TW200403764A - Low metal 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

200403764 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to the manufacture of nano-porous lithospar dielectric films, and to semiconductor devices and integrated circuits including these improved films. The nanoporous film of the present invention is prepared using a silicon-containing prepolymer, and is prepared at a low gelation temperature by a method that does not contain metal ions or a nucleophilic catalyst. [Previous technology] In the future, the size of integrated circuits will be reduced to less than 0.15 micrometers, which will make it more difficult to solve the problems caused by the delay of RC connection, power loss and signal interaction. I believe the dielectric properties of the interval ( Integrated low-dielectric materials (ILD) and inter-metal dielectric (IMD) applications can help solve these problems. Although previous efforts have been made to provide low-dielectric materials for integrated circuits, there is still a long-term need in the art to further improve processing methods and optimize both the dielectric and mechanical properties of the materials used in the manufacture of integrated circuits. One type of material with a low dielectric constant is a nano-porous silica film prepared from a silicon-containing prepolymer by a spin sol-gel technique. The dielectric constant of air is 1, and when air enters a suitable silica material having a nano-sized pore structure, a thin film having a relatively low dielectric constant ("k") can be prepared. Nanosilica materials have attracted attention because they are similar to the precursors and contain organically substituted silanes, such as using tetraethoxysilane (TAS) / methyltriacetoxysilane (MTAS) -derived silicon polymers as Basic substrate, and is used for spin coating ("SOG") and chemical vapor deposition ("CVD") of silica (SiO2) glass currently used. This material has proven high mechanical strength, as shown by the modulus and distribution 84564 200403764 grabbing data. Mechanical properties can be controlled by inch distribution. Nanoporous 2: Amphoteric films have controllable void sizes, and therefore the resulting films :: mesh: because of their pore size and dielectric constant. In addition to low k, the nanometer is thin: the heat of the degree and mechanical strength is reached. The point contains at least lower than the microelectronic characteristics of the integrated circuit = inch size = inch size-, ', and can be used as a semi-conductive Jinyu library The used crushed stone and tetraethoxylate ceramics) are prepared; the dielectric constant of raw crushed stone can be "adjusted" in the wire circumference; and the nano-porous material can be used in the same way as S.aG. Similar equipment is achieved. Therefore, the high porosity of the same material in the silica material is the same, and the number of packages is lower than that of the porous nano-porous film, and the relative density of the material is changed. Other materials = Including the dimensions that require all pores to have substantially small M characteristics, need = the effect of surface chemistry due to the decrease in strength due to porosity 'and its dielectric constant and environmental stability. Density (or porosity) is the main parameter of the nanometer film that controls the dielectric constant of the material. The property of 'JL can be easily changed on a continuous map, from a maximum air gap of 100% to a porosity of 0%. Dense silica. When the porosity increases, the dielectric constant and mechanical strength increase, but the porosity decreases, etc. This suggests that the density range of nanoporous films should be optimally balanced between the low dielectric constant range and mechanical properties required for the desired application. Nanoporous silica films have been previously manufactured in many ways. For example, nanoporous films have been prepared using a mixture of a solvent and a silica precursor, which is deposited on a suitable substrate. Generally, a precursor such as 84564 200403764 in spin coating form on a glass is added to a substrate and then polymerized in the form of a dielectric thin film including nanopores. When the nanoporous film is formed by, for example, spin coating, the film coating is generally catalyzed by an acidic or alkaline catalyst and water, causing polymerization / gelling ("aging") during the initial heating process. Maximum strength 'is not obtained by selecting the pore size and therefore a low molecular weight pore former is used. U.S. Patent No. 5,895,263 describes heating a composition on a substrate such as a wafer by coating the composition including a decomposable polymer and an organic polysilica (that is, a polymer containing condensation or polymerized silicon). The polysilica is further condensed, and the decomposable polymer is decomposed to form a porous dielectric layer to form a nanoporous silica dielectric film. This method is similar to many previous methods used to form nanoporous films on semiconductors, with the disadvantage that f is heated during the aging or condensation process and the polymer is removed to form a nanoporous film. Moreover, the disadvantage is that the organic polysilica contained in the precursor solution will increase the molecular weight after the preparation of the solution. Therefore, the storage solution is dissolved to increase the viscosity during the storage process. 'JL is thin from the storage solution = Increasing the storage time. The organic aggregation is disturbed by the storage time, cooling storage, and precise adjustment of the parameters, which is achieved during the manufacturing process of the microchip circuit. The condition for the formation of W porous structure depends on the cross-linking temperature (or gelation temperature) of the material. It was found that below ^ = ions such as: the positive positivity of two L7 porous structures in solution rotating in accordance with Ic shore use 'ppb level can not be manufactured. However, the urgent need for… Medium Low Metal Concentration is generally practiced as the metal concentration of spinning on 84564 200403764 4 fluid is below 50 ppb. Therefore, there is a need to develop a low-metal nanoporous silica film that can continuously provide a dielectric constant below 2.5 and a pore size with a diameter below 10 ㈣. It has now been discovered that porous silica networks can be formed at low temperatures in low metal spin formulations by using tritium ions or nucleophiles. The role of osmium ions or nucleophiles is to lower the gelation temperature. Because the hard network can be hardened before the pore former is removed, nanoporous films can be manufactured without the need for undesired experimental ions. [Summary of the Invention] The present invention provides a method for manufacturing a nanoporous silica dielectric thin film, which includes the preparation of a pre-cut polymer, a porogen, and a metal-free ion selected from the group consisting of a scandium compound and a nucleophile. Catalyst composition; (b) coating the substrate with the composition to form a film; (c) cross-linking the composition to produce a gel film, and heating and removing the gel film at temperature and during the effective period Virtually all of this pore former. This month, a composition including a prepolymer, a porogen, and a catalyst selected from the group consisting of radium compounds and nucleophiles is also provided. This method provides a method for reducing the temperature at which a porous silica film is formed. The method includes the steps of adding a europium ion or a nucleophile to a prepolymer and a pore former containing stone. [Embodiment] The following nanoporous silica is prepared. Generally, based on silicon, a dielectric constant or k value of about 3 or a dielectric film can be produced by the method of the present invention. 84564 200403764 ^ film (including nanoporous crushed dielectric thin ^ and It can be prepared from a rhenium compound or a nucleophile without metal ions. It can be used as a general-purpose cutting prepolymer composition. It can also include this type = blending-rhenium solvent and / or other ingredients. Know the method, paint you, = Tian by any technical equipment η μΓ cloth common substrate, such as manufacturing semiconducting bone fan, placed as a substrate for integrated circuit ("IC,"), shape guide: The composition is cross-linked to form a thin film. The film is prepared by heating the gelled film under the same plate to remove all pore-forming agents. The film prepared by the method of the invention has many Youzhi "Advantages, including improved mechanical strength, which can produce films that can withstand the processing steps required for the preparation of semiconductors, industrial equipment, and other devices on substrates, and have a stable dielectric constant. Stable dielectric The properties of the electrical constant can be achieved without the need to form nano-porous lithiac dielectric films. The steps required for the method are beneficially achieved under the surface modification step. In addition, the W stone film produced by the method of the present invention can be sufficiently hydrophobic as initially formed. Furthermore, the method of the present invention is directed to prepolymerization of coating The initial polyt (i.e., gelation or aging) of the composition advantageously requires relatively low temperature. In the method 2 of the present invention, the pore size with a diameter of 2 nanometers and the size distribution are uniform. The obtained porous silica film The dielectric constant is generally about 3 or less, more usually about ⑷.3 to about 3.0 ′ and most usually about h7 to about 2.5. The average pore straightness of the film = usually about 1 brittle to about 30 It is more preferably about 1 nm to about 1 (nm), and is usually about 1 nm to about 5 nm. The pore volume of the film is based on the entire volume of the film, and is generally about 5% to about 80%. It should be understood that nanoporous The term "dielectric thin film" refers to a dielectric thin film prepared by the method of the present invention, 84564 -10- / 64, from an organic or inorganic sloped glass substrate material (for example, any applicable hard-based :). "Aging" refers to the "hardened word" on the substrate after the deposition of a combination of other stone-based expulsion compositions. (Iv) means a left shift of · 0H) group, removal of water, and more stable braking ϋ methodology of the film in subsequent processing of the method of manufacturing the micro-son process. The hardening process is performed after gelling and is generally performed by heating, but any other hardening form known in the art may be used, such as by applying energy in the form of electron beams, ultraviolet radiation, and the like. Dielectric films such as spaced dielectric coatings are prepared from palatable compositions coated on a substrate. The art of coating body dielectric precursor composition is known in the art, and the method includes (but is not limited to) spin coating, dip coating, brush coating with roller coating 2 :, cloth = / or chemical gas deposition. When coating these material types to form a thin dielectric material, the surface of the earth material can be prepared by standard and clean methods according to the conditions of the coating. The coating is processed to achieve the desired type; and 舁: The electro-chemical coating is consistent, and the processing steps are selected to suit the selection of :: flooding and the desired final product. Other details of this method and composition are as follows. The < substrate used in the present invention, which is included in the coating of the nano-cut stone film of the present invention, is generally suitable for manufacturing integrated circuit-cut wafers, and the basic material for forming the nano-porous cut stone film is coated by a general method. Before spraying on the substrate = (but not limited to) spin coating, dip coating, brush coating, roll coating, and / or coating the base material to form a nanoporous stone sapphire film, the surface of the substrate may be based on the situation Prepared by standard, known cleaning methods. 84564 • 11-200403764 The weekly substrates of the present invention include semiconductor substrates such as gallium arsenide ("GaAs"), silicon, and silicon-containing compositions such as crystalline silicon, polysilicon, amorphous silicon, and oriented silicon , And silicon dioxide ("Si02 ,,") and mixtures thereof. The substrate < is a surface-selected pattern that produces lines, such as metal, oxide, lice or oxynitride lines. It is formed by the conventional lithographic etching technique. A suitable material for the line includes hafnium oxide

