Precursor and flowable cvd process for making low-k films to fill surface features

Abstract

A method for depositing a silicon-containing film, the method comprising: placing a substrate comprising at least one surface feature in a flowable CVD reactor at a temperature of about-20 DEG C to about 400 DEG C; introducing at least one silicon-containing compound having at least one acetoxy group into the reactor to at least partially react the at least one silicon-containing compound to form a flowable liquid oligomer, wherein the flowable liquid oligomer forms a silicon oxide coating on the substrate and at least partially fills at least a portion of the at least one surface feature. Once cured, the silicon oxide coating has low k and excellent mechanical properties.

Description

[0001] This application is a divisional application of the Chinese patent application with application number 201780053056.5, application date August 25, 2017, and invention name “Precursor and flowable CVD method for manufacturing low-K films to fill surface features”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of Provisional Application No. 62 / 381,222, filed on August 30, 2016, and Application No. 15 / 681,102, filed on August 18, 2017, the disclosures of which are incorporated herein by reference in their entireties. Background Art

[0004] Described herein are methods for making electronic devices. More specifically, described herein are compositions for forming silicon-containing films in a deposition process (e.g., flowable chemical vapor deposition). Exemplary silicon-containing films that can be deposited using the compositions and methods described herein include silicon oxide, silicon nitride, silicon oxynitride, or carbon-doped silicon oxide or carbon-doped silicon nitride films.

[0005] Flowable oxide deposition methods typically use alkoxysilane compounds as precursors for silicon-containing films, which are deposited by controlled hydrolysis and condensation reactions. Such films can be deposited on substrates, for example, by applying a mixture of water and alkoxysilanes to the substrate, optionally with solvents and / or other additives (such as surfactants and porogens). Typical methods for applying these mixtures include spin coating, dip coating, spraying, screen printing, co-condensation, and inkjet printing. After being applied to the substrate and when applying one or more energy sources (such as heat, plasma, and / or other energy sources), the water in the mixture can react with the alkoxysilane to hydrolyze alkoxide and / or aryloxide groups and produce silanol species, which further condense with other hydrolyzed molecules and form oligomers or network structures.

[0006] In addition to physical deposition or applying precursors to a substrate, vapor deposition processes using water and a silicon-containing vapor source for flowable dielectric deposition (FCVD) have been described, for example, in U.S. Patent Nos. 7,541,297; 8,449,942; 8,629,067; 8,741,788; 8,481,403; 8,580,697; 8,685,867; 7,498,273; 7,074,690; 7,582,555; 7,888,233 and 7,915,131 and U.S. Publication No. 2013 / 0230987A1, the disclosures of which are incorporated herein by reference. Typical methods generally involve filling a gap on a substrate with a solid dielectric material by forming a flowable liquid film in the gap. The flowable film is formed by reacting a dielectric precursor that may have Si-C bonds with an oxidant to form the dielectric material. In certain embodiments, the dielectric precursor is condensed and subsequently reacted with an oxidant to form a dielectric material. In certain embodiments, the gas phase reactants react to form a condensed flowable film. Since Si-C bonds are relatively inert to reaction with water, the resulting network can be beneficially functionalized with organic functional groups that impart desired chemical and physical properties to the resulting film. For example, adding carbon to the network can reduce the dielectric constant of the resulting film.

[0007] Another method of depositing silicon oxide films using a flowable chemical vapor deposition process is vapor phase polymerization. For example, the prior art has focused on using compounds such as trisilylamine (TSA) to deposit oligomers containing Si, H, N, which are subsequently oxidized to SiO by exposure to ozone. x Examples of such methods include: U.S. Publication No. 2014 / 0073144; U.S. Publication No. 2013 / 230987; U.S. Patent Nos. 7,521,378, 7,557,420, and 8,575,040; and U.S. Patent No. 7,825,040, the disclosures of which are incorporated herein by reference.

[0008] Regarding the method using trisilylamine (TSA), TSA is typically delivered to the reaction chamber as a gas, mixed with ammonia, and activated in a remote plasma reactor to produce NH2, NH, H and / or N radicals or ions. TSA reacts with plasma-activated ammonia and begins to oligomerize to form higher molecular weight TSA dimers and trimers or other species containing Si, N and H. The substrate is placed in the reactor and cooled to one or more temperatures of about 0 to about 50°C at a specific chamber pressure and TSA / activated ammonia mixture, and the oligomers begin to condense on the wafer surface in a manner that allows them to "flow" to fill the groove surface features. In this way, materials containing Si, N and H are deposited on the wafer and fill the grooves. In certain embodiments, a pre-annealing step is performed to make the film more like SiN. It is desirable to have SiN material because the next process step is oxidation at one or more temperatures of 100-700°C using ozone or water. Due to SiN bond distances and bond angles, it is known that when SiN is oxidized to SiO2, there is an increase in unit cell volume, which prevents the film from shrinking.

[0009] Despite recent activity in the field of flowable chemical vapor deposition and other film deposition processes, problems continue to exist. One of these problems relates to film composition. For example, flowable oxide films deposited from the precursor trisilylamine (TSA) in a vapor phase polymerization process produce films with a high density of Si-H bonds and a wet etch rate in dilute HF solution that is 2.2 to 2.5 times faster than high quality thermal oxides. Such films are not suitable for low-k film applications.

[0010] In many cases, a hardening process can be applied to the flowable film, including thermal annealing, UV curing, or ionic / radical densification. The hardening process can remove carbon groups, hydroxyl groups, and smaller molecular weight species from the deposited material. Figure 1 , which often leaves voids, cracks or spaces in the hardened material. Such films are also not suitable for low-k film applications.

[0011]

[0006] Therefore, there is a need to provide alternative precursor compounds for producing silicon-containing films by flow CVD techniques that have the mechanical integrity and porosity to successfully function as low-k silicon oxide-containing film materials. Summary of the invention

[0012] The compositions or formulations described herein and methods of using the same overcome the problems of the prior art by depositing a silicon-containing film on at least a portion of a substrate surface that provides desired film properties after post-deposition processing. The present invention can provide a silicon-containing film having: i) mechanical integrity in terms of a Young's modulus of about 2 to about 15 GPa, about 4 to about 12 GPa, and in some cases about 6 to about 10 GPa, ii) a porosity of about 10 to about 30 vol%, about 12 to about 25 vol%, and in some cases about 16 to about 22 vol% (e.g., as measured by ellipsometry porosimetry), and iii) a dielectric constant of about 2.2 to about 3.0, about 2.4 to about 2.8, and in some cases about 2.5 to 2.7.

