper" includes bare copper and its oxides), polymer-based packages or board interfaces such as flexible packages based on polyimide, and ball-shaped surfaces soldered to wires or other metal alloys , Glass and polymer. The substrates used include silicon, silicon nitride, silicon oxide, oxysilicon carbide, silicon dioxide, silicon carbide, silicon oxynitride, titanium nitride, nitride button, tungsten nitride, Aluminum, copper, thorium, organosiloxane, organosilicon glass, and fluorinated silica glass. According to other specific examples, the substrate includes materials commonly used in the packaging and circuit board industries, such as stone, copper, glass, and polymer A circuit board composed of the composition can be provided with various conductive circuits on its surface. The circuit board can contain various reinforcements, i-woven non-conductive fibers or glass cloth. The board can be single-sided as well as double-sided. Suitable substrates for the present invention include semiconductor substrates, such as gallium ("GaAs"), silicon and silicon-containing compositions such as crystalline silicon, polysilicon, amorphous silicon, oriented silicon, and dioxide Silicon (" Si02 ") and mixtures thereof. The surface of the substrate is a pattern of selected lines, such as metal, oxide, nitride or oxynitride lines, which can be obtained by the conventional microlithography technique. Formed. Suitable materials for this line include silicon oxide, silicon nitride, nitride number, nitride button, inscription, ingot alloy, copper, copper alloy, boat, tungsten, and silicon oxynitride. The metal used to make these lines The subject matter is taught in commonly assigned U.S. Pat. Nos. 5,780,755; 6,238,494; 6,331,233B1 and 6,348,139B1, and is sold by Honeywell International. These lines form the conductors or insulators of integrated circuits. This is generally about 20 Micron or shorter distance, preferably 1 micron or closer, and preferably a distance of about 0.05 to about 1 micron is closely separated from each other. Other optional characteristics suitable for the surface of the substrate include an oxide layer, such as by silicon -14- 200306 At 282, it is trapped in materials known in the oxygen formed by working gas, such as electricity ..., refined by the technique (" PETEOS ") ^, < tetraethoxysilane oxide, and water-encapsulated prismatic silane oxidation (&Quot; PE Silane ") and Si 〃, ,, D δ formed by chemical vapor deposition, and 丄, 22 lice compound layer, and one or more drawers I ^ ^ into nanosilica Dielectric film. Xixianxianxian The porous stone Xixian film of the present invention can be used. The two early versions of the present invention can be duplicated and / or tiled between, ... sub-surface features, such as the previous circuit element 侔 乃 / 斗, hate. & A < substrate features, s pieces and / or conductive paths. The characteristics of the selected substrate can also be applied to the nano-porous ㈣ = dielectric 4? Film of the present invention, and additional layers can be used to make the resulting integrated circuit-or multiple layers or many electrical ^ = more :, edge. Therefore, 'the substrate of the present invention may be provided with the nanoporous cut stone of the present invention on or above the nanoporous silica film of the present invention during the process of the layer or integrated circuit of the component, as appropriate: material. According to another option, the pores and the silica-bearing tendon < the substrate can be further covered by a non-porous insulating layer known in the art, such as a broken glass cover layer. The crosslinkable composition of the nanoporous film of the present invention comprises one or more kinds of tangible prepolymers which can be condensed immediately. It should have at least two solutions. Reactive groups include alkoxy (RO), ethyl alcohol (Ac0), and the like. Without being bound by the theory and assumptions of the method and composition of the invention (with the limitation, 'believe that water will hydrolyze the reactive groups on the Shi Xi monomer to form a succinyl group (Shi Xi Shao alcohol). The latter will interact with other fever alcohols. Or carry out condensation reaction with other reactive groups, as explained by the following formula:

Si-OH + HO-Si 4 Si-0-Si + H20 Si-OH + R〇.si Si-0-Si + R〇H -15- 200306282

Si-OH is almost AcO-Si — Si-O-Si + AcOH Si-OAe + AcO-Si ^ Si-0-Si + Ac20 R = carbyl or aryl Ac = fluorenyl (CH3CO) These condensation reactions will form Silicon-containing polymer. In a specific example of the present invention, the prepolymer includes a compound represented by Formula I or any combination of compounds: Rx-Si-Ly (Formula I) wherein X is an integer from 0 to about 2, and y is 4-x ( An integer of about 2 to about 4), R is independently an alkyl group, an aryl group, a fluorene group, an alkylene group, an arylene group, and / or a combination thereof; L is independently selected from a negative " electric group, such as an alkoxy group Groups, carboxyl groups, amine groups, amido groups, halides, isocyanate groups, and / or combinations thereof. The most useful prepolymers are provided by Formula I, where X is from about 0 to about 2, y is from about 2 to about 4, R is an alkyl or aryl or fluorene, and L is a negatively charged group, and where Si The hydrolysis rate of the -L bond is greater than that of the Si-OCH2CH3 bond. Therefore, in response to the following responses represented by ⑻ and (b):

(a) Si-L + H20 — Si-OH + HL (b) Si-0CH2CH3 + H20 — Si-OH + HOCH2CH3 The rate of ⑻ is greater than the rate of ⑻. Examples of suitable compounds of formula I include (but are not limited to) ··