Titanium, nitride buttons, aluminum alloys, copper, copper alloys, palladium, tungsten, and oxynitride. The metal objects used to make these lines are taught in commonly assigned U.S. Patent Nos. 5,780,755; 6,23M94; 6,331,233b1m, 348, and i39bi: and are sold by Honelwell International. These lines form a conductor or insulator of the integrated circuit. This is generally closely separated from each other at a distance of about 20 micrometers or less, preferably 1 micrometer or less', and most preferably about 0_05 to about 1 micrometer. Other selection characteristics suitable for the surface of the substrate include an oxide layer, such as an oxide layer formed by heating a silicon wafer in the air, or more preferably a material known in the art (for example, a plasma booster) Oxygen oxide (PETEOS) '% elevated fragmented plutonium oxide ("p㈣fired") and its combination =) Si02 oxide layer formed by chemical stripe deposition, and one or more nanometers formed as appropriate Shi Xishi dielectric thin film. The porous second stone film can be coated to cover and / or tile between the selected electronic surface features, such as previously formed substrates (7L pieces and / or conductive) The characteristics of the selected substrate can also be reduced-additional layers are coated on the nanoporous vermiculite film of the present invention. This low-dielectric film can make the resulting integrated circuit-or multiple layers or many electrical and / Or the% sub-conductor layer insulation. Therefore, the substrate of the present invention may be packaged according to circumstances 84564-12-200403764. In the process of manufacturing a multilayer or multi-component integrated circuit, on the nanoporous silica film of the present invention or with The silicon material formed next to each other. According to another option, the substrate with the nanoporous silica film of the present invention may be further covered with a non-porous insulating layer known in the art, such as a glass cover layer. The crosslinkable composition of a nanoporous film comprises one or more silicon-containing prepolymers that can be condensed immediately. It should have at least two hydrolyzable reactive groups. The reactive groups include alkoxy (RO), Acetyloxy (AcO), etc. Within the limits of the theory and assumptions of the method and composition of the invention, He Da believes that water will hydrolyze the reactive groups on the silicon monomer to form Si-OH groups (silanol). The latter will react with other silanols or with other The basic group undergoes a condensation reaction, which is described by the following formula:

Si-OH + HO-Si-^ Si-0-Si + H20 Si-OH + RO-Si-> Si-0-Si + ROH Si-OH + AcO-Si Si-0-Si + AcOH Si-OAc + AcO- Si ~> Si-O-Si A〇2〇R = alkyl or aryl Ac = fluorenyl or (CH3CO) These condensation reactions will form silicon-containing polymers. 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) where x is an integer from 0 to about 2, and y is 4-x ( An integer from about 2 to about 4), R is independently selected from alkyl, aryl, argon, alkylene, aryl, and / or combinations thereof, and L is independently selected from negatively charged groups such as alkoxy, Carboxyl, amine, amidine-13- 84564 200403764, halide, isocyanate, 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 the hydrolysis rate of the Si-OCH2CH3 bond. Therefore, the following reactions are represented by ⑷ and (b):

⑻ Si-L + H2〇Si-OH + HL (b) Si_OCH2CH3 + H20 Si-OH + HOCH2CH3 The rate of ⑻ is greater than the rate of (b). Examples of suitable compounds of formula I include, but are not limited to:

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

Si (〇COCF3) 4 (trifluoroacetoxy) silane *,

Si (〇CN) 4 tetraisocyanate silane, CH3Si (〇CH2CF3) 3 ginseng (2,2 > trifluoroethoxy) methyl silane, CH3Si (OCOCF3) 3 ginspan (trifluoroacetoxy) methyl silane *, CH3Si (〇CN) 3 methyltriisocyanate silane, [* This will generate an acid catalyst when exposed to water] and / or any combination of the above. According to another embodiment of the present invention, the composition comprises a hydrolysis and condensation reaction, the rabbit is about 150 to about 300,000 amu, or usually about 150 to about 10,000 amu. According to another specific example of the present invention, the silicon-containing prepolymer used in the present invention includes an organic silane, for example, an alkoxysilane containing the following formula II: -RR——si——R R- 11 -14- 84564 200403764 as appropriate , Formula II is an alkylsilane, wherein at least two R groups are independently C14 alkoxy, and if present, they are independently selected from the group consisting of hydrogen, alkyl, phenyl, halogen, and substituted phenyl Group. For the purpose of the present invention, the term fluorenyl includes any other organic group that can be easily hydrolyzed from silicon chain scission at room temperature. The R group can be ethylene glycoxy or propylene glycoxy, etc., but all 4 R groups are methoxy, ethoxy, propoxy or butoxy. The best alkoxy silanes include tetraethoxy Silane (butanes) and tetramethoxysilane.