[0013] In one aspect, the invention described herein provides a method for depositing a silicon-containing film, the method comprising: placing a substrate comprising at least one surface feature in a reactor at a temperature of about -20°C to about 400°C; introducing into the reactor at least one silicon-containing compound having at least one acetoxy group, wherein the at least one silicon-containing compound is selected from:

[0014] I(a) Formula (RCOO) m R 1 n S H p Acyloxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 Selected from linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, linear or branched C2-C6 alkynyl; m=2 or 3; n=1 or 2; p=0 or 1; and m+n+p=4;

[0015] I(b) Formula (RCOO) m (R 2 O) n S H p R 1 q Acyloxyalkoxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; R 2 is selected from linear or branched C1-C6 alkyl; m=2 or 3; m=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; and

[0016] I(c) Formula (RCOO) m (R 3 R 4 NO) n S H p R 1q The acyloxyaminosilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; and R 3 Selected from hydrogen, straight or branched C1-C 10 Alkyl; R 4 is selected from linear or branched C1-C6 alkyl; m=2 or 3; n=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; and

[0017] Plasma is provided into the reactor to at least partially react the at least one silicon-containing compound to form a flowable liquid oligomer, wherein the flowable liquid oligomer forms a coating on the substrate and at least partially fills at least a portion of the at least one surface feature.

[0018] In another aspect, the method of the present invention further comprises the step of heat treating the coating at one or more temperatures of about 100° C. to about 1000° C. to densify at least a portion of the coating and form a hardened layer.

[0019] In yet another aspect, the method of the present invention further comprises the step of exposing the hardened layer to energy selected from plasma, infrared light, chemical treatment, electron beam or ultraviolet light to form a final silicon-containing film.

[0020] Another aspect of the present invention relates to a precursor composition comprising at least one silicon-containing compound having at least one acetoxy group, wherein the at least one silicon-containing compound is selected from:

[0021] I(a) Formula (RCOO) m R 1 n S H p Acyloxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 Selected from linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, linear or branched C2-C6 alkynyl; m=2 or 3; n=1 or 2; p=0 or 1; and m+n+p=4;

[0022] I(b) Formula (RCOO) m (R 2 O) n S H p R 1 q Acyloxyalkoxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; R 2 is selected from linear or branched C1-C6 alkyl; m=2 or 3; m=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; and

[0023] I(c) Formula (RCOO) m (R 3 R 4 NO) n S H p R 1 q The acyloxyaminosilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; R 3 Selected from hydrogen, straight or branched C1-C 10 Alkyl; R 4 Selected from linear or branched C1-C6 alkyl; m=2 or 3; n=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4.

[0024] Another aspect of the invention relates to films obtained by the methods and compositions of the invention.

[0025] Other features and advantages of the present invention will become apparent from the following more detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings, which illustrate by way of example the principles of the invention.

[0026] The embodiments and features of the present invention can be used alone or in combination with each other. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The present invention will be described below with reference to the accompanying drawings, wherein like numbers represent like elements:

[0028] Figure 1 is a SEM micrograph showing a prior art silicon oxide film formed in a trench of a substrate, wherein voids are formed during the hardening process;

[0029] Figure 2 is a SEM micrograph showing a silicon oxide film formed by deposition of diacetoxydimethylsilane with O2 according to the method of the present invention.

[0030] Figure 3 is a SEM micrograph showing the thermal annealing at 300°C for 5 minutes according to the method of the present invention. Figure 2 a silicon oxide film; and

[0031] Figure 4is a SEM micrograph showing the method according to the present invention after UV exposure at 400°C for 10 minutes. Figure 3 of silicon oxide film. DETAILED DESCRIPTION

[0032] The following detailed description provides only preferred exemplary embodiments and is not intended to limit the scope, applicability or configuration of the present invention. The following detailed description of the preferred exemplary embodiments will provide a description of the preferred exemplary embodiments that enable implementation of the present invention for those skilled in the art. Various changes may be made to the functions and arrangements of the elements without departing from the spirit and scope of the present invention as set forth in the appended claims.

[0033] In the claims, letters may be used to identify claimed method steps (e.g., a, b, and c). These letters are used to aid in referring to the method steps and are not intended to indicate the order in which the claimed steps may be performed, unless and only to the extent such an order is specifically recited in the claims.

[0034] The compositions or formulations and methods of using the same described herein overcome the problems of the prior art by depositing silicon-containing films on at least a portion of a substrate surface that provide desirable film properties after post-deposition treatment.

[0035] The present invention relates to semiconductor thin film processing technology. Methods and systems for improving the quality of morphologically adaptive dielectric films on various device structures are described. More specifically, embodiments of the present invention provide methods and systems for forming silicon oxide films with increased density to achieve void-free gap fill for trenches with high aspect ratios. For example, the present invention is particularly suitable for forming high-quality silicon oxide films for filling narrow STI trenches.

[0036] Thus, in one aspect, the present invention provides a method for depositing a silicon-containing film, the method comprising: placing a substrate comprising at least one surface feature in a reactor at a temperature of about -20°C to about 400°C; introducing into the reactor at least one silicon-containing compound having at least one acetoxy group, wherein the at least one silicon-containing compound is selected from:

[0037] I(a) Formula (RCOO) m R 1 n S H p Acyloxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 Selected from linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, linear or branched C2-C6 alkynyl; m=2 or 3; n=1 or 2; p=0 or 1; and m+n+p=4;

[0038] I(b) Formula (RCOO) m (R 2 O) n S H p R 1 q Acyloxyalkoxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; R 2 is selected from linear or branched C1-C6 alkyl; m=2 or 3; m=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; and

[0039] I(c) Formula (RCOO) m (R 3 R 4 NO) n S H p R 1 q The acyloxyaminosilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; R 3 Selected from hydrogen, straight or branched C1-C 10 Alkyl; R 4 is selected from linear or branched C1-C6 alkyl; m=2 or 3; n=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; and

[0040] Plasma is provided into the reactor to at least partially react the at least one silicon-containing compound to form a flowable liquid oligomer, wherein the flowable liquid oligomer forms a coating on the substrate and at least partially fills at least a portion of the at least one surface feature.

