TWI358093B - Repairing damage to low-k dielectric materials usi - Google Patents

Description

1358093 IX. Description of the Invention: [Technical Field] The present invention relates to a method for recovering the hydrophobicity of a surface of an organic silicate glass dielectric film, wherein the organic silicate glass dielectric film is removed The manner in which at least a portion of the pre-existing carbon-containing portion is subjected to etching or ashing treatment 'causes the film to have reduced hydrophobicity. These films are used as insulating materials in the fabrication of semiconductor devices such as integrated circuits ("ic") to ensure low dielectric constant and stable dielectric properties in such films. [Prior Art] As the size of device features in integrated circuits is reduced, interconnect Rc delay, power consumption, and signal crosstalk problems have become increasingly difficult to solve. The integration of low dielectric constant materials for interlayer dielectric (ILD) and inter-metal dielectric (IMD) applications will help solve these problems. Although efforts have been previously made to apply low dielectric constant materials to integrated circuits, there has been a long felt need in the art for further optimization in terms of processing methods and dielectric and mechanical properties of such materials. Device scaling in future integrated circuits Clearly requires the use of low dielectric constant materials as part of the interconnect structure. Most of the alternatives for low dielectric constant materials for sub-1GG nm generation ICs are carbon-containing films formed by either CVD or spin coating methods. During subsequent processing steps, such as plasma etching and photoresist removal using plasma or wet photoresist stripping methods, these low-level materials are significantly damaged, resulting in low-k materials adjacent to the (four) surface. The I addition in and the carbon loss from it. In addition to the higher effective k value, the resulting structure is prone to void formation, outgassing, and bubble formation. These voids, in turn, can cause an increase in leakage current and a decrease in breakdown voltage at high voltages in 96350.doc 1358093. The present invention describes a method for reducing the damage and the resulting problems by treating the crystals with a formazanating reagent after the damage has occurred.

It has been reported that the use of non-destructive ashing chemistry (such as H2/He) can reduce carbon loss and related problems. 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 been shown that post-ashing ashing treatment can restore hydrophobicity and reduce the dielectric constant. It is also shown that post-ash ashing treatment can restore water repellency and reduce the dielectric constant. In this regard, see YS Mor, TC Chang, PT Liu, Τ. sai. Tsai, CW Chen, ST Yan, CJ Chu, WF Wu, F. M. Pan, W. Lur and SM Sze, Journal of Vacuum Science & Technology, B, 2 (4), 1334 (2002); and PG Clark, BD Schwab and JL W. Butterbaugh, Semiconductor International, 26 (9), 46 (2003). One of the advantages of the latter approach is that it allows the use of well-established #刻 and ashing methods. For this purpose, post-ashing treatment is required to repair the damage resulting in the porous SiCOH-based low-k material. This treatment can cause 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 (this void formation 96350.doc 1358093 typically occurs in an untreated porous low dielectric interlayer region during steel annealing), then This post-ashing treatment is desirable. f. The stone smelting agent ("increasing edge agent") can be methylated to the surface of the 〇2-based material. Exposures covered include gas phase exposure (with or without plasma), spin coating and supercritical C〇2. Generally, the SiC0H-based porous low (9) material is prone to void formation in the ILD in the CU damascene process. After the treatment with the enhancer, the resulting structure is significantly more resistant to void formation. Without being bound by any particular theory or mechanism, the Xianxin plasma damage causes carbon loss in the dielectric by replacing the Si_CH3 bond with a Si_〇H bond. In damaged porous dielectrics, the surface of the hole is now covered with a _011 bond. In the presence of tensile stress (such as after Cu annealing), adjacent Si-OH groups can condense, thereby causing local densification. The evolution of the reaction product and the molecular stretching due to the new chain formed results in voids occurring near the center of the ILD space. The toughening agent prevents the formation of voids by replacing most of the _〇11 bond with a Si-O-Si-Rn bond (which avoids the condensation reaction). Thus the formation of voids does not occur. The toughening treatment performed after the dielectric trench and channel formation and etching and ashing steps repairs the carbon loss and damage of the low-k material. This means that the void is prevented and the 4 low-k material can withstand the internal stress caused by the annealing treatment of the metal filling the trench and the channel. The edged treatment is carried out by exposing the surface of the wafer to a liquid or gaseous form of the ruthenium reagent for a period of time sufficient to complete the reaction with the damaged low-k region. High temperature baking can be performed to remove residual solvent and excess extender, as needed. Immediately after the application of the toughening agent or after the baking step, a commercially available low-k dielectric compatible chemical can be used to perform a wet cleaning operation, 96350.doc 1358093. In addition, the effectiveness of the dewatering treatment can be performed prior to the toughening agent treatment. An unpatterned low-k dielectric film can be used to undergo etching and ashing treatment, followed by a toughening agent treatment to verify the effectiveness of the toughening agent treatment. The toughening agent treatment results in an increase in carbon concentration. The carbon concentration can be measured by FTIR, EDX or XPS techniques. In addition, an increase in the water contact angle can be seen, which demonstrates the hydrophobic nature of the treated surface. The film with the toughening agent = also exhibits a low dielectric constant extracted from the C-V measurement compared to the etched/ashed thin film treated without the toughening agent. In patterned wafers, copper plating is used to demonstrate the effectiveness of the toughener treatment by reducing or eliminating voids in the low-k dielectric in the narrow space between the cu channels after copper annealing. The effectiveness is demonstrated by exposing it to a lower profile change in the channel or channel after exposure to the reactive solvent. SUMMARY OF THE INVENTION The present invention provides a method for preventing stress induced void formation in an organic tellurite glass dielectric film on a substrate that has been patterned to form channels therein and a trench, and the organic tellurite glass dielectric film is subsequently subjected to at least one treatment for removing at least a portion of the pre-existing carbon-containing portion and reducing the hydrophobicity of the organic tellurite glass dielectric > And then filling the channels and trenches with a metal, and then the metal is subsequently subjected to an annealing process, which is followed by at least one etchant or ashing agent in the scripture, but filling the channels and channels with a metal Prior to the ditch, the organic tellurite glass dielectric film is contacted with a one-degree composition of the attendant composition and the contact is subjected to a period of time 96350.doc 1358093 effective to restore at least some of the carbonaceous portion to the organic germanium The acid salt glass film increases the hydrophobicity of the organic tellurite glass dielectric film. % The present invention also provides a method for forming a microelectronic coating, comprising: a) applying an organic tellurite glass dielectric film to a substrate. b) in the organic tellurite glass dielectric film Forming a pattern of channels and trenches, and subjecting the organosilicate glass dielectric film to at least one purpose of removing at least a portion of a pre-existing carbon-containing portion and reducing hydrophobicity of the organosilicate glass dielectric film Sexual treatment;

接触 contacting the organic tellurite glass dielectric film with a certain concentration of the activator composition and the contact for a period of time should be effective to increase the hydrophobicity of the organic tellurite glass dielectric film; d) a metal filling the channels and trenches; and e) subjecting the metal to annealing. The present invention provides a microelectronic device produced by a method comprising the steps of: ~ a) coating an organic tellurite glass dielectric film on a substrate; b) forming in the organic tellurite glass dielectric film a pattern of channels and channels, and subjecting the organosilicate glass dielectric film to at least one purpose of removing at least a portion of the carbonaceous portion present and reducing the hydrophobicity of the organosilicate glass dielectric film Processing; c) contacting the lithium silicate glass dielectric film with a concentration of the extender composition and the contact may be effective for increasing the organic stone The hydrophobicity of the electrical film; d) filling the channels and trenches with a metal; and 96350.doc *10-1358093 e) subjecting the metal to annealing. [Embodiment] In the case of the present invention, since the dielectric material of the low dielectric constant of av, which has a low frequency of less than 3, generally allows a faster signal-drying value to be broadcasted, the capacitance effect is reduced. It is especially desirable to have crosstalk between the wires and to reduce the voltage of the drive integrated circuit. A material having a low dielectric constant is a dioxide dioxide which can be applied as a foamed dielectric material. In order to obtain the lowest dielectric value possible, air is introduced into the dioxide dioxide dielectric material. Air has a dielectric constant i, and a relatively low dielectric constant is achieved when introducing air into a nanoporous or nanoporous pore structure of a nano-porous dielectric material ("~ should be understood The term "steel dioxide", unless specifically mentioned as a functional group "si〇2", as used herein, the term "earic dioxide eve" (for example, relating to porous or non-porous " Electrofilm) is intended to mean a dielectric film prepared by the method of the present invention from an organic or inorganic glass base material (e.g., any-containing or a plurality of silk dielectric precursors: suitable starting materials). It should be understood that the singular use of the singular is not intended to be limited thereto, and, where appropriate, includes plural 'for example, the exemplary method of the invention can be described as being applied to and producing a 'film', but It is intended that a plurality of films can be produced by the methods described, illustrated and claimed. The term "film" as used herein with respect to ceria dielectric materials is intended to encompass such ceria. Electrical material The situation may be in any suitable form or shape. Because the nanoporous cerium oxide is similar to the precursors, such precursors include, for example, tetramethoxy sylvestre CTMOS") and/or tetraethoxy shi shou (" The organic matter of TE〇s") replaces Xi Xuan (which is used in the currently used spin-on glass ("s〇G,,) and chemical gas 96350.doc 1358093 phase deposition ("CVD") cerium oxide si 〇 2), therefore nanoporous ceria is attractive. As used herein, the terms "void" and "pore" mean the free volume in which a substance is displaced by a gas or a vacuum is created therein. The composition of the gas is generally not critical, and suitable gases include relatively pure gases and mixtures thereof (including air). The nanoporous polymer may comprise a plurality of pores. The pores are generally spherical, but alternatively or Further having any suitable shape 'comprising a tubular, layered, disc or other shape. The pores may be uniformly or randomly dispersed within the porous polymer. It is also contemplated that the pores may have any suitable diameter. Further At least some of the holes may be joined to adjacent holes to construct a structure having a significant amount of connected or "open" porosity. The nanoporous ceria film has previously been fabricated by a number of methods. The base precursor composition and the method for forming the nanoporous silica dioxide dielectric film are, for example, the following U.S. Patent Nos. 6,048,804, 6,022,812, 6,410,149, 6,372,666. No. 6,509,259, 6,218,497, 6,143,855, 6,037,275, 6,042,994, 6,048,804, 6,090,448, 6,126,733, 6,140,254, 6,204,202, 6,208,041, No. 6,318,124 and 6,319,855, each of which is incorporated herein by reference. Other dielectric-based and low-dielectric materials include inorganic-based compounds, such as the sulfhydryl compounds disclosed in U.S. Patent Application Serial No. 10/078,919, filed on Feb. , NANOGLASS® and HOSP® products available from Honeywell International Inc.). The material can be applied by spin coating on the surface, the material 96350.doc -12-1358093 is dipped, spray coated, chemical vapor deposited (CVD), lightly applied to the surface, and the material is dropped. The dielectric and low dielectric material are coated on the surface and/or by applying a material to the surface. Dielectrics suitable for use in the present invention include (iv) deposition materials such as carbon doped oxides, such as Black Di_nd available from A_ed Matenais, Inc., available from Ν〇ν_δ

