KR20070060117A - Treating agent materials - Google Patents

Abstract

A treating agent composition for increasing the hydrophobicity of an organosilicate glass dielectric film when applied to said film. It includes a component capable of alkylating or arylating silanol moieties of the organosilicate glass dielectric film via silylation, and an activating agent which may be an acid, a base, an onium compound, a dehydrating agent, and combinations thereof, and an optional solvent or mixture of a main solvent and a co-solvent.

Description

Treatment Material {TREATING AGENT MATERIALS}

The present invention relates to a treating agent composition for an organosilicate glass dielectric film. More particularly, the present invention relates to a method for removing at least a portion of an existing carbon-containing portion by performing an etching or an ashing treatment, thereby restoring hydrophobicity to the surface of the organosilicate glass dielectric film with reduced hydrophobicity in the film. It is about. Films thus treated are used as insulating materials to impart low dielectric constants and stable dielectric properties to these films in the manufacture of semiconductor devices such as integrated circuits (“ICs”). The composition comprises a silane based monomer together with a mixture of an activating agent and a solvent or a main solvent and an auxiliary solvent which may be a reactive leaving group, an acid, a base, an onium compound, a dehydrating agent and combinations thereof.

As semiconductor devices are measured with smaller technology nodes, increasingly lower dielectric constant k is required to mitigate RC delay. Similarly, as the shape size in integrated circuits decreases, it becomes increasingly difficult to solve problems related to power consumption and signal cross-talk. To obtain low k (2.5-3.0) in the high density inorganic material, carbon is added to reduce the polarity and consequently reduce k. Porosity is added to the carbon-multi-density matrix to obtain very low k (<2.4) materials. The administration of carbon and pores reduces k, but it has been found that new problems arise during the second half of line processing. In particular, during etching and ashing processes, reactive gases are known to damage carbon on the surface of high density materials. In the case of a low k of porosity, there is a further serious adverse effect that the etching and ashing gases are dispersed through the film, causing serious damage to the internal pore walls. Once the carbon is damaged, the film is rehydroxylate and hydrogen bonds with water. Since water has a dielectric constant of 70, even a small amount of absorption into the porous and high density materials will cause the dielectric constant to increase significantly. In addition, the porous material tends to break after copper annealing due to high-tensile stress fields that can destroy device yield. These are not allowed and result in infeasible substances.

The integration of low dielectric constant materials used in interlevel dielectrics (ILD) and intermetal dielextric (IMD) is believed to help solve these problems. Efforts have been made to apply low dielectric constant materials to conventional integrated circuits, and there is still a need in the art to further improve manufacturing methods and optimization of the dielectric and mechanical properties of these metals. It is clear that device scaling in future integrated circuits will require the use of low dielectric constant materials as part of the internal interconnect structure. Most commonly used as low dielectric constant materials for sub-100nm generation ICs are carbon containing SiO ₂ films made by CVD or spin-on methods. Subsequent processes, such as plasma etching and photoresist removal using plasma or wet strip methods, result in significant damage to these low k materials, thereby reducing fluorine addition and carbon reduction from the low k materials proximate to the etched surface. Occurs. Also, with the effective k rise, the structures of the reactants form pores, and gases are likely to generate and form bubbles. The pores may cause an increase in current leakage and a decrease in breakdown voltage as the voltage sequentially increases. The present invention describes a method of reducing the problems caused by treating the wafer with a siliving agent after the damage and the damage has occurred. It is reported that the use of intact ashing chemicals such as H ₂ / He can reduce carbon consumption and related problems. In this regard, I. Berry, A. Shiota, Q. Han, C. Waldfried, M. Sekiguchi, and O. Escotia, Proceedings-Electrochemical Society, 22,202 (2002); And A. Matsushita, N. Ohashi, K. Inugai, HJ Shin, S. Son, K. Sudo, K. Misawa, I. Matsumoto and N. Kobayashi, Proceedings of IEEE International Interconnect Technology Conference, 2003, See 147 (2003). Alternatively, post-ash treatment of carbon supplementation has also been shown to restore hydrophobicity and low dielectric constant. Post-essing treatments supplementing carbon have been shown to restore hydrophobicity and low dielectric constant. In this regard, YS mor, TC Jang, PT Liu, TM Chi, CW Chen, ST Yan, CJ, WF, FM, W. ruhr; And SM bodies, Journal of Vacuum Science & Technologyy, B, 2 (4), 1334 (2002); And PG Clock, BD Schwab and JW, Bau, Semiconductor International, 26 (9), 46 (2003). The advantage of the latter approach is that well-established etching and ashing processes can be used. In this regard, it is desirable to repair damage occurring in porous SiCOH-based low k materials using post-ash treatment.

One approach to this approach is to repair damaged areas of the inner pore wall on dense surfaces or in the case of porous materials, using re-methylating compounds called treatments. The treating agent reacts with the damaged re-hydroxylated surface to re-alkylate or re-arylate the surface and subsequently restore the dielectric constant. The following scheme shows an example of the re-methylation process: SiOSi (x) (desired surface) + (CH ₃ COOH) y (acetic acid) is obtained by SiOH (damaged surface) + RxSi (OCOCH ₃ ) y (TA). In the case of porous damaged internal pore wall surfaces, re-methylation prevents pore formation. In many cases, the use of processing agents allows the use of low- and ultra-low dielectric constant materials for etching and ash processing of the sea. The treatment results in the replenishment of carbon in the low k film, thereby restoring the resistance to additional damage occurring during hydrophobic and wet cleaning operations. In addition, the recovered low k constant material would be desirable if it exhibited resistance to pore formation occurring in the untreated porous low k level dielectric region during the copper annealing process. The sil rerating agent (“treatment agent”) may methylate the surface of the SiO ₂ base material. Expected exposures include vapor exposure (with or without plasma), spin coating and supercritical CO ₂ . Generally, SiCOH based porous low k materials tend to form pores in the ILD during the Cu damascene process. After treatment, the reactant structure has significant resistance to pore formation. Although not explained by any particular theory or particular mechanism, it is believed that plasma results in carbon loss by replacing Si—CH ₃ bonds with Si—OH bonds. In the damaged porous dielectric, the pore surface is now covered with Si-OH. When tensile stresses are present (such as after Cu annealing), adjacent Si—OH groups can condense, resulting in local densification. The newly formed bonds lead to the development of the elasticity of the reaction product and molecules, and the formation of pores near the center of the ILD space. The treating agent replaces most Si-OH bonds with Si-O-Si-Rx bonds, thereby preventing condensation reactions and thus preventing pore formation.

As a result, pore formation does not occur.

It is also known that the presence of SiO—SiR ₂ —OSi bonds, wherein SiR ₂ — is one example of the functional groups processed in the matrix, may improve the elastic modulus of the porous material. For most porous materials, retention and improvement of modulus of elasticity is required to withstand the added stress. The bond of the treated agent, dimethylsilyl bond, certainly improves the modulus of elasticity. If applied to the weak part of the silicate, an improvement of the material against external stress is expected.

The treatment composition treatment is performed after trenching and via formation of the dielectric, and the etching and ashing steps restore carbon consumption and damage to low k materials. By this means it is possible to prevent pores and to withstand the internal stresses caused by the annealing treatment on the metal filling the trenches and vias.

Treatment Composition The treatment is carried out by exposing the wafer surface to a siliting agent for a time sufficient to complete the reaction with the low K-region damaged in liquid or gaseous form. Optionally, high temperature firing can be performed to remove the remaining solvent and excess treatment. Alternatively, wet cleaning may also be performed using chemicals compatible with commercially available low-k dielectrics immediately after treatment application or after the firing step.

Additionally, in order to enhance the efficiency of treatment treatment, dehydration firing can be carried out before treatment treatment.

The efficiency of the treatment of the treatment can be demonstrated using a low k dielectric film with no pattern formed on which the etching and ashing processes following the treatment have been performed. Successful treatment treatment results in an increase in the carbon concentration that can be measured with FTIR, EDX or XPS technology. In addition, an increase in the water contact angle is observed, indicating the hydrophobic nature of the post-treated surface. Films treated with the treatments also showed lower dielectric constants from the C-V measurements compared to visualized / ashed films not treated with the treatments. In patterned wafers, the efficiency of treatment treatment is low in trenches or vias after exposure to reactive solvents and reduction or removal of pores in low-k dielectrics in narrow spaces between copper trenches after copper annealing treatment following copper plating. Proven by profile change.

It is known that the treating agent may be prepared using an activator which may be an amine, onium compound, alkali metal hydroxide or combinations thereof with a silane based monomer having a reactive leaving group.

In one embodiment, the composition of the present invention

Ethyl acetoacetate, methyl acetoacetate, t-butyl acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, nonyl acetate, 2- (2-butoxyethoxy) ethyl acetate, pentyl acetate, 2 Butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzyl acetate, dimethyl sulfoxide, N-methyl-N-methoxyacetamide, N, N-diethyl-2-pentylacetamide, N, N- Dimethylacetamide, N, N-diethylacetamide, N, N-diphenylacetamide, N, N-dimethylpropionamide, N, N-dimethylisobutyamide, 1,2-dichlorobenzene, chlorotoluene, 1 -Hexanol, 2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol, 4-heptanol, 4-methyl- Further comprising a solvent comprising 3-heptanol, 6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol or a combination thereof .

In another embodiment of the present invention, the composition of the present invention further comprises a mixture, preferably a miscible mixture of primary and auxiliary solvents. The mixture may dissolve components capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film via silication; At this time, the auxiliary solvent has a higher vapor pressure and / or boiling point than the main solvent.

The present invention provides a composition for treating an organosilicate glass dielectric film comprising:

a) a component capable of alkylating or arylating the silanol moiety of the organosilicate glass dielectric film via silication and

b) activator.

The present invention also provides a method comprising:

a) forming an organosilicate glass dielectric film;

b) the organosilicate glass dielectric film and a component capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film via silication; And contacting the composition comprising the activator.

The present invention further provides a method of preventing the formation of stress-induced pores in an organosilicate glass dielectric film on a substrate. Wherein in the organosilicate glass dielectric film, at least a portion of the carbon-containing portion that has existed previously is removed, or the hydrophobicity of the organosilicate glass dielectric film is reduced, and at least a portion of the carbon-containing portion that has existed previously is removed, Or after the at least one step of reducing the hydrophobicity of the organosilicate glass dielectric film is performed, at an effective concentration and effective time to restore at least a portion of the carbon-containing partial hydrophobicity, or to increase the hydrophobicity of the organosilicate glass dielectric film, At least one step is performed including contacting the organosilicate glass dielectric film with the composition. At this time, the composition,

a) a component capable of alkylating or arylating the silanol moiety of the organosilicate glass dielectric film via silication and

b) an activator.

