TW200531183A - Repairing damage to low-k dielectric materials using silylating agents - Google Patents

Abstract

A method for restoring hydrophobicity to the surfaces of organosilicate glass dielectric films which have been subjected to an etchant or ashing treatment. These films are used as insulating materials in the manufacture of integrated circuits to ensure low and stable dielectric properties in these films. The method deters the formation of stress-induced voids in these films. An organosilicate glass dielectric film is patterned to form vias and trenches by subjecting it to an etchant or ashing reagent in such a way as to remove at least a portion of previously existing carbon containing moieties and reduce hydrophobicity of said organosilicate glass dielectric film. The vias and trenches are thereafter filled with a metal and subjected to an annealing treatment. After the film is subjected to the etchant or ashing reagent, but before being subjected to an annealing treatment, the film is contacted with a toughening agent composition to restore some of the carbon containing moieties and increase the hydrophobicity of the organosilicate glass dielectric film.

Description

200531183 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for restoring the hydrophobicity of the surface of an organic silicate glass dielectric film, wherein the organic silicate glass dielectric film is used to remove at least Some of the previously existing carbon-containing moieties were subjected to etching or ashing processes, thereby causing the film to have reduced hydrophobicity. These films are used as insulating materials in the manufacture of semiconductor devices such as " 1C " to ensure low dielectric constant and stable dielectric characteristics in these films. [Prior Art] Tunneling integrated circuits With the reduction in the feature size of the device, interconnect RC delay, power consumption, and signal crosstalk issues have become increasingly difficult to resolve. ## Low for interlayer dielectric (ILD) and intermetal dielectric (IMD) applications The integration of dielectric constant materials will help to solve these problems. Although efforts have been made to apply low dielectric constant materials to integrated circuits, there has long been a need for processing methods and such materials in this technology. The dielectric and mechanical properties are further optimized. The scaling of devices in integrated circuits in the future will obviously require the use of low dielectric constant materials as part of the interconnect structure. = Low dielectric constant redundant at sub-100 nm generations Most alternatives to materials are carbon-containing films formed by any of CVD or spin coating methods. In subsequent processing steps such as the use of electro-wet or wet photoresist In the process of plasma etching and photoresist removal, these low] ^ materials are significantly damaged, which results in the low adjacent to the etched surface] ^ the gas addition in the material and the carbon loss generated from it. In addition to higher effective k values, the resulting structure is susceptible to void formation, outgassing, and blister formation. These voids can in turn lead to an increase in bubble leakage current and a reduction in collapse voltage at high voltages. 96350.doc 200531183 The present invention describes a method of reducing the damage and the problems that arise by treating the wafers with a rhenium silylating agent after the damage has occurred.

It has been reported that the use of non-destructive ashing chemistry (such as H2 / He) can reduce carbon losses and related issues. In this regard, see I. Berry, A. Shiota, Q. Han, C. Waldfrted, M. Sekiguchi & O. Escorcia, Proceedings-Electrochemical Society, 22, 202 (2002); and A. Matsushita, N. Ohashi , K. Inukai, HJ Shin, S. Sone, K. Sudou, K. Misawa, I. Matsumoto and N. Kobayashi, Proceedings of IEEE

International Interconnect Technology Conference, 2003, 147 (2003). Alternatively, it has also been shown that ashing post-treatment with carbon supplementation can restore hydrophobicity and reduce the dielectric constant. It was also shown that the ashing treatment after carbon supplementation can restore water repellency and reduce the dielectric constant. In this regard, see YS Mor, TC Chang, PT Liu? T. M. Tsai, CW Chen? ST Yan, CJ Chu5 WF Wu, FM Pan, W. Lur and SM Sze, Journal of Vacuum Science & Technology, B , 2 (4), 1334 (2002); and PG Clark, BD Schwab and JW Butterbaugh, Semiconductor International, 26 (9), 46 (2003). One advantage of the latter approach is that it allows the use of fairly complete (~ 611 ^ 81 & 1) 1 丨 81 ^ (1) #etching and ashing methods. For this purpose, an ashing treatment is required to repair the damage that caused the porous SiCOH-based low-k materials. This treatment causes carbon to be replenished to the low-k film, thereby restoring hydrophobicity and resistance to further damage during wet cleaning operations. In addition, if the repaired low-k material is found to be resistant to void formation (the void formation 96350.doc 200531183 usually occurs in untreated porous low-layer interlayer dielectric regions during copper annealing), then the Post-ashing is desirable. Silylating agents ("toughening agents") can methylate the surface of SiO2-based materials. Covered exposures include gas phase exposures (with or without plasma), spin coatings, and supercritical CO2. Generally, SiCoH-based porosity is low in the Cu damascene process so that void formation in ILD is likely to occur. After the toughening agent treatment, the resulting structure is significantly more resistant to void formation. Without being bound by any particular theory or mechanism, Xianxin Plasma damage is caused by carbon loss in the dielectric by replacing the Si-CH3 bond with a Si-OH bond. In the damaged porous dielectric, the pore surface is now covered with Si_OH bond. In the presence of tensile stress (such as after Cu annealing), adjacent Si_OH groups can condense, thereby causing local densification. Evolving reaction products and molecular stretching due to the new chains formed cause voids to occur near the center of the ILD space. The toughener prevents the formation of voids by replacing most Si_0H bonds with Si-0-Si-Rn bonds, which avoids condensation reactions. As a result, the formation of voids does not occur. " Toughening treatment performed after the formation of electrical trenches and channels, and after the engraving and ashing steps, repairs the carbon loss and damage of low-k materials. This method prevents voids, and these low-k materials can withstand the internal stress caused by the annealing treatment of the metal filling the trenches and channels. Toughening is performed by exposing the surface of the wafer to a liquid or gaseous form of 曱 silylating agent for a time sufficient to complete the reaction with the damaged area. If necessary, high temperature baking can be performed to remove residual solvents and excess toughener. After applying the toughening agent or immediately after the baking step, optionally use commercially available low-k dielectric compatible chemicals to perform wet cleaning operations. 96350.doc 200531183: where :: have :: _ before processing Dehydration can be performed—An unpatterned low-k dielectric film can be used to withstand etching and ashing, followed by a toughener treatment to verify the effectiveness of the toughener treatment. Successful toughener treatment results in an increase in carbon concentration, which can be measured by FTIR, EDX or XPS technology. In addition, an increase in the water contact angle can be seen, which proves the hydrophobicity f of the treated surface. The film treated with the accelerator is also shown in comparison with the film that has not been treated with rhenium! The ash / ashing film treated with-has a low dielectric constant measured from C々. In patterned wafers, the effectiveness of the accelerator treatment was demonstrated after electroplating copper by reducing or eliminating voids in the low-k dielectric in the narrow spaces between Cu trenches after copper annealing. Its effectiveness can be demonstrated by a lower profile change in the trench or channel after exposure to a reactive solvent. [Summary of the Invention] "Provided by Ming-A method for preventing stress-induced void formation in an organic stone salt-on-salt glass dielectric film on a substrate, which has been patterned to form therein Channels and trenches, and the plexiglass dielectric film is then subjected to at least-a purpose of removing at least-the carbon-containing portion that is present first and reducing the organic silicate glass dielectric = film hydrophobicity And then filling the channels and trenches with a metal and then subjecting the metal to an annealing treatment, the method includes after undergoing at least one etchant or ashing agent, but filling the trenches with a metal: the channels and trenches In other words, contacting the organic petrolate glass film with the activator composition of Dinghandu and the contact time period should be 96350.doc 200531183 can effectively restore at least some of the carbon-containing portion to Organic silicate glass dielectric film and increase the hydrophobicity of the organic silicate glass dielectric film. The present invention also provides a method for forming a microelectronic device, comprising: Organic silicate glass dielectric film coating on a substrate; b) forming the channel pattern and the trench in the organic acid salt of broken glass dielectric films' stone and that the organic acid Xi glass dielectric film is subjected to at least one