Si (OCH2CF3) 4 * (2,2,2-trifluoroethoxy) silane,

Si (OCOCF3) 4 (trifluoroacetoxy) silane *,

Si (OCN) 4 tetraisocyanate silane, CH3Si (OCH2CF3) 3 tris (2,2,2-trifluoroethoxy) methyl silane, 200306282 CH3Si (OCOCi ^ p- (trifluoroacetoxy)) methyl Silane *, CH3Si (OCN) 3A: Toluyltriisocyanate-based silane, [* This will generate an acid catalyst when exposed to water] and / or any combination of the above. According to another specific example of the present invention The composition comprises a polymer synthesized from a compound represented by Formula I by hydrolysis and condensation reactions, wherein the number average molecular weight is about 150 to about 300,000 amu, or usually about 150 to about 10,000 amu. According to another aspect of the present invention In a specific example, the silicon-containing prepolymer used in the present invention includes an organosilane, for example, an alkoxysilane containing the following formula II:

R

-I

R-Si-R type II

R, as appropriate, formula II is an alkyl silane, where at least two R groups are independently CM alkoxy groups, and if present, they are independently selected from hydrogen, alkyl, phenyl, halogen, substituted benzene Group of bases. For the purposes of the present invention, the term alkoxy includes any other organic group that can be easily hydrolyzed from silicon chain scission at room temperature. The R group may be ethylene glycoxy or propylene glycoxy, etc., but preferably all 4 R groups are methoxy, ethoxy, propoxy or butoxy. The most preferred alkoxysilanes include tetraethoxysilane (TEOS) and tetramethoxysilane. According to another option, for example, the prepolymer may be an alkylalkoxysilane described in Formula II, but at least two R groups are independently CM alkylalkoxy groups, and the alkyl group is a CV4 alkyl group. And, if present, it is independently selected from the group consisting of hydrogen, alkyl, phenyl, halogen, and substituted phenyl. According to a specific example, each R is a methoxy group, an ethoxy group, or a propoxy group. According to another specific example, at least -17-200306282 di R group is an alkyl group, wherein the alkyl group is a Gy alkyl group, and the alkoxy group is an alkoxy group. According to yet another preferred embodiment of the vapor phase precursor, at least two R groups are an ether-alkoxy group of the formula (CU6 alkoxy) n (wherein η is 2 to 6). Che Xiajia's g 5th prepolymer contains any one or a combination of, for example, oxy-oxygen benzene, such as tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrakis (methoxyethoxy) Base) silane and tetrakis (methoxyethoxyethoxy) silane, each of which has four bases that can be hydrolyzed and then condensed to produce silica, and alkylalkoxysilicon such as methyldiethoxylithium, Aryl oxysilanes such as phenyltriethoxy _ Shi Xiyan and precursors such as triethoxysilane, which will produce SiH functionality to the film. The most useful users of the present invention are silyl (methoxyethoxyethoxy) silane, silyl (ethoxyethoxy) siloxane, silyl (butoxyethoxyethoxy) silane, silyl (2 _Ethylethoxy) silane, silyl (methoxyethoxy) silane, and silyl (methoxypropoxy) silane. According to still another specific example of the present invention, all of the alkoxysilane compounds described above may be substituted with a leaving group having an acetoxy group and / or a prime group. For example, the precursor may be ethoxyl (CH3-C0-0-), such as ethoxyl-silyl ubiquitin, and / or a compound, such as a burnt compound and / or a combination thereof. Thing. Needle oblique! For the prepolymerized compounds, _ primes are, for example, C1, Br, I, and may contain F depending on the purpose depending on the purpose. Preferred acetoxy-derived prepolymers include, for example, ethylacetoxysilane, methyltriethoxysilane and / or combinations thereof. According to a specific embodiment of the present invention, the silicon-containing prepolymer includes a monomer or a polymer precursor, such as ethoxysilane, ethoxysilane, methoxylithium, and / or a combination thereof. -18-200306282 According to the present invention, a more specific example of fluorene, the silicon-containing prepolymer includes tetraethoxysilane, q to about c6 ^: tomb or aryl-triethoxysilane, and combinations thereof. In particular, as listed below, triethoxysilane is methyltriethoxysilane. The silicon-containing prepolymer is present in an amount of about 10 wt% to about 80 wt% in the entire composition, preferably in an amount of about 20 wt% to about 60 wt% in the entire composition. The composition further contains at least one metal ion-free catalyst which is an iron compound or a nucleophile. The catalyst may be, for example, an ammonium compound, an