Cora Bu can be purchased from ASM Aur〇ra and can be heard from Trik〇n. The phrases "spin coating material",, spin-coated organic material, "spin coating composition" and "spin coating inorganic composition" as used herein are used interchangeably and refer to They may spin coat a solution and composition on a substrate or surface using a spin coating method. Examples of the mercapto compound include a decyl alkane compound such as methyl decane, methyl sesquiterpene oxide, benzene. Base stone yew calcination, phenyl sesquiterpene oxy-oxygenation, sulfhydryl-based stony-based oxygen burning, methyl stupid sesquiterpene oxide, Shishi nitrocarburic polymer, agglomerate polymer and mixtures thereof. The sulfonium alkane polymer encompassed is a perhydroabiazinane having a "transparent" polymer backbone to which a chromophore can be attached. The spin-on glass material also includes a siloxane polymer and a plug-in polymer. a hydroquinone polymer of the formula (Ui〇...Λ) and a hydrogen sesquioxane polymer of the formula (HSi〇15) X, wherein x is greater than about 4. Also includes hydrogen sesquioxanes and alkoxy groups. A total of alk〇xyhydrid〇Siloxane or hydroxyhydrogenated oxane The spin-on glass material additionally includes a compound of the formula (Hqi QSi〇i 5 2). It is a polymer of 5 2 core hydrogenated hydride and a formula (HSi〇i 5 is Rsi〇l 5^ An organohydrogenated sesquiterpene polymer wherein the paws are greater than zero and the sum of the readings is greater than 4' and R is a hospital or aryl group. Some suitable organic hydrated oxygen polymers have from about 4 to about 5总00 of the sum of 11 and 111, wherein the pedigree (: broad c2q alkyl 96350.doc -13 - 1358093 or Gc, 2 aryl. These organic hydrogenated oxazane and organic hydrogen sesquioxanes poly & Some of the specific examples include spin-on polymers, some of which include thiophosphazil, such as: methyl hydride, ethyl chlorite, propyl hydrogen hydride, Tertiary butyl hydrogen hydride, phenyl hydrogen hydride, and hospital-based hydrogenated sesquiterpene, such as: methyl hydrogenated sesquioxanes, ethyl hydrogen sesquioxanes, Propyl hydrogenated sesquioxane, tert-butyl hydroperoxysesquioxane, phenyl hydroperoxysesquioxane, and combinations thereof, as specified below A number of covered spin coating materials are described in the patent application and the application in the application: U.S. Patent Nos. 6,506,497, 6,365,765, 6,268,457, 6,177,199, 6,358,559, 6,218,020, U.S. Patent Application Serial No. 10/001,143, filed on Nov. 6, 218, No. PCT/US00/15772 ' applied for on June 8 of the following year and PCT/us〇〇/00523 filed on January 7, 1999, the entire contents of which are incorporated herein by reference. The organohydrogen hydride and organic oxirane resin solutions can be used to form a caged siloxane polymer film suitable for the manufacture of various electronic devices, microelectronic devices, especially semiconductor integrated circuits, and for electronic and semiconductor components. Various laminate materials including a hard mask layer, a dielectric layer, an etch stop layer, and an embedding etch stop layer. These organohydrogenated hafnoxy resin layers are compatible with other materials that can be used in the ® layer materials and devices, such as diamond-based compounds, bis-damantane-based compounds, ruthenium nucleus compounds, organic dielectric shells, and nanoparticles. Porous dielectric. Compounds that are quite compatible with the organohydrogen hydride oxyalkylene resin layer disclosed herein are disclosed in the following patents: U.S. Patent No. 96350.doc • 14·1358093, No. 6,214,746, No. 6,171,687, No. 6, , 172,128, 6,156,812, US Application No. 60/350,187, filed Jan. 15, 2002, U.S. Patent Application Serial No. 09/538,276, U.S. Patent Application Serial No. 09/544504, U.S. Patent Application Case No. 09/587851, and US 60/347195 filed on January 8, 2002, applied on October 17, 2001? Hey! 'Application? (^1711801/32569, December 31, 2001, PCT/US01/50812, the entire disclosure of which is incorporated herein by reference. The resin has the following general formula: [H-SUJR-SiOuk Formula (1) [Ho.s-SiKs.KgJnCRo.si.o-SiOj 5.! 8]m Formula (2) [H〇_i 〇-Sii.5]n [R--Si〇i.5]m Equation (3) [Η-Si! 5]x[R-Si〇i.5]y[Si〇2]z Equation (4) where: :η and m And or the sum of X, y and z is from about 8 to about 5000, and m*y is selected such that the carbonaceous component is present in an amount of less than about 40% (low carbon organic content = L〇sp) or greater than about 40 % (high carbon organic content = H0SP) is present; R is selected from substituted and unsubstituted, normal and branched alkyl (methyl, ethyl, butyl, propyl, pentyl), alkenyl (vinyl, allyl, isopropenyl), cycloalkyl, cycloalkenyl, aryl (phenyl, phenylhydrazine, naphthyl, anthryl and phenanthryl) and mixtures thereof, and containing a substituent The specific molar percentage is a function of the ratio of the amount of starting material. In some LOSP embodiments, the molar percentage is between about 5 mole percent. A particularly advantageous result is obtained with a carbon-containing substitution 96350.doc 1358093 base in the range of about 25 mole percent. In some HOSP embodiments, the molar percentage is between about 55 mole percent and about 75 mole percent. The carbon-containing substituents in the range of percentages have favorable results. A nanoporous ceria dielectric film having a dielectric constant in the range of about 1.5 to about 4 can also be used as one of the layers. Wn) a nanoporous tantalum oxide film as a ruthenium-based precursor which is aged or condensed in the presence of water and heated sufficiently to completely remove all pore-forming molecules and form voids in the film. The composition comprises a monomer or prepolymer having the formula Rx_Si_Ly, wherein the R is independently selected from the group consisting of an alkyl group, an aryl group, and an L-systemically electronegative moiety, such as an alkoxy group, a amide group, an amine group, a captanamine, and a halogenation group. And isocyanate and combinations thereof, the lanthanide is an integer ranging from 〇 to about 2, and the y is an integer ranging from about 0 to about 4. Other nanoporous compounds can be found in the following patents. Method: US Patent Case No. GW", 6,172'128, 6,214,746, 6,313,185, 6'380'347, and 6,380'270, each of which is incorporated herein by reference. "Cage Structure"; "Cage" ""Cagecompounds" are intended to be used interchangeably and refer to molecules having at least 10 atoms, in which the atoms are arranged such that at least one atom bridge is covalently linked. Two or more atoms of the system. In other words, a cage structure, a cage molecule or a cage compound comprises a plurality of rings formed by covalently bonded atoms, wherein the structure, molecule or compound defines a volume such that the point positioned by the volume does not cross In the case of this ring, it does not leave the volume. The atomic bridge and/or the ring system may comprise - or a plurality of heteroatoms' and may be aromatic, partially saturated or not 96350.doc -16 - 1358093, the it # covered 茏-like structure including the spherical shell a carbon molecule and a crown having at least one atomic bridge. For example, if a diamond compound or an aromatic snail compound does not have one or more atomic bridges, and the Cai compound or the hexagram compound does not have one or more atomic bridges, The aromatic spiro compound is considered to be a scorpion structure. The cage compound encompassed is not limited to only containing dish atoms, but may also include heteroatoms such as N, S, fluorene, p, and the like. Heteroatoms can advantageously be introduced into non-quadrilateral bond angle configurations. With regard to the substituents and derivatization of the cage compounds covered, it is recognized that many substituents and materials are suitable. For example, when the cage compound is relatively hydrophobic, a hydrophilic substituent can be introduced to increase solubility in a hydrophilic solvent, or vice versa. Alternatively, if a polarity is desired, a polar side chain group can be added to the cage compound. Further contemplated suitable substituents may also include thermally labile groups, nucleophilic groups, and electrophilic groups. It is also understood that a functional group (e.g., to promote a crosslinking reaction, a derivatization reaction, etc.) can be utilized in the cage compound. The cage molecule or compound as described in detail herein may also be a group attached to the polymer backbone, and thus can form a nanoporous material in which the cage compound forms a type of void (inside the molecule), and At least a portion of the backbone is crosslinked with itself or another backbone to form another type of void (intermolecular). Additional cage molecules, cage compounds, and variants of such molecules and compounds are described in detail in PCT/US 〇 1 352 569, filed on Jan. 18, 2001. The entire disclosure of which is incorporated by reference. Into this article. The polymers covered may also comprise a wide range of functional or structural moieties including aromatic systems and functional groups. In addition, suitable polymers can be used in a variety of configurations, including homopolymers and heteropolymers, 96350.doc -17-1358093. Moreover, the surrogate polymer can have various forms such as linear, branched, hyperbranched or three dimensional. The molecular weight of the polymer covered covers a wide range: typically between 400 Daltons and 400,000 Daltons or more. Additives may also be used to enhance or impart specific characteristics, including stabilizers, flame retardants, pigments, plasticizers, surfactants, and the like, as is well known in the art of polymers. A compatible or incompatible polymer can be blended therein to provide the desired characteristics. Adhesion promoters can also be used. Hexamethyl diazepine represents these promoters which can be used in combination with available hydroxy functional groups which may be present on surfaces exposed to moisture or humidity, such as cerium oxide. Polymers used in microelectronic applications, specifically for dielectric