A process for removing at least a part of the previously existing H 3 part and reducing the hydrophobicity of the organic silicate glass dielectric film; C) the organic silicate glass dielectric film When the film is in contact with a certain concentration of the toughener composition and the contact goes through a period of time, the weight of the four layers should be effective to increase the hydrophobicity of the organic silicate glass dielectric film; d) filling the channels and channels with a metal Trenches; and e) subjecting the metal to an annealing treatment. The present invention provides a microelectronic device produced by a method including the following steps: a) coating an organic silicate glass dielectric film on a substrate; b) applying the organic silicate glass dielectric film on the substrate; To form a pattern of channels and trenches, and to make the organic silicate glass dielectric dielectric panic meridian at least one other purpose is to remove at least a part of the pre-existing jealousy, and reduce the organic Hydrophobic treatment of silicate glass dielectric film; 0 The organic silicate glass dielectric film is brought into contact with a sintering agent / sphericity initiator composition, and a part of this contact should be able to pass through Effectively increase the hydrophobicity of the organic silicate glass dielectric film; low d) fill the channels and trenches with a metal, and 96350.doc -10- 200531183 e) subject the metal to an annealing treatment. [Embodiment] In the case of the present invention, because " electrical materials " permits faster signal propagation with a low dielectric constant generally lower than 3, reduces capacitance effects and crosstalk between conductors, and reduces drive product The voltage of the bulk circuit, so it is a particularly desirable material with a low dielectric constant is a dioxygen that can be used as a foamed dielectric material. In order to obtain the lowest possible dielectric value, air is introduced into the dioxin dielectric material. Air has a dielectric constant of 1, and a relatively low dielectric constant (" k ") is achieved when 4 is used in a diatomite dielectric material of nano-nano or nano-grade silk materials. It should be understood that when the term "stone dioxide" is used, unless the functional group "S i 02" is specifically mentioned, the term "dioxygen" as used herein, (for example, a porous dielectric film) It is intended to refer to a dielectric film prepared by the method of the present invention from an inorganic glass base material (e.g., a t-starting material containing any or multiple-based dielectric precursors). It should also be understood that the use of the singular terminology herein is not intended to be limited to this, and includes the plural and plural, where appropriate, for example, the exemplary method of the present invention can be described as being applied to a conjunctival, diaphragm, but I would like to borrow Produce multiple films as required by the methods described, exemplified, and applied for. As used herein, the term " film " relating to silicon dioxide dielectric material is intended to encompass any suitable form or shape of the silicon dioxide dielectric depending on the situation. Because nanoporous silica is similar to precursors, such precursors include organic processes such as tetramethoxy 2 (a TMOS ") and / or tetraethoxy stone yaki (,, TE0s "). Instead of, Yuan (/, is used for the spin-on glass ("s〇G") and chemical gas 96350.doc 200531183 phase deposition (" CVD ") silica used in Dangzhao), so nanometer porous Silicon dioxide is attractive. The terms " void, " as used herein, mean a substance in which a substance is replaced by a gas or a free volume in which a vacuum is created. The composition of the gas is usually not critical And suitable gases include relatively pure gases and mixtures thereof (including air). The nanoporous polymer may include a plurality of pores. The pores are generally spherical, but may alternatively or additionally have any suitable shape, including a tube , Layered, disc-like, or other shapes. The pores may be uniformly or randomly dispersed within the porous polymer. It is also contemplated that the pores may have any suitable diameter. It is further encompassed that at least some of the pores may be connected to adjacent pores Build one There was a significant amount of connected or via ,, open "architecture of the porosity. Nanoporous silicon dioxide films have been previously manufactured by many methods. Suitable silicon-based precursor compositions and methods for forming nanoporous silicon dioxide dielectric thin films are, for example, by commonly-owned U.S. Patent Nos. 6,048,804, 6,022,812, 6,41,149 No. 6,372,666, No. 6,509,259, No. 6,218,497, No. 6,143,855, No. 6,037,275, No. 6,042,994, No. 6,048,804, No. 0,090,448, No. 6,126,733, No. 6,140,254, Nos. 6,204,202, 6,208,041, 6,318,124, and 6,3 19,855 are described, all of which are incorporated herein by reference. Other dielectrics and low-dielectric materials include inorganic-based compounds, such as the Shixian compounds disclosed in US Patent Application No. 10/07891 9 filed on February 19, 2002 in the Common Assignment Application; (Examples) In terms of