amine, a scale compound, or a phosphine compound. Examples include tetraorganic ammonium compounds and tetraorganic scale compounds, including tetramethylammonium acetate, tetramethylammonium hydroxide, tetrabutylammonium acetate, triphenylamine, trioctyl, amine, thirty-two Alkylamine, triethanolamine, tetramethylphosphonium acetate, tetramethylammonium hydroxide, triphenylphosphine, trimethylphosphine, trioctylphosphine, and combinations thereof. The composition can include non-metallic, nucleophilic additives that can accelerate the crosslinking of the composition. These include dimethylphosphonium, dimethylformamide, hexamethylphosphotriamide (HMPT), amines, and combinations thereof. The content of the catalyst in the entire composition is preferably about 1 ppm (wt) to about 1000 ppm (per million parts), and the content of the catalyst in the entire composition is preferably about 6 ppm to about 200 ppm. The composition further contains at least one pore-forming agent, which may be a compound or oligomer or polymer, and is selected so that it does not bind to the silicon-containing prepolymer. When removed (for example, by heating), a silica dielectric film having a nano-sized porous structure can be produced. The size of the pores created by removing the porogen is directly proportional to the effective solid diameter of the porogen component selected. The need for any particular pore size (ie, diameter) is defined by the size of the semiconductor device using a thin film. In addition, the pore-forming agent should not be too small to cause pore blockage. For example, the siphon effect in the small-diameter structure leads to the formation of a non-porous (compact) thin 200306282: Furthermore, the diameter change of all pores in the pore distribution of the thin film Should be minimal. In contrast, a pore former is a compound that has a substantially uniform molecular weight and molecular size in a given sample and is not a statistical distribution or range of molecular weight and / or molecular size. Avoiding any significant change in the molecular weight distribution allows a uniform distribution of pore diameters in the film treated by the method of the present invention. If the resulting thin film has a wide pore size distribution: then, such a phenomenon would increase the formation of multiple pores (ie, bubbles), which would cause troubles for the manufacture of reliable semiconductor devices. Furthermore, the porogen should have a molecular weight and structure that can be easily and selectively removed from the film without disturbing the film formation. This is based on the nature of the semiconductor device, and it will limit your processing temperature. In general, the porogen should be removable from the newly formed film at a temperature below, e.g., an appointment. In a special case, depending on the method and material used to form the thin film afterwards, the pore-forming agent is selected within 30 seconds to about 40 years of age, and can be easily removed at a temperature ranging from about to about 100%. Removal of the porogen can be initiated by heating the film at or above atmospheric pressure or in a vacuum, or exposing the film to light shots, or both. Pore formers that meet the above characteristics include compounds and polymers whose stagnation point, sublimation temperature, and / or decomposition temperature (under atmospheric pressure) range from about 100 Å to about 10,000 Å. In addition, the phase-forming pore-forming agent of the present invention contains a molecular weight of, for example, about tune to about _ 'and more preferably about 100 to about 3,000 amu. — Pore-forming agents that are not bonded to silicon-containing prepolymers include poly (alkylene) diethers, poly (arylene) diethers, poly (cyclic diol) diethers, crown ethers, polycaprolactones 3. All blocked polyepoxides, fully blocked protected polyarylene oxides, pd-e, and combinations thereof. The preferred product that does not bind to the cut prepolymer is -20-200306282. Pore agent contains poly (^ 1 alcohol) dimethyl ether, poly (ethylene glycol) bis (s-methyl), Two poly (ethylene glycol) dibenzyl = formate, poly (ethylene glycol) diglyceryl ether, poly (propylene glycol) dimethanol & 1 purpose, poly (propylene glycol) diglycerin, poly (propylene glycol) di Methyl_, 15-crown ether 5, 18-crown ether-6, dibenzocrown ether, dicyclohexyl 48-crown ether-6 'dibenzo_15_crown ether_5, and combinations thereof. The content of the pore-forming agent which is not bonded to the May-containing prepolymer is about 1 to about 50% by weight or more in the entire composition. More preferably, the porogen is present in the composition in an amount of from about 2 to about 20 wt%.