layers, must contain low levels of ionic impurities (usually less than ppm, preferably less than 1 pp ppb). As long as the resulting solution can be applied to a substrate, surface, wafer or laminate, the materials, precursors and layers described herein can be and in many ways designed to be solvated or dissolved in any suitable solvent. Typical solvents are also those which are capable of solvating the monomers, isomeric monomer mixtures and polymers. The solvents contemplated include any suitable pure organic or inorganic molecule or mixture thereof which is volatilized at a desired temperature such as a critical temperature and which promotes any of the above design goals or needs. The solvent may also comprise any suitable unipolar and non-polar compound or mixtures thereof. As used herein, the polarity of a molecule or a compound at the point of or along the molecule or compound establishes characteristics of unequal charge, partial charge 1 or spontaneous charge distribution. As used herein, the term "non-polar" means that a molecule or compound at one point of the molecule or compound or 96350.doc 2 is a molecule or compound that builds an unequal charge, partial charge, or spontaneous scalpel. The characteristics of the cloth. In some of the contemplated embodiments, the solvent or solvent mixture (comprising at least two solvents) comprises a solvent which is considered to be part of the hydrocarbon solvent. The hydrocarbon solvent is a solvent containing carbon and hydrogen. It should be understood that most of the solvents are non-polar; however, a small number of hydrocarbon solvents can be considered polar. Hydrocarbon solvents are usually subdivided into three categories: aliphatic, cyclic, and aromatic. The aliphatic hydrocarbon solvent may comprise a linear compound and a branched chain and may be both a crosslinking compound, however, the aliphatic hydrocarbon solution is considered to be cyclic. The cyclic hydrocarbon solvents are those which have a carbon atom which is at least three (four) to the in-ring structure, similar to the characteristics of the aliphatic smog solvent. The aromatic hydrocarbon solvent is a solvent which usually contains three or more unsaturated bonds, and the aromatic hydrocarbon solvent has a single ring or a polycyclic ring to which a common bond is bonded and/or a polycyclic ring which is fused together. Hydrocarbon solvents covered include toluene, xylene, p-xylene, m-xylene, 1}3,5-trimethylbenzene, Shiliu 6) oil H/trol, naphtha A solvent, alkane , such as pentane, hexane, isohexane, heptane, decane, octane, dodecane, 2-methylbutane, hexadecane, tridecane, pentadecane, cyclopentane, 2, 2 , 4_trimethylpentane, petroleum ether, halogenated hydrocarbons, such as gasified smoke, nitrated hydrocarbons, stupid, antimony, 2-dimethylbenzene, H4 trimethylbenzene, mineral spirits, kerosene, isobutylbenzene , methyl naphthalene, ethyl benzene, light petroleum (ligroine). Solvents specifically contemplated include, but are not limited to, pentane, hexane, heptane, hexane, benzene, toluene, xylene, and mixtures or combinations thereof. In other contemplated embodiments, the solvent or solvent mixture may comprise a solvent that is not part of a compound of the hydrocarbon solvent family, such as a ketone such as propionium, 3-pentanone, diethyl ketone, hydrazine. Ketoethyl ketone and its analogs, alcohols, hydrazines, vinegars, ethers and amines. In other contemplated embodiments, the solvent or solvent mixture may comprise a combination of any of the solvents mentioned herein. = Real:, the solvent comprises water, ethanol, propanol, propylene, benzene, toluene, (4) MW: step coverage: the alternative low dielectric constant material may also contain additional damage. For example, softeners or other protective agents may be added when the low dielectric constant material is exposed to mechanical stress. In other cases where the dielectric material is placed on a smooth surface, an adhesion promoter may be advantageously employed. In other cases, detergents or defoamers may be added. Typically, a precursor is applied to a substrate, for example, in the form of a spin-on glass composition comprising one or more removable solvents, and then polymerized and formed to form a dielectric comprising nanopores. The film is subjected to solvent removal. Forming such nanoporous thin materials (for example, by applying spin coating to a substrate by spin coating) 'The thin film coating is usually catalyzed by an acid or a catalyst and water to cause polymerization during the preliminary heating step. / condensing (aging). If necessary, the film is then hardened (for example by subjecting the film to one or more high temperature heating steps), whereby (among other purposes) remove any residual solvent and The polymerization process is carried out. Other hardening methods include subjecting the film to radiant energy, such as ultraviolet light, electron beam, microwave energy, and the like. Co-owned U.S. Patent Nos. 6,204,202 and 6,413,882 are incorporated by reference. Herein, it provides a sulfhydryl precursor composition and a method for forming a nanoporous germanium germanium dielectric film by degrading or evaporating one or more polymers or oligomers in the precursor composition. U.S. Patent No. 6,495,479, the disclosure of which is incorporated herein by reference to U.S. Patent No. 6,495,479, the disclosure of which is incorporated herein by reference. A method of forming a nanoporous ceria dielectric film by using a compound or a material. The U.S. Patent No. 5,895,263 describes the application of a decomposable polymer and an organic polyoxolite by coating (organic poly-two gas fossils, ie, a composition comprising a condensed or polymerized oxime η), heating the composition to further condense the polydioxo oxime, and decomposing the decomposable polymer to form a porous dielectric layer, thereby forming a porous substrate , a nanoporous ceria dielectric film is formed on the wafer. ▲ a method for applying a precursor to a substrate, aging, hardening, planarizing, and making the film hydrophobic (example) For example, the commonly-owned U.S. Patent Nos. 89,889 and 6, η, 275 are described (other patents are also involved). The substrates and wafers covered herein may include any A substantially solid material is required. The particular desired substrate layer should comprise a thin film glass, a ceramic, a plastic, a metal or a coated metal, or a composite material. In a preferred embodiment, the substrate comprises a stone or stone application. Grain or crystal The surface of the package, such as copper, silver, nickel or gold-plated leadframes, as found on board surfaces such as circuit boards or package interconnect traces, channel walls, or hardener interfaces. The copper of the company includes bare steel and its oxides. It is based on polymer-based packaging or board interfaces found in the practice of imine-based packaging, spherical or spherical surfaces of ships or other metal alloys, glass and a polymer such as polyimine. When considered as adhesion (or even a "substrate," it is defined as another polymer chain. In a more preferred embodiment, the substrate is included in the package. And materials commonly found in the circuit board industry, such as germanium, copper, glass, and another polymer. 96350.doc The top cover of the film (4) is used for the cover (4)) and the half of the film deposition is patterned by (4) and ashing. The formation channel tends to remove the carbon-containing moiety from the organosilicate glass dielectric film; it is a hydrophobic group @) and is replaced with an alcohol group. Undesirable properties are caused when the organosilicate ceramic dielectric film contains a phenolic group. The smelting alcohol and its water absorbing from the air are highly polarizable in the electric field; 0 and thus will increase the dielectric constant of the film and will reduce the resistance to wet cleaning chemical reactions, and Increase volatility evolution. Moreover, when the trenches and channels are filled with metal and subjected to annealing treatment, metal shrinkage induces stress on the channels and trench walls and causes formation of dielectric materials between the channels and trenches. Unwanted gaps. To compensate for this problem, the organic salt glass dielectric film is substantially cut (4) and water to restore the carbonaceous portion and increase the hydrophobicity of the organosilicate ceramic dielectric film. This makes the film resistant to stresses on the walls of the channels and channels, such as stresses caused by metal shrinkage during annealing, stresses from other dielectric layers, and stresses during packaging, thus preventing An undesired void is formed inside the dielectric material between the channels and the trench. Etching and plasma removal of hydrophobic functional groups. Semiconductor Manufacturing Process t Organic silicate glass dielectric films are damaged by the application of corrosive plasma and/or etch reagents to etch trenches and channels into the dielectric film. Plasma is also used to remove the photoresist film during semiconductor device fabrication. The electropolymerization used is usually composed of elemental oxygen, fluorine, hydrogen, carbon, argon, helium or nitrogen (in the form of free radicals, compounds, ions and/or groups). 96350.doc -22· 1J58093 The wood trench: the channel exposed during the etching and/or photoresist removal process is degraded or damaged by the dielectric. Porous dielectric films have a very high surface area, so i is particularly susceptible to damage by plasma damage. Specific. Thus, a silica-based dielectric film having an organic content such as a methyl group bonded to a Si atom is easily degraded via oxygen electricity t. The organic group oxygen = is C 〇 2, and the stanol or Si-OH group remains on the previously observed β hai dielectric surface of the organic group. The porous ceria film depends on the organic groups (on the porous surface) to retain hydrophobicity. The loss of hydrophobicity causes the dielectric constant to rise (the low dielectric constant of the films is a critical requirement for the materials).