Honeywell International lnc. (NANgLASS® and HOSP®). The material can be spin-coated on the surface, the material 96350.doc -12- 200531183 can be impregnated, spray-coated, chemical vapor deposition ((: ¥) 3), roller-coated on the surface, the A material is dripped onto the surface and / or a material is coated on the surface to coat the dielectric and low-dielectric materials. Dielectrics suitable for use in the present invention include CVD deposition materials, such as carbon-doped oxides, for example from a 卯 Matenals, lnc. Black Diamond, commercially available from Koral, Aurora available from ASM, and Orion available from Trikon. As described herein The phrase "spin-coating material", "spin-coating organic materials, spin-coating composition" and, spin-coating inorganic compositions, are interchangeable and their private use can be made by spin-coating. Solutions and compositions on a substrate or surface. Examples of silyl compounds include siloxane compounds such as methylsiloxane, methylsilsesquioxane, phenylsiloxane, phenylsilsesquioxane , Fluorenylphenylsiloxane, methylphenylsilsesquioxane, Azazan polymers, silicate polymers, and mixtures thereof. The covered silazane polymers are perhydrosilazane, which has a transparent `` polymer main chain that can be connected to a chromophore. Spin-on glass materials It also includes sintered sintered polymers and interlocking polymers, hydrosiloxane polymers of the general formula (H ^ .GSiOmA, and hydrogen sesquiterene sintered polymers with formula (HSiOK5) x, where X is greater than about 4. Also includes copolymers of 氲 silsesquioxane and alkoxyhydridosiloxane or hydroxyhydrosiloxane. Spin-coated glass materials also include organic hydrogenated stones of the general formula QSi〇i 5 2 Oxygen fired polymers and organic hydrogenated sesquioxane oxygen fired polymers of the general formula (HSiO! ^ (RSiO! 5) m, where m is greater than zero and the sum of ^ and 大于 is greater than 4 and R is a calcined or aryl group Some suitable organic hydride sintered polymers have a sum of 11 and 111 from about 4 to about 5000, where r is Cl_c2Gfluorenyl 96350.doc -13-200531183 or c ^ -c] 2 aryl. The Other organic hydrogenated siloxanes and organic hydrogenated silsesquioxane polymers are alternative spin-on polymers. Some special features Specific examples include hydrosiloxanes such as: methylhydrosiloxanes, ethylhydrosiloxanes, propylhydrosiloxanes, tertiary butylhydrosiloxanes, phenylhydrosiloxanes, and alkanes Hydrogenated silsesquioxane, such as: methyl hydrogenated silsesquioxane L, ethyl hydrogenated silsesquioxane, propyl hydrogenated silsesquioxane, third butyl hydrogenated silsesquioxane, Phenyl hydrogen silsesquioxane, and combinations thereof. Several covered spin-coated materials are described in the patents and applications granted below: US Patent No. 6,505,497, No. No. 6,365,765, No. 6,268,457, No. 6,177,199, No. 6,358,559, No. 6,218,020, No. 6,361,820, No. 6,218,497, No. 6,359,099, No. 6,143,855, No. 6,512,071, November 2001 US Patent Application No. 10/001143 filed on May 10, PCT / US00 / 15772 filed on June 8, 2000, and pCT / us 00/00523 filed on January 7, 1999, which The entire text is incorporated herein by reference. Organic hydridosiloxane and organic siloxane resin solution can be used to form clathrate sintered polymer film. It is suitable for manufacturing various electronic devices, microelectronic devices, especially semiconductor integrated circuits, and for electronics and semiconductors. Various laminated materials of the module, including a hard cover curtain layer, a dielectric layer, an etch stop layer, and an embedded engraved stop layer. These oxyhydrogen sintered resin layers are compatible with other materials that can be used in laminated materials and devices, such as adamantane-based compounds, bisadamantane-based compounds, silicon core compounds, organic dielectrics, and naphthalene. Find porous dielectrics. The compounds covered by this document that are quite compatible with the organohydrogensiloxane resin layer are disclosed in the following patents: US Patent No. 96350.doc -14- 200531183 Liability Nos. 6,214,746, 6,171,687, 6 No. 172,128, No. 6,156,812, U.S. Application No. 60/350 187 filed on January 15, 2002, U.S. Patent Application No. 09/538276, U.S. Patent Application No. 09/544504, US Patent Application No. 09/58785 1 and US · 60/347195 filed on January 8, 2002, PCT applications PCT / US01 / 32569 filed on October 17, 2001, and December 31, 2001 The PCT application PCT / US01 / 50812 filed, these patents are incorporated herein by reference. A suitable organohydrogensiloxane resin used herein has the following general formula: [H-Si ^ UR-SiO ^ k Formula ⑴ [H〇.5-Si1.5.i.8] n [R〇.5. i.〇-Si01.5.1 < 8] m Formula (2) [Ho-Ko-SUJR-SiOidm Formula (3) [H-Si15] x [R.Si01.5] y [Si02] z Formula ⑷ where: : The sum of η and m or the sum of X, y, and z is about 8 to about 5000, and ㈤ or γ is selected so that the carbon-containing component is less than about 40% (low-carbon organic content = Lossp). ) Or present in an amount greater than about 40% (high carbon organic content = 1 1081>); R is selected from substituted and unsubstituted, normal and branched chain alkyl (methyl, ethyl, Butyl, propyl, pentyl), alkenyl (ethenyl, allyl, isopropenyl, cycloalkyl, cyclodiyl, aryl (phenyl, phenylfluorenyl, Zeyl, allyl and phenanthrene) Group) and mixtures thereof; and the specific mole percentage of carbon-containing substituents is a function of the ratio of the amount of starting material. In some experimental examples, the mole percentage is a mediator, and the mole percentage is 15 Carbon-containing substitutions in the range of about 25 mole percentages are known as particularly advantageous results. Some Hsp In embodiments, favorable results are obtained with carbon-containing substituents in which the mole percentage is in the range of about 55 mole percentage to about 75 mole percentage. The dielectric constant is in the range of about 1.5 to about 4. Nanoporous dioxide dioxide dielectric film can also be used as one of the layers. Lay (layed called nanoporous silicon dioxide film as a silicon-based precursor, aging or condensation in the presence of water) and Sufficient heating to completely remove all pore-forming molecules and form voids in the film. The silicon-based precursor composition contains a monomer or prepolymer having the formula, where "R" is independently selected from alkyl, aryl, hydrogen, and In combination, L is an electronegative moiety, such as an alkoxy group, a carboxyl group, an amine group, an ammonium amine :, a functional compound, an isocyanate, and a combination thereof, and χ is an integer ranging from 0 to about 2 and y is an integer in the range of about 0 to about 4. Other nanoporous compounds and methods can be found in the following patent cases: U.S. Patent Case No. 687, No. 6 ^, No. 6, No. 6,214,746, No. 6,3i3, i85: Nos. 6,380'347 and 6,38〇, 27 (), both of which The way of citation is incorporated herein. The words "cage-like structure", "cage-like molecule," and "cage-like compound" are intended to be used interchangeably and refer to a molecule having at least 1 () atoms, The atomic systems are arranged so that at least one atomic bridge covalently connects two or more atoms of the ring system to σ, and the cage structure, cage molecule or cage compound includes a plurality of covalently bonded atoms. A ring formed, in which the structure, molecule, or compound defines a volume such that a point located in the volume does not leave the volume without crossing the ring. The atomic bridge and / or the ring system may contain-or more heterogens and it may be aromatic, partially saturated or non-saturated. The further 茏 -like structures covered include spherical shell-like carbon molecules and ethers with ether bridges. For example, adamantane or diadamantane is considered to be a 茏 -like structure, and because naphthalene compounds or aromatic spiro compounds do not have or atomic bridges', naphthalene compounds or aromatic compounds are not considered within the scope of this definition. Group spiro compounds are considered cage-like structures. The covered dragon-like compounds are not necessarily limited to carbon atoms only, but may include heteroatoms such as N, s, 0, P, and the like. Heteroatoms can be advantageously introduced into non-quadrilateral bond angle configurations. Regarding the substituents and derivatives of the covered cage compounds, it should be recognized that many substituents and derivatives are appropriate. For example, 'when the caged compound is relatively hydrophobic', it can attract hydrophilic substituents, increase solubility in a hydrophilic solvent, or vice versa. Side chain groups are added to the cage compound. It is further encompassed that suitable substituents may also include thermally labile groups, nucleophilic and electrophilic groups. It should also be understood that functional groups ( For example, to promote cross-linking reactions, derivatization reactions, etc.) Cage molecules or compounds as described in detail herein may also be groups attached to the polymer backbone, and thus can form the following nanoporous materials: 苴 中Cage compounds form a class of voids (inside the molecule), and at least a portion of the main chain is crosslinked with itself or another-backbone to form another type of void (intermolecular). On October 18, 2001 Additional cage molecules, cage compounds and variants of these molecules and compounds are described in detail in the Japanese application ^ ct / us〇i⑽ς. The full text of this document is incorporated herein by reference. ^ The polymers covered are also Can include A wide range of functional or structural parts, including aromatic systems and functional groups. In addition, suitable polymers may have many configurations, including homopolymers and heterogeneous materials. Moreover, alternative polymers—bonded, hyperbranched, or three-dimensional. The molecular weights of the contained compounds are across a wide range of spectroscopy through books ranging from 400 Daltons to 400,000 Daltons or more. 7 As is known in the compound technology, additives can also be used to enhance or impart specific special ingredients, tinctures, flame retardants, pigments, plasticizers, surfactants, and the like. Can be blended and compatible Or incompatible polymers in it to obtain the desired properties. Adhesion promoters can also be used. Hexamethyl 4μ represents a material accelerator, which can be used to expose the surface to moisture or humidity (such as dioxin). Applicable via functional groups where possible. Poetry Microelectronics applications, specifically polymers used in dielectric layers, need to contain low levels of ionic impurities (usually less than i ppm 'preferably less than 10 ppb). As long as the resulting solution Can be applied to substrates, surfaces and wafers Laminated materials, the materials, precursors, and layers described herein can and are designed in many ways to solvate or dissolve them in any suitable solvent. Typical solvents are also those that can Isomeric monomer mixtures and solvents for polymer solvation. Solvents covered include any suitable pure organic or inorganic molecules or mixtures thereof, which molecules volatilize at a desired temperature, such as a critical temperature, and which promote any of the above. A design goal or need is achieved. The solvent may also contain any suitable unipolar and non-polar compounds or mixtures thereof. As used herein, the term "polar" means that a molecule or compound is within the molecule or compound. A feature of unequal charge, partial charge, or spontaneous charge distribution built at a point or along the molecule or compound. As used herein, the term "non-polar π" means that a molecule or compound is at a point in the molecule or compound or 96350.doc -18- 200531183 Build characteristics of uneven, partial, or spontaneous charge distribution along the molecule or compound. In some of the covered embodiments, the solvent or solvent: compound (comprising at least two solvents) comprises solvents that they consider to be part of a hydrocarbon solvent. Hydrocarbon solvents are their solvents containing carbon and hydrogen. It should be understood that 1 = several hydrocarbon solvents are non-polar; however, a few hydrocarbon solvents can be considered polar. Hydrocarbon solvents are usually subdivided into three categories: aliphatic, cyclic, and aromatic. Aliphatic smoke solvents can include both linear and branched and possibly cross-linked compounds, however, aliphatic hydrocarbon solvents are not considered cyclic. Cyclic hydrocarbon solvents are solvents which have characteristics similar to aliphatic hydrocarbon solvents, which contain at least three oriented carbon atoms in a ring structure. Aromatic hydrocarbon solvents are solvents which usually contain three or more unsaturated bonds. The aromatic hydrocarbon solvents have a single ring or are connected by a common bond = polycyclic and / or polycyclic fused together. Hydrocarbon solvents covered include methylben, xylene, p-xylene, m-xylene, trimethylbenzene, naphtha, solvents, naphtha solvents, alkanes such as pentane, hexane , Isohexane, heptane, nonyl, octane, dodecane, 2-methylbutane, hexadecane, tridecanepentadecane, tripentane, 2,2, trimethylpentane Alkanes, petroleum ethers, halogenated hydrocarbons, such as gasified hydrocarbons, nitrated hydrocarbons, benzene, ′, dimethylbenzene, ′ ′ 2,4-trimethylbenzene, mineral spirits, kerosene, isobutylbenzene, methyl Naphthalene, ethyltoluene, 'petroleum (ligr01ne). Particularly covered solvents include, but are not limited to, pentyl, hexane, heptane, cyclohexane, [toluene, xylene, and mixtures or combinations thereof. In other covered embodiments, the solvent or solvent mixture may include solvents that are not part of a compound that is not considered to be a solvent family, such as: ketones, 3-propylpentane, diethyl ketone, fluorenyl Ethyl ketones and their analogs, alcohols, 5 " amidines and amines. In other covered embodiments, the solvent or solvent may include a combination of any of the solvents mentioned herein. In two embodiments, the solvent comprises water, ethanol, propanol, acetone, and benzyl. "Tsunami, Butyrin, Methyl Ethyl Ketone: Two steps covered: alternative low dielectric constant materials can also include another group of one case. 'When low dielectric constant materials are exposed to mechanical stress, two "Ca other protective reagents. In other cases where the dielectric material is placed on a smooth surface, it may be advantageous to use an adhesion promoter. In other cases, cleaning agents or defoamers may be required. -In general, a precursor is applied to, for example, a spin-on glass-breaking composition in the form of a 7-removable solvent on a substrate: and then polymerized and formed to form a nano-pore-containing medium. The way of the electric film is subjected to solvent removal. A When forming such nanoporous films (for example, where the substrate is coated on a substrate by spin coating), during the preliminary heating step, the film coating is usually catalyzed by an acid or alkali catalyst and water to cause polymerization. Action / Gelification (_Aging if needed 'The film is then hardened (for example by one or more high temperature heating steps of the film) to remove (among other purposes) any residual solvent and complete This polymerization process. Other hardening methods include subjecting the film to radiant energy, such as ultraviolet light, electron beam, microwave energy, and the like. Co-owned US Patent Nos. 6,204,202 and 6,413,882 are hereby incorporated by reference. The method provides a Shixiji precursor composition and a method for forming a nanoporous silica dioxide dielectric film by degrading or evaporating one or more polymers or oligomers in the precursor composition. Commonly owned 96350.doc -20- 200531183 Some US patents No. 6,495,479 provide silicon-based precursor composition and its use for degradation from degradation or basic road # 二 飞 for rabbit this rigid drive group A method for forming a silicon dioxide dielectric film of one or more of compounds or polymers among them (Ding, Muxipo, etc.) US Patent No. 5,895,263 5 Tiger describes coating by including a decomposable polymer and an organic oxide stone In the evening (organic poly dioxide dioxide, that is, including condensation or polymerization of mouthpieces), the composition 'heats the composition to further condense the polydioxin and decompose the polymer. Form a porous dielectric layer to form a nano-porous silicon dioxide dielectric film on a substrate (for example, a wafer). ▲ For coating the precursor on the substrate, ageing, hardening, planarizing, and ( Etc.) The method by which the film is hydrophobic is described, for example, by the co-owned Lao Patent Nos. 6,589,889 and 6,037,275 (other patents also cover this). This article covers The substrates and wafers can include any of the required substantially solid materials. "The substrate layer required by the temple should include films, glass, ceramics, plastic, metal or coated metal, or composite materials. In the case of a good Λ handle, the substrate package Shi Xi or Shi Shenhua wrong die or wafer surface, packaging surface as found in copper-plated, silver-plated, nickel-plated or gold-plated lead frames, such as circuit board or package interconnect traces, channel walls or Copper surfaces found in hardener interfaces (considered, copper " including bare copper and its oxides), polymer-based packaging or board interfaces found in polyimide-based flexible packaging , Miscellaneous or other metal alloy solder spherical surfaces, glass and polymers such as polyimide. Considered as cohesive interface: 'You can even define' substrate 'as another polymer chain. In more A preferred embodiment 'The substrate includes materials commonly found in the packaging and circuit board industries, such as silicon, copper, glass, and another polymer. 96350.doc * 21-200531183 Guidance = Γ__Top cover _ film deposition half cover, and hunting and patterning by ashing and ashing to form channels "will tend to be removed from organosilicate glass dielectric films The carbon-containing part (which is a water-based group) is replaced with a residual alcohol group. When the organic petrolatum glass " Electrolyte contains the necessary properties, it is necessary to use it. The water absorbed from the air is highly polarizable in the electric field, so the dielectric constant of the film will be increased, and the resistance to wet cleaning chemical reactions will be reduced, and the volatile evolution will be increased. Also, when When these materials are filled with metal and allowed to pass through M, the shrinkage causes stress on the walls of the channels and trenches and leads to the formation of undesired interiors of the dielectric materials between the channels and trenches. In order to compensate for this problem, the organic silicate glass dielectric film was substantially cut with water by using an additive treatment to restore the carbon-containing portion and increase the hydrophobicity of the organic material glass dielectric film. This makes the film stress on the walls of the channels and trenches (various (Such as stress caused by metal shrinkage during annealing), stress from other dielectric layers, and stress during packaging are resistant, so it prevents the internal formation of dielectric materials between these channels and trenches Unwanted voids. Etching and plasma removal of hydrophobic functional groups. Damage to organic silicate glass dielectric films during semiconductor manufacturing is caused by the application of etched pure electricity and / or the use of etching reagents to channel trenches. And channel etching into the dielectric film. Plasma is also used to remove the photoresist film during the fabrication of semiconductor devices. The plasma used is usually composed of the elements oxygen, fluorine, hydrogen, carbon, argon, helium or nitrogen. (In the form of free atoms, compounds, ions, and / or groups). 96350.doc -22- 200531183 Exposure to these dielectrics during trench, channel, coin, and / or photoresist removal Phases are susceptible to degradation or damage. Porous dielectric films have a very high 2, surface area 'and are therefore particularly susceptible to damage by plasma damage. In particular, organic materials (such as methyl groups bonded to si atoms) Based on dioxide The dielectric film is easily degraded by an oxygen plasma. The organic group oxygen is co2 ′ and the alcohol or 1011 group remains on the surface of the organic group previously formed by the porous group. The porous dioxygen-cut film relies on this And other organic groups (on the surface of the pores) to retain hydrophobicity. The loss of hydrophobicity increases the dielectric constant (the low dielectric constant of these films is a key required characteristic of these materials). The purpose of the remaining residue after the ditch or channel money is carved is also to use the chemical treatment in the professional system. These chemicals are often used; such a rotten nature so that the money is invaded and removed. The organic groups in the dielectric thin films of oxide oxides (especially porous silicon dioxide films). Moreover, this damage causes the films to lose their hydrophobicity. Wet chemical etchants include (such as plug N- Methylpyrrolidone, dimethylformamide, dimethylacetamide