According to another option, for example, the prepolymer may also be an alkylalkoxysilane described in Formula ^, but at least two R groups are independently Cm alkylalkoxy groups, wherein the alkyl group is gcM alkyl, The alkoxy group is Ci0 alkoxy, or ether-alkoxy, and the rest (if present) are independently selected from hydrogen, alkyl, phenyl, and halogen

A group of substituted phenyl groups. According to a preferred embodiment, each of them is methoxy, ethoxy or propoxy. According to another preferred embodiment, at least the diyl group is an alkylalkoxy group, wherein the alkyl group is a Cm alkyl group, and the alkoxy group is an alkoxy group. According to yet another preferred specific example of the precursor of the vapor phase, the ^ -lower R group is of the formula (CW oxygenated fluorenyloxy group (wherein 2 to 6). Preferred silicon-containing prepolymers include, for example, alkoxysilanes Any one or structure ^-such as tetra ^, u isopropoxysilane,

Tetrakis (methoxyethoxy) hard fluorene, tetrakis (methoxyethoxyethoxy), sintered, have four groups that can be hydrolyzed and then condensed to produce crushed stone. Monoethoxysilane, arylalkoxysilane, such as phenyltriethoxy, and the precursors such as diethoxylate, which will produce a new functional group on the film. The most useful of the present invention is (Methoxyethoxyethoxylate, U 84564 -15- 200403764 lactyl ^ oxy) Shi Xiyan, Iso (butoxyethoxyethoxy) silane, Iso (2-ethoxy (Earth) Xixin, mash (methoxyethoxy), and mash (methoxypropoxy). / According to yet another specific example of the present invention, the above alkoxysilane compounds may be all or 卩The knife is substituted with a leaving group having ethoxyl and / or self-priming. For example, the water may be ethoxyl (CH3_c〇_〇_), such as ethoxyl-shixi calcination Mouth and / or dentin compounds, such as dentin silane compounds and / or combinations thereof. For prepolymers, the primes are, for example, a, Br, τ, and may contain F depending on the purpose. .Better Oxygen-derived prepolymers include, for example, ethylene oxide sintering, methyl triethyl alcohol oxyfluorene, and / or combinations thereof. Eighth, according to a specific embodiment of the present invention, the silicon-containing prepolymer includes Monomer or polymer catalysable substance, such as ethoxysilane, ethoxysilane, methoxysilane and / or a combination thereof. / In a more preferred embodiment of the present invention, the cut prepolymer contains tetraethoxy Keystone oxane Cl soil C6 alkyl or aryl-triethoxysilane and its combination. In particular, as listed below, triethyl alkoxy is found as methyltriethyloxy oxane. The content of the prepolymer in the entire composition is about 10% to about 80% by weight, and preferably the content of the prepolymer in the total composition is about 20% to about 60% by weight. For electronic applications, thallium or nucleophilic catalysts can contain metal ions. Examples include sodium hydroxide, sodium sulfate, potassium hydroxide, lithium hydroxide, and germanium-containing catalysts. 'Better' compositions for microelectronic applications It further contains at least one metal ion-free catalyst which is a europium compound or a nucleophile. The catalyst may be, for example, an ammonium compound, an amine, or a scale compound Phosphine compounds. Examples include tetraorganic compounds and -16-84564 200403764 tetraorganic scale compounds, including tetramethylammonium acetate, tetramethylammonium hydroxide, tetrabutylammonium acetate, triphenylamine, Octylamine, dodecylamine, diethanolamine, tetramethylphosphonium acetate, tetramethylphosphonium hydroxide, triphenylphosphine, trimethylphosphine, trioctylphosphine, and combinations thereof. The combination The compounds may include non-metallic, nucleophilic additives, which can accelerate the cross-linking of the composition. These include monomethylsulfonium, -methylmethylamine, methyltriamidine, amines, and combinations thereof. The content of the catalyst in the entire composition is preferably about i ppm to about 200 ppm, and the content of the catalyst in the entire composition is preferably from about ppm to about 200 ppm. The composition further contains at least one pore former. Pore formers can be compounds or oligomers or polymers 'and are selected such that when removed, for example, by heating:' Keho can produce a Θ stone dielectric film with a nano-sized porous structure: The size of the pores resulting from the removal of the pore-forming agent is directly proportional to the effective interbody diameter of the pore-forming agent component selected. Any special pore size (i.e., diameter ^ is defined by the size of the semiconductor device using the thin film. In addition: Poor blockage of pores caused by too small, for example == in this small diameter structure leads to: non-porous (compact) film. Furthermore, the thinness provided = the diameter change of all pores in the gap distribution should be minimal. Better, The finished sample has a substantially uniform molecular weight and molecules: Chemical formula: / or the statistical distribution or range of molecular size. Second, any significant change in the sub-weight distribution can make the thin film of the hair: Uniform distribution. If the Dan gland has a wide X 爻 pore size, the formation of right large pores (that is, air bubbles) will increase-or more, which will be useful for manufacturing reliable semiconductor devices.