Wet chemical treatment is also used in the 1c production process for the purpose of removing residues remaining after the trench or channel is etched. The chemicals used are often so corrosive that they attack and remove organic groups in the ceria-based dielectric film, especially the porous ceria film. Moreover, this damage will cause the films to lose their hydrophobicity. Wet chemical etchants include, for example, decylamine such as hydrazine methyl pyrrolidone, dimethylformamide, dimethylacetamide; alcohols such as ethanol and 2-propanol; alcohol amines such as ethanolamine; Amines of triethylamine; diamines such as ethylenediamine and hydrazine, hydrazine-diethylethylenediamine; triamines such as diethylenetriamine; diglycols such as ethylenediaminetetraacetic acid "EDTA" Organic acids such as acetic acid and citric acid; organic acid ammonium salts such as ammonium tetradecyl acetate; inorganic acids such as sulfuric acid 'phosphoric acid, hydrofluoric acid; fluoride salts such as fluorinated; and ammonium hydroxide and hydrogen a base of oxidized tetradecyl ammonium; and an amine; commercial formulations developed for post-etch wet cleaning, such as EKC 505, 525, 450, 265, 270, and 630 (EKC Corp., Hayward CA), 96350.doc -23- 1358093 and aCT-CMI and ACT__ (Ashiand take Qingshan CA), this is only a few (four) agents known in the art. Ashing includes resins derived from chlorine, [ammonia, ammonia, oxygen, and mixtures derived therefrom] and the like. In order to solve the above problems, the present invention provides a method of imparting hydrophobic properties to an organic salt present on a substrate during the manufacture of a semiconductor or 1C device. The method of the present invention comprises the steps of: (4) subjecting to at least one etchant or ash After the reagent, but before the metal is subjected to the annealing treatment, the (tetra) acid salted glass dielectric film is contacted with the auxiliaries, and the contact is effective for at least some of the The carbon portion is restored to the organic tellurite glass dielectric film and the hydrophobicity of the organic bismuth oxide dielectric thinner is increased; and (b) the unreacted (4) composition, the reaction product, and the mixture thereof are removed. The toughening agent composition comprises at least one toughening agent, i.e., a compound suitable for removing a stanol portion from a damaged ceria dielectric film or a charged derivative thereof. Optionally, the etchant-damaged nanoporous ceria dielectric film is then subjected to a wet cleaning step. In one embodiment, the toughener composition comprises at least one toughening agent composition having the formula: (I) [-SiR2NR'-]n wherein n>2 and may be cyclic; (2) R3SiNR, SiR3; (3) (R3Si)3N; (4) R3SiNR'2; (5) R2Si(NR')2; (6) RSi(NR')3; (7) RxSiCly; (8) RxSi(OH)y (9) R3SiOSiR'3; (l〇) RxSi(〇R,)y; (II) RxSi(OCOR,)y; (12)RxSiHy; (13)RxSi[OC(R,)=R"]4_x And combinations thereof, 96350.doc • 24_ 1358093 wherein X is an integer in the range from 1 to 3, an integer from _ to 3 such 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 independent k free alkyl groups, aryl groups and combinations thereof. The group may be H, an alkyl group, an aryl group, or a treason such as c〇R, c〇NR, or Han. R" can be a base or a base such as COR, CONR, C02R. In another specific embodiment, the toughening agent composition comprises at least one of the following toughening agents or compositions: ethoxylated trimethyl decane, ethoxylated decane, monoethoxy decane, diethyl hydrazine Oxydecane, diethyl methoxy dimethyl decane, methyl triethoxy decane, phenyl triethoxy decane, diphenyl ethoxy decane, methyl triethoxy decane, Dimethyldiethoxy oxime, dimercaptoethoxy oxazetan, methyltrimethoxydecane, dimethyldimethoxydecane, tridecylmethoxydecane, methyl trioxane, two Methyl dioxane, trimethylchlorodecane, methyl decane, dimethyl decane, trimethyl sulphide, methyl ketone, hexamethylcyclotrizepine, bis(dimethylamino) a dinonyl decane, bis(diethylamino) decyl decane, tris(dimethylamino)decyl decane, bis(dimethylamino)phenyl decane, tris(dimethylamino) decane, two Methyl sulphate, sulphate, dimethyl phthalocyanine, dimethyl phthalocyanine diisocyanate, trimethyl ketone Alkyl triisocyanate, 2-trimethylnonyloxypent-2-en-4-one, n-(trimethylformamidinyl)acetamide, 2-(dimethyl fluorene ruthenium) Acetic acid, n-(trimethyl sulfonium), m-wine, trimethyl sulfonium acrylate, trimethyl sulfonium (trimethyl sulphate) Acetate, nonamethyl trisulphone, hexamethyldioxanthine, trimethyl sulphate, triethyl decyl alcohol, triphenyl decyl alcohol, tert-butyl fluorenyl sulphate, two Phenylnonanediol, trimethoxydecane, triethoxysulfonium, 96350.doc -25-1358093 trichlorodecane, and combinations thereof. In a desired embodiment of the invention, the toughening agent comprises dimethyldiethoxydecane. Optionally, the toughener composition comprises a solvent. Suitable solvents include, for example, ketones, ethers, esters, hydrocarbons, and combinations thereof. The toughening agent composition acts as a liquid, gas phase or gas, and/or plasma contact with the ruthenium oxide dielectric film. If in the form of a plasma, the plasma can be derived from a decane compound, a hydrocarbon, an aldehyde, an ester, an ether, and/or combinations thereof. Unless otherwise stated, the term "reagent"(,,agent" or "agents") in this article shall be considered synonymous with the term "reagent"("reagent" or "reagents"). Suitable toughener compositions include one or more toughening agents which are capable of removing stanol groups from an etched and/or ashed organosilicate glass dielectric film which is rendered hydrophobic. For example, the toughening agent is a compound having a molecular formula selected from the group consisting of Formula 1 (1-13): -]n, wherein η>2 and may be cyclic; (2) R3SiNR, SiR3; 3) (R3Si)3N; (4) R3SiNR|2; (5) R2Si(NR')2; (6) RSi(NR-)3; (7) RxSiCly; (8) RxSi(〇H)y; 9) R3SiOSiR'3; (10) RxSi(OR')y; (1 l) RxSi(OCOR')y; (12) RxSiHy; (13) RxSi[OC(R|)=R"]4-x and A combination thereof, wherein x is an integer in the range of 1 to 3, and the oxime is one integer in the range of 3 such that y = 4-x, and each R is independently selected from hydrogen and a hydrophobic organic moiety. Preferably, the group is independently selected from the group consisting of an alkyl group, an aryl group, and a combination thereof. The group may be H, an alkyl group, an aryl group, or a group such as c〇r, C〇nr, (: 〇211. R" It may be an alkyl group or a carbonyl group such as COR, CONR, CO 2 R. The danic base moiety is functionalized or unfunctionalized, and is selected from the group consisting of linear alkyl groups, branched alkyl groups, and cyclic groups. An alkyl group and combinations thereof, and wherein the alkyl moiety in the 96350.doc -26- 1358093 is in the range from Ci to about s. The aryl moiety is substituted or unsubstituted. From C5 to about C1S size range. The toughening agent is preferably ethoxylated decane or, for example, a monomeric compound such as ethoxylated trimethyl decane, ethoxylated decane, diethyl醯 石 夕 、, triethoxy decane 'diethoxy dimethyl decane, decyl triethoxy decane, phenyl triethoxy decane, diphenyl dimethyl decyl oxane , mercapto diethoxy decane, dimethyl diethoxy sulphur, trimethyl ethoxy decane, decyl tridecyl decane, dimethyl dimethoxy decane, trimethyl methoxy Decane, methyl trioxane, dihanyl dichlorodecane, tridecylchlorodecane, methyl decane, dimethyl decane, trimethyl decane, hexamethylene diazoxide, hexamethylcyclotriazide Alkane, bis(dimethylamino)dimethyl decane, bis(diethylamino)dimethyl decane, tris(dimethylamino)methyl decane, tris(dimethylamino)phenyl decane, three ( Diammonium) decane, dimethyl decyl dimethyl decylamine, monomethyl decyl dimethyl decylamine, dimethyl decyl diisocyanate, trimethyl 7-hospital triisocyanate g, 2_trimethylformyloxypenta-2-dibenzo-4-one, η-(trimethylformamidinyl)acetamide, 2_(trimethyldecane Acetate, η-(trimethylformamidinyl)imidazole, tridecylmethyldecylpropynyl ester, -methylmethyl sulphate (dimethyl ketone), acetic acid Nine methyl tripotarite, hexamethyldioxane, tridecyl decyl alcohol, triethyl stanol, phenyl stanol, tert-butyl dimethyl stanol, diphenyl decane diol, Three = base material, triethoxy money, three gas (four) and combinations thereof. In a significant embodiment, the toughening agent is methyltriethoxydecane. In a preferred embodiment, the booster is dimethyldiethoxy oxime. Further extenders include those detailed in U.S. Patent No. 6,208,014.