The composition may optionally contain additional pore formers, wherein the additional pore former has a boiling point, sublimation temperature, or decomposition temperature of about 150 ° C to about 450 ° C. Preferably, the amount of the additional pore former is, for example, about 100 to about 50,000 amu. Preferably additional porogens include agents comprising at least one reactive hydroxyl or amine functional group. The true martial agent is selected from the group consisting of organic compounds, organic polymers, inorganic polymers, and combinations thereof.

Among other parameters, the polymer pore-forming agents suitable for use in the compositions and methods of the present invention are, for example, polyepoxy resins, monoethers of polyepoxy resins, lipid-based polyether-derived acetic acid-based permanganates, and acetal. Aldehyde polymers, poly (caprolactone), poly (valerolactone) wood (methyl methacrylate), poly (vinyl butyral), and / or their figures. When the pore-forming agent is a single bond of polyepoxide, a special specific example thereof is in: ： and to about ^ alkyl ether group r ',, j earth, 々A alkyl chain, and among them Alkyl chain spear or unsaturated, such as polyethylene: alcohol monomethyl ether, or alkyl ether. Called by any theory and hypothesis of how to operate the present invention, it is believed that it is easy to remove from the film. Under the following conditions-or combination: -21-200306282 孔 Pore-forming agent is physically evaporated under the thermal step, (2) the pore-forming agent is degraded to be more acceptable, the molecule, Γ segment, ⑶ makes the pores The bond between the agent and the Si-containing component is broken, and then the pore-forming agent is evaporated from the film, or any combination of modes 丨 _ 3. The pore-forming is heated until the substantial proportion of the pore-forming agent is removed. For example, at least 2 are removed 50 wt% or more pore-forming agent. In particular, in some specific examples, at least about 75 wt% or more of the pore-forming agent is removed depending on the selected pore-forming agent and film material. Therefore, The term means (for listing purposes only) that about 50% to about 75% or more of the original pore former is removed from the coated film. The content of additional pore-forming agent (if used) is preferably about 1 to about 50 wt ° / 0. The content of additional pore-forming agent (if used) in the better composition is about 2 to about 20 wt%. Wang 4 Composition A solvent composition may be included as appropriate. The reference herein / hejian should include a single solvent, polar or non-polar, and / or a combination of compatible solvents selected from a solvent system that can dissolve the ingredients of the Wang 4 composition / Cereals may be included in the composition to reduce its viscosity, and promote its uniform application in the following methods: (such as spin coating, spray coating, dip coating, roll coating, etc.) On the substrate. In order to facilitate the removal of the solvent, the solvent has a relatively low boiling point relative to the boiling point of any selected pore-forming agent and other components. For example, the boiling point of the solvent used in the method of the present invention is about 50 To about 250 ° C, so that the solvent can evaporate from the coating < film and leave the activated part of the precursor composition. For various safety and environmental requirements, the solvent preferably has a high flash point (usually more than 40 C) and relatively low toxicity. Contains, for example, hydrocarbons, and has a group such as c_o_c (ether), -C0_0 (ester), (ketone), 0H (alcohol), and -caN_ -22- 200306282 (amimine) < solvent < absorbs many of these functional groups Solvents and their combinations. ::; Di- is an unrestricted solvent of the composition includes di-n-butyl ether, anisole, propyl steel, 3-pentanone, 2-heptanone, ethyl acetate, n-acetic acid Propyl ester, n-butyl acetate, ethyl lactate, ethanol, 2-propanol, dimethylacetamide, propylene glycol methyl acid acetic acid, and / or a combination thereof. The preferred solvent is not with the prepolymer component containing silicon. The content of the / cereal component is preferably about 10% to πwr / o of the entire composition. More preferably, it is about 20% by weight to about 75% by weight, and most preferably about 20% by weight About 60% by weight. The larger the percentage of the falling agent used, the thicker the resulting film. The larger the percentage of pore-forming agent used, the more porosity is obtained. According to another embodiment of the present invention, the composition may include water (liquid or water vapor). For example, the entire composition can be coated on a substrate and then exposed to the surrounding gas containing water vapor at standard temperature and pressure. Optionally, the composition is prepared before coating on the substrate, so that it contains water in a proportion suitable for the initial precursor aging, but the proportion does not cause the precursor composition to age before coating on the desired substrate. Or gel. By way of example, when water is mixed in the precursor composition, the proportion of water in the composition including water is from about 1: 1 to about 5 depending on the molar ratio of water to 81 atoms in the silicon-containing prepolymer. : 1 exists. ^ It is preferably about 0.1: 1 to about 10: 1, and preferably about 0.5: 1 to about 丨 · 5 i. Those skilled in the art should understand that the specific temperature range of cross-linking and removal of pore-forming agents from nano-porous dielectric films depends on the selected materials, substrates and the required nano-sized pore structure, and can be based on this. The regular operation of other parameters is determined: Generally, the coated substrate is treated, such as by heating, to crosslink the composition on the substrate to produce a gelled film. Soil -23- 200306282 Cross-linking can gel the film in one step by heating the film at a temperature of about 100 to about 25 ° F for about 30 seconds to about 10 minutes. Those familiar with the technique # should also understand that any hardening method known in the art can be used depending on the