84564 -17- 200403764 caused trouble. Furthermore, the porogen should have a molecular weight and structure that is selectively removed from the film without disturbing the film formation. This is due to the nature of the semiconductor device, which generally has an upper processing temperature. In general, the pore former should be removable from the newly formed film at a temperature below, for example, about 450t. In the specific embodiment, depending on the required method and material for forming a thin film afterwards, the pore-forming agent is selected within 30 seconds to about 60 minutes, and can be redundant to about 45 °. 〇 之 温 ^ Move P 佘 easily. & Removal of porosity can be initiated by heating the film at or above atmospheric pressure or in the air, or exposing the film to radiation or both. The four-hole-forming pore-forming agent includes compounds and polymers having a boiling point, sublimation temperature, and / or a degree of decomposition (under atmospheric pressure) of about 150 ° to about 450 °. In addition, the pore-forming hydrazones to which the present invention is applicable include those having a molecular weight of, for example, about 1,000 to about 50,000 amu, and more preferably about 100 to about 3,000 amu. The pore formers suitable for use in the methods and compositions of the present invention include polymers and preferably contain one or more reactive groups such as hydroxyl or amine groups. Among these general parameters, the polymer pore-forming agents suitable for use in the compositions and methods of the present invention are, for example, polyoxyalkylene, monoethers of polyalkylene oxides, diethers of polyalkylene oxides, polycyclic lice: brothers "Diester, fatty polyester, acrylic polymer, acetal polymer water (caprolactone), poly (valerolactone), poly (methyl methacrylate), poly (vinyl butyral) And / or a combination thereof. When the pore-forming agent is a polyalkylene oxide monoether, a special specific example thereof is between 0, 1, ..., and 6 'wutu chain between the oxygen source and the mouth to about Q alkyl groups, and the burning thereof is The base chain is saturated or unsaturated, such as a polyethylene glycol monomethyl bond, a polyethylene glycol dimethyl acid, or a polypropylene glycol mono Tyl acid. Other common pore-forming agents are described in the same patent application number __, which was filed on the same day as the application. It is not pore-forming with the silicon-containing prepolymer = Agent, and contains poly (alkylene) diether, poly (arylene) diether = (cyclodiol) diether, crown ether, polycaprolactone, all capped polyalkylene oxide, completely End-protected polyarylene oxide, pdynorbene, and combinations thereof. Preferred pore formers that do not bind to silicon-containing prepolymers include water (ethylene glycol) monomethyl ether, poly (ethylene glycol) bis (carboxymethyl) ether, and poly (ethylene glycol) diphenyl. Formate, poly (ethylene glycol) diglyceryl ether, poly (propylene glycol) dibenzoate, poly (propylene.diol) diglyceryl ether, poly (propylene glycol) dimethyl ether, 15_crown ether_5 , 18-crown ether_6, dibenzo-18_crown ether_6, dicyclohexyl_18_crown ether-6, dibenzo_15_crown ether · 5, and combinations thereof. In order not to limit any theory or hypothesis of how to operate the present invention, it is believed that "the porogen can be easily removed from the film. The porogen is one of the following or a combination of the following: The porogen is physically under the heating step. Evaporation causes the porogen to degrade into more volatile molecular fragments, (3) breaks the bond between the porogen and the Si-containing component, and then causes the porogen to evaporate from the film, or any combination of modes μ3. The porogen is heated until a substantial proportion of the porogen is removed, for example, at least about 50 wt% or more of the porogen is removed. In particular, in some specific examples, depending on the porogen and film material selected, at least Removes about 75 s% or more of the porogen. Therefore, "essentially," the term means (for example only) removing about 50% to about 75% or more of the original There are porogens. The porogen content in the whole Shao composition is preferably from about 1 to about 50 or more. More preferred compositions have a porogen content of from about 2 to about 20 Wt%. All compositions may optionally include a solvent composition. The "dropping agents" referred to herein as 84564-19-200403764 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 whole composition. It may be included in the composition to reduce its viscosity, and promote its uniform coating on the substrate by standard methods (such as spin coating, spray coating, dip coating, roll coating, etc.). Remove the solvent. The solvent has a relatively low boiling point relative to the boiling point of any selected pore former and other precursor components. For example, the solvent used in the method of the present invention has a boiling point between about 50 and about 25 (rc, Allow the solvent to heal from the coated film and leave the activated part of the precursor composition. In order to meet various safety and environmental requirements, the solvent preferably has a high flash point (usually more than 40.0 and relatively low toxicity) Suitable solvents include, for example, hydrocarbons and solvents having functional groups c_o_c (^), -cao (vinegar), _co · (ketone), _〇H (alcohol), and (ον- (fluoramine)), and many Solvents for functional groups and combinations thereof. For no limitation, the solvent of the composition includes di-n-butyl ether, acetone, 3-pentanone, 2-heptanone, ethyl acetate, n-propyl acetate, n-butyl acetate, ethyl lactate, 6 alcohol, 2- Propanol, dimethylacetamide, propylene glycol methyl ether acetate, and / or combinations thereof. It is better to react with the cut prepolymer component by spraying. The content of the lotion component is preferably about 1 of the total composition. 0% to about%. More preferably about 20% to about 75% by weight, and most preferably about 20% to about 60% by weight. The larger the percentage of solvent used, the thicker the resulting film. The larger the percentage of porogen, the more porosity is obtained. According to another embodiment of the present invention, the composition may include water (water or water vapor). For example, the whole Shao composition may be coated on a substrate, and then Under standard temperature and pressure, it will expose the material to the surrounding gas containing water vapor.