Amines such as ethanol and 2-propanol; alcohol amines such as ethanolamine; amines such as triethylamine; such as ethylenediamine and diamines with diethylethylenediamine; such as triethylenediamine Amines; diamine scripts such as ethylenediamine tetraacetic acid " edta ", organic acids such as ethyl acetate and formic acid, organic acid salts such as tetramethylacetic acid; salts such as sulfuric acid, light, hydrofluoric acid Inorganic acids; tritiated salts such as gasified ammonium; and bases such as ammonium hydroxide and tetramethylammonium hydroxide; and commercial formulations such as Ekc 505, which are developed for post-etching / wash cleaning. 525, 450, 265, 270, and 630 (EKC CorP ·, Hayward CA), 96350.doc -23- 200531183, and ACT-CMI and ACT-690 (Ashland Chemical, Hayward, CA), only enumerated in this technology Several known etchants. Ashing reagents include He Sheng from hydrogen, nitrogen, helium, argon, oxygen, and plasma derived from mixtures thereof, and the like. To solve the above problems, the present invention provides the imparting of hydrophobic properties Method for organosilicate appearing on a substrate during the manufacture of a semiconductor or 1C device The method of the present invention comprises the following steps: (3) combining the organic silicate glass dielectric film with a certain concentration of a toughening agent after being subjected to at least one etchant or ashing agent, but before the metal is subjected to an annealing treatment; And the period of time during which the contact is effective in recovering at least some of the carbon-containing portion to the organosilicate glass dielectric film and increasing the hydrophobicity of the organosilicate glass dielectric film; and (13 ) Remove unreacted toughening agent composition, reaction product, and mixtures thereof. The toughening agent composition includes at least one toughening agent, that is, one suitable for removing silanol portions from a damaged silicon dioxide dielectric film. Compound or a charged derivative thereof. Optionally, the nanoporous silicon dioxide dielectric film damaged by the etchant is then subjected to a wet cleaning step. In one embodiment, the toughener composition includes at least one compound having the following molecular formula: Toughener composition: (I) [-SiR2NR '-] n where n > 2 and may be cyclic; ⑺R3SiNR, SiR3; (3) (R3Si) 3N; (4) R3SiNR'2; (5) R2Si (NR,) 2; (6) RSi (NR,) 3; (7) RxSiCly; (8) RxSi (OH) y; (9) R3SiOSiR, 3; (10) RxSi (〇R,) y; (II) RxSi (〇COR ') y; (12) RxSiHy; (13) RxSi [ OC (Rf) = R "]" and combinations thereof, 96350.doc -24- 200531183 where X is an integer in the range of 1 to 3, and ^ is an integer in the range of 1 to 3 so that y-4-x Each R is independently selected from hydrogen and a hydrophobic organic moiety. The R group is preferably a group of organic moieties consisting of a free radical, an aryl group, and a combination thereof. R, a group may be fluorene, an alkyl group, an aryl group, or a carbonyl group such as coR, coNR, CO2R. R "may be an alkyl group or a carbonyl group such as COR, CONR, CO2R. In another specific embodiment, the toughener composition includes at least one of the following tougheners or compositions: ethoxytrimethylsilane , Ethoxysilane, monoethoxysilane, triethoxysilane, diethoxymethylsilane, methyltriethoxysilane, phenyltriethoxysilane, Diphenyldiethoxysilane, methyltriethoxysilane, difluorenyldiethoxysilane, trimethylethoxysilane, methyltrimethoxysilane, dimethyldimethoxylithium Burning, dimethylmethoxylithium burning, methyl chlorochlorite burning, dimethyldichlorosilane, trimethylchlorosilane, fluorenylsilane, dimethylsilane, trimethylsilylsilane, hexamethyldicarbonate Silazane, hexamethylcyclotrisilazane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethylsilane, tris (dimethylamino) fluorenylsilane, di ( Dimethylamino) phenylsilane, tris (dimethylamino) silane, dimethylphosphosilyldimethylformamide, dimethylsilyldiethylphosphonium, dimethyl Silyl diisocyanate, trimethylsilyl triisocyanate, 2.trimethylsilyloxypent-2-en-4-one, n_ (trimethylsilyl) acetamide, 2- (tri Methylsilyl) acetic acid, n_ (trimethylsilyl) imidazole, trimethylsilylpropionate, trimethylsilylsilyl (trimethylsilyloxyacetate) Trisilazane, hexamethyldisilazane, trimethylsilanol, triethylsilanol, triphenylsilanol, tert-butyldimethylsilazanol, diphenylsilanedi Alcohol, trimethoxysilane, triethoxysilane, 96350.doc -25- 200531183 dichlorite fired, and combinations thereof. In a desired embodiment of the present invention, the sharpener comprises dimethyldiethyl Fluorosilane. Optionally, the Zengwei sharpener composition includes a solvent. Suitable solvents include, for example, the same, scale, self-confidence, smoke and combinations thereof. The toughener composition as a liquid, The gas phase or gas, and / or the plasma is in contact with the damaged silicon dioxide dielectric film. If it is in the form of a plasma, the plasma can be derived from silane compounds, hydrocarbons, Aldehydes, esters, ethers, and / or combinations thereof. Unless otherwise specified, the term "agent" or "agents" in this document should be considered the term "reagent" or "reagents" ") Synonyms. Suitable telecommutant compositions include one or more additives capable of removing silanol groups from a post-cut and / or ashing organic silicate glass dielectric film that must be rendered hydrophobic. Toughening agent. For example, the toughening agent is a compound having a molecular formula selected from the group consisting of Formula 1 (1-13): wherein n > 2 and may be cyclic; R3SiNR, siR3; (3) (R3Si ) 3N; ⑷R3SiNR, 2; (5) R2Si (NR ') 2; (6) RSi (NR') 3; (7) RxSiCly; (8) RxSi (OH) y; (9) R3SiOSiR, 3; (l 〇) RxSi (〇R,) y; (1 l) RxSi (OCOR,) y; (12) RxSiHy; (13) RxSi [OC (R,) = R ”] 4_x and combinations thereof, where X is 1 to An integer in the range of 3, y is an integer in the range of 3 to 3 such that y-4-χ, each R is independently selected from hydrogen and a hydrophobic organic moiety. The R group is preferably a group of organic moieties consisting of a free radical, an aryl group, and a combination thereof. The group may be H, an alkyl group, an aryl group, or a carbonyl group such as cor, coNR, and co2R. R may be an alkyl group or a carbonyl group such as COR, CONR, CO2R. The alkyl moiety is functionalized or non-functionalized, and it is selected from the group consisting of straight-chain alkyl, branched-chain alkyl, cyclic alkyl, and combinations thereof, and its burning in 96350.doc 200531183 The base portion is in a size range from c] to about c] 8. The aryl moiety is substituted or unsubstituted and is in a size range from C5 to about C1S. The early-increasing agent is preferably ethoxylate or (for example) a monomeric compound such as ethoxylated trimethylsilane, ethoxylated silane, diethoxylated oxalate, Ethoxysilane, diethyloxy dimethyl silane, methyltriethyloxy oxalate, benzyl diethyloxy oxalate, diphenyl diethyl oxysilane, methyl dimethyl Ethoxylate, dimethyldiethoxylate, trimethylethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxycholine, methyl formaldehyde Dioxane, dimethyldichloride, trimethylchlorosilane, methylsilane, dimethylsilane, trimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane , Bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethylsilane, tris (dimethylamino) methylsilane, tris (dimethylamino) phenylsilane, tris (di (Methylamino) silane, dimethylsilyldimethylformamide, dimethylsilyldiethylamidamine, dimethylsilyldiisocyanate, dimethylsilyltrimethyl Isocyanate, 2-trimethylsilyloxypent-2-en_ 4-one, η- (dimethylsilyl) acetamide, 2 • (trimethylsilyl) acetic acid, η- ( Trimethylsilyl) imidazole, trimethylsilyl propionate, dimethylsilyl (trimethylsilyloxy) acetate, nonamethyltrisilazine Oxygen, trimethylsilyl alcohol, triethylsilyl alcohol, triphenylsilyl alcohol, tertiary butyl difluorenylsilyl alcohol, diphenylsilyl glycol, dimethoxysilane, triethyl Oxysilane, trigas silane, and combinations thereof. In a significant embodiment, the toughening agent is methyltriethoxysilane. In a preferred embodiment, the toughening agent is dimethyldiethoxysilane. Additional toughening agents include as detailed in U.S. Patent No. 6,208,0014, 96350.doc -27- 200531183 4 Miao Zhixi Xi Fang " ^ Surface modification agents, as described above The patent case is incorporated herein by citation. These multifunctional surface modification reagents can be applied in the form of a gas phase or a liquid, and the beans ^ ^ ^ @ ^ ^, with or without a co-solvent as appropriate. As described in detail in U.S. Pat. No. 6,395,651, suitable co-lubricants include, for example, such as propyl, diisopropylfluorenone, 2-heptanone, 3-pentanone, and other ketones, The disclosure of this patent is incorporated by reference. For example, as detailed in U.S. Patent No. 6,208,014, the surface modification reagent of a certain second car will have two or more functional groups and will react with the surface second alcohol function at the same time will appear in the film structure skeleton ( (framework) should not be reduced to a minimum, and include (eg, Shikou) the surface stone yew alcohol can be condensed with a suitable silanol, such as:

RxSi (〇H) 4.x Formula π Where X-1-3, and each R is an independently selected portion, such as fluorene and / or an organic portion such as an alkyl group, an aryl group or a derivative thereof. When R is an alkyl group, the alkyl moiety T is optionally substituted or unsubstituted, and may be linear, branched, or cyclic, and is preferably in a size range from Cl to about Cu or more And more preferably in a size range from C] to about Cs. When the rule is an aryl group, the aryl moiety is preferably composed of an optionally substituted single aromatic ring, and is in a size range from q to about cls or more, and more preferably from Q Within the range of about q. Among the further options, the aryl moiety is a heteroaryl. In another embodiment, an alkoxysilane can be used as a toughening agent, such as a suitable alkoxysilane such as:

"RxSi (OR,)" wherein R is an independently selected moiety such as fluorene and / or such as alkyl, aryl or its 96350.doc -28- 200531183; -R is an independently selected alkyl or aromatic moiety When it is based on the base group, the base group is optionally a linear, domain, or cyclic ring of substituted or unsubstituted I, and is preferably from about c18 or more, Erganwei π, and more preferably Cl to about the size range. When R or R is a square group% 'Square group portion is preferably composed of a optionally substituted or unsubstituted monoaromatic ring, and is from. To about C18 or greater Within the size range ', and more preferably from C5 to about c8. Among the further options, the' aryl moiety is a heteroaryl group. Therefore, the R group is independently selected from H, methyl, ethyl , Propyl, phenyl, and / or its derivatives' conditions are at least one R-based organic. In one embodiment, both R groups are methyl, and the surface modification reagent is methyltrimethyl Oxysilane. In another embodiment, a suitable silane according to the invention has the formula

RxSi (NR2) 4.x Formula III Where X = 1 to 3, R is independently η, alkyl and / or aryl. Any of R is an alkyl group and / or an aryl group. In a preferred embodiment, r is selected from Η, ch3, C6H5, and R2 and R3 are both CH3. Trifunctional toughening agents therefore include, for example, tris (diamido) methyl spar, bis (dimethylamino) phenyl spar, and / or tris (dimethylamine) spar. In addition, bis-substituted silanes such as hexamethylcyclotrisilazane, bisdimethylaminobisfluorenylsilane, and bisdiethylaminodimethylsilane can be used. In another embodiment, a suitable silane according to the present invention has the following general formula:

RxSi (ON = CR2) 4_x or RxSi [OC (R ') = R ”] 4 Formula IV where x = 1 to 3, and the R group is independently H, alkyl and / or aryl, and R may be H, Alkyl, aryl, alkoxy, or aryloxy, and R, 'may be alkyl or carbonyl. Therefore, the modifiers include, for example, methyltris (fluorenylethylketoxime) silane or 2- 96350.doc -29- 200531183 monomethyl vermiculyloxypentan-2-ox-4-one. In another embodiment, a suitable silane according to the present invention has the following general formula:

RxSi (NCOR2) 4-x or RxSi (NCO) 4-x where x = 1 to 3, and the R group is independently h, alkyl, and / or aryl. Therefore, surface modifying agents include, for example, dimethylsilyldiamine, dimethylsilyldiethylamine, dimethylsilyldiisocyanate, trimethylsilyltriisocyanate. In yet another embodiment, a suitable silane according to the present invention has the following general formula:

RxSiCl4.x Formula V wherein R is H, alkyl, or aryl. In a preferred embodiment, R is CH3. Thus trifunctional surface modification reagents according to formula v include, for example, methyl triazine. In a more preferred embodiment, the capping reagent includes one or more organic ethoxysilanes having the general formula:

(RoxSi (OCOR2) y Formula VI Preferably, X is an integer in the range from 丨 to 2, and may be the same or different from ^, and y is from about 2 to about 3 or more Integer within the range. Suitable organic ethoxylated silanes including polyfunctional alkyl ethoxylated silanes and / or aryl ethoxylated silane compounds include (by way of example only and not limitation) methyltriacetone Oxysilane (,, MTAS ',), dimethyldiethyloxysilane (DMDAS), phenyltriethoxysilane, and diphenyl: stone oxide and combinations thereof. Milk base will increase as the case may be. The toughening agent is mixed with a suitable solvent such as 2-heptanone, applied in the form of a gas phase or a liquid on a nanoporous dioxon surface and subsequently dried = 96350.doc -30- 200531183. In the examples covered A mixture of 50% hexamethyldisilazane (HMDZ) and 50% 3-pentanone is used. The liquid is spin-coated on a surface, substrate or wafer. The coating is then applied at up to 425.0 °. The surface is baked on a baking tray. After baking, pvD barrier and Cu seed deposition are followed. In another covered embodiment, use Mixture of difluorenyldiethyloxysilane (DMDAS) and 3-pentanone. This liquid is spin-coated on a surface, wafer or substrate. The coated surface is then baked on a baking tray at up to 425 steps. After this baking step, pvD barriers and Cu seed deposits are deposited. In another embodiment, a wet cleaning using a chemical such as AP395 or diluted HF is performed after the baking step in the above embodiment. This wet cleaning is suitable Residues of anti-agents remaining after ashing. Low-k dielectric materials that have not been treated after ashing are susceptible to wet cleaning reagents. Zengwei blade treatment significantly improves low-k Resistance of dielectric to wet cleaning. Depending on the process, the copper surface can be exposed during the toughening process, especially at the bottom of the channel. &Amp; Shiqing can also remove any reaction product between the toughener and the exposed steel surface. Specifically, the wet cleaning using AP395 can clean copper previously exposed to the toughener treated with DMDAS (or any suitable Metal or metal alloy) surface. Fill the channels and trenches with a metal; and anneal the metal, metal, metal, and metal. As the term is used herein, metal, means that they are located in the d and f regions of the periodic table. Element, metal-like element. As used herein, 3d, 4d around the nucleus of the element, and phrases such as silicon and germanium have "(zone 1)" meaning electrons with orbits filled with 5d and 6d. Those 96350.doc -31-200531183

element. As used herein, the phrase "f-region" means that they have 4f and 5f dominating electrons surrounding the nucleus of the element, including lanthanides and actinides. Preferred metals include indium, silver, copper, aluminum, tin, bismuth, gallium and alloys thereof, silver-coated copper, and silver-coated aluminum. The term, metal, also includes alloys, metal / metal composites, cermet composites, metal polymer composites, and other metal composites. Annealing may be performed by heating at a temperature of from about 150 ° C. to about 50 ° C. or from 0 ° C. to 250 ° C. for about 10 seconds to about 60 seconds. As long as annealing is performed, these times and temperatures are not critical. In another embodiment, the "/", and π washing can be performed before the feeding process in the first-covering embodiment. The high temperature baking step is performed after the wet washing. One of the advantages of this method can be ... Before making it, harden by baking treatment, wet cleaning can remove excess toughener and any product that reacts with any exposed copper surface: this can cause lower levels in dielectric materials Amount of volatile components and a cleaner copper surface. Both can cause-improved long-term reliability. In another covered embodiment, 'from about to about

