TWI270530B - Use of multifunctional Si-based oligomer/polymer for the surface modification of nanoporous silica films - Google Patents

Abstract

A process for treating a silica film on a substrate, which includes reacting a suitable silica film with an effective amount of a surface modification agent, wherein the silica film is present on a substrate. The reaction is conducted under suitable conditions and for a period of time sufficient for the surface modification agent to form a hydrophobic coating on the film. The surface modification agent includes at least one type of oligomer or polymer reactive with silanols on the silica film. Dielectric films and integrated circuits including such films are also disclosed.

Description

1270530 V. INSTRUCTIONS (1) Please refer to this patent application for the continuation of the application on January 26, 999, the temporary sacred number 60/U 7, 248, the disclosure of which is in the form of In this article. > OVERLAYING Scope The present invention relates to a low dielectric constant vermiculite film and an improved method of making the film on a substrate for use in the fabrication of semiconductor devices, such as integrated devices (n ICs, ). BACKGROUND OF THE INVENTION Since the components of integrated circuits (ICs) are close to and below 〇.丨8 μm, it is believed that interlayer dielectric (ILD) and inter-metal dielectric (IMD) applications require a dielectric constant of $2·5. Electrical insulation layer. ', the sapphire film type material with a low dielectric constant (n kπ ) is a microporous stone, which can be prepared to have a nanometer by introducing air to a relatively low electroconductivity Size pores. Microporous vermiculite is commonly used for glass rotation ("s〇G") and chemical vapor deposition ("CVD") vermiculite (SiOd, which is attractive because it uses a similar precursor, and includes Organically substituted calcined, such as tetramethoxy calcined ("TM0S") and / or tetraethoxydecane ("TE0S,1) and / or mercaptotriethoxy oxalate. It is attractive because it can control the porosity, density, material strength and dielectric constant of the resulting film material. In addition to having a low dielectric constant k, microporous vermiculite provides other advantages, including... 1) Thermal stability Up to 50 °C; 2) a relatively small aperture size, at least numerically smaller than the microelectronic component scale of the integrated circuit; 3) as described above, can be widely used in semiconductors

Page 5 1270530 V. Description of the invention (2) (eg) vermiculite and TE0S materials lend · ^^ ^ Shi Xishi's dielectric constant ability;: 5) can f: Shangxu: factory microporous deposition micropores film. A functional group associated with the microporous vermiculite film was treated with a similar tool as I know 500. Previously available micropores;; = = ; = the presence of polyalcohol (caffe), Shixi oxygen (Si0Si) m in 6 groups including Shi Xi burning species, such as but not limited to methyl, Yiyi H〇R) Where r is the organic appearance (the inverse is as defined above), especially =, alcohol or basestone, high-concentration human effect Xueqitu / ^ ~ structure related to the considerable (internal) surface dielectric often I: 兀% base The role of the group leads to a higher dielectric constant than the required dielectric constant. The adsorption of environmental water can even be added to the environment: ίίίί; 2nd ϊ: the degassing of the electric film, the presence of polar 艮 such restrictions and micropores Shi Xishi ^ Loss. For the gram:, the previous method of use to make the inner surface "night" symmetry and hydrophobic (such as) chlorine agent or blocking agent. Such end-capping agent package an organic anti-i = "disk such as Shi Xi In a previously utilized method of the alcohol group, the inner group is made to: 面, δ Λ 二 二 夕 氮 氮 _ _ 入 入 入 入 入 入 入 入 入 入 入 入 入 入 入 入 入 入 入 入 入 : : : : : : 'Because of the formation of trimethylformane, it is intentionally and relatively ambiguous; a disadvantage of the alkylation group of the oxime is that it is hotter than the original stanol methyl methacrylate. Too stable physical page ^ = 61270530 V. invention is described in (3) may be degassed, lead poisoning during IC.

Another key parameter of the microporous Shishi stone film is mechanical strength. The mechanical strength of a material generally decreases proportionally as the density of the material decreases. For microporous films used as dielectric films for IC devices, the combination of mechanical strength and low dielectric constant is also important. For a given dielectric constant (proportional to the refractive index and density), the density is at least fixed for the unambiguous chemical composition. When the density is fixed, the strength of the microporous vermiculite is maximized by the maximum solid fraction in the film skeleton, but not by the additional chemical groups on the surface of the nanometer-sized pores. Thus, in another drawback, the reactant (e.g., HMDZ) introduces a substantial amount of additional material (trimethylformamyl) to the surface of the pores. The unbalanced mass of trimethyl methacrylate is not used to promote mechanical strength, but it does increase the density of the film and is therefore an obstacle to achieving the lowest possible k value. For these reasons and for semiconductor and/or microprocessing The rapid competitive development of the manufacture of ICs or ICs requires technical improvements in methods. In particular, it is desirable to provide a microporous vermiculite film having a hydrophobic surface and a microporous vermiculite film having a hydrophobic pore surface, and at the same time having the mechanical strength of the hydrophobic film. A successful solution to the required treatment will provide greater material film strength. - the method of the present invention is surprisingly unexpected in this and other problems, and the surface modifying agent is capable of imparting a treated film at the same time as the agent or the reactant ratio. "Xi Xi Shi" electric film hydrophobicity, strength. Therefore, the present invention is applied to the ruthenium film, surface modifier reaction step 1270530 V, invention description (4) = novel method 'formed on the desired substrate ~ The Shishi stone film is present on the substrate, the reverse, the film or the coating. The surface modification agent is made in the vermiculite; two or two pieces and enough oligomers or polymers to react. The invention also provides a composition of c-small alcohol and an integrated circuit having at least one dielectric thin film of the present invention. The method of the present invention processes the dielectric thinness of the vermiculite and reduces the number of dielectric peaks. 'Thinking,' is not significantly reduced outside the material: and the "Electrical value of the available range" provides the 矽L page to reduce the meteorite film as needed to cover, enamel film. And want, Yuanhua " Membrane surface, _ stone ==::::;; rational; in the step-by-step selection of the medium;;: surface modifier and monomer type surface; including oligomeric film, but preferably prepared in advance in the treatment source, Storage and sputum, the second one from another, but want to use the invention new / should be noted 'although not necessarily or gelatinized. If the application of the old Ιΐ 理 石 夕 stone film can be seen before the aging modification treatment or ' After the second: the surface aging can be applied in the present invention. After the fly, the film zrc can be preferably carried out in the gas phase or the liquid phase before the surface modification. In addition, the aspect; the decoration; In the presence of a cosolvent, it should be understood that when the table is carried out, the solvent or cosolvent needs to be effectively dissolved and/or d kg of surface modifying agent without significantly dissolving the film to be treated. Applicable substances used as solvents or co-solvents, including ketones and non-ketones