The surface modification reagent, as described above, is incorporated herein by way of example. The multifunctional surface modifying agents can be applied in the form of a gas phase or a liquid, with or without a cosolvent as appropriate. Suitable co-cooling agents include, for example, acetone, diisopropyl ketone, 2-heptanone, 3-pentanone, and other ketones, as described in commonly-owned U.S. Patent No. 6,395,651. The disclosure of the disclosure is incorporated herein by reference. For example, as described in detail in U.S. Patent No. 6,2, Mu, certain preferred surface modifying agents will have two or more functional groups and will react with surface stanol functional groups while present in the film structure. The material outside the shelf (ameW0rk) is minimized and includes, for example, a surface lysine which can be condensed with a suitable stanol, such as:

RxSi(〇H)4.x Formula II wherein X-Bu3' and each ruler are independently selected, such as η and/or an organic moiety such as an alkyl group, an aryl group or a derivative thereof. When R listens to a group, the alkyl group is optionally substituted or unsubstituted, and may be a direct bond, a bond or a ring, and preferably ranges from Ci to about 〜 or larger. And more preferably: C, to a size range of about Cs. When the aryl group is an aryl group, the aryl moiety is preferably composed of a monosubstituted or unsubstituted monoaromatic ring and is in the range of from c to about C18 or more and more preferably. Within 5 limits. Among the alternatives, the aryl moiety is heteroaryl. In another embodiment, the silk-based Wei can be used as an alkoxy decane such as, for example, the following formula:

RxSi(OR,)4_x Its t ii is an independently selected part, such as a swelling or such as a phenotype, an aryl group or its 96350.doc -28- [jyj one of the biological parts of the genus. Liguang base or aryl part. And may be linear, domain substituted or unsubstituted:::::... and more preferably one size. The diaryl moiety is preferably substituted or unsubstituted by a single case. Without a bad composition, the Japanese pill is in the range of sizes from C:5 to about C1S or more and more preferably in the size range from C5 to about c8. The aryl group is heteroaryl in a further alternative. Thus, the r group is independently selected from the group consisting of hydrazine, methyl, ethyl, propyl, phenyl and/or derivatives thereof, with the proviso that it is at least: organic. In the examples, both (10) groups are methyl and the trifunctional surface modifying reagent is methyl tri-foxydecane. In another embodiment, a suitable Shih-hsing according to the present invention has the following general formula:

RxSi(NR2)4.x Formula m wherein X=1:3 ’R is independently H, a top group and/or an aryl group. Wherein -R is a hospital base and/or an aryl group. In a preferred embodiment, R is selected from the group consisting of H, C6H5, and R2 and R3 are both CH3. Thus, the trifunctional toughening agent includes, for example, tris(diamine)methyldecane, bis(dimethylamino)phenyldecane, and/or tris(dimethylamino)oxime. Further, a di-substituted decane such as hexamethylcyclotriazane, bisdimethylamino dimethyl sulphur and bisdiethylamino dimethyl decane may be used.

In another embodiment, a suitable decane according to the present invention has the general formula: RxSi(〇N=CR2)4_x or RxSi[0C(RI)=R"]4 Formula IV, A x=l-3, and The R group is independently H, an alkyl group and/or an aryl group, and R may be H, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and the ruler may be an alkyl group or a carbonyl group. Therefore, the modification test The agents include, for example, methyl tris(methyl ethyl ketoxime) decane or 2- 96350.doc • 29· 1358093 dimethyl methacrylate pentyl oxy-2-ene -4- ketone. In the examples, suitable decanes according to the invention have the general formula:

RxSi(NCOR2)4.x4RxSi(NCO)4-x wherein x=l-3, the R group is independently η, alkyl and/or aryl. Accordingly, the surface modifying agent includes, for example, dimethyl decyl decylamine, dimethyl decyl dimethylamine, dimethyl decyl diisocyanate, tridecyl decyl triisocyanate. In yet another embodiment, a suitable decane according to the present invention has the following general formula:

RxSiCl4.x Formula V VIII X 1 - 3, R is η, alkyl or aryl. In a preferred embodiment, r is CH3. Thus, a trifunctional surface modifying reagent according to formula ν includes, for example, methyltrioxane. In a more preferred embodiment, the capping reagent comprises one or more organic ethoxylated decane having the formula:

(Ri)xSi(OCOR2)y Formula VI Preferably, the X-based value is an integer ranging from 丨 to 2, and x#y may be the same or different, and y is from about 2 to about 3 or more. An integer in the range. Suitable organoethoxylated decanes including polyfunctional alkyl ethoxy decane and/or aryl ethoxy decane compounds include, by way of example only and not limitation, decyltriethoxy decane (" MTAS"), dimercaptodiethyloxy alkane (DMDAS), phenyltriethoxydecane and dipyridyldimethoxydecane, and combinations thereof. & Optionally, toughening agent and A suitable solvent such as 2_heptanone is mixed and applied to the surface of the nanoporous dioxate in the form of a gas phase or a liquid and then dried by 96350.doc • 30·1358093. In the examples covered, 50% is used. a mixture of hexamethylene diazoxide (HMDZ) and 50% 3-pentanone. The liquid is spin coated onto a surface, substrate or wafer. The coated surface is then baked on a baking tray at up to 425 °C. Baking. The baking is followed by PVD barrier and Cu seed deposition. In another contemplated embodiment, a mixture of dimercaptodimethoxydecane (DMDAS) and 3-pentanone is used. Spin coating on a surface, wafer or substrate. This coating is then applied up to 425 ° C The surface is baked on a baking tray. The baking step is followed by PVD barrier and Cu seed deposition. In another embodiment, the use of a chemical such as AP395 or diluted HF is performed after the baking step in the above embodiment. The wet cleaning is suitable for removing the remaining resist residue after ashing. The untreated low-k dielectric material after etching and ashing is easily attacked by the wet cleaning agent. The toughening agent is treated significantly. Improved resistance of low-k dielectric to wet cleaning erosion. Depending on the process flow, the copper surface can be exposed during the toughening agent treatment, especially at the bottom of the channel. In addition to removing the natural oxide from the copper surface, Wet cleaning can also remove any reaction product between the toughening agent and the exposed copper surface. Specifically, the wet cleaning with AP395 can clean the copper previously treated with the TMDAS toughening agent (or any suitable a metal or metal alloy) surface. Subsequently, a metal can be used to fill the channels and trenches; and the metal is annealed. As used herein, the term "metal" means that they are located in & The elements in the d and f areas of the period, as well as those such as shreds and scorpions, have the class of metal-like elements. The phrase area " as used herein means that there are elements of the 3d, 4d, and (7) orbital electrons surrounding the nucleus of the element, 96350.doc 丄 ϋ 93 elements. The phrase "m " as used herein means that there are elements of the electrons that are filled with 4f and 5f around the nucleus of the element, including lanthanide (10) elements. Preferred metals include indium, silver, copper, aluminum, tin, antimony, gallium and alloys thereof, silver coated copper, and silver coated aluminum. The term "metal" also includes alloys, metal/metal composites, cermet composites, metal polymer laminates, and other metal composites. Annealing can be carried out by heating at a temperature of from about nc to about 350 C or from 200 C to 250 C for about 10 seconds to about 6 seconds. These times and temperatures are not critical as long as annealing is performed.