condition, including applying sufficient energy by exposing the film to electron beam energy, ultraviolet energy, microwave energy, etc., according to methods known in the art To harden the film. Once the film is aged, that is, fully condensed into a solid or substantially solid, the porogen can be removed. The latter should be sufficiently non-volatile that it will cure at the film (K will not evaporate from the film. The pore former is in step ⑹ by using a temperature of about 150 ° C to about 450 ° C, preferably about 15 ° C to The gelled film is heated at about 35 π for about 30, and is removed in about 1 hour. An important feature of the present invention is that the gelation system of the better step (c) is at a temperature not lower than the heating temperature of step 骡 ⑹ For 0 use: This composition can also include additional ingredients such as adhesion promoters, anti-foaming agents, cleaners, flame retarders, pigments, plasticizers, stabilizers and surfactants. This composition can be used for non-micro Applications of electricity, such as matrix materials for thermal insulation, packaging, polymers and ceramic composites, lightweight composites, sound insulation materials, anti-corrosive coatings, bonding agents for ceramic powders and flame retarded coatings. It is particularly useful as a dielectric substrate material in microchips, microchip modules, laminated circuit boards, or printed wiring boards in electronic applications. This composition can also be used as an etch stopper or a rigid photomask. This film can be used by Solution technology formation, such as spraying Roll coating, dip coating, spin coating, flow coating or casting. For microelectronics, spin coating is preferred. -24- 200306282 Better, this combination. It is soluble in the solvent. This solution of the composition Suitable solvents include pure or mixtures of any suitable organic, organic metal, or inorganic molecules that volatilize at the desired temperature. Suitable solvents include aprotic solvents such as cyclic ketones such as cyclopentanone, cyclohexanone Ketones, cycloheptanone, and cyclooctanone; cyclopentamines such as N-alkylpyrrolidone (wherein the alkyl group has about 1 to 4 carbon atoms); and N-cyclohexylpyrrolidone and mixtures thereof. Available here Various other organic solvents are used as long as they can help dissolve the adhesion promoter, and at the same time effectively control the viscosity of the final solution as the coating solution. Various assisting devices such as stirring and / or heating can be used to assist the dissolution. Other applicable Solvents include methyl ethyl ketone, methyl isobutyl ketone, dibutyl ether, cyclic dimethyl polysiloxane V-butyrolactone, y-butyrolactone, 2-heptanone, 3-ethoxy Ethyl propionate, 1-methyl-2-pyrrolidone, and malondione Alcohol methyl ether acetate (PGMEA), and hydrocarbon solvents such as vegetables, xylene, benzene, and toluene. This composition can be used in electrical devices, especially for connection with a single integrated circuit (" 1C ") chip Combined interlayer dielectrics. The surface of an integrated circuit wafer generally has many layers of the composition and multiple layers of metal conductors. It can also include discontinuous metal conductors or between conductors in the same layer or plane of an integrated circuit Areas of this composition. This film can be used for double corrugation (such as copper) processing of integrated circuit manufacturing and substrate metal (such as Ming or Ming / Tungsten) processing. This composition can be such as Michael E. Thomas, π low keff Spin-On Stacked Films for Low Keff Dielectrics '', taught by Solid State Technology (July 2001) (herein incorporated by reference), is used in all spin-stacked films required. This composition can be used in all spin-stacked films with additional dielectrics as taught by commonly assigned U.S. Patent Nos. 6,248,457 B1; 5,986,045; 6,124,411; and 6,303,733 -25-200306282. Analytical test method · Dielectric constant: The dielectric constant is calculated by coating a thin aluminum film on a hardened layer, and then measuring the capacitance-voltage at 1 MHz. Refractive index: Refractive index measurement is accompanied by thickness measurement using a J.A. Woollam M-88 spectral polarized light ellipticity measuring instrument. Use the Cauchy model to calculate the optimal Psi and (5. Unless otherwise stated, the refractive index is measured at a wavelength of 633 nm (details of the ellipsometry for polarized light can be found in, for example, HG Thompkins and William A. McGahan, John Wiley and Sons, Inc., 1999) π-spectrum polarized light ellipticity measuring instrument and reflectometer ff). Average pore diameter •• Using UHP (Ultra High Purity Industrial Gas) N2 on a Micromeretics ASAP 2000 automatic isothermal N2 absorption device to measure the porosity of a sample from a sample impregnated in a liquid nitrogen tank of 77QK The N2 temple temperature line. To prepare the sample, the material was deposited on a silicon wafer using standard processing conditions. For each sample, three wafers were prepared with a film thickness of about 6000 Angstroms. The film was then removed from the wafer with a razor blade. Pre-dry these powdered samples in an oven at 180 ° C before weighing, carefully pour the powder into a 10 mm inner diameter sample tube, and then degas at 180 ° C and 0.01 Torr for 3 hours . A 5 second equilibration interval is then used to automatically measure the adsorption and desorption of N2 adsorption unless analysis shows that it takes a long time. The time required for isothermal measurement is related to the mass of the sample, the pore volume of the sample, the number of measured data points, the equilibrium interval, and the P // Po tolerance (P is the actual pressure of the sample in the sample tube, and P0 is the periphery outside the device Pressure). The device measures the N2 isotherm and converts it to P // Po. -26- 200306282 Developed BET CgTBmnauer, P.H. Emmett, E. Teller; J. Am. Chem. Soc. 60, 309-319 (1938) Brunauer, Emmett, for multilayer gas adsorption on solid surfaces The Teller method) surface area is calculated using the BET theory, using the linear segment of the BET equation that provides R2 fit > 