Ϋϋ P.8 1270530 V. Inventive Note (5), but such a solvent or co-solvent is preferably selected from the group, but such a solvent or co-solvent is preferably selected from the group consisting of ethers, esters, ketones, and glycols. The group consisting of a chlorinated solvent, a low-viscosity oxy-combustion and a suitable mixture thereof, although it is a decorative method surface, pancreas. The self-contained 10 0 on the wafer is mainly produced by the hair of the 3200 to the method of the method or the oligomerization of the agent agent is how thin the stone m. Therefore, the stone film to be treated does not have to be porous, but the microporous dielectric film of the film having a higher surface area pore structure to be treated, and the surface is preferably subjected to a sufficient time for the surface modifier to effectively coat the film. The thin surface modification of the treated microporous vermiculite having a dielectric constant of about 3 or less is preferably from about 1 sec to about i hr (5) ° C to about 30,000 ° C. The lx treated film is preferably formed on a substrate. For example, the crystal of the integrated circuit is also provided with a dielectric thin film dielectric film of about 370 % as compared to the prior art, based on the present invention. It is believed that the dielectric film can be used as well as at least one integrated circuit comprising the method of the present invention. The F〇Urier converted infrared spectrum produced by the method of the present invention showed no significant stanol absorption in the approximate wavelength range under the infrared spectrum. The light fittings are carefully started, and the first column is given the polymer and/or agent for the surface modification treatment of the dielectric film and the hydrophobicity of the material. This method has a variety of reactants based on previous methods compared to the previous use of reverse = mechanical strength I. Although not 35 by the county of the invention, it is believed that the polymer coating on the surface of the microporous (four) (especially nano

The weak part of page 9 is the contact point between the film particles and the grain. 1270530

The coating of the meter-sized pore surface) eliminates the problem of moisture absorption and the mechanical properties of the fine particles or grain-enhancing film composed of the film covering and bonding. Positive Effects on Mechanical Strength of Films For whatever reason, the following examples demonstrate that the methods and reactants of the present invention can actually provide enhanced film strength. The method and reactant of the present invention are used in a vermiculite dielectric film. Several methods for preparing microporous Shishi stone films on substrates are well known in the art. As outlined above, "Invention Background π. In addition, variations and modifications of the generally known methods for preparing microporous films are also disclosed in U.S. Patent Application Serial Nos. 09/046,475 and No. 09/046,473, both of which are incorporated herein by reference. March 25, U98; U.S. Patent Application Serial No. 9/54,262, Shen Jing, April 3, 998; and U.S. Patent Application Serial No. 9/〇55,244° and brother 09/055 , 5 1 6 , both of which were filed on April 6, 1999; and US Patent Application Serial No. 9/379,484, filed on August 23, 999, dated 09/392, 41 3 No., applied for September 9, 1999, and the method is here. No (4) 'Technician IK; 2 methods and materials of the invention are easy to apply to a variety of techniques known to include organic basic dielectric materials), preferably applied to the use of vermiculite h electrical material 'optimized for microporous dielectric 矽 stone " Strength and / or protective hydrophobic coating. In order to provide a better understanding of the scope of the present invention, it should be understood that, unless the S i 〇2 functional group is clearly indicated, the scorpion 丨丨 叮 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨 丨丨(film-related) means a dielectric film prepared by the method of the present invention from its own filler material (ie, any suitable material based on Shixia).

Page 10 1270530 V. Description of invention (7). In addition, it should be understood that the singular terms used herein are not to be construed as being limited to the singular singular, and, as appropriate, the exemplified method of the invention may be described as the application and the production of a film " Exemplary and patented methods of making multiple films. Other term "agent" as used herein may be considered synonymous with "reactant" unless otherwise indicated. Unless otherwise stated, a π-integrated circuit or "1C" is intended to mean a semiconductor product using the methods and compositions of the present invention. Furthermore, although a method of resolving a microporous dielectric material is described herein, it will be readily apparent to those skilled in the art that the methods and compositions provided herein can also be applied to non-porous dielectric vermiculite films. Thus, non-porous films applied to a suitable substrate (such as the semiconductor wafer described below suitable for making integrated circuits) also benefit from the methods and materials provided by the present invention. For example, on the hydrophilic stone film used for the manufacture of insulators and the like of integrated circuits, the following problems occur, such as excessive dielectric constant and current leakage. These additional problems are addressed by the methods and compositions of the present invention. Thin 2 ί / and + & π substrate as described herein includes any suitable composition formed prior to the application of the microporous vermiculite of the present invention to the composition, which is generally suitable for manufacture. The base wafer of the integrated circuit is formed on the micro, and the substrate material used for the i scoop is applied to the substrate by any suitable method: ^ in spin coating, chemical vapor deposition D and dip coating, if necessary: Method of preparing a substrate for coating prior to forming a microporous vermiculite film from a substrate material by methods known in the art

Page 11 1270530 V. INSTRUCTIONS (8) The non-uniqueness of the substrate of the invention includes semiconductor materials such as gallium arsenide, outer bismuth and bismuth-containing compositions [such as crystalline germanium, polycrystalline germanium, amorphous. Its orientation-oriented growth of yttrium and cerium oxide (,, Si(V)] and its mixture into a convex line pattern, :: genus...printing technology, the material for the shape line includes stone, nitride or oxygen Chemical line. Gold, _, bismuth telluride, titanium nitride, tantalum nitride, aluminum, aluminum alloy t^ foot alloy, button, tungsten and bismuth oxynitride. These lines form the integrated electrical distance slightly 8 2 Insulators. These wires are generally about 20 microns or less in each other.

good. Applicable: 铋志 is preferably 1 micron or less, from about 〇·05 to about 1 micron. Other optional features of φ include the previously formed microporous material. The starting material of the inventive process also includes the application of a vermiculite precursor to the base pore stone, such as a glass-on-rotary composition. The film is aged. If an aging step is applied, = by (for example) ammonia and steam treatment promote gelation. Lotus I I, 隹 The process of the present invention is directly applied to the micropores of the wet film after aging. In another alternative embodiment, the process of the present invention is aged as a dried microporous film and on a microporous vermiculite film that has been stored for a period of time after completion of aging. In the process of the present invention, although several alternative aging methods are known for the art, it is preferred to age the film by ammonium hydroxide treatment. If the film is statically aged, the substrate 2 of the branch film and the time and effective conditions for expanding into the film are exposed to 15 Torr of hydrogen and water in the finite chamber.

_丨1_

1270530

Material/Voice Polymer Composition For the purpose of making the density/dielectric constant parameter, the present invention uses a method of modifying one or more polymers of a vermiculite film. Thus, it is included herein that one or more of the composition is capable of forming a surface modifying agent from a monomer to form a surface modifying agent from the monomer, and the monomer precursor is mixed with itself or reacted to form a surface repair (eg, Include a polymer (such as 100 or a polymer (such as 100 or more repeats of the surface modifier required to handle a considerable proportion of the stanol-based coating on the surface. The surface modifier can be self-contained with Shi Xi Alcohol reaction to form a polymer of decane, decyl (dimethylamino) methyl group to achieve a sufficient mechanical strength to achieve the optimal surface composition of the hydrophobic surface/energetic surface to provide a uniform parameter A surface modifying agent prepared by a surface modifying composition which is in contact with a hydrophobic coating. 'When prepared as a monomer precursor, it can promote other types of monomeric coloring agents present in the composition. Surface modification A mixture of less than a repeating unit of a polymer) and/or a plurality of elements. Then, it is coated on a vermiculite dielectric film, where the group is blocked and reacted to form a desired hydrophobically suitable monomer for polymerization, including organic oxime monomers such as methyltriethoxysulfoxide and ruthenium (II). Ethylamino)decyl decane

Human = surface modifiers are more typically prepared from hydrazine-based monomers by hydrolysis/reduction or type-polymerization/reaction, such as decane, decazane, decane, and the like, and mixtures thereof. preparation. Simple as an example and without any limitation, such a reaction proceeds as follows.