84564 -20- 200403764 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 will not cause the precursor composition to be coated on the desired substrate Before aging or gelling. By way of example, when water is mixed in the precursor composition, the proportion of water in the composition including water depends on the molar ratio of water to Si atoms in the silicon-containing prepolymer from about 01 · to about 50: 1 exists. It is more preferably about 0.1 to about 10: 1, and most preferably about 0.5 to about 15: 1. 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 parameters and other parameters is used to measure the system. The coated substrate is treated, such as by heating, to crosslink the composition on the substrate to produce a gelled film. Cross-linking can be performed in step 由 by allowing the film to gel at a temperature of about 100t to about 25 (rc: heating for about 30 seconds to about 10 minutes. Skilled artisans should also understand that any additional techniques can be used as appropriate The hardening method known in the art includes hardening the film by exposing the film to sufficient energy such as electron beam energy, ultraviolet energy, microwave energy, etc., according to methods known in the art. If the synthetic solid or solid solid is used, the pore-forming agent can be removed. The latter should be sufficiently non-volatile so that it will not evaporate from the film before the thin film is cured. The pore-forming agent is used in step ⑷ by using a temperature of about At about 45 ° C, it is preferred to remove the gelled film by heating for about 3G seconds to about 1 hour at a temperature of about 150 ° to about 1 hour. An important feature of the present invention is that the gelation system of the better step ⑷ is at a temperature Do not lower than the heating temperature of step 。. Uses 84564 -21-200403764 This product can also include additional ingredients, such as adhesion promoter, anti-foaming sword, spring spring agent, flame retarder, pigment, plasticizer, stabilizer active agent .this The compound can be used for "1 η" private applications, such as thermal insulation, matrix materials for sealing ceramic materials, lightweight composite materials, insulation materials, anticorrosive coatings, ceramic powder powder binders and fire Delayed coating. ^ The composition is particularly useful as a dielectric substrate material in microchips, microchip modules, laminated circuit boards or printed wiring boards in microelectronic applications. This composition can also be used as an etch stopper Or hard mask. This film can be formed by solution technology, such as spray coating 'roll coating, dip coating, spin coating, flow casting and chemical vapor deposition. For chemical vapor deposition (CVD)', the composition is placed in CVD In the device, it is evaporated and introduced into the chamber containing the substrate to be coated. Evaporation can be achieved by heating the composition above its evaporation point, by vacuum or a combination of the above. Generally, evaporation is at atmospheric pressure. It is achieved at the given temperature, or at a lower temperature (close to room temperature) in vacuum. There are currently three types of CVD: atmospheric pressure krypton (ApcvD), low pressure krypton (LPCVD), and plasma enhanced CVD (pECVD). Each of these methods has advantages Point ° AP (: VI ^ is set at a temperature of about the reaction fork operation based on the mass transfer limit. The deposition is restricted by mass transfer. The temperature control of the deposition chamber is less stringent than other methods because of the relationship between the mass transfer process and temperature. Low. As for the rate at which the reactant reaches is directly related to its concentration in the overall gas, it is important to maintain a uniform phase of the reaction concentration in the overall gas adjacent to the wafer. Therefore, to ensure uniform film thickness on the wafer, Therefore, the reactors operating in the mass transfer restricted area need to be designed so that the surface of all the wafers 84564-22-200403764 are coated with the same flow of reactants. The most widely used APCVD reactor design is to horizontally arrange the wafers And is removed under a gas stream to provide a uniform supply of reactants. In contrast to the APCVD reactor, the LPCVD reactor operates in a reaction rate limited mode. According to the method of operating under reaction rate limiting conditions, the process temperature is an important parameter. In order to maintain uniform deposition in all reactors, the reactor temperature must be uniform in all reactors and on all wafer surfaces. The rate at which the deposited species reach the surface is not as important as constant temperature under conditions where the reaction rate is limited. Therefore, the LPCVD reactor does not need to be designed to supply unchanging reaction streams to all locations on the wafer surface. Under the low pressure of the LPCVD reactor, such as operating at moderate vacuum (30-250 Pa or 0.25 to 2.0 torr) and high temperature (550-600 ° C), the diffusivity of the deposited species will be approximately greater than that at atmospheric pressure. A factor of 1000 increases. The increased diffusivity is partially compensated by the fact that the distance at which the reactants must diffuse increases with the square root below the pressure. The actual effect is that the reactants are transported to the surface of the substrate and the increase in the size of the by-products leaving the surface of the substrate exceeds one level. The LPCVD reactor is one or two main structural designs: a horizontal tube reactor; and (b) a vertical tube isothermal reactor. Horizontal tubular, hot-wall reactors are the most widely used reactors in the VLSI process. It is used to deposit poly-Si, silicon nitride, and undoped and doped Si02 films. It has been found that such a wide range of applications is due to its excellent economy, yield, uniformity, and ability to use large diameter (eg 150 mm) wafers. The vertical flow isothermal LPCVD reactor can also be used for distributed gas feeding technology, so that each wafer can receive an equal amount of fresh reactants. The wafers can again be stacked side by side 84564 -23-200403764, but placed in a perforated quartz cage. The cage is placed under a long, holed quartz reaction gas injection tube, and there is one tube for each reaction gas. The gas is fixed by the ejection tube flowing through the hole of the cage vertically, passing through the wafer, parallel to the wafer surface and entering the exhaust slit under the cage. Use the size, number, and position of cage holes to control the flow of reactive gas to the wafer surface. By appropriately optimizing the design of the cage holes, the same amount of fresh reactant can be supplied to each crystal circle by the vertically adjacent ejection tubes. Therefore, this design can avoid the consumption of reactants on the wafer by the wafer fed with the tube reaction gas at the terminal, without the need for temperature drop, resulting in highly uniform deposition, and it is claimed that low particle contamination can be achieved. The third main CVD deposition method is PECVD. This method is classified not only by pressure zone, but also by its energy input method. In addition to starting and maintaining chemical reactions primarily with thermal energy, PECVD uses rf-induced flow emissions to pass energy into the reactant gas to keep the substrate temperature below the APCVD or LPCVD process temperature. Decreasing the substrate temperature is the main advantage of PECVD, which can prevent the film deposited on the substrate from having sufficient thermal stability to accept other methods of coating. PECVD also enables deposition rates to be improved over those achieved using thermal reactions. Furthermore, PECVD can produce films with unique composition and properties. Desired properties such as good adhesion, low pinhole density, good step-by-step coverage, proper electrical properties, and conversion process with precision line patterns make the film useful in VLSI. PECVD requires control and optimization of many deposition parameters, including rf power density, frequency, and load cycling. The deposition process depends on the compounding and interdependence of these parameters, and the general gas composition, flow rate, temperature and pressure parameters. In addition, for LPCVD, the PECVD method is a surface reaction limitation, and -24- 84564 200403764 therefore requires proper substrate temperature control to ensure uniform film thickness. A CVD system usually contains the following components: a gas source, a gas feed line, a mass flow controller for the metering of the gas into the system, a reaction chamber or reactor, a wafer heating on which a thin film is to be deposited, and some types In the system, the method of adding extra energy by other methods, and the temperature sensor. LPCVD and PECVD systems also include pumps that establish low pressure and emit gases from the chamber. The composition is preferably dissolved in a solvent. The suitable solvents used in this solution of the composition include any suitable organic, organometallic, or inorganic molecules that are pure or mixtures that will evaporate at the desired temperature. Suitable solvents include aprotic solvents, such as cyclic ketones such as cyclopentanone, cyclohexanone, 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. Various other organic solvents can be used here, as long as it 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 suitable solvents include methyl ethyl ketone, methyl isobutyl ketone, dibutyl ether, cyclic dimethyl polysiloxane, butyrolactone, r-butyrolactone, 2-heptanone, 3- Ethyl ethoxypropionate, 1-methyl-2-pyrrolidone, and propylene glycol methyl ether acetate (PGMEA), and hydrocarbon solvents such as osmium, xylene, benzene, and toluene. The composition can be used in electrical devices, especially as an interlayer dielectric combined with a single integrated circuit ("1C") chip connection. The surface of an integrated circuit wafer generally has many layers of the composition and multiple layers of metal conductors. It may also include regions of the composition between discrete metal conductors or conductors in the same layer or plane of a integrated circuit. 84564 -25- 200403764 This film can be formed on a substrate. The substrate herein may include any desired substantially solid material. The most desirable substrate layers include films, glass, ceramics, plastics, metals or coated metals, or composite materials. In a preferred embodiment, the substrate includes a silicon arsenide or gallium die mouth or wafer surface, the package surface is as seen in a copper, silver, nickel, or gold-plated lead frame, and the copper surface is as a circuit board or package connection Seen in the wire, the interface of perforated walls or reinforcements ("copper" includes bare copper and its oxides), polymer-based packaging or board interfaces such as flexible packaging based on polyurethane, wires or other metal alloys Welded spherical surface, silicon oxide, oxysilicon carbide, silicon dioxide, silicon carbide, silicon oxynitride, titanium nitride, nitride button, tungsten nitride, aluminum, copper, tantalum, organosiloxane, Silicone glass and fluorinated silicon glass. According to other specific examples, the substrate includes materials commonly used in the packaging and circuit board industries, such as silicon, copper, glass, and polymers. A circuit board composed of the composition can be provided with various conductive circuits on its surface. The circuit board may contain various reinforcements such as woven non-conductive fibers or glass cloth. The circuit board can be single-sided as well as double-sided. This film can be used for double corrugation (such as copper) processing of integrated circuit manufacturing and substrate metal (such as chain or Ming / tungsten) processing. The composition can be, for example, Michael E. Thomas, "Spin-On Stacked Films for Low keff Dielectrics", Solid State Technology (July 2001) (herein referred for reference) ) Is used in all spin-stacked films required. This composition can be used in all of the teachings of commonly assigned U.S. Patent Nos. 6,248,457B1; 5,986,045; 6,124,411 and 6,303,733 for all dielectrics with additional dielectric properties. Rotary stacked films. Analysis test method 84564 -26- 200403764 Dielectric constant: The dielectric constant is obtained by coating a thin aluminum film on a hardened layer, and then performing capacitance-voltage measurement at 1 MHz, and using the layer after degree Calculate the value of k as it is. Refractive index: Refractive index measured with silicon thickness measurement, using JA