[0041] "Flowable liquid oligomer" refers to a polysiloxane material that is flowable under deposition conditions, wherein the polysiloxane is measured by FTIR. After curing, the flowable liquid oligomer forms a solid carbon-doped porous OSG.

[0042] The silicon-containing film is selected from silicon nitride, silicon carbide, silicon oxide, carbon-doped silicon nitride, silicon oxynitride, and carbon-doped silicon oxynitride film. The composition can be a pre-mixed composition, a pre-mixture (mixed before use in a deposition process), or an in-situ mixture (mixed during the deposition process). Therefore, in the present disclosure, the terms "mixture", "formulation", and "composition" are interchangeable.

[0043] Throughout the specification, the term "silicon oxide" as used herein refers to a film containing silicon and oxygen, which is selected from stoichiometric or non-stoichiometric silicon oxide, carbon-doped silicon oxide, silicon carbon oxynitride, and mixtures thereof.

[0044] In the method of the present invention, generally the first step is to place a substrate comprising at least one surface feature into a reactor at a temperature of about -20°C to about 400°C. Suitable substrates include, but are not limited to, semiconductor materials such as gallium arsenide ("GaAs"), boron nitride ("BN"), silicon, and silicon-containing compositions such as crystalline silicon, polycrystalline silicon, amorphous silicon, epitaxial silicon, silicon dioxide ("SiO2"), silicon carbide ("SiC"), silicon oxycarbide ("SiOC"), silicon nitride ("SiN"), silicon carbonitride ("SiCN"), organosilicate glass ("OSG"), organofluorosilicate glass ("OFSG"), fluorosilicate glass ("FSG"), and other suitable substrates or mixtures thereof. The substrate may further comprise various layers onto which the film is applied, such as antireflective coatings, photoresists, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, or diffusion barriers such as TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, WN, TiSiN, TaSiN, SiCN, TiSiCN, TaSiCN, or W(C)N. The organosilicate glass films of the present invention are preferably capable of sufficient adhesion to at least one of the foregoing materials to pass conventional tensile tests, such as the ASTM D3359-95a strip tensile test.

[0045] In some embodiments, the substrate can be a single crystal silicon wafer, a silicon carbide wafer, an aluminum oxide (sapphire) wafer, a glass sheet, a metal foil, an organic polymer film, or can be a polymer, glass, silicon or metal three-dimensional product. The substrate can be coated with various materials known in the art, including films of silicon oxide, silicon nitride, amorphous carbon, silicon oxycarbide, silicon oxynitride, silicon carbide, gallium arsenide, gallium nitride, etc. These coatings can completely cover the substrate, can be multiple layers of various materials, and can be partially etched to expose the material layer below. There can also be a photoresist material on the surface, which has been exposed and developed with a pattern to partially cover the substrate.

[0046] In some embodiments, the substrate comprises surface features. As used herein, the term "surface feature" refers to a substrate or a partially manufactured substrate that comprises one or more of the following: a hole, a trench, a shallow trench isolation (STI), a via, a reentrant feature, and the like. In a specific embodiment, the surface feature has a width of 100 μm or less, 1 μm wide or less, or 0.5 μm wide or less, or 50 nm wide or less. In this or other embodiments, if present, the aspect ratio (ratio of depth to width) of the surface feature is 0.1:1 or greater, or 1:1 or greater, or 10:1 or greater, or 20:1 or greater, or 40:1 or greater.

[0047] The method for forming the film or coating described herein is a flowable chemical deposition method. Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, thermal chemical vapor deposition (CVD) or plasma enhanced cyclic CVD (PECCVD) methods. An exemplary flowable CVD reactor is disclosed in US Publication No. 2014 / 0073144; it is incorporated herein by reference. As used herein, the term "flowable chemical vapor deposition method" refers to any method in which a substrate is exposed to one or more volatile precursors, which react and / or decompose on the substrate surface to provide a flowable oligomeric silicon-containing substance, and then produce a solid film or material when further processed. Although the precursors, reagents and sources used herein are sometimes described as "gaseous", it should be understood that the precursor can be a liquid or solid delivered to the reactor with or without an inert gas by direct evaporation, bubbling or sublimation. In some cases, the evaporated precursor can be delivered by a plasma generator. In one embodiment, the film is deposited using a plasma-based (e.g., remotely generated or in situ) CVD method. The term "reactor" as used herein includes, but is not limited to, a reaction chamber or a deposition chamber.

[0048] In certain embodiments, the substrate may be exposed to one or more pre-deposition treatments, such as, but not limited to, plasma treatment, thermal treatment, chemical treatment, UV exposure, electron beam exposure, and combinations thereof, to affect one or more film properties. These pre-deposition treatments may be performed under an atmosphere selected from an inert, oxidizing, and / or reducing atmosphere.

[0049] Although the chemical reagents used herein may sometimes be described as "gaseous", it is understood that the chemical reagents can be delivered directly to the reactor as a gas, delivered as a vapor from an evaporating liquid or bubbling a liquid using a carrier gas such as nitrogen, helium or argon, delivered to the reactor as a vapor from a sublimating solid and / or delivered via an inert carrier gas.

[0050] The method of the present invention comprises the step of introducing into a reactor a silicon-containing compound having at least one acetoxy group (also referred to herein as a "precursor"), wherein at least one second compound is selected from the following formulae I(a) to I(c):

[0051] I(a) Formula (RCOO) m R 1 n S H p Acyloxysilane, wherein R and R 1 independently selected from linear or branched C1-C6 alkyl; m=2 or 3; n=1 or 2; p=0 or 1; and m+n+p=4;

[0052] I(b) Formula (RCOO) m (R 1 O) n S H p Acyloxyalkoxysilane, wherein R and R 1 independently selected from linear or branched C1-C6 alkyl; m=2 or 3; m=1 or 2; p=0 or 1; and m+n+p=4; and

[0053] I(c) Formula (RCOO) m (R 2 R 3 NO) n S H p The acyloxyaminosilane, wherein R is selected from a linear or branched C1-C6 alkyl group; R 2 Selected from hydrogen, branched C1-C 10 Alkyl and C4-C 10 Aryl; R 3 Selected from straight or branched C1-C 10 Alkyl; m=2 or 3; n=1 or 2; p=0 or 1; and m+n+p=4.