CH3Si(0C0CH3) + H20~>[-0-Si(CH3)(0C0CH3)-]n + CH3C00H where "has the polymerization of the image (in this case, hydrolysis/condensation), "n"

1270530 V. INSTRUCTIONS (10) An integer from 2 to about 10, 〇〇〇 or greater. The molar ratio of water to monomer in the reaction mixture is readily dependent on the specific product gas #. In a preferred embodiment, the ratio of water to monomer during the reaction is from 节·50:1·5 to about 1.7:0·5 mol/mole. approximately

While not wishing to be bound by the hypothesis theory of how the reactants of the present invention act as a derogatory effect of this illustrative scheme, it is believed that the polymer ^(3)^1 fraction is reacted with stanol (Si-OH) on the surface of porous vermiculite. Functional Group II We believe that the surface modification reagent is primarily attached to the surface oxime alcohol, but m is envisaged that in certain embodiments as desired, the resulting hydrophobic ^ = has a considerable amount of cross-linking that occurs during the formation of the coating. . Θ Thus, a blood-type oxy-oxygenated polymer/oligomer having a plurality of functional groups capable of reacting with stanol (Si-germanium) has the following formula: (-S i XR-〇— )nj where R can be Η The alkyl or aryl 'sense (eg) is selected from one or more of the following: oxime, ethoxylated (_%), dilute oxy (10) 2 = g(ch3)_〇_Si), 肟U2C = N -〇s-Si), alkoxy (R〇_Si), amine (R2N_si) and /, shool (S^OH), n is (for example) from 2 to about 1 Torr or more An integer in the range of large values. In further tJh ^ ^ ^ 7 selection, η is an integer from about 2 to about 1 对. It should also be understood that the size of the cheeks and the η values of the worms and the polymer species (7) ^ χ ^ are generally distributed over a range of values. The type of surface structuring agent includes a sulfonium alkane polymer/oligomer capable of reacting with a sulphuric acid (Si-, ^ functional group), which has the formula:

1270530 V. Description of invention (11)

(-S i XRi -NR2- ) η II wherein 匕 and 匕 are independently Η, alkyl and/or aryl, and lanthanide (for example) is selected from one or more of the following: ethoxycarbonyl (〇c〇CH3) ), alkenyloxy (called "- ΓΡ Μ 3 - 〇 - Sl ), 肟 (R2C = N - 〇S - Si), alkoxy (R0_Si) and amine Si), n is like! Defined. It should be understood that since the skeleton of the indazane polymer is 31 ", the group can provide additional functional groups and derivatization and crosslinking. Suitable for hydrazine alkane reactants: poly(1,2-dimethylazane), (1,2-dimethyl oxime), fluorene-methyl decazane copolymer A quinone alkane resin. These azaxane polymers may be reacted with a suitable amine or nij3 in combination with a desired decane reactant. Another suitable surface modifying agent comprises a decane polymer/oligomer having a plurality of functional groups capable of reacting with stanol (si-OH). It has the general formula: (-Si XR-)ni 11 f wherein R can be H, alkyl or aryl, and x is, for example, selected from one or more of the following moieties: hydrazine, acetoxy (〇c〇) CH3), alkenyloxy group (ch2 = C(CH3)_0-)), ruthenium (R2C = N-Os-Si), alkoxy group (R〇-Si), amine (R2N-Si), n-form I defined. It will also be appreciated that since the backbone of the decane polymer is s i - S1 ' this group may optionally provide additional functional groups and derivatization and crosslinking. Useful general anthracycline reactants for such applications include, for example, polydidecyl decane, polyphenylmethyl decane, and the like, and mixtures thereof. Another type of suitable surface modification includes a carbon hydride polymer/polymer having a plurality of functional groups capable of reacting with a stanol (Si-0H) having the formula:

(-S i K R2 - R3 - ) η IV

Page 15 1270530 V. Description of the invention (12) wherein h and 1?2 are independently oxime, alkyl, aryl, ethoxylated (〇c〇CH3), alkenyloxy (CH2 = C(CH3)- 〇-Si), Os-Si), alkoxy groups (R〇-Si) or amines (R2N-Si), and R3 may be substituted or unsubstituted alkylene or arylene. Commercially available oxane polymers having a plurality of functional groups and stanol groups are also commercially available. For example, the T-1 1 decane reactant series familiar to the skilled person is available from Advanced Microelectronic Materials division of Honeywell (Sunyvale, California). ,

Cal if or ni a). A wide variety of suitable decane and decane polymers are also available from, for example, United Chemical Technology [Bristol, PA]. One or more of the above reactant mixtures represented by a mixture of polymers and/or copolymers of formula I, I I, 11 I and/or IV may also be used in the methods and compositions of the present invention. The surface modifying agent is preferably a hydrolysis/condensation product of a rotating type vermiculite reactant [eg, mercaptotriethoxymethoxydecane ("MTAS") on glass. The "hydrolysis/condensation product of the heart" is accompanied by An ethoxylated polyfunctional oxetane skeleton structure which is formed under suitable conditions via mixing of a suitable solution with a predetermined ratio of water. ^ Method for reacting thin stone dielectric ink with surface repair agent Although the exemplary method for reacting vermiculite film with surface modifier is carried out in liquid phase, the skilled person should understand that the surface modifier can be in the liquid phase (not available or optional) Cosolvent) or gas phase (without or with optional cosolvent')

1270530 ---·---- V. Description of invention (13) To deal with film contact, as described in the year of 1998, its content: the Ministry of the Ministry of the number is limited, but its conditions are limited by the method and As used herein, a desirable range of dielectric constants and mechanically strong surface modifying agents provide a treated dielectric film having a suitable integrator=strength on a substrate for use in a material of the present invention. The gas phase stone film is exposed to the monomer of the gas surface modifier, and the polymer/oligomer effective condition is to lick the surface of the film to a certain amount, and it should be understood that the polymer/Shi Xi Xuan Partially terminated. The body should show a satisfactory boiling point / tomb gas J. Na; :, r,,, τ ^ hydrophobic surface. The monomer of the warm surface modifier which is ideal for gas-enhanced and heat-stable surface modification should have a suitable vapor pressure as an example and without any two-consumption. Simple about 5. 〇托. Applicable surface: Limit: Suitable for the vapor of the monomer - should be from about ! to (t〇rr). The vapor pressure of the monomer is preferably from about 5 to about 100 Torr. The monomer used for the surface modifier is preferably from about 5 to about 100 Torr. Formed as the body of the present invention; f: pressed from about 10 to about 5. The best. mixing. The applicable co-solvent is: f is in the liquid phase and the applicable solvent/cosolvent. Any other selected material Y core agent, in which the surface modifying agent can be dissolved and the stanol dissolved on the surface is treated to dissolve the dielectric material or the interference is easy to borrow. Vapor and/or hydration, and such co-solvents include ethers, after completion of the surface modification reaction. As an example and without any limitation, 8 hydrazine, ketone, glycol ether, chlorinated solvent, low on page 17, 1270530, invention, (14) viscosity oxirane, and suitable mixtures of such solvent species. The skilled person will appreciate that the π low viscosity π for oxane applications is well known in the art, preferably from about 1 to about 10 centistokes, preferably from about 160 to about 3. Molecular weight in the range of 80 Daltons (D a 1 t ο ns ). Typical low viscosity alkane used in the process of the invention is commercially available, for example, from Dow C 〇 r n i n g.