In the example, the wet cleaning can be performed prior to the baking treatment in the first covered embodiment. This high temperature baking step is performed after the wet cleaning. One of the advantages of this method may be that the wet scrubber removes any excess product that reacts with any of the exposed copper surfaces before it is "hardened" by the baking process. This can result in a lower amount of volatile components in the dielectric material and a clearer copper surface. Both can lead to an improved long-term reliability. In another

In the examples covered, additional dehydration baking i _ to 12 paradoxes were imposed from about 1 至 to 乡 00 C before the treatment of the (IV) UTA. This dehydration roasting removes any moisture absorbed by the damaged low-k dielectric. Removing the moisture from the dielectric at the booster treatment table makes the treatment more effective. In an alternate embodiment, the builder composition is provided by exposing the organic silicate dielectric dielectric film of the sizing agent to electropolymerization derived from any of the above. In the __ typical program towel, the organic #acid glass dielectric film is placed in a plasma generation chamber, such as a plasma enhanced chemical vapor deposition (PECVD) system, which will increase the gas phase of the (tetra) ruthenium composition. And the argon gas phase is passed through the electricity generating chamber; then the RF energy source is activated to build the plasma; including argon gas at 96350.doc -32 - 1358093 helps to promote plasma formation. The plasma consists of an ionic fragment derived from a toughener composition; for example, the ion fragment CH3Si+ is derived from methyl decane (CHsSiH3). This fragment reacts with the stanol group to form a hydrophobic Si-CHs moiety. Any of the above toughening agent compositions can be used for the surface treatment of the electric raft. Other suitable toughening compositions for plasma initiated surface modification include core/! 2 alkyl and aromatic hydrocarbons. The most preferred hydrocarbon is methane. Other reagents for the plasma-initiated builder composition include aldehydes, esters, acid chlorides, and assays. Suitable aldehydes include acetaldehyde and benzofural; suitable esters include ethyl acetate and methyl benzoate; suitable acid vapors include acetamidine and benzyl chloride; and suitable ethers include diethyl ether and anisole . A wide variety of single-wafer or multi-wafer (batch) plasma systems can be used for this method; such systems include so-called downstream ashers such as the Gas〇nics L3510 photoresist ashifier, such as the Appiied Matenals P5000 PECVD Dielectric Deposition System or Reactive Ion Etching ("RIE") system. In summary, the conditions for the plasma process are in the following ranges: chamber temperature of 20 ° C to 450 ° C; 50 至 to 1 〇〇〇 W 2 RF power; chamber pressure of 0.05 to 100 ton *; 5 seconds Plasma treatment time to 5 minutes; and surface modification flow rate of 100-2000 seem; inert gas flow rate (usually argon) of 1 〇〇 2 〇〇〇 sccm. Those skilled in the art will appreciate that the present invention is also intended to encompass a method of imparting a hydrophobic surface to a porous and/or non-porous, damaged or undamaged cerium oxide dielectric film by applying the above-described plasma surface treatment. A semiconductor device or 1C fabricated using such methods is also an integral part of the present invention. The treated dielectric layer and materials can be used or incorporated into any suitable electronic 96350.doc -33- 1358093 component. Electronic components as referred to herein are generally considered to comprise any dielectric implant or laminate electrical component that is an electroniC-based product. The electronic components covered include f-boards, chip packages, circuits: dielectric components, printed wiring boards, and other components of circuit boards such as capacitors, inductors, and resistors. Electronically based products may be "completed" in the sense that they are intended to be used in the industry or by other consumers. Examples of completed consumer products include televisions, computers, cell phones, pagers, palm-sized managers 'Portable radios, stereo radios for cars and remote controls. Also covers, for example, circuit boards, chip packages and keyboards, intermediate products, which can be used in finished products. The electronic device can also include prototype components in any stage of development from a conceptual model to a final scale-up mock-up. A prototype may or may not contain all of the actual components intended for the finished product, and the prototype may have components that are constructed from composite materials to exclude their initial effects on other components when initially tested. Electronic products and components can comprise laminates, laminate components, and laminates for use in the assembly of components or products. The following non-limiting examples are illustrative of the invention. Example 1 A series of 6000A NANOGLASS E nanoporous ceria films purchased from Honeywell Internati〇nal, Inc, SunnyvaIe, California were coated onto a 200 mm 矽 substrate and subsequently exposed to a TEL DRM_85 etcher. Etching based on qF8 and ashing based on 〇2. 96350.doc • 34- 1358093 Evaluation of two toughening agents (ΤΑ-1 and ΤΑ-2) » These toughening agents are applied to the wafer using a standard spin-on dielectric (SOD) applicator and the crystals are applied The round plate was baked at 125 ° C, 200 ° C and 3 50 ° C for 1 minute. Film thickness and refractive index were measured using ellipsometry. The elemental composition was analyzed using FTIR. The dielectric constant was measured on a .1 MHz Hg probe. The thermal stability of the film was evaluated by thermal desorption mass spectrometry (TDMS). A single level metal Cu damascene structure was prepared using a 3000A NANOGLASS E film as the ILD and 2000A TEOS oxide as the cap layer. Cu annealing was performed at 200 ° C for 1 hr in an N 2 atmosphere, followed by a focused ion beam scanning electron microscope (FIB-SEM) to detect voids in the ILD. After Cu chemical mechanical polishing (CMP), an automated probe was used to electronically test 25 grains per wafer. The properties of the hardened NANOGLASS® E film are presented in Table I. Table I. General Characteristics of Hardened NANOGLASS^E Films Technical Results Aperture BET 20A Refractive Index Elliptical Method 1.24 Dielectric Constant ΜΗζ@1ΜΗζ 2.2 Elasticity Nanoindentation 4.5 Gpa Hardness Nanoindentation 0.4 Gpa Thermal Stability Isothermal TGA <1% weight loss observed from the FTIR spectrum of NANOGLASS E: Compared with the hardened film, the etching and ashing treatment resulted in a 30-40% reduction in CH and Si-C content and Si-OH and H- The OH bond is significantly increased. The addition of the agent treatment resulted in c-H and Si-C content close to the C-H and Si-C content of the hardened film. TA-2 is more effective than ΤΑ-1 in replenishing carbon and reducing Si-OH and H-0H bonds. 96350.doc •35· 1358093 After etching and ashing, the dielectric constant of the low-k film becomes high (>3 〇). This is estimated to be due to moisture adsorption of Si-OH groups. This toughening agent treatment will reduce the value to near the level after hardening. Table π shows that after etching and ashing, the NANOGLASS E film is hydrophilic and has a high etching rate in most wet cleaning chemical reactions, making it unsuitable for wet cleaning. The TA-1 treatment renders the film hydrophobic and resistant to some wet cleaning chemicals. Table π. After etching-ashing (control) and after etching-ashing and TA1 treatment (ΤΑ-1) affecting nano GLASS E film exposed to various wet cleaning chemicals, wet cleaning condition residual rate (A /min) DI water contact angle (degrees) Control TA-1 Control TA-1 No wet cleaning <10 122 A (diluted HF) >1000 0 33 112 B (aqueous acidity) 5 0 <10 118 C( Semi-aqueous fluoride) 25 14 <10 <10, organic amine) 70 23 <10 47 TDMS spectrum of the dielectric film at 400 ° C shows volatile substances in the TA-1 treated film The evolution is similar to that of the etched and ashed film. The TA-2 treated film exhibited a significantly improved thermal stability with low amounts of volatiles.

In the case of control (i.e., no toughening agent), significant voids were observed 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 person. 1^31311811 "&,>1. Ohashi, K. Inukai, HJ Shin, S. Sone, K. Sudou, K_ Misawa, I. Matsumoto and N_Kobayashi, Proceedings of IEEE 96350.doc • 36· 1358093

International Interconnect Technology Conference, 2003, 147 (2003); and J. C. Lin, R. A. Augur, B. J. Daniels, S. L. Shue, C. H. Yu, and M. S. Liang j Proceedings of Advanced Metallization Conference 2002, 637 (2002)). The tensile stress from the Cu annealing treatment is estimated to be the driving force for void formation. Wafers treated with yttrium-1 or TA-2 show exactly void-free after Cu annealing. Therefore, it is proved that the "cure" damage to the porous low-k material is an effective way to avoid void formation due to external stress. Line-to-line leakage current is not affected by toughener treatment* The control wafer exhibits a broad distribution of serpentine resistance. It has been found that high resistance trailing tails are attributed to defects such as bubbling, Cu dip and pitting, which may be caused by moisture trapped in the damaged ILD zone. The toughener treated wafer exhibits a tight resistance distribution because moisture retention and associated defects are eliminated. Although the median capacitance is not affected by the toughening agent treatment, the processed comb capacitor structure has a higher yield due to fewer pit/float defects. The effects of treatment-induced damage on NANOGLASS® E and other similar Si-based films have been disclosed. The post-ashing treatment with the toughening agent TA-1 or TA-2 restores the properties of an undamaged material. Tougheners have proven successful in SLM structures, which cause the elimination of ILD voids and the high yield of interconnect test structures. Example 2 A 6000A HOSP(R) film commercially available from Honeywell International Inc., Sunnyvale, California was formed on a Si wafer by standard spin coating methods. The films were hardened in N2 at 400 °C. 96350.doc • 37- 1358093 Introducing plasma damage into the films by subjecting them to the following treatments:

Etching: 1000 W/40mT/10 seem C4F8/200 sccn^O/30〇 ’D

Sccm

Ar/100 seem N2, 40〇C (20 seconds). Ashing: 400 W/45 mT/100 seem 02, 40 ° C (20 seconds). The toughening process was performed using a mixture of 27% DMDAS in 3-pentanone. After spin coating the toughener material, the films were each baked at 125 ° C, 200 ° C and 3501 for 1 min. The following results were recorded: The measured value of the dielectric constant (k) of the toughening agent after etching and ashing before etching and ashing 2.7 3.0 2.8Γ^ FTIR (CH/SiO ratio) 0.0235 0.017 0.020^^ H2o contact angle (°) 104 26 Destructive Strength (MV/cm) 5.51 4.1 5.12^\ Example 3

Formed on a Si wafer by a standard spin coating method available from HoneyWeU

International Inc., Sunnyvale, California purchased 6 into the NANOGLASS 1.9 film. The films were hardened in N2 at 425 °C. Plasma damage is introduced into the films by subjecting them to the following treatments: Etching: 1000 W/40 mT/10 seem C4F8/2OO seem CO/300 seem Ar/1 0i3 seem N2, 40°C (20 second). Ashing: 400 W/45 mT/100 seem 02, 40 ° C (20 seconds). Attenuator treatment was carried out using a mixture of 27% DMDAS in 3-pentanone. After spin coating the toughener material, at 125. (:, 200 ° C and 350 ° C N2 96350.doc -38 - 1358093 each of these films were baked for 1 min. The following results were recorded: Measurement of etching and ashing before etching and ashing after toughening agent treatment Post-dielectric constant (k) 1.83 2.69 1.94 FTIR (CH/SiO ratio) 0.0078 0.0027 0.0054 Destructive strength (MV/cm) 4.51 1.22 3.76 Example 4 Give plasma damage to a commercial by subjecting it to the following treatment in sequence Porous CVD low-k dielectric film: Etching: 40 mT, 1400 W 160 Ar/80 CF4/20 〇2 40 mT, 1400 W, 20 s Ashing: 400 W/45 mT/100 seem 02, 40°C ( Toughening agent treatment was carried out 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. Min. The following results were recorded: Measurement value Etching and etching and ashing after toughening agent treatment dielectric constant (k) 2.36 2.76 2.39 FTIR (CH/SiO ratio) 0.02473 0.0149 0.013 Destructive strength (MV/cm 5.06 3.07 4.77 Example 5 Prepared by conventional baking method using 125 ° C, 200 ° C and 35 〇t:

6000A NANOGLASS film available from Honeywell International Inc., Sunnyvale, California. UV hardening (3 min) at 425 °C was used instead of the conventional in-furnace hardening (60 min). And the plasma is damaged by subjecting it to the following treatment: 96350.doc -39- face: 1000 W/40 mT/10 seem C4F8/2OO seem CO/300 seem Α"100 sccmN2, 40〇 C (20 seconds) Ashing: 400 W/45 mT/100 seem 02, 40 ° C (30 seconds) Toughener treatment was carried out using a mixture of 27% DMDAS in 3-pentanone. After spin coating the toughener material, the films were each baked at 125 ° C, 20 (TC and 350 ° C N2 for 1 min. Using UV-curing NANOGLASS as the dielectric material, using the conventional route described in Example 2 Copper single damascene patterned structure. Prior to metallization (PVD barrier and Cu seed deposition and Cu plating), some wafers were coated with a toughener, followed by baking at up to 35 (TC). After metallization, all samples were placed. Annealing at 200 ° C for 50 min. The presence of voids was measured by a focused ion beam scanning electron microscope. The following results were recorded: a. Blanket wafer measurement etching and ashing before etching and ashing Dielectric constant (k) after toughening agent treatment 2.1 2.85 2.25 FTIR (CH/SiO ratio) 0.0082 0.0045 0.0075 Destructive strength (MV/cm) 5.06 3.07 4.77 b. SLM patterned wafer example 6 by subjecting it to sequential The following treatment introduces plasma damage into a 6000 A furnace hardened NANOGLASS film available from Honeywell International Inc., Sunnyvale, California: Insects: 1000 W/40 mT/10 seem C4F8/2OO seem CO/300 seem Ar/100 sccmN2, 40°C (20 seconds) (One of the following methods) 96350.doc -40- 1358093 〇2 ashing: 400 W/45 mT/100 seem 02, 40°C (2〇s or 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 is carried out using a mixture of 9% DMDAS in 2-heptanone. After spin coating the toughener material at 125 ° C, 200 The films were baked for 1 min at ° C and 350 ° C in N2. Recorded as - F results: ashing type k (no toughening agent treatment) k (after toughening agent treatment) 02, 20 s 2.98 " 2.36 20.8 〇2, 30 s 『11 — 2.42 22.2 〇2, 70 s 3^3 2.63 25.5 N2/H2 45 s 3M 2.5 17.8 N2/H2 135 s 3.23 2.7 16.4 Example 7 by making It is sequentially subjected to the following treatment to introduce plasma damage into the hardened NANOGLASS film in a 6000-person furnace: Etching: 1000 W/40 mT/l 〇sccm c4F8/200 seem CO/300 seem Ar/100 sccmN2, 40 〇C (20 seconds) Ashing (one of the following methods): To test the effect of the queue time before the booster treatment, place the sample under ambient conditions for a different time from 1 hr to 360 hr, followed by a toughening agent deal with. Toughening agent treatment was carried out using a mixture of 4.5% DMDAS in 2-heptanone. After spin coating the toughener material, at 125. (:, 200. (: and 35CTC N2 each of these films were baked for 1 min. 96350.doc 41 The following results were recorded: Q-time (hr) k (after toughening agent) 1 2.24 3 2.28 27 2.31 72 2.29 240 2.38 360 2.32 1358093 Example 8 A plasma-induced damage is introduced into a 6000A furnace hardened NANOGLASS film by subjecting it to the following treatment, which is available from Honeywell International Inc., Sunnyvale, California. • Money engraving: 1000 W/40 mT /10 seem C4F8/200 seem CO/300 seem

Ar/100 seem N2, 4 (TC (20 sec). Ashing (one of the following methods). Toughening agent treatment was performed using a mixture of 18.8% DMDAS in 2-heptanone. After spin coating the toughener material, The films were baked on the baking tray for 1 min at different temperatures. The carbon recovery was measured as a percentage of the carbon added by the toughening agent treatment and the amount of carbon lost during the plasma damage process. Carbon measurement as the ratio of CH (2975 cm·1) peak to SiO peak (1055 cm·1) 0 The following results were recorded: Baking temperature % C recovery K-value 75 〇 C 66 2.95 10 (TC 2.82 125 〇 C 2.74 150°C 65 2.72 175〇C 136 2.5 200°C 127 2.34 225〇C 127 2.3 96350.doc • 42· 1358093

The present invention has been particularly shown and described with reference to the preferred embodiments thereof, but those skilled in the art can readily understand that various changes and modifications can be made without departing from the spirit of the invention. And scope. The scope of the present application is intended to be understood as covering the disclosed embodiments, their alternatives as discussed above, and all equivalents thereof.

96350.doc -43-

Claims (1)