The present invention further provides a method of manufacturing a microelectronic device, comprising:

a) forming an organosilicate glass dielectric film on the substrate;

b) removing at least a portion of the carbon-containing moiety previously present in the organosilicate glass dielectric film or performing at least one step of reducing the hydrophobicity of the organosilicate glass dielectric film;

c) a sila of the organosilicate glass dielectric film and the organosilicate glass dielectric film through silicide, at a concentration and time effective to restore at least a portion of the carbon-containing portion that has existed previously or to increase the hydrophobicity of the organosilicate glass dielectric film. Components capable of alkylating or arylating knol moieties; And contacting the composition comprising the activator.

The present invention further provides a method of manufacturing a microelectronic device, comprising:

a) applying an organosilicate glass dielectric film on the substrate;

b) at least one forming vias and trench patterns in the organosilicate glass dielectric film, removing at least some of the carbon-containing portions previously present in the organosilicate glass dielectric film, or reducing the hydrophobicity of the organosilicate glass dielectric film Performing the above processing;

c) contacting said organosilicate glass dielectric film with a treating composition at a concentration and time effective to increase the hydrophobicity of the organosilicate glass dielectric film. Wherein the treating agent composition comprises a component capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film through silication; And activators.

In the context of the present invention, a dielectric material having a low dielectric constant of 3 or less is generally preferred, since it enables fast signal propagation, reduces power storage effects and leakage between wires, and requires a low voltage for driving integrated circuits. . The present invention relates to both porous and non-porous materials. One of the materials having a low dielectric constant is silica, which is used as a foaming dielectric material. For the lowest possible dielectric value, air is introduced into the silica dielectric material. Air has a dielectric constant of 1, and when air is introduced into the silica dielectric material in the form of nanopores or nanometer-sized life-saving structures, a relatively low dielectric constant ("k") is obtained. If the term "silica" is used, the term "silica" as used herein, for example in connection with porous and non-porous films, is used herein unless the term "SiO ₂ " functional group is specifically mentioned. By organic glass based material, for example, a dielectric film made by the method of the present invention from any suitable starting material containing at least one silicon based dielectric precursor. In addition, the use of a singular term herein is not intended to be limiting and may include a plurality as appropriate. For example, the exemplary methods of the present invention may be described as being applied to "films" or producing "films", but may be produced on several sheets of film by the above described, illustrated and claimed methods as needed. The term "film" as used herein in reference to a silica dielectric material includes any other suitable form or aspect in which such silica dielectric material is optionally employed. For example, recently employed spin-on-glass ("SOG") and chemical vapor deposition ("CVD") silica SiO ₂ Nanoporous silicas are attractive because they use similar precursors containing organic-substituted silanes such as tetramethoxysilane ("TMODS") and / or tetraethoxysilane ("TEOS"). As used herein, the terms "pores" and "holes" refer to where free volume or vacuum occurs in which mass is replaced by gas. Gas compositions are not generally determined, but suitable gases include relatively pure gases, including air, and mixtures thereof. Nanoporous polymers may contain many pores. The holes are generally spherical but may optionally have any shape, including, optionally or additionally, tubular, plate, disc or other shapes. The pores may be constantly or optionally dispersed in the porous polymer. The holes are believed to have any suitable diameter. It is further believed that at least some of the holes are connected with adjacent holes to form a structure having a substantial amount of connected or "open" holes.

Nanoporous silica films have conventionally been produced by various methods. Suitable silicon-based precursor compositions and methods of making nanoporous silica dielectric films are described, for example, in the following co-US patents 6,048,804, 6,022,812; 6,410,149; 6,372,666; 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; 6,318,124 and 6,319,855, all of which are incorporated herein by reference.

Other dielectric and low dielectric materials are generally silicose-based (for example, commercially available from Honeywell International Inc.) in registered pending US patent application Ser. No. 10/078919, filed February 19, 2002. Inorganic-based compounds), which may be disclosed in the NANOGLASS ^® and HOSP ^® products). The dielectric and low dielectric materials may be applied by spin coating the material onto a surface, applying the material by dip coating, spray coating, chemical vapor deposition (CVD), rolling on the surface, and applying the material to the surface. It can be applied by dropping onto the phase and / or by applying the substance onto the surface. Dielectrics useful in the present invention include carbon-doped oxides, such as Black Diamond commercially available from Applied Material, Inc., and Coral commercially available from Novellus. CVD plating materials such as Aurora, commercially available from ASM, and Orion, commercially available from Trikon.

As used herein, the terms "spin-on material", "spin-on organic material", "spin-on composition" and "spin-on inorganic composition" may be interchanged with each other, and the spin coating application process By such solutions and compositions that are rotated on or on a substrate used in the invention. Silicone-based compounds include siloxane compounds such as methylsiloxane, methylsilsesquinoic acid, phenylsiloxane, phenylsilsesquinoxane, methylphenylsiloxane, methylphenylsilsesquinoxane, silazane polymers, silicate polymers, and mixtures thereof. . The expected silazane polymers are perhydrosilazanes that have a "transparent" polymer backbone when the chromophore is attacked. Also, spin-on-glass material is hydro gensil having the siloxane polymer and a block polymer represented by the general formula _{(H 0 -1.0 SiO 1 .5-2.0)} x and x is greater than the formula 4 (HSiO _{1 .5)} x access Quinoxane polymers are included. Also included are copolymers of hydrogensilsesquinoxane and alkoxyhydridosiloxanes or hydroxydridosiloxanes. In addition to spin-on glass materials, organohydridosiloxane polymers of the general formula (H _{0 -1.0} SiO _{1.5 -2.0} ) _n (R _{0 -1.0} SiO _{1.5 -2.0} ) _m and the general formula (HSiO _{1 5)} is _n (RSiO include organic hydrido room sesquioleate Noksan polymer _{1 0.5) m.} Wherein m is greater than 0, the sum of n and m is greater than 4, and R is alkyl or aryl. Some useful organohydridosiloxane polymers have a sum of n and m from about 4 to about 5000, where R is a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₁₂ aryl group. The organohydridosiloxane and organohydridosilsesquinoxane polymers are optionally spin-on polymers. Some specific examples include alkylhydridosiloxanes such as methylhydridosiloxane, ethylhydridosiloxane, propylhydridosiloxane, t-butylhydridosiloxane, phenylhydridosiloxane; And alkylhydridosilsesquis such as methylhydridosilsesquioxane, ethyl hydridosilsesquioxane, propylhydridosilsesquioxane, t-butylhydridosilsesquioxane, phenylhydridosilsesquioxane Butyric acid and combinations thereof. Some anticipated spin-on materials are described in the following published patents and pending applications, which are incorporated herein by reference in their entirety: US Pat. No. 6,506,497; 6,365,765; 6,268,457; 6,177,199; 6,358,559; 6,218,020; 6,361,820; 6,218,497; 6,359,099; 6,143,855; 6,512,071, US Patent Application No. 10/001143, filed November 10, 2001; PCT / US00 / 15772, filed June 8, 2000 and PCT / US00 / 00523, filed January 7, 1999.

It is used to prepare siloxane polymer film caged with a solution of organohydridosiloxane and organosiloxane resin, which polymer film can be used for various electronic devices, micro-electronic devices, especially semiconductor integrated circuit and hard mask layer, user layer, etching It is useful in the manufacture of multilayer materials for various electronic and semiconductor components, including stop layers and buried etch stop layers. This organohydridosiloxane resin layer is compatible with multilayer materials such as adamantane-based compounds, diamatane-based compounds, silicon-core compounds, organic dielectrics and nanoporous dielectrics and other materials that may be used in the device. Compounds that are compatible with the organohydridosiloxane resin layers anticipated herein are described in US Pat. No. 6,214,746; 6,171,687; 6,172,128; 6,156,812, filed Jan. 15, 2002, US application 60/350187; US Patent Application 09/53827; U.S. Patent Application 09/544504; US Patent Application 09/587851 and US 60/347195, filed Jan. 8, 2002; PCT Application PCT / US01 / 32569, filed October 17, 2001; PCT application PCT / US01 / 50812, filed December 31, 2001, all of which are incorporated herein by reference.

Organohydridosiloxanes suitable for use in the present invention have the general formula:

_{[H-Si 1 .5] n} [R-SiO 1 .5] m Formula (1)

_{[H 0 .5-1.0 Si 1 .5-1.8]} n [R 0 .5-1.0 SiO 1 .5-1.8] m formula (2)

_{[H 0 -1.0 Si 1 .5]} n [R-SiO 1 .5] m formula (3)

_{[H-Si 1 .5] x} [R-SiO 1 .5] y [SiO 2] z formula (4)

here :

The sum of n and m or the sum of x, y and z is from about 8 to about 5000, and m or y is in an amount of less than 40 percent of carbon-containing components (low organic content = LOSP) or in an amount of at least 40 percent (high organic Content = HOSP); R is substituted and unsubstituted, general and branched alkyl (methyl, ethyl, butyl, propyl, pentyl), alkenyl groups (vinyl, allyl, isopropenyl), cycloalkyl, cycloalkenyl groups, aryl (phenyl groups Benzyl groups, naphthalenyl groups, anthracenyl groups and phenanthrenyl groups) and combinations thereof; The molar ratio percentage of the carbon containing substituents is also a function of the ratio to the amount of starting material. In some LOSP embodiments, particularly good results are obtained when the mole percent of carbon containing substituents is in a range between about 12 mole percent and about 25 mole percent. In some HOSP embodiments, good results are obtained when the mole percent of carbon containing substituents is in the range of about 55 to about 75 mole percent.

Nanoporous silica dielectric films having dielectric constants ranging from about 1.5 to about 4 can be used as one of the layers. The nanoporous silica film is laminated to a mature or condensed silicon-based precursor in the presence of water, heated sufficiently, substantially removes all of the porogen, and forms pores in the film. The silicon-based precursor composition comprises monomers or prepolymers having the formula Rx-Si-Ly. Wherein R is independently selected from alkyl groups, aryl groups, hydrogen and combinations thereof, L is an electronegative moiety such as alkoxy, carboxy, amino, amido, halide, isocyanato and combinations thereof, x is about An integer in the range of 0 to 2, and y is an integer in the range of about 2 to 4. US Patent 6,171,687, which is incorporated herein in its entirety; 6,172,128; 6,214,746; 6,313,185; 6,380,347; And 6,380,270 to other nanoporous compounds and methods.