Woollam M-88 spectral polarized light ellipsometry was performed. The Cauchy model is used to calculate the optimal Psi and (5. Unless otherwise stated, the refractive index is measured at a wavelength of 633 nm v (details of polarized light roundness measuring instruments can be found in, for example, H.G. ^

Thompkins and William A. McGahan, John Wiley and Sons, Inc., 1999) "Spectral Polarized Light Ellipsometer and Reflectometer"). Lu average pore diameter: On a Micromeretics ASAP 2000 automatic isothermal N2 absorption device, UHP (Ultra High Purity Industrial Gas) N2 was used to immerse a sample in a sample tube in a liquid nitrogen tank at 77 ° K to measure the porosity Sexual N2 isotherms. To prepare the samples, the materials were first deposited on hard crystal circles 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 powder samples in an oven at 180 ° C before weighing. Carefully pour the powder into a 10 millimeter-meter inner diameter sample tube, then degas at 180 ° C and 0.01 Torr &gt; 3 hours. 'Then use the 5-second equilibration interval 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 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 ambient pressure outside the device ) Is proportional. The device measures the N2 isotherm and converts n2 to P / Po. Appearance of BET (S. Cheng runauer, P.H. Emmett, G. Geller; J. Am. Chem. Soc. 84564 -27- 200403764 60, 309-319 (1938) revealed multilayer gas adsorption on solid surfaces The Brunauer, Emmett, and Teller methods are used.) The surface area is calculated from the lower P / Po region of the N2 absorption isotherm using the linear segment of the BET equation that provides R2fit> 0.9999. The pore volume is under the relative pressure P / Po value (usually P / Po ~ 0.95, which is the isothermal plane area with complete condensation). It is assumed that the density of the absorption element is the same as that of liquid N2, and all pores are filled in the P / Po The condensing N2 below is calculated from the volume of N2 absorbed. The pore size distribution is based on the Kelvin equation theory, using BJH from the N2 isotherm (EP Barret, L. G.! Oyner, P. P. Halenda; J. Am. Chem. Soc., 73, 373-380 (1951 )) The pore size distribution is calculated from the adsorption wall of the N2 isotherm. This uses the Kelvin equation, the curve of which is related to the suppression of vapor pressure, and the Halsey equation, which describes the thickness of the absorbed N2 monolayer versus P / Po to convert the condensed N2 volume versus P / Po into a special range of pore sizes. Pore volume. The average cylinder pore diameter D is the diameter of a cylinder 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. The following non-limiting examples are provided to illustrate the invention. Example 1 This example shows the production of nanoporous silica with a pore former having a high concentration of sodium. 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 (including a magnetic stir bar)). (PGMEA). Combine these ingredients in an Nr environment (N2 bagging). The bottle is also connected to the N2 environment to prevent ambient moisture from entering -28- 84564 200403764 solution (standard temperature and pressure). The reaction mixture was heated to 80 ° C. (:, Then add 5 grams of water to the bottle. After the addition of water is complete, cool the reaction mixture to ambient temperature, then add 426 grams of polyethylene glycol monomethyl ether ("PE0"; MW550 amu) (with &gt; (3,000,000 Na) was used as a pore-forming agent, and continued to stir for another 2 hours. Subsequently, the resulting solution was filtered through a 0.2 micron filter to obtain the main batch of the precursor solution for the next step. The solution was deposited on a series of 8-inch silicon wafers, each wafer was on a rotating table and rotated at 2500 rpm for 30 seconds. The water present in the precursor caused the thin film coating to be inserted into the first oven with the wafer Substantially condensing in time. Insertion into the first oven as described below occurs within 10 seconds of completion of the spin. Each coated wafer is then transferred to a series of flood boxes that are continuously preset a specific temperature. One minute each. In this example, there are three flood boxes, and the preset flood box temperatures are 8 (TC, 175t, and 30 {rc.) When each wafer passes through each of three separate ovens. Expulsion by heating. Each wafer is cooled after being gradually heated by two ovens, and The manufactured dielectric film is measured by polarized light rate to determine its thickness and refractive index. Each film is coated with a wafer and then under nitrogen flow and thief-step hardening-hour. Prepared from the liquid precursor of the present invention The non-porous film has a refractive index of M, and k has a degassing ratio of 3.2. In comparison, the refractive index of air is 10. The porosity of the porous rice film of the present invention is therefore directly proportional to the volume of its air. Thin ^ The baking thickness is 5920 angstroms, the baking refractive index is 1 234, the hardened angstroms, and the hardened refractive index is 丨 .231. The resulting hardened thin and thin, the pores of the hardened thin tendon are about 43%. (See the "page" of the table below.) In the table,., R is measured under the surrounding conditions (U / U u). The dielectric constant based on the surrounding capacitance is called 84564 -29- 200403764. The wafer is heated on a 200 ° C heating plate for 2 minutes to remove the absorbed water vapor, and then the capacitance of the film is measured again. The dielectric constant mainly dewatering is called k degassing. Example 2 (comparative ) This example shows the production of nanoporous silica with a pore former with a low concentration of sodium. Stone. Crude PEO (polyethylene glycol monomethyl ether, MW = 550) with a high concentration of sodium is purified by mixing crude PEO with water in a weight ratio of 50:50. The mixture is removed by ion exchange resin The filtrate was collected and vacuum-evaporated, and water was removed to make a pure, low-metal PEO (with <100 ppb of Na). The procedure of Example 1 was then repeated, but the high-metal PEO was replaced with a low-metal PEO. It was estimated to form The outgassing value of k is 3.03, the film basically collapses and the porosity is only about 7%, which is 43% lower than that of Example 1 (comparative example). The baking thickness of the film is 4179 angstroms and the baking refractive index is 1.353. The hardened thickness is 3875 angstroms and the hardened refractive index is 1.331 (see item 2 in the table below). Example 3 Example 2 was repeated except that sodium cations (sodium hydroxide (see item 3) or sodium sulfate (see item 4)) were added to restore a low k value. Add sodium hydroxide (NaOH, 23 ppm) or sulfuric acid # 3 (Na2SO4, 40 ppm) to the ion-exchanged PEO and precursor master batch. The film was deposited on the wafer by spin coating at 2400 rpm or 3500 rpm. After spin coating, the film was heated on three hot plates at temperatures of 80 ° C, 175 ° C and 300 ° C. After baking, the film was hardened for one hour under a stream of nitrogen at 425 ° C. The results of k and the R.I. of the post-hardened film are listed in the table below. Example 4 -30- 84564 200403764 Example 2 was repeated, but this example added tetraorganic ammonium (TMAA) (items 5, 6 and 7), TMAH (item 8) or TBAA (item 9) ions to restore low k . Various amounts of TMAA were added to the ion-exchanged PEO and precursor batches. In some cases, a small amount of methyltriethoxysilane (MTAS, 1%, see item 6) was added to the solution as an in-situ surface modifier to make the surface low in hydrophilicity. By depositing the thin film on the wafer at 2400 rpm or 3500 rpm. After spin coating, the films were heated on heating plates at temperatures of 80 ° C, 175 ° C, and 300 ° C for one minute each. After baking, the film was hardened for one hour under a stream of nitrogen at 425 ° C. For items 5 and 6, the average pore size diameter is 2.5 nm. The k and R.I. results of the post-cured film are shown in the table below. It has been shown that when the concentration of ammonium ion is greater than about 65XHT9 mole / g solution, the k value is less than 2.5, which is equivalent to about 3 ppm (weight) TMAA. Example 5 This example shows the manufacture of nanoporous silica prepared from a porogen with a low concentration of sodium and a commercially available methylsiloxane polymer (Honeywell ACCUGLASS (R) SPIN-ON GLASS 512B). Crude PEO (polyethylene glycol monomethyl ether, MW = 550) with a high concentration of sodium is purified by mixing crude PEO with water in a weight ratio of 50:50. The mixture was passed through an ion exchange resin to remove the metal. The filtrate was collected and subjected to vacuum distillation, and water was removed to make pure, low-metal PEO (with &lt; 100 ppb of Na). The resulting PEO (4.88 g) and butanol (48 g) were mixed with ACCUGLASS® SPIN-ON GLASS 512B (43 g). Therefore, the resulting solution was filtered through a 0.2 micron filter to obtain a main batch of precursor solution for the next step. This solution was then deposited on a series of 8-leaf stone wafers, each wafer was on a rotating table and rotated at 3000 rpm for 30 seconds. The presence of water in the precursor causes the film coating to substantially condense as the wafer is inserted in the first oven at -31-84564 200403764. Insertion into the first oven as described below occurred within 10 seconds of completion of the rotation. Each coated wafer is then transferred to a series of ovens that are continuously preset to a specific temperature for one minute each. In this example, there are three ovens, and the preset oven temperatures are 80 ° c, 175 ° c, and 300 ° C. When each wafer passes through each of three separate ovens, PEO is expelled by such continuous heating. Each wafer is cooled after being gradually heated in the three ovens, and the dielectric thin film manufactured by polarized ellipticity measurement is used to determine Its thickness and refractive index. Each film-coated wafer was further hardened for one hour under a stream of nitrogen at 425 ° C. The film collapsed and could not form a porous structure. The baked thickness of the film was 1690 angstroms, the baked refractive index was 1.395, the hardened thickness was 1615 angstroms, and the hardened refractive index was 1.367. The porosity of the resulting hardened film was about 5 ° /. (See item 10 in the table below). Example 6 Example 5 was repeated, but this example added tetraorganic ammonium (TMAA (item 11)) ions to restore low k. TMAA (10 ppm) was added to ion-exchanged PEO (3.64 g), butanol (13 g), and ACCUGLASS® SPIN-ON GLASS 512B (25 g). The film was deposited on the wafer by spin coating at 2000 rpm. After spin coating, the film was heated on three hot plates at 125 ° C, 200 ° C, and 350 ° C for one minute. After baking, the film was allowed to harden for one hour under a stream of nitrogen at 425 ° C. The k and R.I. results of the post-cured film are shown in the table below. The porosity of the resulting applied film is about 40%. The average pore size diameter is 2.5 nm. Table 1 Sub-additive concentration Ppm PEO K around k degassing △ k final NaPpb hardened RI hardened thickness, Angstrom 1 0 crude 2.60 2.36 0.24 285 1.231 5619 2 0 low metal 3.62 3.03 0.59 &lt; 25 1.331 3875 84564 -32 -200403764 3 40 (Na2S04) Low metal 2.21 2.10 0.11 1.232 7244 4 23 (NaOH) Low metal 2.24 2.21 0.03 1.246 5479 5 6 (TMAA) Low metal 2.34 2.23 0.11 43 1.209 6127 6 6 (TMAA) Low metal 2.24 2.13 0.11 43 1.218 6319 7 3 (TMAA) Low metal 2.65 2.38 0.27 95 1.248 6495 8 22 (TMAH) Low metal 2.27 2.10 0.17 &lt; 25 1.215 7871 9 100 (TBAA) Low metal 2.55 2.27 0.28 65 1.213 7716 10 0 Low metal n / a N / an / a &lt; 25 1.367 1615 11 10 (TMAA) Low metal 2.41 2.24 0.17 &lt; 25 1.215 6467 Example 7 The following example (item 1 of Table II) shows condensation (also referred to as silanol-based cross-linking) The reaction was impaired at 300 ° C without TMAA. For illustration purposes, no porogen was added. 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) (PGMEA). Combine these ingredients in the Nr 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 ° C, and then 1.5 g of water was added to the bottle. After the addition of water was completed, the reaction mixture was cooled to ambient temperature, and the resulting solution was passed through a 0.2 micron filter to obtain a main batch of precursor solution for the next step. This solution was then deposited on a series of 8-pair Shi Xi wafers, each wafer was on a rotating table and rotated at 2500 卬 m for 30 seconds. The presence of water in the precursor causes the film coating to substantially condense as the wafer is inserted into the first hot plate. Insertion of the first 84564 -33-200403764 heating plate as described below occurred within 10 seconds of completion of the rotation. Each coated wafer is then transferred to a series of hot plates continuously preset to a specific temperature for one minute each. In this example, there are three ovens, and the preset oven temperatures are 80 ° C, 175 ° C, and 300 ° C, respectively. Each wafer was cooled after being gradually heated in a three-oven oven, and a dielectric thin film manufactured by measuring the ellipticity of polarized light was used to determine its thickness and refractive index, and silanol (SiOH, v: 3100-3800) was measured using FTIR. 11-1) Area ratio of p-methyl (0 «3, \ /: 2978 〇11-1). For the 3 kA thin film with 111 of 1.41 ± 0.01, it was found that (Si) OH has a CH3 greater than 20. The FTIR spectrum of the baked film indicates a large amount of silanol (see Figure 1). Each film-coated wafer was further hardened for one hour under a nitrogen stream at 425 ° C. The (Si) OH to CH3 ratio of the obtained film was 2. Example 8 Example 7 was repeated, but this example added tetraorganic ammonium (TMAA) (item 2). This example illustrates that the condensation reaction at 300 ° C is catalyzed by the TMAA present. The film was deposited on the wafer by spin coating at 2400 rpm. After spin deposition, the films were heated on hot plates at 80 ° C, 175 ° C, and 300 ° C for one minute. After baking, the film was analyzed by FT1R to determine the area ratio of silanol (SiOH) to methyl (CH3). For a 3 kA film with an RI of 1.41, the silanol ((SiOH) to methyl (CH3) ratio was found to be about 4. The reduction in silanol was better explained by the FTIR spectrum of the film (see Figure 1). Figure 1 shows the FTIR spectrum of the decrease in silanol content: Post-baking term 1 &gt; &gt; Post-baking term 2> Post-curing, term 1 = Post-curing term 2. Each film-coated wafer It was further hardened for one hour under a nitrogen stream at 425 ° C. The (Si) OH to CH3 ratio of the obtained film was 2. 84564. -34- 200403764