1358093 Patent Application No. 093129863 (Replacement of Chinese Patent Application No. (April, 2010) X. Patent Application Range: A method for preventing stress-induced void formation in an organic tantalate glass dielectric film on a substrate The organic tellurite glass dielectric film is patterned to form channels and trenches therein, and the organic tellurite glass dielectric film is subsequently subjected to at least one to remove at least a portion of the pre-existing carbon-containing portion and a treatment for reducing the hydrophobicity of the organic tellurite glass dielectric film, and then filling the channels and trenches with a metal, and then the metal is subsequently subjected to an annealing process, the method comprising: pre-existing at least one removal After the treatment of the carbonaceous portion, but prior to filling the channels and trenches with metal, the organic tellurite glass dielectric film is contacted with a concentration of the toughener composition and the contact is subjected to a period of time Effectively recovering at least some of the carbonaceous portions to the organic tellurite glass dielectric film and increasing the organic tellurite glass dielectric The hydrophobic membrane. 2. The method of claim 1, wherein the removing at least a portion of the pre-existing carbon-containing portion and reducing the hydrophobicity of the organic tellurite glass dielectric film comprises at least one of the following: etchant treatment, ash Treatment, wet stripping, cleaning, and PECVD. 3. The method of claim 1, wherein the organic tantalate glass dielectric film is formed by a spin-on glass material or a chemical vapor deposition material. 4. The method of claim 1 wherein the toughening agent composition comprises a component for the alkylation or arylation of the stanol moiety via oximation of the organosilicate glass dielectric film. 5. The method of claim 1 which further comprises the step of removing the unreacted toughening agent group 96350-1000422.doc 1358093, the reaction product, and the mixture thereof. 6. The method of claim 1, further comprising the subsequent step of heating the increased hydrophobic organic >5 silicate glass dielectric film. The method of claim 1, wherein the organic tellurite glass dielectric film is nanoporous. 8. The method of claimant, wherein the organosilicate ceramic dielectric film is substantially non-porous. 9. The method of claim 1 wherein the toughening agent composition comprises at least one. The at least one compound has a formula selected from the group consisting of: [-SiR2NR, -]n wherein n > 2 and may be cyclic, (10) urchin, (iv) (10), R3SiNR, 2, coffee (10), 2 , Edition (10)·);, μ, RxSi(〇H)y. R3Si〇SiR-3 > RxSi(OR-)y . RxSi(〇C〇R')y . RxSiHy, RxSi[〇C(R, ) = R"] 4 χ and combinations thereof, wherein 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 a hydrogen or an organic moiety, and R" is an alkyl group or a carbonyl group. 10. The method of claim 1 wherein the activator composition comprises at least one compound selected from the group consisting of:醯oxytrimethyl shi xi xi, acetoxy oxime oxime, diethylene ethoxy oxime, triethyl ethoxy: burning, diethylene oxy ruthenium, methyl triethyl ethoxylate Burning, phenyldiethyl ethoxylate Xixuan, diphenyldiethyl ethoxylate, sparkling methyl triethoxy shixi, dimethyldiethoxy zexi, triterpene ethoxylate, 96350 -1000422.doc -2- 1358093 A Trimethyl decane, dimethyl dimethoxy decane, trimethyl methoxy decane, methyl trichloro decane, dimethyl dioxane, trimethylchlorodecane, methyl decane, dinonyl decane , trimethyldecane 'hexamethyldioxane, 2-trimethyldecynyloxypent-2-en-4-one, η-(tridecyldecylalkyl)acetamide, 2-( Trimethylsulfonylalkyl)acetic acid, η-(trimethylformamidinyl)imidazole, trimethylsulfonylalkylpropiolate, trimethyldecyl (trimethylformamoxy)-acetic acid Ester, nonamethyltriazane, hexamethyldiazepine, trimethyl sulphate, triethyl sulphate, triphenyl sulphate, tert-butyl dimethyl sulphur , diphenyl sylvestre diol, trimethoxy decane, triethoxy decane, trichloro decane, hexamethylcyclotriazane, bis decyl dimethyl decane, bis diethylamino dimethyl Base decane, tris(diamine)methyl decane, tris(dimethylamino)phenyl decane, tris(dimethylamino), dimethyl sulfonyl dimethyl decylamine, dimercapto曱矽alkyldiethylammonium, Dimercaptomethyl decyl diisocyanate, trimethyl methacrylic acid triisocyanate, and combinations thereof 11. 12. 13. 14. The method of claim 1 wherein the toughening agent composition comprises dimethyl bis The method of claim 1 wherein the toughener composition comprises a solvent selected from the group consisting of ketones, ethers, esters, hydrocarbons, and combinations thereof. Wherein the toughener composition contacts the organic tantalate glass dielectric film in a state selected from the group consisting of liquid, gas phase, gas and plasma. A method for forming a microelectronic device, comprising: a) applying an organic tantalate glass dielectric film to a substrate; 9635〇-l〇〇〇422.d, 1358093 b) in the organic tellurite glass Dielectric thin θ ^ to form a pattern of channels and trenches in the film 'and make the organic phosphatite granules when the cage is subjected to at least one to remove at least a portion of the pre-existing content < 3 carbon portion and reduce the hydrophobicity of the organic bismuth silicate glass dielectric film; c) the organic phosphite glass linoleamide; enamel film and a certain concentration of toughening agent The contact of the composition and the frequency of the contact is effective for increasing the hydrophobicity of the organic tantalate glass dielectric film; d) filling the channels and trenches with metal; and e) subjecting the metal to annealing treatment . The method of claim 14 wherein the treatment of removing at least a portion of the pre-existing carbon-containing portion and reducing the hydrophobicity of the organic tantalate glass dielectric film comprises at least one of the following treatments: surname treatment, ashing Treatment, wet stripping treatment, cleaning treatment and PECVD treatment. 16. The method of claim 14 wherein the toughening agent composition comprises a component for alkylating or arylating the stanol by the formazanization of the organosilicated glass dielectric film. 17. The method of claim 14, further comprising the step of removing the unreacted toughening agent composition, the reaction product, and the mixture thereof. 18. The method of claim 14, further comprising the subsequent step of heating the increased hydrophobic organosilicate glass dielectric film. 19. The method of claim 14, wherein the organic acid salt glass dielectric film is nanoporous. 20. The method of claim 14, wherein the organic tellurite glass dielectric film is substantially non-porous. 96350-1000422.doc 1358093. The method of claim 14, wherein the toughening agent composition comprises at least A δ species having a formula selected from the group consisting of: [•SiR2NR-]n wherein η>2 and may be cyclic, R3SiNR, siR3, (R3Si)3N, R3SiNR, 2, R2Si (NR ')2, RSi(NR')3, RxSiCly, RxSi(〇H)y, R3Si〇SiR.3, Rxsi(〇R')y, RxSi(〇c〇R,)y, RxSiHy, RxSi[〇C (R,) = R "] 4.x and combinations thereof, wherein 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_χ, each R is independently selected from hydrogen and hydrophobic The organic moiety, R' is hydrogen or an organic moiety, and R" is a burnt or a few. 22. The method of claim 14, wherein the toughening agent composition comprises at least one compound selected from the group consisting of ethoxylated trimethyl oxime, ethoxylated decane, diethyl hydrazine Oxy decane, triethoxy decane, diethyl methoxy dimethyl decane, methyl triethoxy decane, phenyl triethoxy decane, diphenyl dimethyl decyl oxane, A Triethoxy decane, bis-f-diethoxy decane, trimethyl ethoxy decane, methyl trimethyl decyl decane, dimethyl dimethoxy decane, trimethyl methoxy sulphur, f Dichlorohydrazine, dimethyl dichlorite, trimethyl gas sulfoxide, methyl decane, dinonyl decane, tridecyl decane, hexamethyl diazepane, 2-dimethyl A sulphonate oxypenta-2_dilute_4-_, n_(trimethyl fluorene 'alkyl) acetamidine, 2-(trimethylformamidine)acetic acid, n_(trimethyl fluorene Base) imi, dimethyl methacrylate, propylene, vinegar, trimethylmethanoate (dimethyl ketone), acetate, hexamethyltriazine , hexamethyl 96350-1000422.doc 1358093 monooxane, trimethylstanol, triethyl stanol, triphenyl decyl alcohol, second butyl dimethyl decyl alcohol, diphenyl fluorene diol trimethoxy decane, triethoxy Base decane, trioxane, hexamethylcyclotriazane, bis-methylaminodimethyl decane, bis diethylamino dimethyl decane tris(dimethylamino)methyl decane, tris (dimethyl Amino)phenyl decane, tris(dimethylamino), tartar, dimethylglycosyl dimethylamine, dimethylformyldiethylamine,methylmethanthine Anisophthalic acid vinegar, trimethyl methacrylate, triacetate, and combinations thereof. 23. The method of claim 14, wherein the toughening agent composition comprises dimethyldiethoxylate. The method of claim 14, wherein the extender composition comprises a solvent selected from the group consisting of a ketone, an ether, an ester, a hydrocarbon, and a group A thereof, such as a claim-method, wherein the Z-combination product is selected The state of the group of free liquid, gas phase, gas, and plasma contacts the salted glass dielectric film. The method of claim 15, wherein the surname comprises an atom, an ion and/or a group selected from the group consisting of oxygen, oxygen, hydrogen, nitrogen, and combinations thereof. 27. The method of claim 15, wherein the __-wet_agent 2 comprises at least one reagent selected from the group consisting of: awake amine, amide, amine, amine, triamine, acid, and Its combination. 28. The method of claim 14, wherein the treatment of removing at least a portion of the pre-existing human carbon portion and reducing the hydrophobicity is carried out in a reagent selected from the group consisting of: a compound of the compound: ethanolamine III Ethylamine, N,N-diethylethylenediamine, diamine, 1 methyldiamine'amine, Ethylene 96350-1000422.doc 1358093 Aminetetraacetic acid, organic acid, acetic acid, formic acid, tetramethyl acetic acid , sulfuric acid, sulphuric acid, hydrofluoric acid, fluorinated, hydrogen peroxide, tetramethylammonium hydroxide, amines and combinations thereof, with the limitation that the combinations are agents which are not mutually neutralized. 29. A microelectronic device produced by the method comprising the steps of: a) coating an organic tantalate glass dielectric film on a substrate; b) forming a channel and a groove pattern in the organic salt glass And subjecting the organic salt glass dielectric film to at least - (d) to remove at least a portion of the pre-existing carbonaceous film and reducing the hydrophobicity of the organic tantalate glass dielectric film. Contacting the organic bismuth silicate glass dielectric thin plaque-, human, and turbulent toughening agent composition, and the contact time of the contact can effectively increase the hydrophobicity of the organic bismuth oxide glass dielectric film d) filling the channels and trenches with metal; and e) subjecting the metal to annealing. 96350-1000422.doc