Suitable solvent/cosolvents are generally employed at a concentration ranging from about 0.5 to about 99% by weight or more, based on the total solution weight. Typical ethers used in the process of the invention include diethyl ether, diisopropyl ether, dibutyl ether, and mixtures thereof. Typical esters used in the process of the invention include ethyl acetate, isopropyl acetate, n-butyl acetate, and mixtures thereof. Typical hydrocarbons used in the process of the invention include n-hexane, n-heptane, cyclohexane, toluene, and mixtures thereof. Typical ketones used in the process of the invention include acetone, 3-pentanone, decyl-butyl ketone, and mixtures thereof. Typical glycol ethers useful in the process of the invention include tris(ethylene glycol) dimethyl ether, tetra(ethylene glycol) dimethyl ether, and tris(propylene glycol) dimethyl ether. Typical chlorinated solvents for use in the process of the invention include 1,2-dichloroethene, carbon tetrachloride, chloroform and mixtures thereof. As shown in the following examples, 3-pentane I is a preferred cosolvent, and the 3-pentanone is used in a weight percentage of from about 0.5 to about 9 9 or more, based on the total solution weight, from about 5 0 More preferably 80% by weight. In a typical embodiment of the invention, the single system is mixed with an aqueous solvent or co-solvent which is a hydrolyzed/condensed product formed in the presence of water. The water content of the co-solvent is from about 0.05% or more. The water content of the solvent or co-solvent is preferably from about 0.05% to about 10% or more. The water content of the solvent or cosolvent is preferably from about 0.5% to about 4%.

O:\62\62459.ptd Page 18 1270530

V. INSTRUCTIONS (15) The solution is mixed with different predetermined proportions of the cosolvent solution, and the method of applying the method to the dielectric film on the substrate is as follows: rotating the solution containing the hydrolysis/condensation solution or the suspension liquid to various The 3 water co-solvent on the test film was dichotomized from about 5 to about 9 Torr or greater percent by weight. The concentration of the monomer in the co-solvent is preferably from about 5 to about 5. %. The concentration of the monolayer in the co-solvent is preferably from about 1Q to the paste% = from about 55. 5G:1 to about 1: G.5G mole/mole. Monomer and water: S7A5: / l to about 1: 〇. 75 is better. In the following examples, the single system is exemplified by MTAS. Subsequently, the substrate and treated film are heated to a sufficient temperature to remove the remaining surface modifying agent and solvent in time. In a preferred embodiment, the film is subsequently cured. Heating steps in multiple stages as appropriate Each stage utilizes similar or different times and temperatures, or combined into a single processing step. For example, in air, at 175 or 32 分别, respectively. 〇 Heat treatment. The treated film is cured after $, such as curing at 4 ° C. Surface treatment with other parties, one monomer surface, one surface modification, as described in the background of the invention, a previously utilized method of capping a certain group of dialkyl alcohol on the pore surface of a dielectric film using introduced film pores An organic anti-depot compound [such as hexamethyldioxane (HMDZ)] is allowed to react with a surface stanol group. The reaction is terminated by the formation of a hydrophobic trimethylformamidine alkyl group. As noted above, one disadvantage of using a trimethylmethanyl group is that it is less stable to hydrazine, may vent during further processing of 1C, and cause poisoning; however, an alternative embodiment of the present invention uses this alternative method. In combination with the methods and compositions of the present invention, for example, using the methods and compositions of the present invention

19th![

Amendment 1270530 Case No. 89Π1054 V. INSTRUCTIONS (16) The monomer of the hydrophobic surface caps the stanol group. The combination treatment advantageously provides additional capping of the internal stanol, such as the capping of the ceramsite on the surface of the film inside the pore structure of the microporous film, which is believed to further reduce the dielectric constant of the film. Further, the oligomer or copolymer surface modifier of the present invention is capable of blocking the surface of the film, increasing mechanical strength and improving hydrophobicity, and suppressing gas evolution during the treatment. The combination process can be carried out in order, i.e., the film is first reacted with a monomer type surface modifying agent and subsequently reacted with the oligomer or copolymer surface modifying agent of the present invention. Preferably, the reaction is carried out simultaneously, i.e., (1) forming a solution of the oligomer or polymer surface modifier, and then (2) adding an additional amount of the selected monomer to the solution. Subsequently, the mixed solution is applied onto the dielectric film to be treated by the aforementioned method. A number of monomer type surface modifiers and methods for making hydrophobic, low dielectric microporous vermiculite films are described, for example, in the U.S. Serial Nos. 60/098,068 and 09/140,855, both of which are incorporated herein by reference. Applicants apply on August 27, 1998; Nos. 09/234, 609 and 09/235, No. 186, both of which are incorporated herein by reference. Preferred monomer type surface modifiers are compounds having a group selected from the group consisting of Formulas V(1) to (6) and mixtures thereof: (1) R3SiNHSiR3, (2) RxSiCly, (3) RxSi (OH)y, ( 4) R3 S1OS1R3, (5) RxSi (〇R)y and / or (6) RxSi (OC〇CH3)y, where x is an integer from 1 to 3, y is from 1 to 3 and y = 4 - An integer of x, each R is independently selected from the group consisting of hydrogen and a hydrophobic organic moiety. Preferably, the R group is independently selected from the group consisting of an alkyl group, an aryl group, and a mixture thereof.

O:\62\62459-930730.ptc Page 20 1270530 V. INSTRUCTIONS (17) Groups wherein the alkyl moiety is substituted or unsubstituted, and alkoxy, branched alkyl, cycloalkyl and The group consisting of the mixture is composed of a portion from 2 c to about c18. The aryl moiety is taken from, = substituted, and its size varies from c5 to about C18. The monomer type two agent is preferably ethoxylated decane, such as ethoxylated succinyl succinyl oxy dimethyl decane, methyl triethyl ethoxy oxane, J yl 2 decane, diphenyl Ethyl ethoxy decane; and/or trimethyl ethoxy sulphate, trimethyl methoxy sulphur, sulphur, sylvestre, ketone, ketone, ketone, ketone矽 ) ) ) ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : Vinegar (dimethyl dimethyl ketone (dimethyl fluorenyloxy)-acetic acid vinegar, hexamethyl sulphate: ke sigma kimono, hexamethyl bismuth oxide, trimethyl sulphate: dicohol, Triphenyl zephyrol, third __butyl dimethyl-ethyl oxalate diol and mixtures thereof. The leaf-based oxime, the surface modification of the monomer type is mixed with a suitable solvent (such as acetone) or a liquid, The form is applied to the surface of the microporous oxidized stone, and then dried. The surface modification agent of the 匕 early type includes polyfunctional surface modifier ϊίΠΠί SEQ ID NO: 9/235, 186, all of which It can be applied in liquid form, and if necessary, with or without a solvent-assisting agent, such as, for example, propionate, 3_penta, and diiso-valley, as described in the US Patent of July 7 The serial number Γ substance ' 09/111, G84 #u, the disclosure of which is incorporated herein by reference.