The terms "cage structure", "cage molecule" and "cage compound" may be used interchangeably, such that at least one crosslink is covalently bonded to two or more atoms in the ring system. It means a molecule having at least 10 atoms arranged. In other words, a cage structure, a cage molecule, or a cage compound contains many rings formed by covalent bonds of atoms, where the point located with the volume does not pass through the ring without passing through the ring. The structure, molecule or compound is limited in volume because it cannot escape. The crosslinking and / or ring system may comprise one or more hetero atoms, and in particular may be substituted or unsubstituted aromatic. Furthermore, expected cage structures include fullerenes and crown ethers having at least one crosslink. For example, within the scope of this definition, adamantane or diamantan is considered a cage structure, but a naphthalene compound or an aromatic spiro compound does not have one or more crosslinks. It is not considered a cage structure. The expected cage compound need not necessarily be limited to carbon atoms alone, and may also include heteroatoms such as N, S, O, P, and the like. Heteroatoms may advantageously be introduced in non-square crystal bond angle forms. With regard to substituents and derivatives of the expected cage structure, many substituents and derivatives are considered suitable. For example, when the cage compound is relatively hydrophobic, a hydrophilic substituent may be added in order to increase the solubility in the hydrophilic solvent, and vice versa. Optionally, polar side chains can be added to the cage compound if polarity is desired. It is also contemplated that suitable substituents may also be infused with heat labile groups, nucleophiles and electron affinity groups. It is also natural that functional groups can be used in the cage compound (eg, to promote crosslinking reactions, induction reactions, and the like). As detailed herein, the cage molecule or compound may be a functional group attached to the polymer backbone, thus forming nanoporous material when the cage compound forms one type of pores (inside the molecule) and In the case where at least one part of the main chain is crosslinked with itself or with another main chain, it is possible to form another type of pores (inside the molecule). Additional cage molecules, cage compounds, and variations of such molecules and compounds are described in detail in PCT / US01 / 32569, filed Oct. 18, 2001, the entirety of which is incorporated herein. Anticipated polymers may also include a wide range of functional groups or structural moieties containing aromatic and halogenated groups. Furthermore, suitable polymers can have a variety of forms including single polymers and heteropolymers. Preferred polymers also have various forms such as linear, branched, super-branched, or three-dimensional. The expected molecular weights of polymers generally range over a broad range between 400 Daltons and over 400000 Daltons. In addition, additives known in the polymer art may be used, including stabilizers, fire retardants, pigments, plasticizers, surfactants, and the like, to enhance or impart specific properties. In order to impart the desired properties, it is possible to mix polymers which are mixed or not. Adhesion promoters may also be used. Such enhancers are represented by hexamethyldisilizane, which can be used to react with a hydroxylation reactor whose surface may appear on the surface, such as silicon dioxide exposed to moisture or moisture. Preferably the polymers used in microelectronic applications include low levels of ion impurity, especially between dielectric layers.

The materials, precursors and layers described herein may be present and may be designed to be solvated or dissolved in a suitable solvent in a variety of ways, provided that the resulting solution can be applied to a substrate, surface, wafer or laminated materials. have. In addition, solvents capable of solvating monomers, isomer monomer mixtures and polymers are typical solvents. Anticipated solvents include any suitable compound or mixture of organic or inorganic molecules that may be volatilized at a desired temperature, such as a critical temperature, or may facilitate any of the design goals or needs described above. The solvent may also include any suitable polar and nonpolar compounds or mixtures thereof. As used herein, the term "polar" means a property of a molecule or compound that exhibits a non-uniform charge, partial charge, or arbitrary charge distribution, either along or along a molecule or compound. As used herein, the term "nonpolar" means a property of a molecule or compound that exhibits a uniform charge, partial charge, or arbitrary charge distribution at or along a portion of the molecule or compound. In some intended embodiments, the solvent or solvent mixture (including two or more solvents) includes a solvent that is considered to be part of a hydrocarbon-based solvent. The hydrocarbon solvent is a solvent containing carbon and hydrogen. It will be appreciated that most of the hydrocarbons are nonpolar, but very few hydrocarbon solvents are also considered polar. Hydrocarbon solvents can generally be divided into three classes: aliphatic, cyclic and aromatic. The aliphatic hydrocarbon solvent may include both a linear compound and a branched compound capable of crosslinking. However, aliphatic compounds are not considered to be cyclic. Cyclic hydrocarbon solvents are similar to aliphatic hydrocarbon solvents and are solvents containing at least three carbon atoms to form a ring structure. Aromatic hydrocarbon solvents are solvents having multiple rings connected by a single ring or a general bond and / or multiple rings fused together and generally containing three or more unsaturated bonds. Expected hydrocarbon solvents include toluene, xylene, p-xylene, m-xylene, mesitylene, solvent naphtha H, solvent naphtha A, pentane, hexane, isohexane, heptane, nonane, octane, dodecane, 2-methyl Alkanes such as butane, hexadecane, tridecane, pentadecane, cyclopentane, 2,2,4-trimethylpentane, petroleum ether, chlorinated hydrocarbons, nitrified hydrocarbons, benzene, 1,2-dimethylbenzene, 1,2 Halogenated hydrocarbons such as, 4-trimethylbenzene, mineral spirits, kerosene, isobutylbenzene, methylnaphthalene, ethyltoluene, ligroin, and the like. Particularly preferred solvents include, but are not limited to, pentane, hexane, heptane, Cyclohexane, benzene, toluene, xylene and mixtures or combinations thereof.

In other anticipated embodiments, the solvent or solvent mixture is considered part of a hydrocarbon solvent family of compounds such as ketones such as acetone, 3-pentanone, diethyl ketone, methylethyl ketone, and the like, alcohols, ketones, esters, ethers and amines. Unsupported solvents may be included. In another expected embodiment, the solvent or solvent mixture may comprise a combination of any of the solvents mentioned herein. In some embodiments the solvent comprises water, ethanol, propanol, acetone, ethylene oxide, benzene, toluene, ether, cyclohexanone, butyrolacetone, methylethylketone and anisole.

It is further contemplated that the low dielectric constant material selected may also include additional components. For example, when the low dielectric constant material is exposed to mechanical stress, softeners or other protective agents may be added. In other cases, adhesion promoters may be usefully employed when the dielectric material is placed on a smooth surface. In other cases, detergents or anti-foaming agents may be preferred. Generally a spin-on-glass composition comprising a precursor of this type, for example one or more removable solvents, is applied to the substrate in this manner, polymerized and then subjected to solvent removal to include nanometer-sized configurations. A dielectric film is produced.

When forming such a nanoporous film, for example, a precursor is applied to the substrate by spin coating, the film coating is generally catalyzed with an acid or base catalyst and water, and polymerized / gelled during the initial heating step ( "Aging"). The film is then cured, for example, by performing one or more high temperature heating steps, especially heating steps to remove the remaining solvent and to complete the polymerization process. Other curing methods for irradiating the film with radiation energy, such as ultraviolet light, electron beams, microwave energy, and the like, are also included.

US co-patents 6,204,202 and 6,413,882, incorporated herein by reference, provide methods for decomposing or vaporizing a silicon-based precursor composition and one or more polymers or oligomers present in the precursor composition to form nanoporous silica dielectric films. U.S. Patent 6,495,479 provides a process for preparing nanoporous silica dielectric films by decomposing or vaporizing a silicon-based precursor composition and one or more compounds or polymers present in the precursor composition. U.S. Patent 5,895,263 applies a composition comprising a decomposable polymer and an organic polysilica, i.e., a condensed or polymerized silicone polymer, and heats the composition to further condense the polysilica, and decomposes the degradable polymer to form a porous dielectric layer. Forming a nanoparticle is described for forming a nanoporous silica dielectric film on a substrate, such as a wafer.

Processes for applying precursors to substrates that age, cure, planarize and impart hydrophobicity to the film are described in other patents, such as US Pat. Nos. 6,589,889 and 6,037,275. Substrates and wafers contemplated by the present invention may include any desired substantially solid material. Particularly preferred substrate layers include films, glass, ceramics, plastics, metals or coated metals or mixed materials. In a preferred embodiment the substrate is one found in a silicon or germanium arsenide die or wafer surface, a packaging surface such as that found in a copper, silver, nickel or gold plated solder, an integrated circuit or package interconnect. Same copper surface, via-wall or reinforcement interface ("copper" includes consideration for pure copper and its oxidation), polymer-based packages or plates such as those found in polyimide-based flux packages Interfacial, lead or other metal alloy solder ball surfaces, and polymers such as glass and polyimide. The "substrate" may be limited to another polymer chain, considering the adhesive interface. In a more preferred embodiment, the substrate comprises materials common in the field of packaging and integrated circuits such as silicon, copper, glass and other polymers.

Cap film deposition processes by PECVD and subsequent semiconductor processes such as via and trench formation by patterning using etching and ashing, atomic layer deposition, physical vapor deposition, and chemical vapor deposition treatment are hydrophobic groups from organosilicate glass dielectric films. There is a tendency to remove the carbon containing moieties and replace them with silanol groups. Undesirable properties appear when the organosilicate glass dielectric film contains silanol groups. Silanol and the water they can absorb in the air can have a high polarity in the electric field, resulting in an increase in the dielectric constant of the film, weakening the resistance to wet cleaning chemicals, and increasing volatility. In addition, when filling trenches and vias with metal and annealing, metal shrinkage induces pressure on the vias and trench walls, resulting in undesirable holes in the dielectric metal between the vias and / or trenches. .

To solve this problem, the organosilicate dielectric film is made substantially free of silanol and water by treating the carbon containing portion with a treatment that increases the hydrophobicity of the glass silicate glass dielectric film. This makes film resistance to vias and trench walls, such as induced by metal shrinkage during annealing, pressure from other dielectric layers and pressure during packaging, which is undesirable in the dielectric metal between the vias and / or trenches. To prevent it from being formed.

Etching and plasma remove hydrophobic functional groups. Damage to the organosilicate glass dielectric film during the semiconductor manufacturing process is caused by the application of aggressive plasma and / or etching reagents to etch trenches and vias inside the dielectric film. Plasma is also used to remove photoresist films during fabrication of semiconductor devices. The plasma generally consists of oxygen, fluorine, hydrogen, carbon, argon, helium or nitrogen. (In the form of free atoms, compounds, ions and / or radicals)

Dielectric films exposed to such plasma during trench, via, etch and / or photoresist removal processes are readily degraded or damaged. Porous dielectric films have a large surface area and as a result are particularly vulnerable to plasma damage. In particular, silica-based dielectric films having organic components (organic components such as methyl groups bonded to Si atoms) are readily degraded by oxygen plasma. The organic group is oxidized to CO ₂ , and silanol or Si—OH groups remain on the dielectric surface where the organic group previously existed. Porous and non-porous low dielectric constant silica films are maintained hydrophobic by these organic groups (existing on the surface). This hydrophobic loss increases the dielectric constant. (The low dielectric constant of the film is the most important property of these materials.)

In IC fabrication, wet chemical treatment is also used to remove residues left after trench or via etch. The chemicals are often very aggressive, capable of attacking and removing organic groups in silica-based films, especially porous silica films. This damage causes the dielectric film to lose hydrophobicity again. Wet chemical etchantes include, for example, amides such as N-methylpyrrolidinone, dimethylformamide, dimethylacetamide; Alcohols such as ethanol mill 2-propanol; Alcohol amines such as ethanol amine; Amines such as triethylamine; Diamines such as ethylenediamine and N, N-diethylethylenediamine; Triamines such as diethylenetriamine, diamine acids such as ethylenediaminetetraacetic acid "EDTA"; Organic acids such as acetic acid and formic acid; Ammonium salts of organic acids such as tetramethylammonium acetate; Inorganic acids such as sulfuric acid, phosphoric acid, hydrofluoric acid; Fluorine salts such as ammonium fluorine; And bases such as ammonium hydroxide and tetramethyl ammonium hydroxide; And hydroxyl amines; After etching such as EKC 505, 525, 450, 265, 270 and 630 (EKC Corp., Hayward CA), and some etchant known in the art called ACT-CMI and ACT-690 (Ashland Chemical, Hayward, CA) Commercially developed products used for wet cleaning are included. The ashing agents include plasma generated from hydrogen, nitrogen, helium, argon, oxygen and mixtures derived from them, and the like.

To solve the above problems, the present invention provides methods for imparting hydrophobicity to an organosilicate glass dielectric film on a substrate during semiconductor fabrication or IC device processing.

The methods of the invention restore at least some carbon containing portions of the organosilicate glass organic film or increase the hydrophobicity of the organosilicate glass organic film after applying at least one etchant or ashing reagent and before the metal is annealed. Contacting said organosilicate glass organic film and a treating composition at an effective concentration and an effective time; And (b) removing the unreacted treatment composition, the reaction product, and mixtures thereof. The treatment composition comprises at least one treatment agent, ie a compound or a charged derivative thereof, suitable for removing the silanol moiety from the damaged silica dielectric film. Then optionally the silica dielectric film damaged in the etchant is subjected to a wet cleaning step.

All of the above treating agent compositions include components capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film via silication, and activators which may be acids, bases, onium compounds, dehydrating agents, and combinations thereof. The compositions are also optionally, but preferably, selected from the selected solvents or main and auxiliary solvents capable of dissolving the components and activators capable of alkylating or arylating the silanol moiety of the organosilicate glass dielectric film via the silicides described above. Mixtures.

Suitable treatment compositions include one or more treatment agents capable of removing silanol groups from the surface of the etched and / or ashed organosilicate glass dielectric film that preferably has hydrophobicity. These may be silane, silazane, silanol or carboxysilyl. For example, the treating agent is a compound having the following formula.

Formula I (1-13): (1) [-SiR ₂ NR'-] _n where n> 2 and may be a cycle; (2) R ₃ SiNR'SiR ₃ , (3) (R ₃ Si) ₃ N; (4) R ₃ SiNR '₂; (5) R ₂ Si (NR ′) ₃ ; (7) R _x SiCl _y ; (8) R _x Si (OH) _y ; (9) R ₃ SiOSiR ' ₃ , (10) R _x Si (OR') _y , (11) R _x Si (OCOR ') _y , (12) R _x SiH _y ; (13) R _x Si [OC (R ') = R "] _4-x or a combination thereof.

Wherein x is an integer ranging from 1 to 3, y is an integer ranging from 1 to 3 satisfying y = 4-x, and R is each independently selected from hydrogen and hydrophobic organic moieties. The R group is preferably an organic moiety consisting of alkyl, aryl and combinations thereof. The R 'group may be H, alkyl, aryl, or carbonyl such as COR, CONR, CO ₂ R. The R ″ group may be alkyl or carbonyl such as COR, CONR, CO ₂ R.

For all treatments, the reactive silyl group is, but is not limited to, -Cl, -Br, -I, -OR, -NRx (where x = 1), -OCOR, -OCO2R, -NRCOR, -NRCO ₂ R And hydrolyzable leaving gruop such as -NRCONR, -SR, -SO ₂ R. In the reaction of the treatment agent, hydrolysis may occur with moisture present during treatment agent application and processing, or pre-hydrolysis may be forced during the manufacturing process.

The alkyl moiety may be a functional group or a non-functional group and is derived from straight chain alkyl, branched alkyl, cyclic alkyl and combinations thereof. In addition, the alkyl moiety here ranges in size from C ₁ to C ₁₈ . The functionalization may be carbonyl, halide, amine, alcohol, ether, sulfonyl or sulfide. The aryl moiety may be substituted or non-substituted and the size is in the range of about C ₅ to C ₁₈ . The treatment agent is acetoxysilane or, for example, acetoxysilane, diacetoxysilane, triacetoxysilane, acetoxytrimethylsilane, diacetoxydimethylsilane, methyltriacetoxysilane, phenyltriacetoxysilane, diphenyldia Cetoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, methyl Silane, dimethylsilane, trimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethylsilane, tri (dimethylamino) methylsilane, tri (dimethylamino ) Phenylsilane, tri (dimethylamino) silane, dimethylsilyldiformamide, dimethylsilyldiacetamide, dimethylsilyl diisocyanate, trimethylsilyl Triisocyanate, 2-trimethylsiloxypent-2-en-4-one, n- (trimethylsilyl) acetamide, 2- (trimethylsilyl) acetic acid, n- (trimethylsilyl) imidazole, trimethylsilylpropiolate, Trimethylsilyl (trimethylsiloxy) -acetate, nonamethyltrisilazane, hexamethyldisiloxane, trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilanol, diphenylsilanediol, trimethoxy Monomer compounds such as silane, triethoxysilane, trichlorosilane and combinations thereof. In one notable embodiment, the treating agent is methyltriacetoxysilane. In a preferred embodiment the treating agent is dimethyldiacetoxysilane.

Additional treatments include multi-functional surface modifiers disclosed in detail in US Pat. No. 6,208,014, which is incorporated herein by reference. Such multi-functional surface modifiers may be applied in vapor or liquid form, optionally with or without an auxiliary solvent.

For example, as specifically described in US Pat. No. 6,208,014, certain preferred surface modifiers may have two or more functional groups, and may react with surface silanol functional groups while minimizing the mass present outside the framework of the film. Surface silanol, which may be condensed with a suitable silanol such as, for example, R _x Si (OH ₂ ) _4-x .

Where x = 1-3 and R are each independently selected from moieties such as H and / or organic moieties such as alkyl, aryl, or derivatives thereof. When R is alkyl, the alkyl moiety may be optionally substituted or unsubstituted, may be straight chain, branched, or cycle, preferably in the range of C ₁ to about C ₁₈ or more, and C ₁ It is even more preferable that it is the range of C- ₈ . When R is aryl, the aryl moiety is optionally substituted or unsubstituted, and C ₅ It preferably consists of a single aromatic ring having from C _{18 to at} least C, more preferably C ₅ to C ₈ . In another option, the aryl moiety is hetero aryl.

In another embodiment, an alkoxy silane such as RxSi (OR ') 4-x may be used as the treatment agent. Wherein R is each independently selected from moieties such as H and / or organic moieties such as alkyl, aryl, or derivatives thereof; R 'is independently selected from alkyl or aryl moieties. When R or R 'is alkyl, the alkyl moiety is optionally substituted or unsubstituted, can be straight chain, branched or cycle, preferably in the range of C ₁ to about C ₁₈ or more, Even more preferred is the range of C ₁ to C ₈ . When R or R 'is aryl, the aryl moiety is optionally substituted or unsubstituted, and C ₅ It preferably consists of a single aromatic ring having from C _{18 to at} least C, more preferably C ₅ to C ₈ . In another option, the aryl moiety is hetero aryl. Thus, the R groups are independently selected from H, methyl, ethyl, propyl, phenyl, and / or derivatives thereof provided that at least one R is an organic group. In one embodiment, two R are methyl and the trifunctional surface modifier is methyltrimethoxysilane.

In another embodiment, suitable silanes according to the invention have the general formula R _x Si (NR ₂ ) _4-x . Wherein X = 1-3 and R is independently H, alkyl and / or aryl. Any R is alkyl and / or aryl. In a preferred embodiment, R is selected from H, CH ₃ , C ₆ H ₅ and R ₂ and R ₃ are both CH ₃ . Thus, the trifunctional treatment agent may include, for example, tris (dimethylamino) methylsilane, tris (dimethylamino) phenylsilane and / or tris (dimethylamino) silane. In addition, disubstituted silanes such as hexamethylcyclotrisilazane, bisdimethylaminodimethylsilane and bisdiethylaminodimethylsilane may also be used.

In another embodiment, suitable silanes according to the invention have the general formula R _x Si (ON = CR ₂ ) _4-x or R _x Si [OCOR ') = R "] _4-x , wherein x = 1 -3, R is independently H, alkyl, and / or aryl, and R "is alkyl or carbonyl. Thus, the modifier is, for example, methyltris (methylethylketoxime) silane or 2-trimethylsiloxypent-2-en-4-one, respectively.

In another embodiment, suitable silanes according to the invention have the general formula of R _x Si (NCOR ₂ ) _4-x or R _x Si (NCO) _4-x . Wherein x = 1-3 and the R group is independently H, alkyl, and / or aryl. Thus, surface modifiers include, for example, dimethylsilyldiformamide, dimethylsilyldiacetamide, dimethylsilyldiisocyanate, trimethylsilyltriisocyanate.

In another embodiment, suitable silanes according to the invention have the general formula of R _x SiCl _{4 -x} . Wherein x = 1-3 and R is hydrogen, alkyl or aryl. In a preferred embodiment, R _x is CH ₃ . Thus, trifunctional surface modifiers include, for example, methyltrichlorosilane.

In a still more preferred embodiment, the treating agent comprises at least one organoacetoxysilane having the general formula

(R1) _x Si (OCOR ₂ ) _y

x is an integer in the range of 1 to 2, x and y may be the same or different, and y is an integer in the range of about 2 to 3 or more.

Useful organoacetoxysilanes, including multi-functional alkylacetoxysilanes and / or arylacetoxysilane compounds, are by way of example simply and without limitation, methyltriacetoxysilane (“MTAS”), dimethyldiacetoxysilane ( "DMDAS"), phenyltriacetoxysilane and diphenyldiacetoxysilane and combinations thereof.

The component capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film via silicide is present in the treatment agent at about 0.1% to 100% by weight, more efficiently at about 0.1% to 50% by weight. Most efficiently, 3% to 30% by weight.

The treating agent composition containing the activator may be an activator which may be an acid, a base, an onium compound, a dehydrating agent, a hydroxide or a combination thereof. Useful activators include amines, ammonium compounds, phosphonium compounds, sulfonium compounds, iodonium compounds, hydroxides, alkoxides, acid halides, silanolates, amine salts, and combinations thereof. Activators which may be alkyl amines, aryl amines, alcohol amines, and mixtures thereof, may suitably have a boiling point of at least about 100 ° C., typically at least about 125 ° C., and more generally at least 150 ° C. . Useful acid activators are non-exclusively hydrochloric acid, sulfuric acid, nitric acid, boric acid, ethyl sulfuric acid, chlorosulfonic acid, phosphonitrile chloride, iron chloride, zinc chloride, tin chloride, ammonium chloride, trifluoroboron, methanesulfonic acid , Trifluoromethanesulfonic acid, iron chloride hexahydrate or combinations thereof.

Useful activators which are dehydrating agents non-exclusively include phosphorus halides, phosphorus pentoxides, phenylphosphonic dichlorides and phenyl phosphorodichloridates and combinations thereof.

Useful amine activators include primary amines, secondary amines, tertiary amines, ammonia and quaternary ammonia salts. Monoethanolamine, diethanolamine, triethanol amine, monoisopropanolamine, tetraethylenepentamine, 2- (2-aminoethoxy) ethanol; 2- (2-aminoethylamino) ethanol and combinations thereof are useful amines.

In a preferred embodiment of the invention, the activator comprises tetramenylammonium acetate, tetrabutylammonium acetate or a combination thereof. Other activators include sodium hydroxide, cesium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide. The activator is generally present in the treatment agent at about 0.0001% to about 10% by weight, more typically at about 0.001% to about 1% by weight, and most typically at about 0.01% to 0.1% by weight. Exists in%

The treatment composition includes a component capable of dissolving an alkylating or arylating silanol portion of the organosilicate glass dielectric film through a silicide and a solvent capable of dissolving an activator.

In one embodiment, the solvent comprises a solvent or a mixture of primary and auxiliary solvents, the mixture dissolving components and activators capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film through silicidation. To; The auxiliary solvent has a higher vapor pressure and / or boiling point than the main solvent. In one embodiment, the main solvent has a boiling point of about 100 ° C to 300 ° C, preferably about 110 ° C to about 250 ° C, even more preferably about 130 ° C to about 180 ° C. In one embodiment, the auxiliary solvent has a boiling point of about 1 ° C. to about 100 ° C. higher than the main solvent. In another embodiment, the auxiliary solvent has a boiling point about 10 ° C. to 70 ° C. higher than the main solvent. In another embodiment, the auxiliary solvent has a boiling point of about 20 ° C. to 50 ° C. higher than the main solvent.

The solvents and main solvents may be one or more ketones, ethers, esters, hydrocarbons, alcohols, carboxylic acids, amines, amides and combinations thereof. Useful main solvents non-exclusively include 3-pentanone, 2-heptanone, gammabutyrolacetone, propylene glycolmethyl ether acetate, acetic acid and combinations thereof.

 Solvents and auxiliary solvents are ethyl acetoacetate, methyl acetoacetate, t-butyl acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, nonyl acetate, 2- (2-butoxyethoxy) ethyl Acetate, pentyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzyl acetate, dimethyl sulfoxide, N-methyl-N-methoxyacetamide, N, N-diethyl-2-phenylacet Amide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-diphenylacetamide, N, N-dimethypropionamide, N, N-dimethylisobutyamide, 1,2- Dichlorobenzene, chlorotoluene, 1-hexanol, 2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol, 4- Heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol or combinations thereof . The auxiliary solvent preferably contains ethyl acetoacetate, dimethyl sulfoxide, 1-hexanol or a combination thereof. The main solvent is preferably present in an amount of about 0.1 to about 99.9% by weight of the miscible mixture in the mixture, more preferably in an amount of about 50 to 99% by weight, and about 70 to 97% by weight of It is even more preferred to be present in amount. The auxiliary solvent is preferably present in the mixture in an amount from about 0.1 to 99.9% by weight of the miscible mixture, more preferably from about 0.5 to 50% by weight of the miscible mixture, even more preferably miscible. Present in about 1 to 30% by weight of the mixture.

The total amount of solvent present in the treating agent composition is about 0.1 to 99.9% by weight, more generally 50% to 99% by weight, most generally 70% to 97% by weight. In another embodiment of the present invention, the treatment composition includes a supercritical solvent, such as supercritical carbon dioxide.

Optionally, the treating agent includes a corrosion inhibitor such as copper and chelated corrosion inhibitor. These may include benzotriazoles, tolyltriazoles, and combinations thereof. The corrosion inhibitor, when employed, is generally in an amount from about 0.001% to about 10% by weight, more typically from about 0.01% to 5% by weight, most typically from about 0.2% to Present in about 1% by weight.

The treatment composition is prepared by mixing the selected ingredients into a mixture. The treatment composition is contacted with the damaged silica dielectric film by liquid, vapor or gas and / or plasma. If in plasma form, the plasma may be derived from silane compounds, hydrocarbons, aldehydes, esters, ethers and / or combinations thereof. The term "agent" or "agents" herein should be considered to be the same as "reagent" or "agents" unless otherwise indicated. Optionally, the treatment comprises a subsequent process of removing the unreacted treatment composition, the reaction product and mixtures thereof and / or a subsequent heating step to increase the organosilicate glass dielectric film hydrophobicity.

In another embodiment, a wet cleaning process using a chemical such as AP395 or diluted HF is performed after the firing step in the above embodiments. The wet clean is useful to remove any resist residues remaining after the ash. Untreated low k dielectric materials after etching and ash are susceptible to attack by the wet cleaner. The treatment treatment significantly improves the resistance of the low k dielectric to attack on wet cleaning liquids.

As the process flows, the copper surface is exposed during treatment treatment, especially at the bottom of the vias. In addition, the wet cleaning removes the naturally occurring oxide layer from the copper surface and also removes any reaction product between the treatment agent and the exposed copper surface. In particular, wet cleaning using AP395 can clean the copper (or suitable metal or metal alloy) surface previously exposed to treatment with DMDAS.

As used herein, the term "metal" refers to the elements in the d- and f-blocks of the Periodic Table of the Elements together with compounds having metal-like properties such as silicon and germanium. As used herein, the term "d-block" refers to elements with electrons filling the 3d, 4d, 5d and 6d orbitals surrounding the nucleus of the element. As used herein, the term "f-block" refers to an element having electrons filled in 4f and 5f orbitals surrounding the nucleus of the element, including lanthanide and actinide elements. Preferred metals include indium, silver, copper, aluminum, copper, aluminum, tin, bismuth, gallium and alloys thereof. The term "metal" includes alloys, metal / metal synthesis, metal ceramic synthesis, metal polymer synthesis, as well as other metal synthesis.

In another embodiment, the wet cleaning may be performed before the firing process in the first expected embodiment before the firing process. After wet cleaning, a high temperature firing step can be performed. The advantage of this method is that it is possible to remove excess reaction agent and any reaction product of the exposed copper surface before the wet cleaning is cured by the firing step. This results in low volatility of the dielectric material and the cleaned copper surface. Both result in improved long term reliability.

In another anticipated embodiment, additional dehydration calcining is performed for 1 to 120 minutes at 100-400 ° C. prior to treatment (TA) treatment. The dehydration calcined removes moisture absorbed by the damaged low k dielectric. Removing moisture from the dielectric before treating the agent allows for a more effective treatment.

In an alternative embodiment, the treating agent composition is provided by exposing an etchant-damaged organosilicate glass dielectric film to a plasma derived from any of the treating agents mentioned above. In a typical process, the organosilicate glass dielectric film is placed in a plasma generating chamber, such as a plasma chemical vapor deposition (PECVD) system; Steam and argon vapor of the treatment composition pass through the plasma generation chamber; The RF energy source is then activated to produce a plasma; The argon gas is included to increase the plasma formation. The plasma consists of ion fragments derived from the treatment composition; For example, CH ₃ Si ⁺ ion fragments are produced from methylsilane (CH ₃ SiH ₃ ). These fragments react with silanol groups to produce a hydrophobic Si—CH ₃ moiety. Any of the above treatment agent compositions can be used in such plasmas that induce surface treatment.

Other treatment compositions suitable for plasma induced to surface treatment include C ₁ -C ₁₂ alkyl and aromatic hydrocarbons. Most preferred hydrocarbon is methane. Other reagents used in plasma derived from the surface treatment composition include aldehydes, esters, chloride acids, ethers. Suitable aldehydes include acetaldehyde and benzaldehyde; Suitable esters include ethyl acetate and methyl benzoate; Suitable chloride acids include acetyl chloride and benzyl chloride; Suitable ethers include diethyl ether and anisole. Various single wafer or multiple batch plasma systems can use this process; Such systems include so-called downstream ashers such as the Gasonics L3510 photoresist asher, PECVD dielectric lamination systems such as Applied Materials P5000, or reactive ion etching ("RIE") systems. Broadly the conditions for the plasma process are within the following ranges: chamber temperature 20 ° C. to 450 ° C .; RF power, 50 W to 1000 W; Chamber pressure, 0.05-100 Torr; Plasma treatment time, 5 seconds to 5 minutes; And surface modification flow rate 100-2000 sccm; Inert gas flow rate (typically argon), 100-2000 sccm.

Those skilled in the art also envision that the present invention encompasses methods of imparting hydrophobic surfaces to silica dielectric films, porous and / or non-porous, whether or not damage has occurred by applying the plasma surface treatment described above. can do. Microelectronic devices such as semiconductor devices or ICs fabricated using this method are also part of the present invention. Microelectronic devices can be manufactured by methods that include:

a) applying an organosilicate glass dielectric film over the substrate;

b) forming vias and / or trench patterns in the organosilicate glass dielectric film and removing at least a portion of the previously contained portions of carbon in the organosilicate glass dielectric film, or the hydrophobicity of the organosilicate glass dielectric film Performing at least one treatment to reduce the temperature;

c) contacting the organosilicate glass dielectric film and the treatment composition at a concentration and time effective to increase the hydrophobicity of the organosilicate glass dielectric film, wherein the treatment agent composition is via silicide to the silanol portion of the organosilicate glass dielectric film Components containing alkylation or arylation, amines, onium compounds, alkali metal hydroxides and combinations thereof, and miscible mixtures of the above-described main solvents and the above-described auxiliary solvents or only the above-mentioned auxiliary solvents); Then optionally firing at about 80 ° C. to about 500 ° C. for at least about 10 seconds.

In one embodiment, firing may be done by heating to a temperature of about 90 ° C to about 450 ° C. In another embodiment, the heating may be at a temperature of 100 ° C to 400 ° C. In another embodiment, the heating may be at a temperature of 125 ° C to 350 ° C. Such heating may be carried out from about 10 seconds or more, preferably about 10 seconds to 60 minutes. The next step is to d) fill the vias and / or trenches with metal by any method known in the art; And then e) optionally annealing the metal. In one embodiment, annealing may be accomplished by heating the device at a temperature of about 150 ° C to 350 ° C. In another embodiment, annealing can be accomplished by heating the device to a temperature of about 200 ° C. to 250 ° C., and the annealing can be performed for about 10 seconds to 60 minutes.

The microelectronic device, dielectric layer and material may include or use any suitable electronic component. As expected herein, electronic components are generally considered to include any dielectric or multilayer dielectric components that can be used in ion-based products. Prospective electronic components include circuit boards, chip packaging, dielectric elements of circuit boards, printed-wiring boards and capacitors, other elements of circuit boards such as inductors and resistors.

Electronic-based products can be completed in the sense that they can be used by industry or other consumers. Examples of finished consumer products are televisions, computers, mobile phones, pagers, palm-type products, portable radios, car stereos and remote controls. Also expected are intermediate products such as circuit boards, chip packaging and keyboards that are potentially used in finished products.

Electronic products may also include prototype components at any stage of development, from conceptual models to mock-ups of final size. Prototypes may or may not contain all of the actual components intended for the final product, and prototypes may have several components made from mixed materials to negate their initial effects on other components during initial testing. Can be. Electronic products and components may include multilayer materials, multilayer components, and stacked components in manufacture for use in the component or article.

Example  1 (2- Heptanone  + Acetic acid)

1.257 g of 1% tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI53201), 44.24 g of 2-heptanone (Ultra Pure Solutions Inc., Castroville, CA 85012) and 4.49 g of dimethyldiacetoxysilane (Gelest , Tullytone, PA 19007) are mixed together in a 60 ml particle free high density polyethylene bottle. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.1 μm using a Teflon filter. Place approximately 2.0-3.0 ml of product on 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon consuming porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The wafer is placed at 2500 rpm for 30 seconds to form a film The film is heated with elevated temperature to 125 ° C., 200 ° C. and 350 ° C. for 1 minute in an N ₂ atmosphere.

The results are shown below.

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.34 3.18 2.28 FTIR CH / SiO peak recovery,% 71

In a similar manner, 2.0-3.0 ml of product was placed on an 8 "Si-wafer, spun and then fired.

The result is: KAL 2132: defect frequency +5000 counts / cm ²

Example  2

2- Heptanone  + Hexanol

0.0126 g tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is added to 1.247 g 1-hexanol and stirred until the mixture is dissolved, followed by 44.24 g of 2-heptanone (Ultra Pure Solutions Inc , Castroville, CA 85012) and 4.49 g of dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007) are added into a 60 ml particle free high density polyethylene bottle. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.1 μm using a Teflon filter. Place approximately 2.0-3.0 ml of product on 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon consuming porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The film is rotated at 2500 rpm for 30 seconds to form a film, and the film is heated under elevated temperature to 125 ° C., 200 ° C. and 350 ° C. for 1 minute in an N ₂ atmosphere.

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.34 3.18 2.32 FTIR CH / SiO peak recovery,% 66

In a similar manner, 2.0-3.0 ml of product was placed on an 8 "Si-wafer, rotated and calcined. The result is: KAL 2132 defect frequency 224-458 counts / cm ²

Example  3

Dimethyl sulfoxide

0.0126 g tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is added to 1.247 g of dimethylsulfoxide and stirred until the mixture is dissolved, followed by 44.24 g of 2-heptanone (Ultra Pure Solutions Inc , Castroville, CA 85012) and 4.49 g of dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007) are added into a 60 ml particle free high density polyethylene bottle. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.1 μm using a Teflon filter. Place approximately 2.0-3.0 ml of product on 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon-depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The product is placed and the wafer is spun at 2500 rpm for 30 seconds to form a film The film is heated under elevated temperature to 125 ° C., 200 ° C. and 350 ° C. for 1 minute in an N ₂ atmosphere, as shown below.

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.34 3.18 2.65 FTIR CH / SiO peak recovery,% 34

In a similar manner, 2.0-3.0 ml of the product was placed on an 8 "Si-wafer, rotated and calcined. The results were as follows: KAL 2132 defect frequency 177-885 counts / cm ²

Example  4

ethyl Acetoacetate

0.0126 g tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is added to 45.49 g of ethyl acetoacetate and stirred until the mixture is dissolved, followed by 4.49 g of dimethyldiacetoxysilane (Gelest, Tullytone). , PA 19007) is added to a 60 ml particle free high density polyethylene bottle. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.1 μm using a Teflon filter. Place approximately 2.0-3.0 ml of product on 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon-depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The product is placed and the wafer is spun at 2500 rpm for 30 seconds to form a film The film is heated under elevated temperature to 125 ° C., 200 ° C. and 350 ° C. for 1 minute in an N ₂ atmosphere, as shown below.

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.34 3.18 2.35 FTIR CH / SiO peak recovery,% 49

In a similar manner, 2.0-3.0 ml of the product was placed on an 8 "Si-wafer, rotated and calcined. The results were as follows: KAL 2132 defect frequency 237 -390 counts / cm ²

Example  5

2- Heptanone  + Dimethyl sulfoxide

0.0126 g tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is added to 1..247 g dimethylsulfoxide and stirred until the mixture is dissolved, followed by 44.24 g of 2-heptanone (Ultra Pure Solutions) Inc., Castroville, CA 85012) and 4.49 g of dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007) are added into a 60 ml particle free high density polyethylene bottle. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.1 μm using a Teflon filter. Place approximately 2.0-3.0 ml of product on 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon-depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The product is placed and the wafer is spun at 2500 rpm for 30 seconds to form a film The film is heated under elevated temperature to 125 ° C., 200 ° C. and 350 ° C. for 1 minute in an N ₂ atmosphere, as shown below.

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.34 3.18 2.33 FTIR CH / SiO peak recovery,% 79

In a similar manner, 2.0-3.0 ml of product was placed on an 8 "Si-wafer, rotated and calcined. The result is as follows: KAL 2132 defect frequency 227-1520 counts / cm ²

Example  6

2- Heptanone  + Ethyl acetate

0.0126 g tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is added to 1..247 g ethyl acetoacetate and stirred until the mixture is dissolved, followed by 44.24 g of 2-heptanone (Ultra Pure Solutions Inc., Castroville, CA 85012) and 4.49 g of dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007) are added into a 60 ml particle free high density polyethylene bottle. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.1 μm using a Teflon filter. Place approximately 2.0-3.0 ml of product on 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon-depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The product is placed and the wafer is spun at 2500 rpm for 30 seconds to form a film The film is heated under elevated temperature to 125 ° C., 200 ° C. and 350 ° C. for 1 minute in an N ₂ atmosphere, as shown below.

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.34 3.18 2.30 FTIR CH / SiO peak recovery,% 82

In a similar manner, 2.0-3.0 ml of product was placed on an 8 "Si-wafer, rotated and calcined. The result is as follows: KAL 2132 defect frequency 0.9-1.8 counts / cm ²

Example  7

2- Heptanone  + Ethyl Acetoacetate

Tetrabutyl dissolved in 2-peptanone in 37.6 g of a 0.255% solution (0.359 g tetramethylammonium acetate + 140.00 g ethyl aceto acetate) in tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) dissolved in ethyl acetoacetate. 84.90 g 0.5% solution of ammonium acetate (2.175 g tetrabutylammonium acetate + 435 g 2-heptanone), 1242.50 g of 2-heptanone (Ultra Pure Solutions Inc., Castroville, CA 85012) and diketyldiacetoxysilane (Gelest , Tullytone, PA 19007) are added to a 2 L particle free high density polyethylene bottle. The solution is mixed vigorously for 1 minute. After mixing, the diluted precursor is subjected to two-way filtration using a 0.04 micron filter (Meissner CSPM 0.04-442). Place approximately 2.0-3.0 ml of product on 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon-depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The product is placed and the wafer is spun at 2500 rpm for 30 seconds to form a film The film is heated under elevated temperature to 125 ° C., 200 ° C. and 350 ° C. for 1 minute in an N ₂ atmosphere, as shown below.

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.34 3.18 2.21 FTIR CH / SiO peak recovery,% 96

In a similar manner, 2.0-3.0 ml of product was placed on an 8 "Si-wafer, rotated and calcined. The result is: KAL 2132 defect frequency 1.7-1.9 counts / cm ²

Example  8

2- Heptanone  + Ethyl Acetoacetate

Tetrabutyl dissolved in 2-peptanone in 37.6 g of a 0.255% solution (0.359 g tetramethylammonium acetate + 140.00 g ethyl aceto acetate) in tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) dissolved in ethyl acetoacetate. 84.90 g of 0.5% solution of ammonium acetate (2.175 g tetrabutylammonium acetate + 2-heptanone weight 435.00 g), 1242.50 g of 2-heptanone (Ultra Pure Solutions Inc., Castroville, CA 85012) and dimethyldiacetoxysilane ( 135.00 g of Gelest, Tullytone, PA 19007) are added to a 2 L particle free high density polyethylene bottle. The solution is mixed vigorously for 1 minute. After mixing, the diluted precursor is subjected to two-way filtration using a 0.04 micron filter (Meissner CSPM 0.04-442). Place approximately 2.0-3.0 ml of product on 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon-depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The product is placed and the wafer is spun at 2500 rpm for 30 seconds to form a film The film is heated under elevated temperature to 125 ° C., 200 ° C. and 350 ° C. for 1 minute in an N ₂ atmosphere, as shown below.

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.34 3.18 2.35 FTIR CH / SiO peak recovery,% 96

In a similar manner, 2.0-3.0 ml of product was placed on an 8 "Si-wafer, rotated and calcined. The result was as follows: KAL 2132 defect frequency 20.6 counts / cm ²

Example  9

9.72 g of dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007), 26.0 g of 3-pentanone (Ultra Pure Solution Inc., Castroville, CA 85012), 280 ppm of tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is prepared by adding together 60 ml of particle free high density polyethylene bottles. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film. Place about 2.0-3.0 ml of the precursor on a 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The film is then spun at 2500 rpm for 30 seconds to remove the volatile species The film is heated in an air atmosphere for 1 minute at elevated temperatures to 125 ° C., 200 ° C. and 350 ° C. The results are shown below:

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.2 3.1 2.3 FTIR (CH / SiO Ratio) 0.0085 0.0048 0.0083 H2P contact angle 78 <20 101

Example  10

9.72 g of dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007), 26.0 g of 2-heptanone (Ultra Pure Solution Inc., Castroville, CA 85012), 280 ppm of tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is prepared by adding together 60 ml of particle free high density polyethylene bottles. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film. Place about 2.0-3.0 ml of the precursor on a 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The film is then spun at 2500 rpm for 30 seconds to remove the volatile species The film is heated in an air atmosphere for 1 minute at elevated temperatures to 125 ° C., 200 ° C. and 350 ° C. The results are shown below:

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.2 3.1 2.3 FTIR (CH / SiO Ratio) 0.0085 0.0048 0.0073

Example  11

9.72 g of dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007), 26.0 g of 2-fflfplene glycol methyl ether acetate (General Chemical., Hollister, CA95023), 280 ppm of tetramethylammonium acetate (Aldrich Chemical Company, Milwaukee, WI 53201) is prepared by adding together 60 ml of particle free high density polyethylene bottles. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film. Place about 2.0-3.0 ml of the precursor on a 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The film is then spun at 2500 rpm for 30 seconds to remove the volatile species The film is heated in an air atmosphere for 1 minute at elevated temperatures to 125 ° C., 200 ° C. and 350 ° C. The results are shown below:

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.2 3.1 2.3 FTIR (CH / SiO Ratio) 0.0085 0.0048 0.0078

Example  12

9.72 g of dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007), 26.0 g of 2-heptanone (Ultra Pure Solution Inc., Castroville, CA 85012), 2800 ppm of tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is prepared by adding together 60 ml of particle free high density polyethylene bottles. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film. Place about 2.0-3.0 ml of the precursor on a 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The film is then spun at 2500 rpm for 30 seconds to remove the volatile species The film is heated in an air atmosphere for 1 minute at elevated temperatures to 125 ° C., 200 ° C. and 350 ° C. The results are shown below:

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.2 3.1 2.3 FTIR (CH / SiO Ratio) 0.0083 0.00482 0.0091

Example  13

2.65 g of dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007), 26.0 g of 2-heptanone (Ultra Pure Solution Inc., Castroville, CA 85012), 2800 ppm of tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is prepared by adding together 60 ml of particle free high density polyethylene bottles. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film. Place about 2.0-3.0 ml of the precursor on a 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The film is then spun at 2500 rpm for 30 seconds to remove the volatile species The film is heated in an air atmosphere for 1 minute at elevated temperatures to 125 ° C., 200 ° C. and 350 ° C. The results are shown below:

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.2 3.04 2.22 FTIR (CH / SiO Ratio) 0.0099 0.0066 0.0010

Example  14

2.65 g dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007), 26.0 g 2-heptanone (Ultra Pure Solution Inc., Castroville, CA 85012), 4200 ppm tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is prepared by adding together 60 ml of particle free high density polyethylene bottles. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film. Place about 2.0-3.0 ml of the precursor on a 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The film is then spun at 2500 rpm for 30 seconds to remove the volatile species The film is heated in an air atmosphere for 1 minute at elevated temperatures to 125 ° C., 200 ° C. and 350 ° C. The results are shown below:

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.2 3.04 2.30 FTIR (CH / SiO Ratio) 0.0099 0.0066 0.0105

Example  15

0.810 g dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007), 26.0 g 2-heptanone (Ultra Pure Solution Inc., Castroville, CA 85012), 4200 ppm tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is prepared by adding together 60 ml of particle free high density polyethylene bottles. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film. Place about 2.0-3.0 ml of the precursor on a 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The film is then spun at 2500 rpm for 30 seconds to remove the volatile species The film is heated in an air atmosphere for 1 minute at elevated temperatures to 125 ° C., 200 ° C. and 350 ° C. The results are shown below:

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.2 3.04 2.40 FTIR (CH / SiO Ratio) 0.0089 0.0052 0.0071

Example  16

9.72 g dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007), 26.0 g 2-heptanone (Ultra Pure Solution Inc., Castroville, CA 85012), 4200 ppm tetramethylammonium acetate (Aldrich Chemical, Milwaukee, WI 53201) is prepared by adding together 60 ml of particle free high density polyethylene bottles. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film. Place about 2.0-3.0 ml of the precursor on a 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The film is then spun at 2500 rpm for 30 seconds to remove the volatile species The film is heated in an air atmosphere for 1 minute at elevated temperatures to 125 ° C., 200 ° C. and 350 ° C. The results are shown below:

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.2 3.04 2.17 FTIR (CH / SiO Ratio) 0.0099 0.0066 0.0112

Example  17

Two precursors were prepared to compare the effect of a treatment with and without tetramethylammonium acetate. The first precursor is 9.72 g dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007), 26.0 g 3-pentanone (Ultra Pure Solution Inc., Castroville, CA 85012), 280 ppm tetramethylammonium acetate (TMAA) (Aldrich Chemical Company, Milwaukee, WI 53201) is prepared by adding together a 60 ml particle free high density polyethylene bottle. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film.

The second precursor is 9.72 g of dimethyldiacetoxysilane (Gelest, Tullytone, PA 19007) and 26.0 g of 3-pentanone (Ultra Pure Solution Inc., Castroville, CA 85012) in a 60 ml particle free high density polyethylene bottle The precursor is prepared by adding together. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film.

Place about 2.0-3.0 ml of each precursor on a 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon-depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ) The film is then spun at 2500 rpm for 30 seconds to remove volatile species, each of which is heated in an air atmosphere at elevated temperature to 125 ° C., 200 ° C. and 350 ° C. for 1 minute, respectively. have:

Measure Etching & Essence ILD ILD after etching & ashing YMAA ILD After TA Processing After TA without YMAA ILD Dielectric constant (k) 2.2 3.15 2.35 2.98 FTIR (CH / SiO Ratio)  0.0085  0.00510  0.0081  0.0059

Example  18

3.25 g of hexamethylchlorotrisilazane (Gelest, Tullytone, PA 19007) and 25.0 g of 2-heptanone (Ultra Pure Solution Inc., Castroville, CA 85012) were added to a 60 ml particle free high density polyethylene bottle to form a precursor. To prepare. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film. Place about 2.0-3.0 ml of the precursor on a 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The film is then spun at 2500 rpm for 30 seconds to remove the volatile species The film is heated in an air atmosphere for 1 minute at elevated temperatures to 125 ° C., 200 ° C. and 350 ° C. The results are shown below:

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.2 3.35 2.66 FTIR (CH / SiO Ratio) 0.0085 0.0046 0.0078

Example  19

6.5 g bis (dimethylamino) dimethylsilane (Gelest, Tullytone, PA 19007) and 22.0 g 2-heptanone (Ultra Pure Solution Inc., Castroville, CA 85012) are combined together in a 60 ml particle free high density polyethylene bottle To prepare the precursor. The solution is mixed vigorously for 1 minute. After mixing the diluted precursor is filtered to 0.2 μm using a Teflon film. Place about 2.0-3.0 ml of the precursor on a 8 "etched (C ₄ F ₈ , 20s) and ashed (plasma O ₂ ; 20s) carbon depleted porous SiCOH film (~ 4000 mm thick NANOGLASS-E ^® ). The film is then spun at 2500 rpm for 30 seconds to remove the volatile species The film is heated in an air atmosphere for 1 minute at elevated temperatures to 125 ° C., 200 ° C. and 350 ° C. The results are shown below:

Measure Etching & Essence ILD ILD after etching & ashing After TA ILD Dielectric constant (k) 2.2 3.35 2.6 FTIR (CH / SiO Ratio) 0.0083 0.0045 0.0087

While the invention has been described and described in detail with reference to preferred embodiments, it is believed that various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the invention. The claims are intended to cover all disclosed embodiments, the described options, and their equivalents.

Claims (52)

a) components capable of alkylating or arylating the silanol moiety of the organosilicate glass dielectric film via sillation; b) A composition for treating an organosilicate glass dielectric film comprising an activating agent. The method of claim 1, The composition further comprises a solvent or a mixture of primary and auxiliary solvents, The solvent or mixture of primary and auxiliary solvents dissolves components and activators capable of alkylating or arylating the silanol moiety of the organosilicate glass dielectric film via silication; The auxiliary solvent is a composition for treating an organosilicate glass dielectric film, characterized in that having a higher vapor pressure and / or boiling point than the main solvent. The method of claim 1, The activator composition for treating an organosilicate glass dielectric film comprising an acid, a base, an onium compound, a dehydrogenating agent hydroxide or a combination thereof. The method of claim 2, The solvent or main solvent is a composition for treating an organosilicate glass dielectric film comprising 3-pentanone, 2-heptanone, gammabutyrolacetone, propylene glycol methyl ether acetate, acetic acid or a combination thereof. The method of claim 2, The auxiliary solvent is a composition for treating an organosilicate glass dielectric film, characterized in that having a boiling point of about 1 ℃ to about 100 ℃ higher than the main solvent. The method of claim 2, And the auxiliary solvent has a boiling point of about 10 ° C. to about 70 ° C. higher than that of the main solvent. The method of claim 2, The auxiliary solvent is a composition for treating an organosilicate glass dielectric film, characterized in that having a boiling point of about 20 ℃ to about 50 ℃ higher than the main solvent. The method of claim 2, The solvent or the main solvent is a composition for treating an organosilicate glass dielectric film comprising one or more of ketones, ethers, esters, hydrocarbons, alcohols, carboxylic acids, amines, amides or combinations thereof. The method of claim 2, The solvent or auxiliary solvent is ethyl acetoacetate, methyl acetoacetate, t-butyl acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, nonyl acetate, 2- (2-butoxyethoxy) Ethyl acetate, pentyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzyl acetate, dimethyl sulfoxide, N-methyl-N-methoxyacetamide, N, N-diethyl-2-phenyl Acetamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-diphenylacetamide, N, N-dimethypropionamide, N, N-dimethylisobutyramide, 1,2 -Dichlorobenzene, chlorotoluene, 1-hexanol, 2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol, 4 -Heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol or combinations thereof An organosilicate glass dielectric film comprising a composition for treatment. The method of claim 2, The auxiliary solvent is an organosilicate glass dielectric film (organosilicate glass dielectric film) composition containing ethylacetoacetate, dimethyl sulfoxide, 1-hexanol, N, N- dimethylacetamide or a combination thereof. The method of claim 2, The mixture is a composition for treating an organosilicate glass dielectric film comprising 2-heptanone and ethyl acetoacetate. The method of claim 2, Wherein said main solvent is present in said mixture in an amount of from about 0.1 to about 99.9% by weight, based on said mixture. The method of claim 2, And the auxiliary solvent is present in the mixture in an amount of about 0.1 to about 99.9% by weight, based on the mixture. The method of claim 1, The activator comprises at least one amine, ammonium compound, phosphonium compound, sulfonium compound, iodonium compound, hydroxide, alkoxide, acid halide, silanolate, amine salt or combinations thereof A composition for treating an organosilicate glass dielectric film. The method of claim 1, And the activator comprises at least one alkyl amine, aryl amine, alcohol amine, or a combination thereof. The method of claim 1, The activator is a composition for treating an organosilicate glass dielectric film comprising at least one primary amine, secondary amine, tertiary amine, ammonia, quaternary ammonium salt or a combination thereof. The method of claim 1, The activator is a composition for treating an organosilicate glass dielectric film comprising tetramethylammonium acetate, tetrabutylammonium acetate or a combination thereof. The method of claim 1, The activator is hydrochloric acid, sulfuric acid, nitric acid, boric acid, ethyl sulfuric acid, chloro sulfuric acid, phosphonitrile chloride, iron chloride, zinc chloride, tin chloride, ammonium chloride, boron trifluoride, methane sulfonic acid, trifluoromethane sulfonic acid, chloride A composition for treating an organosilicate glass dielectric film comprising iron hexahydrate or a combination thereof. The method of claim 1, Wherein said activator comprises at least one phosphorus halide, phosphorus pentoxide, phenylphosphonic dichloride, and phenyl phosphorodichloride or a combination thereof. The method of claim 1, The activator is a composition for treating an organosilicate glass dielectric film comprising sodium hydroxide, cesium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide or a combination thereof. The method of claim 1, The component capable of alkylating or arylating the silanol moiety of the organosilicate glass dielectric film via said silicide may be selected from the formula [-SiR2NR '-] n, where n> 2 and a cycle; R ₃ SiNR'SiR ₃ , (R ₃ Si) ₃ N; R ₃ SiNR ₂ ′; R ₂ Si (NR ′) ₂ ; RSi (NR ') ₃ ; R _x SiCl _y , R _x Si (OH) _y ; R ₃ SiOSiR '₃; R _x Si (OR ') _y ; R _x Si (OCOR ') _y ; R _x SiH _y ; R _x Si [OC (R ') = R "] at least one compound having _4-x or a combination thereof, Wherein x is an integer ranging from 1 to 3, y is an integer ranging from 1 to 3 that satisfies y = 4-x, Each R is independently selected from hydrogen and hydrophobic organic moieties, R 'is hydrogen or an organic moiety, R ″ is an alkyl or carbonyl group organosilicate glass dielectric film treatment composition. The method of claim 1, Components capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film through the silicide are acetoxytrimethylsilane, acetoxysilane, diacetoxysilane, triacetoxysilane, diacetoxydimethylsilane, and methyltria. Cetoxysilane, Phenyltriacetoxysilane, Diphenyldiacetoxysilane, Methyltriethoxysilane, Dimethyldiethoxysilane, Trimethylethoxysilane, Methyltrimethoxysilane, Dimethyldimethoxysilane, Trimethylmethoxysilane, Methyl Trichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, methylsilane, dimethylsilane, trimethylsilane, hexamethyldisilazane, 2-trimethylsiloxypent-2-en-4-one, n- (trimethylsilyl) acetamide , 2- (trimethylsilyl) acetic acid, n- (trimethylsilyl) imidazole, trimethylsilylpropiolate, trimethylsilyl (trimethylsiloxy) -acetate, nonamethyltrisila , Hexamethyldisiloxane, trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilanol, diphenylsilanediol, trimethoxysilane, triethoxysilane, trichlorosilane, hexamethylchlorotri Silazane, bisdimethylaminodimethylsilane, bisdiethylaminodimethylsilane, tris (dimethylamino) methylsilane, tris (dimethylamino) phenylsilane, tris (dimethylamino) silane, dimethylsilyldiformamide, dimethylsilyldiacetamide A composition for treating an organosilicate glass dielectric film comprising dimethylsilyl diisocyanate, trimethylsilyltriisocyanate or a combination thereof. The method of claim 1, The component capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film via the silicide comprises dimethyldiacetoxysilane; The activator is a composition for treating an organosilicate glass dielectric film containing tetramethylammonium acetate. The method of claim 1, A component capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film through the silicide is a composition for treating an organosilicate glass dielectric film comprising dimethyl diacetoxysilane. The method of claim 1, A component capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film via the silicide and the activator comprises an organosilicate glass dielectric film comprising a mixture of tetramethyl ammonium acetate and tetrabutyl ammonium acetate film) composition for treatment. The method of claim 1, The composition is a composition for processing an organosilicate glass dielectric film further comprising a corrosion inhibitor. a) forming an organosilicate glass dielectric film; b) contacting the organosilicate glass dielectric film with a composition comprising an activator and a component that alkylates or arylates the silanol portion of the organosilicate glass dielectric film via silication. The method of claim 27, The composition further comprises a solvent or a mixture of primary and auxiliary solvents, wherein the solvent or mixture of primary and auxiliary solvents comprises a component that alkylates or arylates the silanol portion of the organosilicate glass dielectric film via silication and Dissolving the activator; The auxiliary solvent is characterized in that it has a higher vapor pressure and / or boiling point than the main solvent. The method of claim 28, (i) the solvent or main solvent comprises one or more ketones, ethers, esters, hydrocarbons, alcohols, carboxylic acids, amides or combinations thereof; And (ii) solvents or auxiliary solvents, ethyl acetoacetate, methyl acetoacetate, t-butyl acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, nonyl acetate, 2- (2-butoxyethoxy Ethyl acetate, pentyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzyl acetate, dimethyl sulfoxide, N-methyl-N-methoxyacetamide, N, N-diethyl-2- Phenylacetamide, N, N-dimethylacetamide, 1,2-dichlorobenzene, chlorotoluene, N, N-diethylacetamide, N, N-diphenylacetamide, N, N-dimethypropionamide, N , N-dimethylisobutyamide, 1-hexanol, 2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol, 4-heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol or combinations thereof Characterized in that the method. The method of claim 27, Wherein said activator comprises one or more acids, bases, onium compounds, dehydrating agents or combinations thereof. The method of claim 27, The organosilicate glass dielectric film is porous. The method of claim 27, Wherein said organosilicate glass dielectric film is substantially not porous. The method of claim 27, And wherein said silicide alkylating or arylating the silanol portion of the organosilicate glass dielectric film comprises dimethyldiacetoxysilane. The method of claim 27, The component for alkylating or arylating the silanol portion of the organosilicate glass dielectric film via the silicide comprises dimethyldiacetoxysilane, Wherein said activator comprises a mixture of tetramethylammonium acetate and tetrabutyl ammonium acetate. The method of claim 27, And the treating agent composition is contacted with the organosilicate glass dielectric film in a state selected from the group consisting of liquid, vapor, gas and plasma. The method of claim 27, And the treating agent composition comprises a supercritical solvent. The organosilicate glass dielectric film is subjected to at least one step of removing at least some of the carbon-containing moieties previously present or reducing the hydrophobicity of the organosilicate glass dielectric film, After removing at least a portion of the carbon-containing moieties previously present or at least one step of reducing the hydrophobicity of the organosilicate glass dielectric film, the organosilicate glass dielectric film and a) organosilicate glass dielectric film through silicidation Contacting a composition comprising a component that alkylates or arylates the silanol moiety of b) and b) an activator at a concentration and time effective to restore some carbon containing partial hydrophobicity or to increase the hydrophobicity of the organosilicate glass dielectric film. A method of preventing the formation of stress-induced pores in an organosilicate glass dielectric film on a substrate. The method of claim 37, The composition further comprises a solvent or a mixture of primary and auxiliary solvents, The solvent or mixture of primary and auxiliary solvents dissolves the components and activators capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film through the silicide, The auxiliary solvent is characterized in that it has a higher vapor pressure and / or boiling point than the main solvent. The method of claim 40, (i) the solvent or main solvent comprises one or more ketones, ethers, esters, hydrocarbons, alcohols, carboxylic acids, amides or combinations thereof; And (ii) solvents or auxiliary solvents are ethylacetoacetate, methylacetoacetate, t-butyl acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, nonyl acetate, 2- (2-butoxyethoxy ) Ethyl acetate, pentyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzyl acetate, dimethyl sulfoxide, N-methyl-N-methoxyacetamide, N, N-diethyl-2- Phenylacetamide, N, N-dimethylacetamide, 1,2-dichlorobenzene, chlorotoluene, N, N-diethylacetamide, N, N-diphenylacetamide, N, N-dimethypropionamide, N , N-dimethylisobutyamide, 1-hexanol, 2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol, 4-heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol or combinations thereof How to. The method of claim 39, Said activator comprises one or more acids, bases, onium compounds, dehydrating agents, or combinations thereof. a) forming an organosilicate glass dielectric film on a substrate b) applying the organosilicate glass dielectric film to at least one step of removing at least a portion of the carbon-containing portion previously present or reducing the hydrophobicity of the organosilicate glass dielectric film c) restoring a carbon-containing portion previously present, wherein the composition comprises an activator and a component capable of alkylating or arylating the silanol portion of the organosilicate dielectric film with the organosilicate dielectric film Contacting at a temperature and time effective to increase the hydrophobicity of the organosilicate glass dielectric film. The method of claim 41, wherein The composition further comprises a solvent or a mixture of primary and auxiliary solvents, wherein the solvent or mixture of primary and auxiliary solvents is capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film via silication. Dissolve the components and activators, The auxiliary solvent is characterized in that it has a higher vapor pressure and / or boiling point than the main solvent. The method of claim 42, wherein (i) the solvent or main solvent comprises one or more ketones, ethers, esters, hydrocarbons, alcohols, carboxylic acids, amides or combinations thereof; And (ii) The solvent or auxiliary solvent is ethyl acetoacetate, methyl acetoacetate, t-butyl acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, nonyl acetate, 2- (2-butoxye Methoxy) ethyl acetate, pentyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzyl acetate, dimethyl sulfoxide, N-methyl-N-methoxyacetamide, N, N-diethyl-2 -Phenylacetamide, N, N-dimethylacetamide, 1,2-dichlorobenzene, chlorotoluene, N, N-diethylacetamide, N, N-diphenylacetamide, N, N-dimethypropionamide, N, N-dimethylisobutyamide, 1-hexanol, 2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol , 4-heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol or a combination thereof Method comprising. The method of claim 42, wherein The method further comprises the subsequent step of heating the organosilicate glass dielectric film. a) applying an organosilicate glass dielectric film onto a substrate; b) forming vias and trench patterns in the organosilicate glass dielectric film, removing at least a portion of the carbon containing portion previously present in the organosilicate glass dielectric film, or the organosilicate glass dielectric film Performing at least one treatment to reduce the hydrophobicity of the; c) increasing the hydrophobicity of the organosilicate glass dielectric film with a treating agent composition comprising the organosilicate glass dielectric film and a component and an activator capable of alkylating or arylating the silanol portion of the organosilicate glass dielectric film through silication. Contacting at a concentration and time effective to produce a microelectronic device. The method of claim 45, The method is a) optionally firing at about 80 ° C. to about 400 ° C. for at least about 10 seconds; after that b) filling vias and / or trenches with metal; after that c) optionally annealing the metal; The method further comprises a subsequent step consisting of. The method of claim 45, The method further comprises a subsequent step of removing the unreacted treatment composition, the reaction product, and mixtures thereof. The method of claim 45, The composition further comprises a solvent or a mixture of primary and auxiliary solvents, The solvent or mixture of primary and auxiliary solvents dissolves the components and activators that alkylate or arylate the silanol portion of the organosilicate glass dielectric film via silication, The auxiliary solvent is characterized in that it has a higher vapor pressure and / or boiling point than the main solvent. The method of claim 48, (i) the solvent or main solvent comprises one or more ketones, ethers, esters, hydrocarbons, alcohols, carboxylic acids, amides or combinations thereof; And (ii) The solvent or auxiliary solvent is ethyl acetoacetate, methyl acetoacetate, t-butyl acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, nonyl acetate, 2- (2-butoxye Methoxy) ethyl acetate, pentyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzyl acetate, dimethyl sulfoxide, N-methyl-N-methoxyacetamide, N, N-diethyl-2 -Phenylacetamide, N, N-dimethylacetamide, 1,2-dichlorobenzene, chlorotoluene, N, N-diethylacetamide, N, N-diphenylacetamide, N, N-dimethypropionamide, N, N-dimethylisobutyamide, 1-hexanol, 2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol , 4-heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol or combinations thereof Characterized in that it comprises. The method of claim 49, Said activator comprises one or more acids, bases, onium compounds, dehydrating agents, or combinations thereof. A microelectronic device manufactured by the method of claim 46. 47. The method of claim 46 wherein Removing at least a portion of the previously present carbon containing portion or reducing the hydrophobicity of the organosilicate glass dielectric film may comprise at least one etching treatment, ashing treatment, wet stripping treatment. stripping treatment, cleaning treatment, atomic layer deposition, physical vapor deposition and chemical vapor deposition treatment.