RI SiO-H / SiC-H, 1.41 2 1.41 2 1 &quot;,. — Ύ 勹 乾 乂 I 土 一 回 一月, but those skilled in the art should be able to easily understand the various changes and modifications without departing from the invention &lt; Spirit and scope. It is hoped that the scope of patent application will cover the specific examples of disclosure, their changes, and all equivalent examples. [Brief description of the figure] Fig. 1 shows the FTIR spectrum of the thin film of Example 8, in which the content of silanol is decreased ... Post-baking channel 1 &gt; &gt; Post-baking channel 2 &gt; Post-hardening, channel 2 and post-hardening channel 2. 84564 35-

Claims (1)

200403764 Scope of patent application: 1. A method for manufacturing nano-porous silica dielectric thin film, including: preparing a silicon-containing prepolymer, a pore-forming agent, / ^ ^ ^ and selected from the group consisting of a rhenium compound And nucleophile-free metal ion catalyst composition; (b) coating the substrate with the composition to form a thin film; (c) cross-linking the composition to produce a gel film, and then heating the composition at a certain temperature Remove all of the pore formers for a period of time from the gelled film. Consistently effective 2. 3. 4. 5. 6. For example, the method of claim 1 in the patent scope, and the pore volume of the porous dielectric stone film of China and Japan, based on the volume of the film, is about 5% to about ㈣. Such as applying for a patent Fan Yuandi! The method according to item 2, wherein the dielectric constant of the obtained nanoporous crushed-stone dielectric film is about 3 or less. For example, the method of claim 1 in the patent scope, wherein the average pore diameter of the nanomite stone dielectric film is in a range of about 1 nm to about 30 nm. For example, the method of claim 1 in the patent scope, wherein the catalyst is selected from the group consisting of a compound, an amine, a scale compound, and a phosphine compound. For example, the method of claim 1 in the patent scope, wherein the catalyst is selected from the group consisting of four organic ammonium compounds and four organic scale compounds. For example, the method of claim 1, wherein the catalyst is selected from the group consisting of tetramethylammonium ethyl salt, tetramethylammonium hydroxide, tetrabutylammonium acetate, tritylamine, trioctylamine, -A group consisting of dodecylamine, triethanolamine, tetramethylphosphonium acetate, tetramethylphosphonium hydroxide, triphenylphosphine, trimethylphosphine, trioctylphosphine and combinations thereof. For example, if the method of claim 1 is applied for, the composition further includes 84564 200403764 Non-metallic and nucleophilic additives that crosslink the composition. 9. The method according to item 1 of the patent application scope, wherein the composition further comprises a nucleophilic additive that can accelerate the crosslinking of the composition, and the additive is selected from the group consisting of dimethyl block, dimethyl methylamine, and hexamethyl Phosphorus triamine, group of amines and combinations thereof. 10. The method of claim 1, wherein the composition further comprises water, and the molar ratio of water to Si is about 0.1: 1 to about 50: 1. U. The method of claim 1, wherein the composition includes a silicon-containing prepolymer of formula I: Rx-Si-Ly (formula I) where X is an integer from 0 to about 2, and y is 4 Χ (an integer from about 2 to about 4); R is independently selected from the group consisting of alkyl, aryl, hydrogen, alkylene, aryl, and combinations thereof; L is a negatively charged group, which is Independently selected from the group consisting of an alkoxy group, a carboxyl group, an ethoxyl group, an amine group, a sulfonium group, a compound, an isocyanate group, and a combination thereof. 12. The method of claim n of claim 1, wherein the composition comprises a polymer formed by condensing a prepolymer of formula I, wherein the number average molecular weight of the polymer is from about 150 to about 300,000. amu. 13. The method according to item 1 of the patent application range, wherein the composition comprises a silicon-containing prepolymer selected from the group consisting of ethoxylated oxalate, ethoxysilane, methoxysilane, and combinations thereof. 14. The method of claim i, wherein the composition comprises a composition selected from the group consisting of tetraethoxysilane, Ci to about c6 alkyl or aryl-triethoxysilane 84564 200403764 and combinations thereof Group of sand-containing prepolymers. 15. For example, the method of claim 14 of the scope of patent application, in which the triethoxysilane is methyl triethyl donkey oxide crushed. 16. The method as claimed in the patent application, wherein the composition comprises a compound selected from the group consisting of (2,2,2 ·: fluoroethoxy stilbene, tris (trifluoroethylpyroxy)), tetraisochloroacetate The group consisting of Jizhenyan, ginseng (2,2,2-trifluoroethoxy) methylsilane, ginseng (trifluoroethoxy) methylsilane, fluorenyl triisocyanate silane and combinations thereof Silicon-containing prepolymer. 17. The method according to item 丨 of the patent application, wherein the stagnation point, sublimation point, or decomposition temperature of the pore-forming agent is about 150 ° C to about 450 ° C. The method in which step 联系 is performed at a temperature lower than the heating temperature of step 骡 (d). 19. The method according to the scope of the patent application, wherein step ⑷ includes bringing the film at a temperature of about 100 t: to about 25 ( Heating at TC for about 30 seconds to about 10 minutes. 20. The method according to item No. of the patent application, wherein step ⑷ includes heating the film at a temperature of about 150 C to about 450 C for about 30 seconds to about 1 hour. 21. The method according to item 1 of the patent application scope, wherein the molecular weight of the pore-forming agent is about 100 to about 50,000 amu. The method of the first item of the scope of interest 'wherein the pore-forming agent is selected from the group consisting of polyalkylene oxide, a monoether of polyalkylene oxide, two of polyalkylene oxide, polyepoxide, and bisether. , Fatty polyester, propionic acid polymer, acetic acid polymer, poly (caprolactone), poly (valerolactone), poly (methyl methacrylate), poly (vinyl butyral) and The group consisting of combinations thereof. 23. The method according to item 1 of the patent application range, wherein the pore former comprises polyepoxy 84564 200403764 alkyl monoether, which is between an oxygen atom and ^ to about Q alkyl ether groups Containing C! To about C6 alkyl groups, and wherein the alkyl chain is substituted or unsubstituted. 24. The method according to item 23 of the patent application, wherein the polyalkylene oxide monoether is a polyethylene glycol monoether Methyl ether or polypropylene glycol monobutyl ether. 25. The method of claim 丨, wherein the content of the pore-forming agent in the composition is about 1 to about 50 wt% of the composition. 26. For example, the method of claiming a patent scope, wherein the composition further comprises a solvent. 27. For example, the method of claiming a patent scope, wherein the composition Solvent included &Apos; Its amount is from about 10 to about 95 wt% of the composition. 28. The method according to the patent application No. α, wherein the composition still includes a solvent having a stagnation point of about 50 to about 25 ° C. 29. The method according to the patent application, wherein the composition further includes a solvent selected from the group consisting of hydrocarbons, Solvents in the group consisting of vinegar, acetone, ketone, alcohol, amidine and combinations thereof. 30. The method of claim 26, wherein the solvent is selected from the group consisting of a di-n-butyl bond, anisole, acetone, 3-pentanone, 2-heptanone, ethyl acetate, n-propyl acetate, n-butyl acetate Ester, ethyl lactate, ethanol, 2-propanol,: methylacetamide, propylene glycol ethyl ether acetate, and combinations thereof 31. A method of nanoporous dielectric film in item 1 is Formed on the substrate. It is as described in the patent application scope 32. A semiconductor device, a porous dielectric film, which includes nanometers as described in the patent application scope item 31, which is an integrated circuit. 33. For example, please refer to the semiconductor device of item 32 of the patent. 84564 200403764 34. A composition comprising a prepolymer containing pulverization, a porogen, and a catalyst selected from the group consisting of a compound and a nucleophile. 35. The composition of claim 34, wherein the catalyst does not contain A ions. 36. The composition of claim 34, which may additionally include a solvent. 37. The composition of claim 35, wherein the metal-free catalyst is tetramethylammonium acetate. 38. The composition of claim 34, wherein the silicon-containing prepolymer includes a combination of a leaving group mainly composed of ethoxyl. 39_ The composition according to item% of the scope of patent application, wherein the combination consisting of ethoxybenzyl as the main leaving group includes tetraacetoxy oxalate and melamine = diethylene glycol oxysilane. 40. The composition of claim 34, wherein the pore former comprises ethylene glycol monomethyl ether. a 41. The composition of claim 34, wherein the pore former comprises propylene glycol dimethyl ether. &quot; 42. The composition according to claim 34, wherein the pore former comprises polyethylene glycol dimethyl ether. Water 43. The composition of claim 34, wherein the pore former comprises polypropylene glycol monobutyl ether. ^ 44. A precursor for stabilizing a nanoporous film, comprising a composition such as the 35th item in the patent application. 45 · A composition for spin coating, which includes a composition such as item% of the scope of patent application. 84564 200403764 46. A film comprising a composition as described in the application spring. [Special] Target coating of 45 items for spin coating 47. A stable nanoporous thin thin film 仏 仏, the membrane includes silicon polymer and is selected from the group consisting of tritiated compounds and nucleophiles 4〇 4 ^, Feng Aixin Formation ^ does not contain metal ion catalyst. 48. According to item 47 of the scope of application for a patent, Yang Minai's non-porous film, wherein the film &lt; average pore diameter is less than or equal to about 10 nm. 49. For example, the scope of the application for patent No. 47 _ /, yttrium tintin, non-porous thin film, wherein the average pore diameter of the hafnium film is less than or equal to about 5 nm. 50. For example, the scope of patent application No. 47 Ling Borrow Order Taizhi # 导 _ 牟 / 贝 疋% 疋 奈 non-porous film, wherein the metal ion-free catalyst is tetramethylammonium acetate. 5 !. The stabilized nanoporous film according to item 47 of the application, wherein the Shixi I-containing prepolymer includes a combination of a leaving group mainly composed of ethoxyl. 52. The stabilized nanoporous film according to item 47 of the Chinese Patent Application, wherein the combination of acetylacetoxy as the leaving group includes tetraethoxysilane and methyltriacetoxyacetate. . 53. —A method for reducing the temperature of forming a porous silica film, including the step of adding a europium ion or a nucleophile to a silicon-containing prepolymer and a pore former 0 84564 6-