Page 21

IH 1270530 V. INSTRUCTIONS (18) For example, certain preferred surface modifying agents have two or more g-b groups as described in U.S. Patent Serial No. 09/235,186, the disclosure of which is incorporated herein by reference. Minimizing the presence of materials outside the framework of the film structure while reacting with surface stanol functional groups, including stanols of the formula:

Ri S i (〇R2 )3 VI It is: r, r2 is an independently selected moiety such as ... or an organic moiety (such as an alkyl group, a square group or a derivative thereof). When or 1 is an alkyl group, the alkyl moiety is optionally substituted or unsubstituted, and I may be a straight chain, a branched or a ring system, and its size preferably varies from Ci to about Cls or higher, from q. It is better to about Q. When the field h is an aryl group, the aryl moiety is preferably composed of a single aromatic ring which is optionally substituted or unsubstituted, and has a size ranging from Cs to about ~ or higher, from C: 5 to , 々 (: 8) More preferably, in further selection, the aryl moiety is not a heteroaryl group. Thus, the heart or the 1 line is independently selected from the group consisting of H, methyl, ethyl, propyl, phenyl, and/or its organism, but the conditions thereof Limiting at least one of h or hydrazine is organic. In one particular embodiment, & and 1 are both methyl, and the multifunctional surface modifying agent of formula VI is decyltrimethoxydecane. In another embodiment The applicable decane of the present invention has the following formula:

RiSi(NR2R3)3 VII wherein R1, /2 and the card are independently oxime, alkyl and/or aryl. When either of r, r3 is an alkyl group and/or an aryl group, it defines a boundary between the heart and the heart as in the above formula VI. In a preferred embodiment of formula VI1, R! is selected from the group consisting of ruthenium, CH3, and CeH5, and both & A are methyl. Thus, the formula of the trifunctional monomer type of the formula π

Page 22

IM 1270530 V. INSTRUCTIONS (19) Surface modifiers include, for example, hydrazine (dimethylamino) decyl decane, hydrazine (diphenyl decane and/or decyl (dimethylamino) decane. - methylamino) In another embodiment, the present invention is applicable to decane

R1Si(〇N = CR2R3)3 VIII wherein R and R3 are independently oxime, alkyl and/or aryl. When any of R is an alkyl group and/or an aryl group, it is as defined above for the formula jR3. In a preferred embodiment, 'ΜH: 2HCH, 'the surface of the trifunctional monomer type of the formula νπ is (eg, methyl ketone (methyl ethyl ketone oxime) decane. TW is included in In another embodiment, the invention is applicable to decane and R^iCla Ιχ ^ · Π", alkyl or aryl. When the heart is a burnt or aryl group, include... methyl three gas stone. Body Type Surface Conditioning Agent In a more preferred embodiment, the blocking agent comprises - an organic ethoxylated decane of the formula:

(R1)xSi(0C0R2)y X X is preferably an integer having a value ranging from 1 to 2, and may be an integer ranging from about 2 to about 3 or more. S is different, y is used as an example of a polyfunctional alkyl ethoxy decane and/or a smelting compound of the organic ethoxylates as an example / a gas base (_AS), phenyl triethoxy oxime And - / stupid base - a dioxygen stone and its mixture. Oxydecane

1270530

V. INSTRUCTIONS (20) The microporous dielectric film formed on the microporous dielectric film is formed as follows: about 2%% -: large pores, and the shape of the pores is about 1 millimeter. Micron to about i 〇〇 'from about 2 house micron to about 3 〇 nanometer better 'best from about 3 nm to: ° Γ" ?L ^:) ^ ^ ^ ^ ^ 0-1 ;

The micro-cut stone film produced by St. gram 3 is preferably less than about 3. Insult: dielectric constant. The microporous dielectric film of the present invention has a higher electrical constant from about jUh, from about 13 to about 2 and most from about 1.7 to about 2. Yan Wangwen lived in the film of the stone-shaped stone stone of the seat, understand that in the beneficial results of the m step, can: : t applied to microelectronics and / or integrated circuit products in the non-^ ^ "electric materials (the non-porous interface The electrical material can be used to phase out the low dielectric constant and/or the pores of the bamboo. The bamboo heart is used for the non-polar and similar functions to borrow, and to make such materials include environmental humidity. (for example) by:; non-porous Shishishi-based dielectric material ("_"), dip or 嗔 coating 1 ==, film [such as chemical vapor deposition end capping similar materials. , He Qichen has the desire to form a thin method of surface stanol. However, what is produced, the side to which the present invention is applied = free sulphate which absorbs environmental moisture. Because of the non-porous Shi Xishi dielectric s surplus, this free Shishi Hyun alcohol is capped, even

Page 24 1270530

The following non-limiting examples further explain and explain the present invention. ί 5% MMTAS-derived a solution of a siloxane polymer, which is provided with an electric film, and the methoxide-derived siloxane polymer is 7G per repetition. Contains an average of 1.5 reactive functional groups.

Hydrolyzed MTAS for the surface of the huangbei will be methyltriethoxy decane ["MTAS,;; purchased from United Chemicals, Pennsylvania, United Chemical Technology Corporation (United Chemical)

c, hnol〇gies, Brist〇1, pA)] was purified by vacuum distillation before use. A low water content (< 250 PPM) 23-pentanone [Pasfac, Pacific Pac] was applied. 116 g of 3-pentanone was placed in a 500 ml flask containing 178 g of water and placed in a magnetic stir bar. Then 29 grams of MTAS was added to the above 3-pentanone/water mixture with appropriate stirring and stirring was continued at room temperature overnight to yield a clear, colorless solution. The product was analyzed by gas chromatography-mass spectrometry and found to have no hydrazine in the product, meaning that the MTAS had all reacted. The solution was then filtered through a 微米·2 μm Teflon (trademark) filter. For use in the following surface treatments. Preparation of microporous film

A micronized vermiculite precursor was synthesized by adding 208 ml of tetraethoxysilane, 94 ml of triethylene glycol monoterpene ether (TIEGMME), 16.8 ml of deionized water and 0.68 ml of 1 nitric acid in a round bottom flask. . The solution was heated to about 80 C with vigorous stirring (starting with heating and mixing) and refluxed for 1.5 hours to form a clear solution. The resulting solution was cooled to room temperature, then diluted to 25% by weight with ethanol, and filtered through a micron Tef 1 〇 (trademark) filter.

1270530 V. INSTRUCTIONS (22) Approximately 2 ml of the microporous vermiculite precursor was deposited on a 4 inch tantalum wafer and then spun at 250 0 revolutions per minute for 3 seconds. The resulting film was then gelled/aged in a vacuum chamber in the following manner. 1. Drain the chamber to 250 Torr. - 2· 15 m/liter (μ) ammonium hydroxide was heated and equilibrated at 45 π, introduced into the chamber, and the pressure was increased to 66 Torr over 1 Torr. 3. Refill the chamber with air and remove the film from the chamber for the next step of surface treatment/solvent exchange. Surface-Offected Oligomer/Polymer Treatment The surface treatment/solvent exchange of the film was carried out under the following conditions: 1. A reagent for surface treatment was prepared as described above. : The aged film was placed on a rotating chuck; rotated at 250 rpm. Rotate ί = about 30 ml of the above solution was dried while the film was dried and the solution was transferred 4 times out of the film: ί = film: 25 ° ° rpm / spin drying for 10 seconds, then the film was removed from the chuck and heat treated. Heat treatment