400. (: Perform another dehydration baking! Fine to coffee-. The dehydration supply removes any moisture absorbed in the damaged low-k dielectric. Remove the moisture from the dielectric before adding This treatment is more effective. In an alternative embodiment, the toughener composition is obtained by exposing an etchant-damaged organosilicate glass dielectric film to a plasma derived from any of the above-mentioned service agents. Provided. In a typical process, the osmite glass dielectric film is placed in a plasma generation chamber, and the slurry enhanced chemical vapor deposition (PECV system; the gas phase of the composition and argon The gas phase passes through the plasma generation chamber; then the power source is activated to build the electropolymerization; including argon gas to 96350.doc -32- 200531183 helps to promote the formation of the plasma. The plasma is derived from the toughener composition Ionic fragment composition; for example, the ionic fragment CH3Si + is derived from methyllithoxane (CHsSiH3). This fragment reacts with the silanol group to form a hydrophobic Si-CH3 moiety. Any of the above can be used A toughening agent composition is used for this plasma-induced surface modification. Other suitable toughening agent compositions for quality treatment include Ci-C] 2 alkyl and aromatic hydrocarbons. The best hydrocarbons are pinane. Other reagents for the plasma-induced toughening agent composition include tritium, ester, and acid. Chlorides and ethers. Suitable knees include acetic acid and benzoic acid; suitable esters include ethyl acetate and ethyl benzoate; suitable acidic chlorides include ethyl acetate and benzoyl chloride; and suitable ethers include diethyl ether and benzene Ether. A wide variety of single- or multi-wafer (batch) plasma systems can be used for this method; these systems include so-called downstream ashers such as Gasonics L3510 photoresist ashers, such as AppHed Materials The PECVD dielectric deposition system or reactive ion etching (nRIEn) system of P5000. In general, the conditions for the plasma method are in the following ranges: · Chamber temperature of 20C to 450C; 50W to 1000W RF power; chamber pressure of 0.05 to 100 ton *; plasma treatment time of 5 seconds to 5 minutes; and surface modification flow rate of 100-2000 seem; inert gas flow rate of 100-200 sccm (Usually argon.) Those skilled in the art should understand that the present invention also It is intended to include a method for imparting a hydrophobic surface with a porous and / or non-porous, damaged or undamaged dielectric oxide film by applying the above-mentioned plasma surface treatment. A semiconductor device or 1C manufactured using these methods Also part of this invention. Processed dielectric layers and materials can be used in or incorporated into any suitable electronic 96350.doc -33- 200531183 component. Electronic components, as covered herein, are generally considered to include components that can ... Electronic (electrical-based) products of any dielectric group two electrical components. The covered electronic components include circuit boards, chip packages-2 :: electrical components, printed wiring boards, and capacitors, inductors and resistors Other components of the circuit board. Electron-based products may be " completed " in the sense that they are intended for use in the health industry or by other consumers. Examples of completed consumer products include televisions, computers, mobile phones, pagers, handheld managers, portable radios, car S stereo radios and remote controls. It also covers "intermediate" products such as circuit boards, chip packages, and keyboards, which can be used in finished products. I Electronic devices can also include everything from a conceptual model to a final scale-up mock-up A prototype component at any stage of development. A prototype may or may not contain all of the actual components intended in the finished product, and the prototype may have some construction made of composite materials to exclude its initial effect on other components when initially tested Effect components. Electronic products and components may include laminated materials, laminated components, and components laminated for use in the component or product. The following non-limiting examples are used to illustrate the present invention. Example 1 will be listed from Honeywell International , Inc, Sunnyvale,

600000a Nan〇GLASS E nanoporous silicon dioxide film purchased from California was coated on a 200 mm silicon substrate and then exposed to a C4F8-based etch and based on a TEL DRM-85 etchant. 2 of the ashing treatment. 96350.doc -34- 200531183 Evaluation of two toughening agents (TA-1 and TA-2). The tougheners were applied to wafers using a standard spin-on dielectric (SOD) applicator, and the wafers were hot plate baked at 125 ° C, 200 ° C, and 350 ° C, respectively. After 1 minute. Ellipsometry was used to measure the film thickness and refractive index. Elemental composition was analyzed using FTIR. The dielectric constant was measured on a 0.1 MHz Hg probe. The thermal stability of the film was evaluated by thermal desorption mass spectrometry (TDMS). A single-level metal Cu mosaic structure was prepared using 3000A NANOGLASS E film as the ILD and 2000 human TEOS oxide as the cap layer. Cu annealing was performed in a N2 environment at 200 ° C for 1 hr, and then a focused ion beam scanning electron microscope (FIB-SEM) was used to detect voids in the ILD. After Cu chemical mechanical polishing (CMP), an automated probe was used to electronically test 25 dies per wafer. Table I shows the properties of the hardened NANOGLASS®E film. Table I · General characteristics of the hardened NANOGLASS®E film Technical results Aperture BET 20A Refractive index elliptic symmetry 1.24 Dielectric constant ΜΙΜ @ 1ΜΗζ 2.2 Elasticity coefficient nanoindentation 4.5 Gpa Hardness nanoindentation 0.4 Gpa Isothermal stability TGA < 1% weight loss from FTIR spectrum observation of NANOGLASS E. Compared with hardened films, this etching and ashing treatment resulted in a 30-40% reduction in CH and Si-C content and Si-OH and H The -OH bond increased significantly. Toughener treatment results in C-H and Si-C contents close to the C-H and Si-C contents of the hardened film. TA-2 is more effective than TA-1 in replenishing carbon and reducing Si-OH and H-0H bonds. 96350.doc -35- 200531183 After etching and ashing, the dielectric constant (k) of the low-k film becomes higher (> 30). It is estimated that this is attributed to the moisture adsorption of Si-OH groups. This toughening treatment reduces the value of k to a level close to that after hardening. Table II shows that after etching and ashing, in most wet cleaning chemical reactions, the NANOGLASS E film is hydrophilic and has a high etching rate, making it unsuitable for wet cleaning. TA-1 treatment makes the film hydrophobic and resistant to some wet cleaning chemicals. Table II · Effects of Surname-Ashing (Control) and After Etching-Ashing and TA ”(TA-1) on NANGLASS £ Films Exposed to Various Wet Cleaning Chemicals / Strict Cleaning Conditions 1 Insect engraving rate (A / min) DI water contact angle (Tang) Control TA-1 Control TA-1 wet cleaning < 10 122 A (diluted HF) > 1000 0 33 112 B (aqueous acidity) 5 0 < 10 118 c (semi-aqueous fluoride) bu 25 1 14 < 10 < 10D (organic amine) 70 23 < 10 47 At 400 ° C, the tdMS spectrum of the dielectric film is shown by TA-1 The evolution of volatile substances in the treated film is similar to that of the film after etching and ashing. TA-2 treated films exhibited significantly improved thermal stability with low levels of volatiles. In the control case (ie no toughener), significant voids were seen between the ILD gaps after Cu annealing. No voids were observed before annealing. Similar observations on porous low-k materials have been previously reported (see A. Matsushita, N.

〇hashi, K. Inukai, H. LShin, S. Sone, K. Sudoii, K. Misawa, I. Matsumoto, and Ν Kobayashi, Proceedings of IEEE 96350.doc 200531183