0.9999, from the lower P / Po region of the N2 absorption isotherm. The pore volume is under the relative pressure P / Po value (usually P / Po ~ 0.95, which is an isothermal plane area with complete condensation). It is assumed that the density of the absorbed N2 is the same as that of the liquid N2, and all pores are filled in the P / Po The following condensation] ^ 2, calculated from the volume of N2 absorbed. The pore size distribution is based on the Kelvin equation theory, using BJH (E. P. Barret, L. G. Joyner, P. Halenda; J. Am. Chem. Soc., 73, 373-380 (1951)) Pore size distribution, calculated from adsorption wall of% isotherm. This uses the Kelvin equation, the curve of which is related to the suppression of vapor pressure, and the Haisey equation, which describes the thickness of the absorbed monolayer versus p / Po to convert the condensed N2 volume to P / Po into a special range of pore sizes. Pore volume. The average cylinder pore diameter D is the diameter of a round carcass having the same apparent BET surface area Sa (m2 / g) and pore volume Vp (cc / g) as the sample, so D (nm) = 4000 Vp / Sa. ΕΠΚ: The FTIR spectrum silicon was obtained using a Nicoiet Magna 550 FTIR spectrometer, which was obtained according to the transmission mode. The substrate background spectrum was obtained on an uncoated substrate. The thin film spectrum was obtained using a substrate as a background. The thin film spectrum is then analyzed for changes in peak position and intensity. The following non-limiting examples are provided to illustrate the invention. -27- 200306282 ^ Example 1 This example shows the production of nanoporous stone spar based on a pore former having a reactive end-capping group. The precursor was obtained by combining 10 g of tetraethoxysilane, 10 g of methyl triethoxysilane, and 17 g of propylene glycol methyl ethyl acetate (in a 100-ml round-bottomed bottle with a magnetic stir bar). PGEMA). Combine these ingredients in the ν2_ environment (N2 bagging). The bottle is also connected to the N2 environment to prevent ambient moisture from entering the solution (standard temperature and pressure). The reaction mixture was heated to 80 t: 15 g of water was then added to the bottle. After the addition of water was completed, the reaction mixture was cooled to ambient temperature, and then 426 g of polyethylene glycol monomethyl ether (CTEO " MW550 amu) was added as a pore-forming agent, and stirring was continued for another 2 hours. 'Subsequently, the resulting solution was filtered through a 0.2-micron filter to obtain the next batch of the precursor solution in the main batch. This solution was then deposited on a row of 8 small evening wafers, each wafer was on a turntable, and turned on the surface for 30 seconds. The presence of water in the precursor towel causes the film coating to condense substantially as time passes as the wafer is inserted into the baking phase. Insertion into the first supply box as described below occurred within 10 seconds of completion of rotation. Each coated wafer is then transferred into a series of ovens for one minute at a predetermined temperature. In this example, there are three ovens, and the preset oven temperatures are stage, 200 C, and 350 C, respectively. As each wafer passes through each of the three separate ovens, it is driven out by continuous heating. After each wafer is subjected to three-oven step-by-step heat treatment, the manufactured dielectric film is measured with a polarized light ellipsometry to measure its thickness and refractive index. 49ς 〇Γ, industrial storage fork fortified wafers were further hardened for one hour under nitrogen / 425 C. The film should have a thickness of 6770 angstroms and a refractive index of ⑽. The Ying -28-200306282 of the prepared film is 10% (see item 1 in the table below). In the table, the capacitance of the film is measured under ambient conditions (room tile and humidity). The dielectric constant based on the surrounding capacitance is called around k. The wafer was heated on a 200 ° C heating plate for 2 minutes to remove the absorbed moisture, and the capacitance of the film was measured again. The dielectric constant that mainly removes water and gas is called k degassing. The difference between the two values of k is that Akyc ^ k ^ -k & y / k ^ ji ^ 100% is one of the hydrophobicity indicators of a given film. Various amounts of PEO (5.43 and 5.04 grams of items 2 and 3, respectively) were added to the nanoporous films with different dielectric constants, and the Ak% was greater than 10% (see 2 in the table below) And item 3). The hardened film was also measured by FTIR to determine the area ratio of the methyl group (SiC, v: 1277.4 cnr1) to silicon oxide (SiO, v: 1055.0 cm-1). Generally, the SiC / SiO ratio is 0.0250 and 0.0264. The average pore diameter is 2.1-2.2 nm. Example 2 Example 1 was repeated, but this example used poly (ethylene glycol) monomethyl ether ("DMEPEO"; MW550 amu) as a pore-forming agent. The example shows that more hydrophobic films are obtained. In one example, a small amount Methyltriethoxysilane (MTAS, 2%, see item 6) is added to the solution as an in-situ surface modifier to produce a low hydrophilic surface. By spin coating at 1000 rpm or 1500 rpm The film is deposited on the wafer by a cloth. After spin coating, the film is heated for one minute on three hot plates at 125 ° C, 200 ° C, and 350 ° C. After baking, the film is heated at 425 ° C and nitrogen flow for 1 hour, the RI and SiC / SiO results of the post-hardened film are listed in the table below. The Ak% value is below 8.5%, and the SiC / SiO ratio is 0 · 0282 ± 0 · 0001 (see 4 , Item 5). When the super MTAS (2%) is added, the Ak% value of the obtained film is 2.2% more hydrophobic (see item 6). -29- 200306282 item one pore former top hardening Dielectric constant SiC / SiO type quantity (g) * Emission coefficient around k degassing △ k% FTIR ratio 1 PEO 4.26 1.230 2.55 2.29 10.20 0.0264 2 PEO 5.43 1.2 10 2.59 2.25 13.13 0.0258 3 PEO 5.04 1.225 2.49 2.18 12.45 0.0250 4 DMEPEO 5.43 1.203 2.21 2.02 8.60 0.0280 5 DMEPEO 6.98 1.171 1.98 1.87 5.56 0.0283 6 DMEPEO * 4.26 1.205 2.23 2.18 2.24 0.0289 The amount of porogen is 10 g of tetraethylpyrene Oxysilane and 10 g of methyltriacetamidine