The film from the above process was then heated in air for two 60 second heating steps. Jude and 3 20C t: curing in the furnace 3. After a minute, the film was measured by a refractive index and thickness system (Wool lam) ellipsometer in the obtained film. The method is not to use the Wuleym to measure the dielectric constant. The dielectric constant is as follows: (4) ς雷 & M 〇 S 电 ^ ("MOSCAP") structure by standard 1270530 V, invention description (23) CV ( Current-voltage) curve method measurement. To form the M〇SCAp structure, aluminum is passed through a circular dot mask _ to the film, and the film is deposited on the back side of the wafer. Appropriate bias is applied to the MOSPCAP and then the capacitance is measured in megahertz. This method was used to determine the dielectric constant in all subsequent examples. Determining the mechanical strength of the film The force required to break the film is measured by standard method of plugging. The film to be tested is placed on the substrate wafer i' to lay an aluminum layer on top of the thin layer to prevent the epoxy from penetrating the pore structure. The epoxy:lip plug is then epoxidized to the upper portion of the aluminized film. - 曰 "β test force pulls the plug away from the film until a ': mouth: 'that is, the tensile force measured immediately before the bad as the bolting strength; m two is exactly as: For example, the tether is defined as mechanical damage The instantaneous force is measured in the following pounds per square inch ("KPSI"). The force of the piece and the measured film properties in thousands are summarized in the table below:

Example 2 This example illustrates the preparation of a dielectric film from 3 〇u MTAS-derived ruthenium, and the simplification derivative: 液 liquid treatment 疋 contains 1 reactive functional group.兀 口 物 重复 重复 羞 羞 羞 羞 羞 羞 羞 羞 羞 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 ς ς ς ς ς ς ς 76 3 g 3~ pent 1270530 V. Inventive Note (24) The ketone was added to a 25 〇 ml flask containing 2.67 g of water and placed in a magnetic stir bar. Then 32.7 *MTAS was added to the above pentanone/water compound with appropriate stirring and stirring was continued at room temperature overnight to yield a clear, colorless solution. The product was analyzed by & gas chromatography-mass spectrometry, and no enthalpy was found in the product. 'It means that MTAS has reacted. This solution was filtered through a 〇·2 μm Teflon (trademark) filter and used for the following surface treatment. Preparation of a microporous film A microporous vermiculite precursor prepared in the above example was deposited on a 4 inch tantalum wafer and then rotated at 2500 rpm for 30 seconds. The film was then gelled/aged in a vacuum chamber using the three-step process described in Example 1 above. The surface treatment/solvent exchange of the film was carried out by the four-step method described in Example 1 using the above surface modification reagent. The film obtained from the above method was then heated in a two-step process and cured under nitrogen as described in Example 1. The refractive index, dielectric constant and pull test were carried out as in Example 1. The measured film properties are shown in the table below. Table 2 Refractive Index Film Thickness (A) Dielectric Constant Pull (kilograms per square inch) 1.3144 6115 ~~"13 __3. 96 Example 3 ^Example Description 2%% core-derived alkane polymer solution The dielectric film is treated, and the MTAS-derived siloxane polymer has a reactive functional group per unit B.

Hydrolyzed MTAS for use as in Example 1 Obtained and prepared MTAS and 3-pentacral. Add 122 g of 3-pentanone.

1270530 V. INSTRUCTIONS (25) Place a magnetic stir bar in a 500 ml flask of 5 liters of water. Then, 30.5 g of MTAS was added to the above 3_pentane/water mixture, and continued = warm stirring overnight to give a clear, colorless solution. No gas was found in the product produced by gas chromatography _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ This solution was then passed through a 0.2 micron TeflQn (trademark) filter for use in the following surface treatment. 1 Preparation of microporous film = 2 ml of the microporous stone precursor prepared as described above was deposited on the = Shihwa wafer and then rotated at 2500 rpm for 3 sec. The film was then gelled/aged in a vacuum chamber using the three-step process described in Example 1 above. The film was subjected to a four-step method as described in Example 1 by a surface treatment/solvent exchange surface modifier, and then the film obtained from the above process was heated in a two-step process and cured as described in Example 1. The refractive index, dielectric constant and plug test were carried out as described in Example 1. The measured film properties are shown in the table below.

Example 4 This example illustrates the preparation of a dielectric film by treatment with 1% by weight of a MTAS-derived oxalate polymer solution.

Hydrolyzed MTAS for surface preparations. MTAS and 3-pentanone were obtained and prepared as in Example 1 above. Add 1 85 4 g of 3-ketone to a 500 ml flask containing 1.68 g of water and place the magnetic stir bar

Page 29 1270530 V. Inventive Note (26); then, under appropriate mixing, 20.6 grams of "force to the above 3_ pentane / water mixture, followed by stirring at room temperature overnight, resulting in a clear, & color solution The product was analyzed by gas chromatography-mass spectrometry, and Mm was not found in the product, meaning that MTAS was reacted. The solution was then filtered through a 微米2 μm Ten〇n (trademark) vessel, and the following surface treatment was performed. Use a microporous film to make + about 2 ml of the above example! The prepared microporous vermiculite precursor is deposited on a 1 inch/inch wafer, and then rotated at 250 0 rpm for a second. In the direct work:: The film was gelled/aged by the three-step method described in Example 1 above: the surface treatment/solvent exchange was carried out by the four-step method described in Example 1 only. The two-step method is heated and solidified in the nitrogen gas from the above process. The refractive index, the number of media/film and the test are carried out as described in the example. The measured properties of the thin media are shown in the following table: Refractive index [•1933 number example 5^ film thickness (A) —~587Ϊ 109^.MTAS-derived 矽Oxygen preparation is prepared by the solution of the leaching solution of the ruthenium, and the ruthenium film, the MTAS-derived oxirane polya31.5 reactive functional groups. The MTAS is as in the above example! Obtain and prepare the mtas*3_ word to add 5 grams of water containing 2 grams. . In a milliliter flask, put: 2 magnetic

Page 30 1270530 V. Description of invention (27). Then, 24.8 g of Μ T A S was added to the above 3-pentanone/water mixture under appropriate dropping, and stirring was continued at room temperature overnight to give a clear, colorless solution. The product was analyzed by gas chromatography-mass spectrometry, and no product was found in the product, meaning that MTAS had reacted. This solution was then filtered through a 微米 2 μm Tefl〇n (trademark) filter for use in the following surface treatment. Preparation of microporous film Approximately 2 ml of the microporous smectite precursor prepared as described in Example 1 above was deposited on a 4 inch tantalum wafer and then spun at 2500 rpm for 3 seconds. The film was then gelled/aged in a vacuum chamber using the three-step process described in Example 1 above. The surface treatment/solvent exchange of the film was carried out by the above-described surface modifying agent by the four-step method described in Example 1. The film obtained from the above process was then heated in a two-step process, and the refractive index, dielectric constant, and plug test were carried out as described in Example 。. The measured film properties are shown in the table below. , , and refractive index (A) 1·1766 6694

This example is for comparison and explanation only for ordering a single film. These films are not coated with a polymer/polymer. The complex A microporous film was subjected to about 2 ml of a microporous vermiculite wafer prepared as described in the above Example, and then rotated at 2,500 rpm for 3 seconds. The film was subsequently gelled/aged in a vacuum chamber using the procedure of Example 1 bis.