International Interconnect Technology Conference, 2003, 147 (2003); and J. C. Lin, R. A. Augur, B. Daniels, S. L. Shue, C. H. Yu, and M. S. Liang, Proceedings of Advanced Metallization Conference 2002, 637 (2002)). The tensile stress from the Cu annealing process is estimated as the driving force for void formation. Wafers treated with TA-1 or TA-2 show no voids after Cu annealing. Therefore, it has been proven that 'the repair' of the damaged C-loss is an effective way to toughen the porous low-k material to avoid the formation of voids due to external stress. Wire-to-wire leakage current is not affected by toughener treatment. The control wafer showed a wide distribution of serpentine resistance. It was found that the high-resistance tail is due to defects such as buoys, Cu immersion, and pitting, which may be caused by moisture trapped in the damaged ILD area. Because moisture retention and related defects are eliminated, the toughened wafer exhibits a tight resistance distribution. Although the median capacitor is not affected by the toughener treatment, the treated comb capacitor structure has a higher yield due to fewer pit / bubble defects. The effects of processing-induced damage on NANOGLASS®E and other similar Si-based films have been revealed. The post-ashing treatment with the toughening agent TA-1 or TA-2 can restore the properties of an undamaged material. It has been proven that the successful application of Zengweier in SLM structures results in the elimination of ILD voids and high yields of interconnect test structures. Example 2 A 6000A HOSP silicon film commercially available from Honeywell International Inc., Sunnyvale, California was formed on a Si wafer by a standard spin coating method. The films were hardened in N2 at 400 ° C. 96350.doc -37- 200531183 Plasma damage was introduced into these films by subjecting them to the following processes in order: Etching: 1000 W / 40mT / 10 seem C4F8 / 200 sccn ^ O / 300 seem Ar / 100 seem N2 , 40 ° C (20 seconds). Ashing: 400 W / 45 mT / 100 seem 02, 40 ° C (20 seconds). Toughener treatment was performed using a mixture of 27% DMDAS in 3-pentanone. After spin-coating the toughener material, the films were baked at 125t :, 200 ° C, and 350 ° C N2 for 1 minute each. The following results were recorded: Measured value Dielectric constant (k) after etching and ashing and toughening agent treatment before ashing 2.7 3.0 2.81 FTIR (CH / SiO ratio) 0.0235 0.017 0.020 H2o contact angle (°) 104 26 85 Breaking Strength (MV / cm) 5.51 4.1 5.12 Example 3 By a standard spin coating method, a 6000A NANOGLASS 1.9 silicon film, which can be obtained from Honey well International Inc., Sunnyvale, California, was formed on a Si wafer. The films were hardened in N2 at 425 ° C. Plasma damage was introduced into these films by sequentially subjecting them to the following treatments: Etching: 1000 W / 40 mT / 10 seem C4F8 / 200 seem CO / 300 seem Ar / 100 seem N2, 40 ° C (20 seconds ). Ashing: 400 W / 45 mT / 100 seem 02, 40 ° C (20 seconds). A 27% DMDAS in 3-penta g of the same mixture was used to perform the Zengwei knife treatment. After spin coating the toughener material, the films were baked at 125 ° C, 200 ° C, and 350 ° C N2 96350.doc • 38- 200531183 for 1 minute each. The following results were recorded: Measured value 1 Dielectric constant (k) 1.83 2.69 1.94 FTIR (CH / SiO ratio) 0.0078 0.0027 0.0054 Breaking strength (MV / cm) ) 4.51 1.22 3.76 Example 4 A plasma porous CVD low-k dielectric film was imparted to a commercial grade porous CVD film by subjecting it to the following processes: Etching: 40 mT, 1400 W 160 Ar / 80 CF4 / 20 02 40 mT , 1400 W, 20 s Ashing: 400 W / 45 mT / 100 seem 02, 40 ° C (30 seconds). Toughener treatment was performed using a mixture of 27% DMDAS in 3-pentanone. After spin coating the toughener material, the films were baked at 125 ° C, 200 ° C, and 350 ° C N2 for 1 minute each. The following results were recorded: Measured value Dielectric constant (k) 2.36 2.76 2.39 FTIR (CH / SiO ratio) 0.02473 0.0149 0.013 Breaking strength (MV / cm) 5.06 3.07 4.77 Example 5 A conventional baking method of 125 ° C, 200 ° C, and 35 ° t was used to prepare a 6000 person NANOGLASS film that can be obtained from Honeywell International Inc., Sunnyvale, California. Use UV hardening (3 min) at 425 ° C instead of conventional furnace hardening (60 min). And subject it to plasma damage by sequentially subjecting it to the following treatments: 96350.doc • 39- 200531183 Etching: 1000 W / 40 mT / 10 seem C4F8 / 200 seem CO / 300 seem Ar / 100 sccmN2, 40. C (20 seconds) Ashing: 400 W / 45 mT / 100 seem 02, 40 ° C (30 seconds) Perform a toughener treatment using a mixture of 27% DMDAS in 3-pentanone. After spin coating the toughener material, the films were baked at 125 ° C, 200 ° C, and 350 ° C N2 for 1 minute each. Using a UV-cured NANOGLASS as a dielectric material, a copper single damascene patterned structure was constructed using the conventional approach described in Example 2. Before metallization (PVD barrier and Cu seed deposition and Cu plating), some wafers are coated with a toughening agent and then baked at up to 350 ° C. After metallization, all samples were annealed at 200 ° C for 50 min. The presence of voids was determined using a focused ion beam scanning electron microscope. The following results were recorded: a. Blanket wafer measured values Etching and ashing Etching and post ashing toughener treatment Dielectric constant (k) 2.1 2.85 2.25 FTIR (CH / SiO ratio) 0.0082 0.0045 0.0075 Breaking strength (MV / cm) 5.06 3.07 4.77 b. Example 6 of SLM patterned wafers Plasma damage was introduced into a 6000 A furnace hardened NANO GLASS film by sequentially subjecting it to the following treatment, which can be obtained from Honeywell International Inc., Sunnyvale, California bet: I Worm: 1000 W / 40 mT / 10 seem C4F8 / 200 seem CO / 300 seem Ar / 100 sccmN2, 40 ° C (20 seconds) Ashing (one of the following methods) 96350.doc -40- 200531183 〇2 ashing · 400 W / 45 mT / 100 seem 〇2, 4 (Tc (2〇s ^ 70 s) or N2 / H2 ashing · 500 W / 45 mT / 500 seem N2 / 125 seem H2 10 ° C (45 s or 135 s) Toughener treatment was performed using a mixture of 90 / 〇DMDAS in 2-heptanone. After the toughener material was spin-coated, it was applied at 125t, 200 ° C and Each of these films was baked for 1 min in TC n2. Results such as the ashing type Γ were recorded: k (without toughening agent tile to; k (degree of k at the toughening agent ° /. Decrease 〇2, 20 s 2.98 ^ 236 ^ ~ ^ ~ 20.8 02, 30 s 3.11 2A2 -— 22.2 〇2, 70 s 3.53 Z63 25.5 Ν2 / Η2 45 s 3.04— ^ Z5 ~ 17.8 Ν2 / Η2135 s 3.23 '— 2Π 16.4 Example 7 by It is subjected to the following treatments in order to introduce plasma damage into the 6000a furnace to harden the NANOGLASS film: Famous insect carving: 1000 W / 40 mT / lscccin C4f8 / 200 seem CO / 300 seem

Ar / 100 sccmN2, 40 ° C (20 seconds) Ashing (one of the following methods): To test the effect of queue tinie before toughener treatment, place the sample in ambient conditions for 1 hr to 360 At different times of hr, a booster treatment was performed. Zengwei knife treatment was performed using a mixture of 4.5% DMDAS in 2-heptyl. After spin-coating the toughener material, the films were baked at 125 ° c, 200 ° C, and 350 ° C N2 for 1 minute each. 96350.doc -41-200531183 recorded the following results: Q-Time (hiOk (after toughening agent) 1 2.24 3 2.28 27 2.31 72 2.29 240 2.38 360 2.32 Example 8 The electricity was charged by subjecting it to the following processes in order Introduced into the 6000A furnace to harden NANO GLASS film, which can be formed from Honeywell International Inc., Sunnyvale, California. Etching: 1000 W / 40 mT / 10 seem C4F8 / 200 seem CO / 300 seem Ar / 100 seem N2 , 40 ° C (20 seconds). Ashing (one of the following methods). Perform a toughener treatment using a mixture of 18% DMDAS in 2-heptanone. After spin coating the toughener material, at different temperatures, Bake these films on a baking tray for 1 minute each. Measure the percentage of carbon added by carbon recovery as a toughener treatment and the amount of carbon lost during plasma damage. Use FTIR to measure the carbon amount as CH The ratio of (2975 enT1) peak to SiO peak (1055 cm_1) 0 recorded the following results: Baking temperature% C recovery K-value 75 ° C 66 2.95 100 ° C 2.82 125 ° C 2.74 150 ° C 65 2.72 175 ° C 136 2.5 200 ° C 127 2.34 225 ° C 127 2.3 96350.doc -42- 200531183 250 ° C -----— ---- ^ 121 _ 2.19 300 ° C ---- up. X --- 127 __ ^ 2.17 350 ° C — 103 2.2 Although the present invention has been specifically shown with reference to preferred embodiments And described, but it is not difficult for those who are familiar with this technology to understand various changes and modifications can be made without departing from the spirit and scope of the present invention. It is intended to understand the scope of this application patent covering the disclosed embodiments, other Equals the alternative methods discussed above and all their equivalents.

96350.doc 43-

Claims (1)