The batch size of oxysilicon is subject to change. Pore size / volume data item Sub-average pore size diameter (nm) Pore volume (cc / g) 1 2.10 0.564 2 2.17 0.527 3 2.20 0.744 4 2.85 0.837 5 3.48 0.977 6 N / AN / A Although the present invention has been specifically shown and Reference is made to preferred specific examples, but those skilled in the art should readily understand that various changes and modifications can be made without departing from the spirit and scope of the present invention. It is hoped that the scope of patent application will cover the specific examples of disclosure, their changes, and all equivalent examples. -30-

Claims (1)

200306282 Pick up, apply for patents and enquiries: 1.-A method for manufacturing nano: porous' porous silica dielectric thin film, including the preparation of a group consisting of a silicon-containing prepolymer, a europium compound, and a nucleophile A composition of a metal ion catalyst and a pore-forming agent not bonded to a silicon-containing prepolymer; (b) coating the substrate with the composition to form a film; ； crosslinking the composition to produce a gel film, And: in the temperature and effective period, the gel film is heated to substantially remove all the pore-forming agent. 2. The method of claim 1 in the β patent, wherein the volume of the pore-volume thin film of the nano-polysparite dielectric is about 5% to about 80%. 3. The method according to item 丨 of the scope of patent application, wherein the dielectric constant of the obtained nanoporous stone spar is about 3 or less. 4. The method according to item 丨 of the patent application range, wherein the average pore diameter of the nanoporous crushed-stone dielectric film is about 1 nm to about 30 nm. 5. For the method of applying the scope of the patent Θ, the pore-forming agent is selected from the group consisting of poly (methylene) diether, poly (arylene) diether, poly (cyclic diol) diether, and crown ether. The group consisting of fully-terminated polyalkylene oxide, fully-terminated polyarylene oxide, polinynbene, and combinations thereof. 6. The method according to the patent application, wherein the pore-forming agent is selected from the group consisting of poly (ethylene-alcohol) dimethyl ether, poly (ethylene glycol) bis (kisylmethyl) bond, and poly (ethylene glycol). ) Dibenzoic acid, poly (ethylene glycol) propyl methyl ether, poly (ethylene glycol) monoglyceryl ether, poly (propylene glycol) dibenzate, poly (propylene glycol) dibutyl ether, water (propylene —Alcohol) dimethyl ether, poly (propylene glycol) diglyceryl ether, 15-crown ether 5, 200306282 18-crown ether benzo-18_crown ether-6, dicyclohexyl 8 • crown ether,: ': * >-A group consisting of dibenzo-15-pyrene ether-5, and combinations thereof. 7. The method according to item 1 of the patent application scope, wherein the catalyst is selected from the group consisting of an ammonium compound, an amine, a scale compound, and a phosphine compound. 8_ The method according to item 1 of the patent application range, wherein the catalyst is selected from the group consisting of a tetraorganic ammonium compound and a tetrabasic scale compound. 9. The method of claim 1, wherein the catalyst is selected from the group consisting of tetramethylammonium acetate, tetramethylammonium hydroxide, tetrabutylammonium acetate, triphenylamine, and trioctylamine , Tri-dodecylamine, triethanolamine, tetramethylphosphonium acetate, tetramethylphosphonium hydroxide, triphenylphosphine, trimethylphosphine, trioctylphosphine, and true conjugates. 10_ The method according to item 1 of the patent application scope, wherein the composition still contains non-metallic, nucleophilic additives that can accelerate the composition X-linkage. 11. The method according to item 1 of the patent application range, wherein the composition further comprises a nucleophilic additive that can accelerate the X-linkage of the composition, and the addition is selected from the group consisting of dimethylphosphonium, dimethylformamide, hexamethylene A group consisting of triammonium amine, amines, and combinations thereof. 12. The method according to claim i of the application, wherein the composition further comprises water, and the molar ratio of water to the Si atom in the Wei system is from about 0 to about 50: 1. 13. The method according to the scope of patent application, wherein the composition includes a silicon-containing prepolymer of the following formula: Rx-Si-Ly (^ 1) where X is an integer from 0 to about 2, and y & 4_x (about An integer of 2 to about 4); R is independently selected from the group consisting of an alkyl group, an aryl group, a hydrogen group, an alkylene group, an alkylene group, and a combination of 200306282; :: 孓 心 一 L is negatively charged Ϊ— Group, which is independently selected from the group consisting of alkoxy, carboxyl, ethylenoxy, amine, amido, and! | Groups of compounds, isocyanate groups, and combinations thereof. 14. The method of claim 13, wherein the composition comprises a polymer formed by condensing a prepolymer of formula I, wherein the average number of the polymer is about 150 to about 300, 〇〇〇amu 〇15. The method of claim i, wherein the composition comprises a silicon-containing group selected from the group consisting of ethoxysilane, ethoxysilane, methoxysilane, and combinations thereof. Prepolymer. 'Wherein the composition includes a member selected from It is methyltriethoxysilane. 16. The method according to item 1 of the scope of patent application. Tetraethoxysilane, C, to about Γ ΐ A group of silicon-containing prepolymers. 19 · If the method in the scope of patent application is applied for item 1, the temperature is lower than the heating temperature of step (d). 20 · If the method in the scope of patent application is applied for, the item "yi" is still at the turn of step (c). In connection with the Wenwan method, the stagnation point of the additional pore former also includes the additional pore former, whose sublimation point or decomposition temperature is about 150 ° C to 200306282 and about 450 ^. 211 2L is the method of applying for patent%: circle Η, wherein step ⑹ includes heating the film at a temperature of about 100 C to about 250 ° C for about 30 seconds to about 10 minutes. 