Page 31 1270530 V. INSTRUCTIONS (28) The surface treatment/solvent exchange of the film was carried out according to the method of Example 1, but when preparing the surface modification reagent, 5 g of MTAS and 95 g of 3-pentanone were mixed (Example 1, respectively) Said) to form a clear, colorless solution. The film obtained from the above process was then heated in a two-step process, as in Example 1 above, under nitrogen. The refractive index, dielectric constant and plug test were carried out as described in Example 1. The measured film properties are shown in the table below. Table 6

Example 7

* This example illustrates the preparation of a thin film by treatment with a (monomer) formamidine surface reactant followed by treatment with 25% MTAS-derived alumoxane polymer solution.

And the Μ T A S derived Shi Xi 夤ψ ^ ifn ^ ^ ^ w A 7 rolling sedimentation compound repeat unit contains an average of 15

Reactive functional group. J · 〇 表面 表面 修 MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT Gram 3 - _ _. Then in the appropriate Jieji; will 3 above the solution. To include hydrolyzed MTAs, 7 plus

Filter through a 0.2 micron buffer before processing.斤 侍 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Gel/Aging: The knife is rotated for 30 seconds. Use the following secluded room to evacuate the chamber to 250 Torr.

Page 32 1270530

V. INSTRUCTIONS (29) 2. Heat and equilibrate 15 mol/L ammonium hydroxide to the chamber and increase the pressure to 66 Torr. 5, knife 5 lead 3 · The chamber is sucked to 250 Torr. 4. Heat and balance 15 moles/liter of hydroxide. 〇 Into the chamber to increase the pressure to 66 Torr. 5 minutes, 5 minutes, refill the chamber with air, and remove the aged film from there. The aged film is then subjected to surface treatment/solvent exchange. The solution 1 used for the surface treatment/solvent exchange was prepared as described in Example i. The MTAS prepared as a table was dissolved in 3-pentanone to give 5% by weight of mtas: The surface treatment/solvent exchange of the film was carried out under the following conditions.戍 & 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Each film was transferred to the enamel film at 2 rpm (4) and dried for 1 〇 second, and was removed from the chuck, and 175 and the film were respectively placed in the process gas. C heat treatment for 60 seconds to produce a dried film obtained by drying the dried matrix/valency polymer. The hydrolyzed film 1 is used for the surface treatment/solvent treatment from the above Conditions: 25 2 = The dried film was placed on a rotating chuck and rotated at 250 rpm. Under two Si drying, about 3 ml of the above hydrolyzed fission solution was spun on the diaphragm for 20 seconds.

ΗΒ page 33 1270530

5. Description of the Invention (30) + 3· The film was then spin-dried at 2,500 rpm for 1 Torr, and then the film was removed from the chuck and subjected to heat treatment. Subsequently, the film obtained from the above process was heat-treated at 175 and 32 〇 0 Torr for 60 seconds. It was then cured in a heating oven at 4 Torr for 30 minutes under nitrogen. The refractive index and thickness of the resulting film were measured by a Woo 11 am ellipsometer. Dielectric Constant Measurement The dielectric constant was determined by the standard cv (current_voltage) curve technique as described in Example 1 above. Film Mechanical Strength Measurement The cohesive strength of the film was measured by a plug test as described in the Examples above. The modulus of the prepared film was measured by a χρ-type nano hardness tester (Nan〇 Indenter XP) [MTS Systems, 〇ak Ridge, tn 3783〇]. The measurement provides the modulus of the film in gigapascals (1 〇 6 Newtons per square meter). Table 7

Refractive index film thickness (A) Dielectric constant Cohesive strength (thousand pounds per square inch) Modulus (gigapascals) Case 7 data (multifunctional polymer treatment) L2565 7823 2.4 8.3 6.3 Paste 6 data (without MTAS monomer treatment of water) 1.1665 7518 1.98 1.5 N/A

It can be understood from Table 7 above that the performance of a film treated with a typical polyfunctional polymer/oligomer control is relatively improved over that of a film treated with only a MTAS monomer. Its cohesive strength is increased by 5 times, and the dielectric constant is moderately increased.

Page 34 1270530 V. Description of invention (31) Plus. EXAMPLE 8 This example illustrates the preparation of a dielectric film using a 5% monomeric methylation reaction (MTAS monomer) and 25% of a MTAS-derived alkoxylate polymer and the MTAS derived oxime The oxyalkylene polymer has an average of 1.5 reactive functional groups per repeating unit. Hydrolyzed MT AS for complex surface modification:

MTAS and 3-pentanone were obtained and prepared as in Example 1 above. 25 g of order 43 was mixed with 750 g of 3-pentanone, and then 5.3 g of water was added while the solution was properly mixed. The solution was then stirred overnight. 5.4 g of MTAS was added to the 8.5 5 gram clear solution obtained from the subsequent steps. The resulting clear, colorless solution was passed through a 0.2 micron filter prior to surface treatment. A microporous film was prepared, a microporous vermiculite precursor was synthesized, and sputter deposited on an 8 inch tantalum wafer and then gelled/aged in a vacuum chamber as described in Example 7 above. The surface of the gold/oligomer is decomposed into the MTAS polymer solution of the axis 3. The surface treatment/solvent exchange of the film uses the following conditions: J turns the aged film onto the rotating chuck and

2. Rotate about q on the film for 20 seconds without drying the film. 3 () ml of the hydrolyzed MTAS solution and then spin-dry the film at 25 rpm for 1 , second, then

Page 35 1270530

The chuck is removed and thinned and then self-heated for 60 seconds. The resulting film was measured. The membrane is heat treated. Above, the film of 釭 = 丨 7 5 and 3 2 在 in the air. Then, it is cured in a heating furnace at 400 ° C for 5 minutes in nitrogen. The refractive index and thickness are obtained by the Woolham ellipsometer.

This method illustrates a simplified co-processing method for the sulfonation of surface stanols from MTAS monomers and hydrolyzed MTAS polymer groups (with examples; compared to vehicle I. The result is the physical properties of the film (dielectric constant, The film properties obtained by the method of Example 7 were similar. Further Example 9 This example illustrates the treatment of a ruthenium film with a decaneization reagent (MTAS monomer) followed by a 25% MTAS-derived oxirane polymer solution\ And the MTAS-derived methoxyalkane polymer contains a reactive functional group per repeating unit. , , , J i · 5

For the surface modification of the huangbei, the MTAS is used to mix 250 mM MTAS with 750 g of 3-pentanone, then add 1 5 · 3 g of water, and the same k ▲ tax mix > The solution was then stirred overnight. The resulting clear, colorless solution was passed through a 〇 2 μm filter prior to use in the surface treatment. Further, a microporous film was prepared to synthesize a microporous stone precursor, which was spin-deposited on an 8-inch tantalum wafer and then gelled/aged in a vacuum chamber as described in Example 7 above. ,

O:\62\62459.ptd Page 36 1270530 V. Inventive Note (33) Lijin-Rabbit Reclamation Surface Treatment a I The method of Example 8 is used to hydrolyze the MTAS polyant composition of the present example. Perform surface treatment/solvent exchange of the film to decompose MTAS “Material °c plus H from I, tt ί ί, 7, film * 2 gas at 175 and 3 2 〇 respectively;; c. Curing in the furnace for 30 minutes, and the thickness is as described in Example 1 above. 5553⁄4-1.2826 6439 Table 9 Strength (thousand pounds) — 8729 ^ ___2 Λ ^ This method shows a @ f, + γ - One --- thin like physical properties = electric method * compared with example 8), and provide a class although it has been described that the number of electric enthalpy, cohesive strength). should be recognized without leaving the invention The examples, but those skilled in the art, such changes and improvements are subject to change and improvement. The various references are intended to be used to disclose the scope of the meat. All of them are referred to in this way;