200531183 • Scope of patent application: 1. A method for preventing the formation of stress-induced voids in an organic silicate glass dielectric film on a substrate. Channels and trenches are formed therein, and the organosilicate glass-breaking dielectric film is then subjected to at least one kind to remove at least a portion of the carbon-containing portion present and reduce the silicate glass dielectric film: aqueous And subsequently filling the channels and trenches with metal, and then subjecting the metal to an annealing treatment, the method comprising: after undergoing at least: removal of a pre-existing carbonaceous portion, but after filling with metal = 忒Before waiting for the channel and the trench, the organic silicate glass dielectric film is contacted with a concentration of the toughener composition and the period of time during which the contacting is effective to restore at least some of the carbonaceous portion of the material to the Organic silicate glass dielectric films and increase the hydrophobicity of the organic silicate glass dielectric films. 2. = The method of claim 1, wherein the treatment of removing at least a part of the preexisting carbon-containing portion and reducing the hydrophobicity of the organic petrosate glass dielectric film includes at least one of the following treatments: an etchant treatment, Ashing treatment, wet peeling treatment, cleaning treatment and PEcvd treatment. 3. The method of claim 1, wherein the organic silicate glass dielectric film is formed of a square-coated glass material or a chemical vapor deposition material. 4. The method of claim 1, wherein the toughener composition comprises a component for partially alkylating or arylating silanol through the silylation of the organic silicate glass dielectric film. 5. The method of claim 1, further comprising removing the unreacted toughener group 96350.doc 200531183 a subsequent step of the reaction product and the mixture thereof. The method of claim 1, further comprising the subsequent step of heating the increased hydrophobic organic silicate glass dielectric film. Rice is porous. The method as in item 1 has no holes in the body. The method of claim 1, wherein the organic silicate glass dielectric film is Nai 8. The organic silicate glass dielectric film is large 9. Wherein the toughener composition contains at least A compound having at least one compound selected from the group consisting of: [-body-] n where n > 2 and may be cyclic, R3S called, (R3Si) 3N ^ R3SlNR-2 ^ R2Si ( NR-) 2 > RSi (NR ') 3 ^ RxSiCly. Rxsi (〇H) y, R3Si0SiR, 3, RxSi (〇RI) y, ⑽⑴ Coffee, ^, RdiHy, RxSi [oc (R,) = R, ,] 4 x and combinations thereof, y where x is an integer in the range of 1 to 3, y is an integer in the range of 1 to 3 such that y = 4-x, and each R is independently selected from hydrogen and a hydrophobic organic moiety, Into hydrogen or an organic moiety, and R is an alkyl group or a plurality of groups. 10. The method of claim 1, wherein the toughening agent composition comprises at least one compound selected from the group consisting of ethoxysilane trimethylsilane, ethoxysilane, diethylfluorene Oxysilane, triethoxysilane, diethoxysilane, silane, methyltriethoxysilane, phenyldiethoxysilane, diphenyldiethoxysilane, Methyl diethoxy, dimethyl diethoxy, trimethyl ethoxylate, 96350.doc 200531183 methyl trimethoxysilane, dimethyl dimethoxysilane, trimethyl methyl Oxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilicon element, methyl crushed burn, monomethyl crushed burn, tri-taumenyl burn, hexamethyldisulfide burn , 2-trimethylmethoxanylpentan-2-en-4-one, n- (trimethylmethoxanyl) acetamidamine, 2- (trimethylsilyl) acetic acid, (Trimethylmethoxyl) imidazole, trimethylsilylsilylpropionate, trimethylsilyl (dimethylsilyloxy) -acetate, nonamethyltrisilyl nitrogen Alkane, hexamethyl Disiloxane, trimethylsilanol, triethylsilanol, triphenylsilanol, third butyldimethylsilanol, diphenylsilanediol, trimethoxysilane, triethoxy Silane, trichlorosilane, hexamethylcyclotrisilazane, bisdimethylaminodimethylsilane, bisdiethylaminodimethylsilane, tris (dimethylamino) methylsilane, tris (dimethyl) Amine) phenylsilane, tris (dimethylamino) silane, dimethylsilyldiamine, dimethylsilyldiethylamine, dimethylsilyldiisocyanate, trimethylsilyl Silyl triisocyanate, and combinations thereof. 11. 12. 13. 14. The method of claim 1, wherein the toughener composition comprises dimethyldiethyloxysilane. A method according to item 1, wherein the toughening agent composition comprises a solvent consisting of a group consisting of ketone, ether, ester, hydrocarbon, and a combination thereof. The method of claim 1, wherein the toughener composition contacts the organic silicate glass dielectric film in a state selected from the group consisting of a liquid, a gas phase, a gas, and a plasma. A method for forming a microelectronic device, comprising:) coating an organic silicate glass dielectric film on a substrate; 96350.doc 200531183 b) forming a channel and a trench in the organic phosphonium glass dielectric film Patterning, and subjecting the organic petrolite glass dielectric film to at least one treatment to remove at least a portion of the pre-existing carbon-containing portion and reduce the hydrophobicity of the organic petrolite glass dielectric film; C) contacting the #machine stone silicate glass dielectric film with the-$ concentration increase composition and the time period during which the contacting is effective to increase the hydrophobicity of the organic silicate glass dielectric film; d) filling the channels and trenches with metal; and e) subjecting the metal to an annealing treatment. 15. 16. 17. 18. 19. 20. ^ The method of claim 14, wherein at least a portion of the pre-existing stone-containing anti-portion is removed and the hydrophobicity of the organic material salt glass dielectric film is reduced. At least one of the following processes: an etchant process, an ashing process, a wet peeling process, a cleaning process, and a PECVD process. A method as claimed in claim 14, wherein the composition comprises-a component for methylation, sintering, alcoholation, or arylation via methylation of the organic material salt glass dielectric film. :: 求 项 14 的 # To go, it further comprises the step of removing unreacted Zengwei knife agent, and the mouthpiece, reaction products and mixtures thereof. The method of claim 14, further comprising the step of heating the increased hydrophobic organic silicate glass dielectric film. The method of claim 14, wherein the organic silicate glass dielectric film is nanoporous. The method of claim 14, wherein the organic silicate glass dielectric film is substantially non-porous. "" 96350.doc 200531183 2 1 · The method of claim 14 'wherein the accelerator composition comprises at least one compound having a formula selected from the group consisting of: [-SiR2NR'-] n where n > 2 and may be cyclic, R3SiNR, siR3, dSi) 3N, R3SiNR'2, R2Si (NR ') 2, R§i (NR,) 3, RxsiCly, RxSi (OH) y, R3SiOSiR'3, RxSi (〇R ′) y, RxSi (〇c〇R,) y, RxSiHy, RxSi [OC (R ') = R ”] 4-x and combinations thereof, where x is an integer in the range of 1 to 3, and y is An integer in the range of 1 to 3 such that y = 4-x, each R is independently selected from hydrogen and a hydrophobic organic moiety, R ′ is hydrogen or an organic moiety, and R ″ is an alkyl group or a carbonyl group. The method of 14, wherein the toughening agent composition comprises at least one compound selected from the group consisting of ethoxytrisyl oxalate, ethoxysilane, diethoxysilane, triacetate Ethoxysilane, diethoxydimethyl silane, methyltriethoxysilane, benzyl dioxysilane, diphenyl diethoxysilane, methyltriethyl Silicon oxide Alkane, difluorenyldiethoxysilane, trimethylethoxysilane, fluorenyldimethoxylithium oxalate, difluorenyldimethoxylithium oxalate, trifluorenyloxysilane, methyltrichloro Silane, dimethyldisilane, trimethylchlorosilane, fluorenylsilane, dimethylsilane, trimethylsilane, hexamethyldisilazane, 2-trimethylsilyloxypentane-2 _Ene_4_fluorene, n_ (trimethylphosphonium silyl) acetamide, 2- (trimethylphosphonium silyl) acetic acid, (trimethylphosphonium silyl) flavor, dimethylmethylate Glyoxylic acid g, trimethylmethoxanyl (dimethylsilyloxy) _acetate, nonamethyltrisilazane, hexafluorenyl 96350.doc 200531183 disiloxane, trimethyl Fluorenylsilanol, triethylsilanol, triphenylsilanol, second butyl monomethyllithium alcohol, diphenylsilyl alcohol, trimethoxysilyl alcohol, diethoxysilyl alcohol, Trichlorosilane, hexamethylcyclotrisilazane, bisdimethylamidodimethylsilane, bisdiethylaminodimethylsilane, tris (dimethylamino) methylsilane, tris (dimethylamino) ) Phenylsilane, tris (dimethylamino) ) Silane, dimethylsilyldimethylamine, dimethylsilyldiethylamine, dimethylsilyldiisocyanate, trimethylsilyltriisocyanate, and combinations thereof. 23. The method according to claim 14, wherein the toughening agent composition comprises dimethyl diethyl oxy crush. 24. The method according to claim 14, wherein the toughening agent composition comprises a system selected from the group consisting of ketones , Ethers, esters, hydrocarbons, and combinations thereof. 25. The method of item 14, wherein the toughener composition is contacted in a state selected from the group consisting of a body, a milk phase, a gas, and an electropolymer. The organic stone s salt glass dielectric film. The method of corpse month 14, wherein the aftermath agent is a method comprising items selected from the group consisting of atoms, ions, and / or groups consisting of oxygen, gas, and combinations thereof to item 14, wherein the last name agent is a Wet afterglow agents, amines are a wide variety of reagents selected from the group consisting of: i 4 sub, alcohol amines, amines, triamines, acids, bases, and combinations thereof. 2 8 · The method of finding item 14 in the mouth and month, part of the carbon in the basin. Part of the pre-existing 4 compound treatment includes using at least one kind of reagent selected from the group consisting of Proceedings of Diethyl Ethyl Alcohol \ Ethanolamine, Ethylenediamine ", Diethylethylenediamine, Diethylenetriamine, Amine, Ethyl: 96350.doc 20053lm Amine Tetraacetic Acid, Organic Acid, Acetic Acid, Formic Acid, Tetramethylammonium acetate, phosphoric acid sulfuric acid, hydrofluoric acid, sodium hydroxide, sulfonium oxide, tetrahydroxide hydroxide, and combinations thereof are subject to the limitation that these combinations are reagents that do not neutralize each other. 29 • A microelectronic device produced by a method comprising the following steps: a) coating an organic lysate salt-breaking dielectric film on a substrate; b) forming a channel and Quasi-ditch pattern, and subjecting the organic phosphonium salt-breaking dielectric film to at least one-to remove at least a part of the previous; ; Treatment of the hydrophobicity of the electrical thin film; c) contacting the organic petrosate glass dielectric film with a "binder composition of a certain concentration" and one of the contact θ ^ -t- uu rb ^ The system can effectively increase the hydrophobicity of the organosilicate glass-breaking dielectric film; d) filling the channels and trenches with a metal; and e) subjecting the metal to an annealing treatment. 96350.doc 200531183, 7. Designated representative map: (1) The designated representative map of this case is: (none) (2) The component symbols of this representative map are briefly explained: 8. If there is a chemical formula in this case, please disclose the features that can best show the invention Chemical formula: (none) 96350.doc