[0054] In the above formula and throughout the specification, the term "straight chain alkyl" means a straight chain functional group having 1 to 10, 3 to 10, or 1 to 6 carbon atoms. In the above formula and throughout the specification, the term "branched chain alkyl" means a straight chain functional group having 3 to 10 or 1 to 6 carbon atoms. Exemplary straight chain alkyls include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl. Exemplary branched chain alkyls include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, and neohexyl. In certain embodiments, the alkyl group may have one or more functional groups attached thereto, such as, but not limited to, alkoxy, dialkylamino, or a combination thereof. In other embodiments, the alkyl group does not have one or more functional groups attached thereto. The alkyl group may be saturated or unsaturated.

[0055] In the above formula and throughout the specification, the term "aryl" refers to an aromatic cyclic functional group having 3 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl.

[0056] In the above formula and throughout the specification, the term "alkenyl" refers to a group having one or more carbon-carbon double bonds and having 2 to 12, 2 to 10, or 2 to 6 carbon atoms. Exemplary alkenyl groups include, but are not limited to, vinyl or allyl.

[0057] The term "alkynyl" refers to a group having one or more carbon-carbon triple bonds and having 2 to 10 or 2 to 6 carbon atoms. Exemplary alkynyl groups include, but are not limited to, ethynyl.

[0058] In certain embodiments, one or more alkyl or aryl groups in the formula can be "substituted" or have one or more atoms or radicals that replace, for example, hydrogen atoms. Exemplary substituents include, but are not limited to, oxygen, sulfur, halogen atoms (e.g., F, Cl, I or Br), nitrogen, alkyl and phosphorus. In other embodiments, one or more alkyl, alkenyl, alkynyl, aromatic group and / or aryl groups in the formula can be unsubstituted.

[0059] In certain embodiments, the substituent R in the above formula 1 , R 2 and R 3 Any one or more of may be linked to the C—C bond in the above formula to form a ring structure when they are not hydrogen. As will be appreciated by the skilled person, the substituents may be selected from linear or branched C1-C 10 Alkylene moiety; C2-C 12 Alkenylene moiety; C2-C 12 Alkyne moiety; C4-C 10 Cycloalkyl moiety; and C6-C 10 In these embodiments, the ring structure can be unsaturated, such as a cycloalkyl ring, or saturated, such as an aromatic ring. In addition, in these embodiments, the ring structure can also be substituted or unsubstituted. In other embodiments, the substituent R 1 , R 2 and R 3 Any one or more of are not connected.

[0060] In embodiments where the silicon-containing precursor comprises a compound of Formula I(a), examples of precursors include the following:

[0061]

[0062] Examples of compounds of formula I(a) include diacetoxydimethylsilane, diacetoxymethylsilane, triacetoxymethylsilane, diacetoxydivinylsilane, diacetoxymethylvinylsilane, triacetoxyvinylsilane, diacetoxydiethynylsilane, diacetoxymethylethynylsilane and triacetoxyethynylsilane.

[0063] In embodiments where the silicon-containing precursor comprises a compound of Formula I(b), examples of precursors include the following:

[0064]

[0065] Examples of compounds of formula I(b) include diacetoxymethoxymethylsilane, diacetoxydimethoxysilane and triacetoxymethoxysilane.

[0066] In embodiments wherein the silicon-containing precursor comprises a compound of formula I(c):

[0067]

[0068] Examples of compounds of formula I(c) include diacetoxydimethylaminooxymethylsilane, diacetoxybis(methylethyl)aminooxymethylsilane and diacetoxydiethylaminooxymethylsilane.

[0069] The silicon-containing precursor compounds described herein can be delivered to a reaction chamber, such as a CVD or ALD reactor, in various ways. In one embodiment, a liquid delivery system can be used. In an alternative embodiment, a combined liquid delivery and flash process unit, such as a turbo evaporator manufactured by MSP Corporation, Shoreview, MN, can be used to enable low volatility materials to be delivered volumetrically, which results in repeatable delivery and deposition without thermal decomposition of the precursor. In a liquid delivery configuration, the precursors described herein can be delivered in pure liquid form, or can be used in a solvent formulation or composition comprising the same. Therefore, in certain embodiments, the precursor formulation can include a solvent component having suitable properties (such as may be desired and advantageous in a given end-use application) to form a film on a substrate.

[0070] The silicon-containing precursor compound is preferably substantially free of halide ions, such as chloride ions or metal ions such as Al. As used herein, the term "substantially free" as it relates to halide ions (or halides) or metal ions such as chloride, fluoride, bromide, iodide, Al 3+ Ion, Fe 2+ , Fe 3+ 、Ni 2+ , CR 3+When refers to each halide ion or metal ion is less than 5ppm (by weight), preferably less than 3ppm, more preferably less than 1ppm, most preferably 0ppm. Known chloride or metal ion acts as a decomposition catalyst for silicon precursor. Chloride at a significant level in the final product can cause silicon precursor degradation. The gradual degradation of silicon precursor can directly affect the film deposition process, making it difficult for semiconductor manufacturers to meet film specifications. In addition, the higher degradation rate of silicon precursor has a negative impact on shelf life or stability, thereby making it difficult to ensure a shelf life of 1-2 years. In addition, known silicon precursors form flammable and / or pyrophoric gases, such as hydrogen and silane, when decomposed. The composition comprising the precursor compound of the present invention is substantially free of such decomposition products. Therefore, the accelerated decomposition of silicon-containing precursors brings safety and performance issues related to the formation of these flammable and / or pyrophoric gaseous byproducts.

[0071] The silicon-containing precursor according to the present invention that is substantially free of halides can be achieved by (1) reducing or eliminating chloride sources during chemical synthesis, and / or (2) implementing an effective purification process to remove chloride from the crude product so that the final purified product is substantially free of chloride. The chloride source can be reduced during the synthesis process by using a reagent that does not contain halides, such as chlorodisilane, bromodisilane or iododisilane, so as to avoid the production of by-products containing halide ions. In addition, the above reagents should be substantially free of chloride impurities so that the resulting crude product is substantially free of chloride impurities. In a similar manner, the synthesis should not use halide-based solvents, catalysts or solvents containing unacceptably high levels of halide contamination. The crude product can also be treated by various purification methods so that the final product is substantially free of halogen acid radicals, such as chlorate radicals. Such methods are fully described in the prior art and may include, but are not limited to, purification methods such as distillation or adsorption. Distillation is generally used to separate the desired product from impurities by utilizing differences in boiling points. Adsorption can also be used to utilize the different adsorption properties of the components to achieve separation so that the final product is substantially free of halides. Adsorbents such as commercially available MgO-Al2O3 mixtures can be used to remove halides such as chlorides.

[0072] For those embodiments involving compositions comprising a solvent as described herein and at least one silicon-containing compound, the selected solvent or mixture thereof does not react with the silicon compound. The amount of solvent in the composition by weight percentage is 0.5 wt % to 99.5 % or 10 wt % to 75 %. In this or other embodiments, the solvent has a boiling point similar to the boiling point (bp) of the precursors of Formulas I(a), I(b) and I(c), or the difference between the boiling point of the solvent and the boiling point of the silicon precursors of Formulas I(a), I(b) and I(c) is 40°C or less, 30°C or less, or 20°C or less, 10°C or less, or 5°C or less. Alternatively, the range of the difference between the boiling points begins at any one or more of the following endpoints: 0, 10, 20, 30 or 40°C. Examples of suitable ranges of boiling point differences include, but are not limited to, 0°C to 40°C, 20°C to 30°C, or 10°C to 30°C. Examples of suitable solvents in the composition include, but are not limited to, ethers (e.g., 1,4-dioxane, dibutyl ether), tertiary amines (e.g., pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylethylenediamine), nitriles (e.g., benzonitrile), alkyl hydrocarbons (e.g., octane, nonane, dodecane, ethylcyclohexane), aromatic hydrocarbons (e.g., toluene, mesitylene), tertiary amino ethers (e.g., bis(2-dimethylaminoethyl) ether), or mixtures thereof.

[0073] In a specific embodiment, the introducing step, wherein at least one silicon-containing compound is introduced into the reactor, is performed at one or more temperatures ranging from -20°C to 1000°C, or from about 400°C to about 1000°C, or from about 400°C to about 600°C, or from about -20°C to about 400°C. In these or other embodiments, the substrate comprises a semiconductor substrate comprising surface features.

[0074] The method of the present invention includes providing an in-situ plasma or remote plasma source to at least partially react at least one silicon-containing compound to form a flowable liquid oligomer, wherein the flowable liquid oligomer forms a coating on the substrate and at least partially fills at least a portion of at least one surface feature. Energy is applied to at least one silicon-containing compound, a nitrogen source (if used), an oxygen source, other precursors or a combination thereof to initiate a reaction and form a silicon-containing film or coating on the substrate. Such energy can be provided by, but is not limited to, heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-rays, electron beams, photons, remote plasma methods and combinations thereof. In certain embodiments, a secondary RF radio frequency source can be used to change the plasma characteristics at the substrate surface. In embodiments where deposition involves plasma, the plasma generation process can include a direct plasma generation process, in which the plasma is directly generated in the reactor, or a remote plasma generation process, in which the plasma is generated outside the reactor and supplied to the reactor.

[0075] The volume flow ratio of the precursor to the oxygen-containing or nitrogen-containing source can be from about 40: 1 to about 0.2: 1, from about 20: 1 to about 1: 1, and in some cases from about 6: 1 to about 2: 1. In one embodiment of the present invention, the composition comprises a silicon-containing precursor of the present invention and at least one oxygen-containing or nitrogen-containing source. In another embodiment of the present invention, the composition comprises an oligomer obtained from a precursor of the present invention and at least one oxygen-containing or nitrogen-containing source.

[0076] In a specific embodiment, the plasma is selected from, but is not limited to, nitrogen plasma; a plasma comprising nitrogen and helium; a plasma comprising nitrogen and argon; an ammonia plasma; a plasma comprising ammonia and helium; a plasma comprising ammonia and argon; a helium plasma; an argon plasma; a hydrogen plasma; a plasma comprising hydrogen and helium; a plasma comprising hydrogen and argon; a plasma comprising ammonia and hydrogen; an organic amine plasma; a plasma comprising oxygen; a plasma comprising oxygen and hydrogen, and mixtures thereof.

[0077] In another embodiment, the plasma source is selected from, but not limited to, a carbon source plasma, including a hydrocarbon plasma, a plasma comprising a hydrocarbon and helium, a plasma comprising a hydrocarbon and argon, a carbon dioxide plasma, a carbon monoxide plasma, a plasma comprising a hydrocarbon and hydrogen, a plasma comprising a hydrocarbon and a nitrogen source, a plasma comprising a hydrocarbon and an oxygen source, and mixtures thereof.

[0078] As previously described, the method deposits a film on at least a portion of a substrate surface comprising surface features. The substrate is placed in a reactor and maintained at one or more temperatures of about -20°C to about 400°C. In a specific embodiment, the temperature of the substrate is lower than the walls of the chamber. The substrate temperature is maintained at a temperature below 100°C, preferably below 25°C, most preferably below 10°C and above -20°C.

[0079] In certain embodiments, the reactor is operated at less than atmospheric pressure or 750 torr (10 5 In other embodiments, the pressure of the reactor is maintained in the range of about 0.1 Torr (13 Pa) to about 10 Torr (1333 Pa) or less.

[0080] In the presence of plasma energy, the silicon-containing compounds react with each other and form oligomers, which condense as liquids on the substrate surface (liquid oligomers) and at least partially fill features on the substrate. However, direct use of the film so deposited can result in a dielectric that is too porous and does not have sufficient mechanical strength. Therefore, certain embodiments of the present invention are used to further process the silicon oxide layer so deposited to improve the film quality by increased density and still achieve void-free gap filling. "Void-free" refers to a visual determination obtained by observing a SEM or TEM of the deposited and cured film.

[0081] In a preferred embodiment, the flowable liquid oligomer is thermally annealed at one or more temperatures from about 100°C to about 1000°C to densify at least a portion of the material and then subjected to broadband UV treatment at a temperature from 100°C to 1000°C.

[0082] In order to prevent void formation, crosslinking is required during processing. For example, when diacetoxydimethylsilane is heated, acetic anhydride molecules are lost and Si-O-Si bonds are formed. The loss of acetic anhydride molecules leads to the generation of nanoscale pores. Due to the presence of two acetoxy groups on each silicon atom, crosslinking formation leads to long chains. To produce three-dimensional crosslinking, a precursor with three acetoxy functional groups is required. In other embodiments, an oxidant (O2 or CO2) is preferably added to produce three-dimensional crosslinking. The film density is generally 1.5 to 2.0 g / cm for silicon oxide or carbon-doped silicon oxide. 3 , and for silicon nitride or carbon-doped silicon nitride is typically 1.8 to 2.8 g / cm 3 Such films are therefore suitable for low-k material applications. The dielectric constant k achieved is typically 2.5 to 2.8, or 2.5 to 3.0 for carbon-doped silicon oxide.

[0083] In certain embodiments, the resulting silicon-containing film or coating may be exposed to a post-deposition treatment, such as, but not limited to, a plasma treatment, including, but not limited to, hydrogen plasma, helium plasma, argon plasma, ammonia plasma, water (H2O) plasma, oxygen plasma, ozone (O3) plasma, NO plasma, N2O plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma, and combinations thereof, chemical treatment, ultraviolet exposure, infrared exposure, electron beam exposure, and / or other treatments to affect one or more properties of the film.

[0084] In some embodiments, after the heat treatment the material is exposed to plasma, infrared light, chemical treatment, electron beam, or UV light to form a dense film.

[0085] The above steps define one cycle of the methods described herein; and the cycle can be repeated until the desired thickness of the silicon-containing film is obtained. In this or other embodiments, it should be understood that the steps of the methods described herein can be performed in various orders, can be performed sequentially or simultaneously (e.g., during at least a portion of another step), and any combination thereof. The corresponding steps of supplying compounds and other reagents can be performed by changing the duration of supplying them to change the stoichiometric composition of the resulting silicon-containing film.

[0086] In one embodiment of the invention, at least one of the following films or features may be formed or deposited on the silicon-containing film of the invention: i) for planarization, ii) copper (e.g., to fill vias), and iii) a dielectric film. In one aspect, the invention comprises a substrate comprising a patterned structure having at least one feature (e.g., a via or trench) on which a film of the invention (e.g., carbon-doped silicon oxide) is deposited and a film comprising a barrier layer (e.g., at least one of cobalt, silicon carbonitride, silicon nitride, carbon oxynitride, TiN, and TaN) is deposited on the film of the invention.

[0087] The following examples are provided for the purpose of further illustrating the present invention, but are in no way intended to limit the present invention.

[0088] Therefore, the present invention provides at least the following:

[0089] 1. A method for depositing a silicon-containing film, the method comprising:

[0090] placing a substrate comprising at least one surface feature in a reactor having a temperature of about -20°C to about 400°C;

[0091] Introducing into the reactor at least one silicon-containing compound having at least one acetoxy group, wherein the at least one silicon-containing compound is selected from:

[0092] I(a) Formula (RCOO) mR 1 n S H p Acyloxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 Selected from linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, linear or branched C2-C6 alkynyl; m=2 or 3; n=1 or 2; p=0 or 1; and m+n+p=4;

[0093] I(b) Formula (RCOO) m (R 2 O) n S H p R 1 q Acyloxyalkoxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; R 2 is selected from linear or branched C1-C6 alkyl; m=2 or 3; m=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; and

[0094] I(c) Formula (RCOO) m (R 3 R 4 NO) n S H p R 1 q The acyloxyaminosilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; and R 3 Selected from hydrogen, straight or branched C1-C 10 Alkyl; R 4 is selected from linear or branched C1-C6 alkyl; m=2 or 3; n=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; and

[0095] An in-situ plasma or a remote plasma source is provided to the reactor to at least partially react the at least one silicon-containing compound to form a flowable liquid oligomer, wherein the flowable liquid oligomer forms a coating on the substrate and at least partially fills at least a portion of the at least one surface feature.

[0096] 2. A method according to claim 1, wherein the plasma is selected from a plasma comprising nitrogen based on an in-situ or remote plasma source, a plasma comprising nitrogen and helium based on an in-situ or remote plasma source, a plasma comprising nitrogen and argon based on an in-situ or remote plasma source, a plasma comprising ammonia based on an in-situ or remote plasma source, a plasma comprising ammonia and helium based on an in-situ or remote plasma source, a plasma comprising ammonia and argon based on an in-situ or remote plasma source, helium plasma, argon plasma, hydrogen plasma, a plasma comprising hydrogen and helium based on an in-situ or remote plasma source, a plasma comprising hydrogen and argon based on an in-situ or remote plasma source, a plasma comprising ammonia and hydrogen based on an in-situ or remote plasma source, an organic amine plasma based on an in-situ or remote plasma source, a plasma comprising oxygen based on an in-situ or remote plasma source, a plasma comprising oxygen and hydrogen based on an in-situ or remote plasma source, and mixtures thereof.

[0097] 3. A method according to claim 1, wherein the plasma is selected from a plasma containing carbon or hydrocarbons based on an in-situ or remote plasma source, a plasma containing hydrocarbons and helium based on an in-situ or remote plasma source, a plasma containing hydrocarbons and argon based on an in-situ or remote plasma source, a plasma containing carbon dioxide based on an in-situ or remote plasma source, a plasma containing carbon monoxide based on an in-situ or remote plasma source, a plasma containing hydrocarbons and hydrogen based on an in-situ or remote plasma source, a plasma containing hydrocarbons and nitrogen based on an in-situ or remote plasma source, a plasma containing hydrocarbons and oxygen based on an in-situ or remote plasma source, and mixtures thereof.

[0098] 4. The method according to item 1, further comprising the step of heat treating the coating at one or more temperatures of about 100°C to about 1000°C to densify at least a portion of the coating and form a hardened layer.

[0099] 5. The method according to item 4, further comprising the step of exposing the hardened layer to energy selected from plasma, infrared light, chemical treatment, electron beam or ultraviolet light to form a final silicon-containing film.

[0100] 6. A method according to item 5, wherein the above steps define one cycle of the method and the cycle can be repeated until a desired thickness of the silicon-containing film is obtained.

[0101] 7. The method of item 1, wherein the at least one silicon-containing compound having at least one acetoxy group comprises diacetoxydimethylsilane.

[0102] 8. The method according to item 1, wherein the acyloxysilane of formula I (a) is selected from:

[0103]

[0104] wherein R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl and isobutyl; and R 1 Selected from methyl, ethyl, vinyl, allyl and ethynyl.

[0105] 9. The method according to item 1, wherein the acyloxyalkoxysilane of formula I(b) is selected from:

[0106]

[0107] wherein R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl and isobutyl; R 1 is selected from the group consisting of methyl, ethyl, vinyl, allyl and ethynyl; and R 2 Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl and isobutyl.

[0108] 10. The method according to item 1, wherein the acyloxyaminooxysilane of formula I(c) is:

[0109]

[0110] Where R and R 1 R is independently selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl and isobutyl; 1 is selected from the group consisting of methyl, ethyl, vinyl, allyl and ethynyl; and R 3 and R 4 Independently selected from methyl and ethyl.

[0111] 11. The method of item 1, wherein the silicon-containing film has a dielectric constant of <3.0 as measured by capacitance-voltage measurement and a porosity of >10% as measured by ellipsometry porosimetry.

[0112] 12. A silicon-containing film precursor comprising at least one silicon-containing compound selected from:

[0113] I(a) Formula (RCOO) m R 1 n S H p Acyloxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 Selected from linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, linear or branched C2-C6 alkynyl; m=2 or 3; n=1 or 2; p=0 or 1; and m+n+p=4;

[0114] I(b) Formula (RCOO)m (R 2 O) n S H p R 1 q Acyloxyalkoxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; R 2 is selected from linear or branched C1-C6 alkyl; m=2 or 3; m=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; and

[0115] I(c) Formula (RCOO) m (R 3 R 4 NO) n S H p R 1 q The acyloxyaminosilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; and R 3 Selected from hydrogen, straight or branched C1-C 10 Alkyl; R 4 is selected from linear or branched C1-C6 alkyl; m=2 or 3; n=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4;

[0116] The silicon-containing compound reacts with plasma to form the silicon-containing film.

[0117] 13. The precursor according to item 12, further comprising at least one solvent.

[0118] 14. The precursor according to item 12, further comprising at least one of an oxygen-containing source and a nitrogen-containing source.

[0119] 15. The precursor according to item 12, further comprising at least one oligomer of at least one of the silicon-containing compounds.

[0120] 16. The precursor according to item 14, comprising diacetoxydimethylsilane and at least one oxygen-containing source.

[0121] 17. A silicon-containing film obtained by the method according to item 1 on a substrate having at least one surface feature, the silicon-containing film having a dielectric constant of <3.0 as measured by capacitance-voltage measurement and a porosity of >10 vol% as measured by ellipsometry porosimetry.

[0122] Example

[0123] The flowable chemical vapor deposition (FCVD) films are deposited onto medium resistivity (8-12Ωcm) single crystal silicon wafer substrates and Si pattern wafers. In certain embodiments, the resulting silicon-containing film or coating may be exposed to a pre-deposition treatment such as, but not limited to, plasma treatment, thermal treatment, chemical treatment, ultraviolet exposure, infrared exposure, electron beam exposure, and / or other treatments that affect one or more properties of the film.

[0124] Deposition can be performed on a modified FCVD chamber on an Applied Materials Precision5000 system using either the silane or TEOS process kit. The chamber has direct liquid injection (DLI) delivery capability. The precursor is a liquid and its delivery temperature depends on the boiling point of the precursor.

[0125] To deposit an initial flowable carbon-doped oxide film, typical liquid precursor flow rates are 100-5000 mg / min, oxygen (or carbon dioxide) flow rates are 20-40 sccm, and in-situ plasma power densities are 0.25-3.5 W / cm 2 , pressure is 0.75-12 Torr. In order to densify the flowable film thus deposited, the film is thermally annealed and / or UV vacuum cured at 100 to 1000°C, preferably 300 to 400°C using a modified PECVD chamber. The thickness and refractive index (RI) are measured at 632nm by a SCI reflectometer or a Woollam ellipsometer. Typical film thicknesses are 10 to 2000nm. The adhesion properties and hydrogen content (Si-H, CH and NH) of the silicon-based film are measured and analyzed by a Nicolet transmission Fourier transform infrared spectroscopy (FTIR) device. All density measurements are completed using X-ray reflectivity (XRR). X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) analysis are performed to determine the elemental composition of the film. The flowability and gap filling effects on the patterned wafer are observed at a resolution of 2.0nm using a cross-sectional scanning electron microscope (SEM) of a Hitachi S-4800 system. The porosity of the film is measured by ellipsometry porosimetry.

[0126] The flowable CVD deposition was performed using a design of experiments (DOE) approach. The experimental design included: precursor flow rate of 100 to 5000 mg / min, preferably 500 to 2000 mg / min; oxygen (or CO2) flow of 0 sccm to 1000 sccm, preferably 0 to 100 sccm; pressure of 0.75 to 12 Torr, preferably 6 to 10 Torr; RF power (13.56 MHz) of 50 to 1000 W, preferably 100 to 500 W; low frequency (LF) power of 0 to 100 W; and deposition temperature of -20 to 400 ° C, preferably -20 ° C to 40 ° C. DOE experiments were used to determine which process parameters produced the best film with good flowability.

[0127] Deposition of low-K films using diacetoxydimethylsilane as a precursor

[0128] In this experiment, the process conditions used to deposit a flowable porous low-k film with the most favorable film properties were as follows: Power = 200 W, Gap = 200 mils, Pressure = 6 to 10 Torr, Temperature = 30 to 35°C, Diacetoxydimethylsilane = 1500 to 2000 mg / min, He = 200 sccm, O2 = 40 to 60 sccm. The flowable film was thermally annealed at 300°C for 5 minutes and then UV cured at 400°C for 10 minutes.

[0129] Films with RI of 1.37 and k of 2.6 to 2.7 were obtained on a blank substrate. The porosity of the film was 19 to 20%. The modulus of the film was 10.4 GPa at a processing pressure of 8 Torr; the hardness was 1.84 GPa. This modulus and hardness are consistent with conventional PECVD porous low-k films.

[0130] Now refer to Figure 2 , Figure 2 A cross-sectional SEM is shown, demonstrating good gap filling achieved by deposition of diacetoxydimethylsilane with O2. Figure 3 , Figure 3 The results of thermal annealing at 300°C for 5 minutes are shown in Figure 2 The film was UV cured at 400 °C for 10 min ( Figure 4 ). Now refer to Figure 4 . Figure 4 SEM shows that after UV exposure at 400℃ for 10 minutes Figure 3 Micrograph of a silicon oxide film.

[0131] Although the principles of the present invention have been described above in conjunction with the preferred embodiment, it should be clearly understood that this description is made by way of example only and not as a limitation on the scope of the present invention.

Claims

1. A method for depositing a silicon-containing film, the method comprising: placing a substrate comprising at least one surface feature in a reactor having a temperature of about -20°C to about 400°C; Introducing into the reactor at least one silicon-containing compound having at least one acetoxy group, wherein the at least one silicon-containing compound is selected from: I(a) Formula (RCOO) m R 1 n S H p Acyloxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 Selected from linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, linear or branched C2-C6 alkynyl; m=2 or 3; n=1 or 2; p=0 or 1; and m+n+p=4; I(b) Formula (RCOO) m (R 2 O) n S H p R 1 q Acyloxyalkoxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; R 2 is selected from a linear or branched C1-C6 alkyl group; m=2 or 3; m=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; and I(c) Formula (RCOO) m (R 3 R 4 NO) n S H p R 1 q The acyloxyaminosilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; and R 3 Selected from hydrogen, straight or branched C1-C 10 Alkyl; R 4 is selected from linear or branched C1-C6 alkyl; m=2 or 3; n=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; and An in-situ plasma or a remote plasma source is provided to the reactor to at least partially react the at least one silicon-containing compound to form a flowable liquid oligomer, wherein the flowable liquid oligomer forms a coating on the substrate and at least partially fills at least a portion of the at least one surface feature.

2. The method of claim 1, wherein the plasma is selected from a plasma comprising nitrogen based on an in-situ or remote plasma source, a plasma comprising nitrogen and helium based on an in-situ or remote plasma source, a plasma comprising nitrogen and argon based on an in-situ or remote plasma source, a plasma comprising ammonia based on an in-situ or remote plasma source, a plasma comprising ammonia and helium based on an in-situ or remote plasma source, a plasma comprising ammonia and argon based on an in-situ or remote plasma source, helium plasma, argon plasma, hydrogen plasma, a plasma comprising hydrogen and helium based on an in-situ or remote plasma source, a plasma comprising hydrogen and argon based on an in-situ or remote plasma source, a plasma comprising ammonia and hydrogen based on an in-situ or remote plasma source, an organic amine plasma based on an in-situ or remote plasma source, a plasma comprising oxygen based on an in-situ or remote plasma source, a plasma comprising oxygen and hydrogen based on an in-situ or remote plasma source, and mixtures thereof.

3. The method of claim 1, wherein the plasma is selected from an in-situ or remote plasma source-based plasma comprising carbon or hydrocarbons, an in-situ or remote plasma source-based plasma comprising hydrocarbons and helium, an in-situ or remote plasma source-based plasma comprising hydrocarbons and argon, an in-situ or remote plasma source-based plasma comprising carbon dioxide, an in-situ or remote plasma source-based plasma comprising carbon monoxide, an in-situ or remote plasma source-based plasma comprising hydrocarbons and hydrogen, an in-situ or remote plasma source-based plasma comprising hydrocarbons and nitrogen, an in-situ or remote plasma source-based plasma comprising hydrocarbons and oxygen, and mixtures thereof.

4. The method of claim 1, further comprising the step of heat treating the coating at one or more temperatures of about 100°C to about 1000°C to densify at least a portion of the coating and form a hardened layer.

5. The method of claim 4, further comprising the step of exposing the hardened layer to energy selected from plasma, infrared light, chemical treatment, electron beam or ultraviolet light to form a final silicon-containing film.

6. The method of claim 5, wherein the above steps define one cycle of the method, and the cycle can be repeated until a desired thickness of the silicon-containing film is obtained.

7. The method of claim 1, wherein the at least one silicon-containing compound having at least one acetoxy group comprises diacetoxydimethylsilane.

8. The method according to claim 1, wherein the acyloxysilane of formula I(a) is selected from: wherein R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl and isobutyl; and R 1 Selected from methyl, ethyl, vinyl, allyl and ethynyl.

9. The method according to claim 1, wherein the acyloxyalkoxysilane of formula I(b) is selected from: wherein R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl and isobutyl; R 1 is selected from the group consisting of methyl, ethyl, vinyl, allyl and ethynyl; and R 2 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl and isobutyl.

10. The method according to claim 1, wherein the acyloxyaminooxysilane of formula I(c) is: Where R and R 1 R is independently selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl and isobutyl; 1 is selected from the group consisting of methyl, ethyl, vinyl, allyl and ethynyl; and R 3 and R 4 Independently selected from methyl and ethyl.

11. The method of claim 1 , wherein the silicon-containing film has a dielectric constant of <3.0 as measured by capacitance-voltage measurement and a porosity of >10% as measured by ellipsometry porosimetry.

12. A silicon-containing film precursor comprising at least one silicon-containing compound selected from: I(a) Formula (RCOO) m R 1 n S H p Acyloxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 Selected from linear or branched C1-C6 alkyl, linear or branched C2-C6 alkenyl, linear or branched C2-C6 alkynyl; m=2 or 3; n=1 or 2; p=0 or 1; and m+n+p=4; I(b) Formula (RCOO) m (R 2 O) n S H p R 1 q Acyloxyalkoxysilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; R 2 is selected from a linear or branched C1-C6 alkyl group; m=2 or 3; m=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; and I(c) Formula (RCOO) m (R 3 R 4 NO) n S H p R 1 q The acyloxyaminosilane, wherein R is selected from hydrogen, linear or branched C1-C6 alkyl; R 1 is selected from a linear or branched C1-C6 alkyl group, a linear or branched C2-C6 alkenyl group, a linear or branched C2-C6 alkynyl group; and R 3 Selected from hydrogen, straight or branched C1-C 10 Alkyl; R 4 is selected from linear or branched C1-C6 alkyl; m=2 or 3; n=1 or 2; p=0 or 1; q=0 or 1, and m+n+p+q=4; The silicon-containing compound reacts with plasma to form the silicon-containing film.

13. The precursor according to claim 12, further comprising at least one solvent.

14. The precursor of claim 12, further comprising at least one of an oxygen-containing source and a nitrogen-containing source.

15. The precursor of claim 12, further comprising at least one oligomer of at least one of the silicon-containing compounds.

16. The precursor of claim 14, comprising diacetoxydimethylsilane and at least one oxygen-containing source.

17. A silicon-containing film obtained by the method according to claim 1 on a substrate having at least one surface feature, the silicon-containing film having a dielectric constant of <3.0 as measured by capacitance-voltage measurement and a porosity of >10 vol% as measured by ellipsometry porosimetry.

Images