O:\62\62459.ptd Page 37 1270530

O:\62\62459-930730.ptc第38页

Claims (1)

Ϊ270530 fe:崇号89111054 Revision 95. Heart to find the supplement of the shape of the material containing less micro-production 10 10 for the anti-system patent patent __-------------^ _ _______ 1 A method of treating a vermiculite film on a substrate, comprising reacting a cerox-containing vermiculite film with a composition comprising a surface modifying agent, wherein the sterol-containing vermiculite film is present on a substrate, wherein the reaction Performing a reaction between the surface modifying agent and the stone film containing the linalkanol to form a hydrophobic coating on the film, and wherein the surface modifying agent comprises at least one stone on the stone film of the shixi A polymer or a polymerized oxime for the reaction of the sulphuric acid group. The method of claim 1, wherein the reaction is carried out in the presence of a solvent or a cosolvent. 3. The method according to claim 1, wherein the vermiculite film is a porous dielectric film, and the microporous dielectric film has a pore structure comprising stanol, wherein the reaction is carried out for a sufficient period of time to make the surface The modifier produces a treated microporous vermiculite film having a dielectric constant of 3 or less. 4. According to the method of claim 3, a microporous vermiculite film having a dielectric constant ranging from 1.1 to 0 is produced. 5. According to the method of the first application of the patent scope, the temperature in the range of °C to 300 °C. 6. According to the method of the first application of the patent scope, the time is from 1 second to 1 hour. 7. A polymer or oligomer according to the method of claim 1 and wherein the polymer or oligomer comprises a functional group which will react with the chopped alcohol. 8. The method of claim 7, wherein the surface modifying agent is prepared by reacting a suitable monomer with water in a solvent. Wherein the reaction is based on wherein the reaction is based on the surface modifier O:\62\62459-950822.ptc Page 39 1270530 _ Case No. 89110054 Revision of the year of the month _* VI. Patent application scope 9. According to the method of claim 2, wherein the solvent or cosolvent system It is selected from the group consisting of ethers, esters, ketones, glycol ethers, hydrocarbons, chlorinated solvents, low viscosity oxiranes, and mixtures thereof. The method of claim 2, wherein the co-solvent is selected from the group consisting of ethers, esters, ketones, glycol ethers, hydrocarbons, chlorinated solvents, low-viscosity, and a mixture thereof. 1 1. The method of claim 8, wherein the single system is selected from the group consisting of decane, decane, decane, carbon decane, and mixtures thereof. 1 2. The method of claim 8, wherein the water system is present in the cosolvent at a concentration of from 0.5 to 10% by weight of the cosolvent. 1 3. The method of claim 8, wherein the water system has a molar ratio of from 0.5 to 0.5:1.5 to 1.5 in the monomer during the reaction. presence. The method of claim 8, wherein the monomeric compound is selected from the group consisting of decyltriethoxydecane, phenyltriethoxydecane, decylaminodecyldecane, A group consisting of hydrazine (dimethylamino)phenyl decane, hydrazine (diethylamino) decyl decane, and mixtures thereof. The method of claim 1, wherein the composition comprises a polymer or polymer surface modifier and a monomer surface modifier, wherein the single system and the stanol group on the vermiculite film reaction. 1 6. The method of claim 1, wherein the vermiculite film is treated with a monomeric surface modifying agent, wherein the single system reacts with a sulphuric acid alcohol group on the vermiculite film. 1 7. The method according to item 8 of the patent application, further comprising O:\62\62459-950822.ptc Page 40 1270530 _ Case No. 89110054 ?. Year of the F-day correction _; VI. After the patent application scope is completely reacted, add at least one additional monomer to the solution, wherein the monomer And reacting with a stanol group on the vermiculite film. 18. The method of claim 15, wherein the monomeric surface modifying agent is selected from the group consisting of decane, decane, decane, carbon decane, and mixtures thereof. The method of claim 15, wherein the monomer surface modifier is selected from the group consisting of ethoxylated tridecyl decane, diethyl methoxy decyl decane, methyl triethoxy methoxy. Decane, phenyltriethoxydecane, diphenyldiethoxycarbonyl calcination, trimethylethoxycracking, trimethylmethoxycranane, 2-tridecyloxy-2 -penten-4-one, n-(tridecylmethyl decyl) acetamide, 2-(trimethylformamido)acetic acid, n-(trimethylcarbenyl)imidazole, tridecyl hydrazine Alkyl propiolate, trimethylmethanyl (trimethylmethoxymethyl)-acetate, nonamethyltriazane, hexamethyldioxane, hexamethylene dioxane , tridecyl decyl alcohol, triethyl decyl alcohol, triphenyl sulphate, tri-butyl bis-decyl alcohol, diphenyl decane diol, hydrazine (dimethylamino) methyl decane , hydrazine (diammonium) phenyl decane, decyl (nonylamino) decane, decyl trimethoxy oxetane, decyl fluorenyl (hydrazinoethyl ketoxime) decane, decyl trichloro decane and a group of mixtures. A dielectric film produced by a method of reacting a cerium-containing vermiculite film with a composition comprising a surface modifying agent, wherein the stone-containing stone film is present in a substrate, wherein the reacting proceeds such that the surface modifying agent reacts with the stanol-containing vermiculite film to form a hydrophobic coating on the film, and wherein the surface modifying agent comprises at least one and the cerium-containing alcohol Oligomer or polymerization of the reaction of the group on the stone O:\62\62459-950822.ptc Page 41 1270530 _ Case No. 89110054 Leap Year A Month Day Amendment _^ VI. Application for patent scope. 2 1 . The dielectric film according to claim 20, wherein the film is subjected to a plug test to exhibit a film breaking strength of more than 2 psi, and a dielectric constant of from 1 to 1 to 3. 0. . 2 2 . An integrated circuit comprising at least one dielectric film according to claim 20 of the scope of the patent application. 2 3. According to the integrated circuit of claim 22, the surface modifying agent is prepared by reacting a suitable monomer with water in a solvent. 2 4. The integrated circuit of claim 23, wherein the solvent is selected from the group consisting of ethers, esters, ketones, glycol ethers, chlorinated solvents, low viscosity alkane, and mixtures thereof. 2 5 . The integrated circuit of claim 23, wherein the monomer is selected from the group consisting of a decane, a decane, a decane, a carbon decane, and a mixture thereof. 2 6 . The integrated circuit of claim 23, wherein the water system is present in the cosolvent at a concentration of from 0.5 to 10% by weight of the cosolvent. The integrated circuit of item 26, wherein the water is present in the single system at a molar ratio of from 0.5 to 1.5 to 1.5:0.5 during the reaction. 2 8. The integrated circuit according to claim 24, wherein the monomer compound is selected from the group consisting of decyltriethoxydecane, phenyltriethoxydecane, and decylamino. A group consisting of decane, hydrazine (dimethylamino)phenyl decane, hydrazine (diethylamino) decyl decane, and mixtures thereof. O:\62\62459-950822.ptc第42页