22. If the scope of patent application is the first! The method of item 1, wherein step (i) comprises heating the film at a temperature of about 150 ° C to about 450t: for about 30 seconds to about 丨 hours. 23. The method of claim 1, further comprising an additional porogen, wherein the molecular weight of the additional porogen is about 100 to about 50000 amu. '. 24. If the method according to item [] of the patent application scope further includes an additional pore-forming agent, wherein the additional pore-forming agent includes a reagent including at least one reactive hydroxyl or amine functional group, the reagent is selected from the group consisting of organic compounds, A group of organic polymers, inorganic polymers, and combinations. 25 · If the scope of patent application is the first! The method according to the item, further comprising an additional pore-forming agent, wherein the additional pore-forming agent is selected from the group consisting of a polyalkylene oxide, a monoether of a polyalkylene oxide, a fatty polyester, a malonic acid polymer, and an acetal polymerization. Group of compounds, poly (caprolactone), poly (caprolactone), poly (methylpropionate), poly (vinyl butyral) and combinations thereof. 26. If the scope of patent application is the first! The method of claim further includes an additional pore-forming agent, wherein the additional pore-forming agent includes a polyalkylene oxide monoether including a q to about q alkyl chain between an oxygen atom and ^ to about A alkyl ether groups And wherein the alkyl chain is substituted or unsubstituted. 27. The method of claim 26, wherein the polyalkylene oxide monoether is polyethylene glycol monomethyl ether or polypropylene glycol monobutyl ether. 28 · If the scope of patent application is the first! The method of claim, wherein the content of the pore-forming agent in the composition is about 1 to about 50 wt% of the composition. 200306282 29. The method for applying for item No. 1 of the special hair circumference, wherein the composition further comprises a solvent. 1 :: 30. The method according to item 1 of the patent application range, wherein the composition further comprises a solvent 'in an amount of about 10 to about 95 wt% of the composition. 31. The method of claim 1 in which the composition further comprises a solvent having a stagnation point of about 50 to about 250 ° C. 32. The method of claim 1, wherein the composition further comprises a solvent selected from the group consisting of hydrocarbons, esters, ethers, ketones, alcohols, amidines, and combinations thereof. 33. The method of claim 29, wherein the solvent is selected from the group consisting of di-n-butyl ether, anisole, acetone, 3-pentanone, 2-heptanone, ethyl acetate, n-propyl acetate, and acetic acid. A group consisting of n-butanol, 2-propanol, dimethylacetamide, glycerol methyl acetate and combinations thereof. 34 ·: A nanoporous dielectric thin film 'is formed on a substrate by a method as described in the first paragraph of the patent application. 35. A semiconductor device comprising a nanoporous dielectric thin film such as Shen Huang ^ Fu Ru Jia Ming Xun Li Qian Wai item 34. 36. If the semiconductor device according to item 35 of the scope of patent application is an integrated circuit. 37. A pore-forming agent which is not bonded to the cut prepolymer, which is selected from the group consisting of poly (fluorenyl) diether, poly (arylene) dipass, poly (cyclic diol) diacid, and coronal puzzle A group consisting of fully-terminated polyepoxides, fully-terminated polyarylene oxides, polynorbene, and combinations thereof. 38. For example, the pore-forming agent in item 37 of the scope of patent application is selected from the group consisting of poly (ethylene diether, poly (ethylene glycol) diamidine) and poly (ethylene glycol) diphenyl 200306282. Polyglycol) diglyceryl ether, poly (propylene glycol) dibenzoate, poly (propylene glycol) diglyceryl ether, poly (propylene glycol) dimethyl acid, 15_crown ether 5, 18-crown ether-6 Group consisting of dibenzo-18-crown ether-6, dicyclohexyl-18-crown ether-6, dibenzo-15-crown acid-5, and combinations thereof. 39. A composition comprising a silicon-containing prepolymer and a pore-forming agent which is not bonded to the silicon-containing prepolymer, and is selected from the group consisting of free poly (alkylene) diethers and poly (arylene) diethers. , A group consisting of poly (cyclic diol) diether, crown ether, polycaprolactone, fully-end-capped polyepoxy resin, end-capped polyarylene oxide, and combinations thereof. 40. If the composition in the scope of patent application 39 is applied, it additionally includes a metal ion-free catalyst II 41. If the composition in the scope of patent application 40 is applied, the metal ion-free catalyst is tetramethyl Ammonium acetate. 42. The composition according to item% of the patent application scope, wherein the silicon-containing prepolymer includes a combination of a leaving group mainly composed of an ethoxy group. 43. The composition according to item 42 of the patent application, wherein the combination having an ethoxyl group as the leaving group includes tetraethoxylsilane and methyltriethoxylsilane. 44. A spin-coating composition comprising a composition such as item% of the scope of patent application. 45. A film ' comprising a spin-coating composition as claimed in item 44 of the patent application. 46 · A method for controlling the pore size of porous stone stone films, including the preparation of tritium containing a prepolymer containing debris, selected from the group consisting of tritium compounds and nucleophiles-6- 200306282: metal ion catalyst And a pore-forming agent composition; (b) coating the substrate with the composition to form a film; (c) cross-linking the composition to produce a gel film; and (d) applying the gel at a temperature and effective period The condensed film is heated to substantially remove all of the pore-forming agent; the method includes using a pore-forming agent that is not bonded to the silicon-containing prepolymer. 200306282 Dyeing and designation of representative representatives: (1) The designation of representative representatives in this case is: (). (2) A brief description of the representative symbols of the components in this representative drawing: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: