Compositions for carbon-doped silicon-containing films and methods of using same - Patents.com

Abstract

Compositions and methods are disclosed for using the compositions in the manufacture of electronic devices. Compounds, compositions and methods are disclosed for depositing silicon-containing films with low dielectric constant (<4.0) and high oxygen ashing resistance, such as, but not limited to, carbon-doped silicon oxide.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 341,635, filed May 13, 2022.

[0002] Described herein are compositions and methods for the manufacture of electronic devices.More specifically, described herein are compounds, compositions including compounds, and methods for depositing low dielectric constant (<4.0) and high oxygen ashing resistance silicon-containing films, such as, but not limited to, carbon-doped silicon oxide, carbon-doped silicon nitride, and carbon-doped silicon oxynitride. [Background technology]

[0003] There is a need in the art to provide compositions and methods of using the compositions for depositing high carbon content (e.g., carbon content of about 10 atomic % or more as measured by X-ray photoelectron spectroscopy (XPS)) doped silicon-containing films for certain applications within the electronics industry.

[0004] No. 8,575,033 describes a method for depositing silicon carbide films on a substrate surface, which includes the use of a vapor-phase carbosilane precursor and may employ a plasma-enhanced atomic layer deposition process.

[0005] U.S. Patent Application Publication No. 2013 / 022496(A) teaches a method for forming a dielectric film having Si-C bonds on a semiconductor substrate by atomic layer deposition (ALD), the method including: (i) adsorbing a precursor on a surface of the substrate; (ii) reacting the adsorbed precursor with a reactant gas on the surface; and (iii) repeating steps (i) and (ii) to form a dielectric film having at least Si-C bonds on the substrate.

[0006] WO 14134476 A1 describes a method for depositing a film comprising SiCN and SiOCN. A particular method comprises exposing a substrate surface to a first and a second precursor, the first precursor being of the formula (X y H 3-y Si)zCH 4-z (X y H 3-y Si)(CH 2 )(SiX p H 2-p )(CH 2 )(SiX y H 3-y (X y H 3-y Si)(CH 2 ) n (SiX y H 3-y ), where X is a halogen, y has a value from 1 to 3, z has a value from 1 to 3, p has a value from 0 to 2, and n has a value from 2 to 5, and the second precursor comprises a reducible amine. Certain methods also include exposing the substrate surface to an oxygen source to provide a film comprising carbon-doped silicon oxide.

[0007] Hirose, Y., Mizuno, K., Mizuno, N., Okubo, S., Okubo, S., Yanagida, K. and Yanagita, K. (2014)) "Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium" U.S. Patent No. 2014 / 287596(A) describes a method of manufacturing a semiconductor device, which includes forming a thin film containing silicon, carbon, and carbon on a substrate by performing a predetermined number of cycles, which include supplying a precursor gas containing silicon, carbon, and halogen elements and having a Si-C bond and a first catalytic gas to the substrate, and supplying an oxidizing gas and a second catalytic gas to the substrate.

[0008] Hirose, Y., Mizuno, N., Yanagita, K. and Okubo, S. (2014) "Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium." U.S. Patent No. 9,343,290(B) describes a method of manufacturing a semiconductor device, which includes forming an oxide film on a substrate by performing a cycle a predetermined number of times. The cycle includes supplying a precursor gas to the substrate and supplying ozone gas to the substrate. In supplying the precursor gas, the precursor gas is supplied to the substrate in a state where no catalyst gas is supplied to the substrate, and in supplying the ozone gas, the ozone gas is supplied to the substrate in a state where an amine-based catalyst gas is supplied to the substrate.

[0009] US Pat. No. 9,349,586(B) discloses thin films having desirable etch resistance and low dielectric constant.

[0010] US 2015 / 0044881(A) describes a method for forming a film containing highly doped carbon with high controllability. A method for manufacturing a semiconductor device includes forming a film containing silicon, carbon, and a predetermined element on a substrate by performing a predetermined number of cycles. The predetermined element is one of nitrogen or oxygen. The cycle includes supplying a precursor gas to the substrate, the precursor gas including at least two silicon atoms, carbon, and a halogen element per mole, and having a Si-C bond, and supplying a modifying gas including the predetermined element to the substrate.

[0011] The reference entitled "Highly Stable Ultrathin Carbosiloxane Films by Molecular Layer Deposition", Han, Z. et al., Journal of Physical Chemistry C, 2013, 117, 19967 teaches growing carbosiloxane films using 1,2-bis[(dimethylamino)dimethylsilyl]ethane and ozone. Thermal stability shows that the films are stable below 400°C with little loss in thickness at 60°C.

[0012] Liu et al., Jpn. Appl. Phys., 1999, Vol. 38, 3482-3486, reported that H of polysilsesquioxane deposited by spin-on technique 2 Teaches the use of plasma. 2 The plasma provides a stable dielectric constant and improves the thermal stability and O 2 Improve ash (plasma) treatment.

[0013] Kim et al., Journal of the Korean Physical Society, 2002, Vol. 40, 94, reported that H on PECVD carbon-doped silicon oxide films 2 It is taught that plasma treatment improves leakage current density (by 4-5 orders of magnitude) and increases the dielectric constant from 2.2 to 2.5. 2 The post-plasma carbon-doped silicon oxide film is less damaged during the oxygen ashing process.

[0014] Posseme et al., Solid State Phenomena, 2005, Vol. 103-104, 337, reported that different H 2 / Inert plasma treatment is taught. k is H 2 There is no improvement after plasma treatment, suggesting the absence of bulk modification.

[0015] There is a need to develop a liquid composition for chlorosilane precursors, such as 1,1,3,3-tetrachloro-1,3-disilacyclobutane, that is suitable for vapor phase delivery methods for ALD applications. The composition must meet certain important requirements for successful commercialization, including: the solvent must not react with the chlorosilane, the chlorosilane chemical must be highly soluble in the solvent; the chlorosilane must not precipitate or phase separate during transportation when exposed to low temperatures; the solvent must be manufacturable with high purity and must be dried to low water content; the formulated solution must have an acceptable viscosity; and the vapor pressure of the solvent must be similar to that of the chlorosilane chemical. Summary of the Invention

[0016] The compositions described herein meet these criteria. The compositions and methods described herein overcome the problems of the prior art by providing compositions or formulations for depositing conformal silicon-containing film formations having one or more of the following properties: i) a dielectric constant of less than 4.0, ii) an etch rate (e.g., 0.22 Å / s in 1:99 dilute HF) that is 0.5 times or less than the etch rate of thermal silicon oxide (e.g., 0.45 Å / s in 1:99 dilute HF) as measured in dilute hydrofluoric acid, and a carbon content of about 10 atomic percent (at%) or more as measured by X-ray photospectroscopy (XPS). ii) Oxygen ashing resistance, i.e., the sensitivity of the film's dielectric constant and its wet etch rate in dilute HF (dHF) resulting from subjecting the film to an oxygen ashing process or exposing the film to oxygen plasma is reduced. (iv) The resulting film has chlorine impurities of less than 2.0 at.%, preferably less than 1.0 at.%, and most preferably less than 0.5 at.%. Oxygen ashing resistance is measured by dHF immersion. 2 The oxygen ashing resistance can also be quantified by the damage thickness of the film after the ashing process (e.g., damage thickness <50 Å). 2This is an example where the film dielectric constant after the ashing process is still 4.0.The desirable properties that can be achieved by the present invention are described in more detail in the following examples.

[0017] In one particular embodiment, the compositions described herein can be used in a method for depositing a carbon-doped silicon oxide film using thermal atomic layer deposition (ALD).

[0018] In one aspect, a composition for depositing a silicon-containing film is disclosed, the composition comprising: (a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane; and (b) a solvent selected from the group consisting of mesitylene (bp 165° C.), 2-methyl-nonane (bp 167° C.), 1,2,4,5-tetramethylpiperazine (bp 166° C.), ethoxy-benzene (bp 171° C.), and 1-ethyl-4-methyl-benzene (bp 162° C.).

[0019] In one aspect, a composition for depositing a silicon-containing film is disclosed, the composition comprising: (a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane; and (b) mesitylene.

[0020] In another aspect, disclosed is a method for forming a carbon-doped silicon oxide film having a carbon content ranging from 15 atomic % to 30 atomic % via a thermal ALD process, the method comprising: a) placing one or more substrates including surface features in a reactor; b) heating the reactor to one or more temperatures ranging from ambient temperature to about 550° C., and optionally maintaining the reactor at a pressure of 100 torr or less; c) introducing a composition into the reactor comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene; d) purging the reactor with an inert gas; and e) providing a nitrogen source to the reactor to provide a nitrogen source. f) purging with an inert gas to remove reaction by-products; g) repeating steps c-f to provide a carbon-doped silicon nitride film of a desired thickness; and h) treating the resulting carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to about 1000° C., or from about 100° C. to about 400° C., according to one embodiment, to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film; and exposing the carbon-doped silicon oxide film to a plasma comprising hydrogen.

[0021] In yet another aspect, a method for forming a carbon-doped silicon oxide film having a carbon content in the range of 15 atomic % to 30 atomic % via a thermal ALD process is disclosed, the method comprising the steps of: a) placing one or more substrates including surface features in a reactor; b) heating the reactor to one or more temperatures ranging from ambient temperature to about 150° C., optionally maintaining the reactor at a pressure of 100 torr or less; and c) reacting 1,1,3,3-tetrachloro-1,3-disilacyclobutane, methacrylonitrile, tetrachloromethane, tetrachloromethane, tetrachloromethane, tetrachloromethane, tri ... The method includes the steps of: introducing a composition comprising ethylene and a catalyst into a reactor; d) purging the reactor with an inert gas; e) supplying water vapor into the reactor to react with 1,1,3,3-tetrachloro-1,3-disilacyclobutane in the presence of the catalyst to form a carbon-doped silicon oxide film; and f) purging the reactor with an inert gas to remove any reaction by-products, and repeating steps c) to f) to obtain a carbon-doped silicon oxide film of a desired thickness.

[0022] In yet another aspect, a stainless steel container containing the composition of the present invention is disclosed.

[0023] The embodiments of the present invention may be used alone or in various combinations with each other. [Brief description of the drawings]

[0024] [Figure 1] FIG. 1 shows an overlay of vapor pressure curves for 1,1,3,3-tetrachloro-1,3-disilacyclo-butane and mesitylene.

[0025] [Diagram 2] Figure 1 shows the concentration of a 20 wt% solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene as a function of the percentage of material used in the vessel during the vapor draw delivery process. The squares represent the concentration profile when the vessel was maintained at 70°C. The circles represent the concentration profile when the vessel was maintained at 80°C.

[0026] [Diagram 3]Concentrations of common stainless steel metals are shown in this plot, along with an assay for a 20 wt % solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene stored in a stainless steel commercial container.

[0027] [Figure 4] 1 shows the growth per cycle (GPC) of a film deposited with a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] Described herein are compositions and methods for depositing carbon-doped silicon-containing films (e.g., having a carbon content of about 10 atomic % or more as measured by XPS) via a deposition process, such as, but not limited to, a thermal atomic layer deposition process. Films deposited using the compositions and methods described herein exhibit very low etch rates, e.g., at least 0.5 times lower than thermal silicon oxide, as measured in dilute hydrofluoric acid (e.g., about 0.22 Å / s or less or about 0.15 Å / s or less in dilute HF (0.5 wt %, i.e., 1:99 dilute HF), or etch rates that are 0.1 times or less than thermal silicon oxide (0.15 Å / s), or etch rates that are 0.05 times or less than thermal silicon oxide (0.02 Å / s), or etch rates that are 0.01 times or less than thermal silicon oxide, and also exhibit variability in other tunable properties, such as, but not limited to, density, dielectric constant, refractive index, and elemental composition.

[0029] In certain embodiments, the silicon precursors described herein and methods of using same provide one or more of the following characteristics in the following manner. First, an as-deposited reactive carbon-doped silicon nitride film is formed using a silicon precursor containing two Si-C-Si bonds and a nitrogen source. Without wishing to be bound by any theory or explanation, it is believed that some of the Si-C-Si bonds from the silicon precursor remain in the resulting as-deposited film, providing a high carbon content of at least 10 atomic % or more (e.g., about 20 to about 30 atomic %, about 10 to about 20 atomic %, and in some cases about 10 to about 15 atomic % carbon) as measured by XPS. Second, when the as-deposited film is exposed to an oxygen source such as water, intermittently during the deposition process, as a post-deposition treatment, or a combination thereof, at least some or all of the nitrogen content in the film is converted to oxygen to provide a film selected from a carbon-doped silicon oxide film or a carbon-doped silicon oxynitride film. Nitrogen in the as-deposited film is released as one or more nitrogen-containing by-products, such as ammonia or amine groups.

[0030] In this or other embodiments, the final film is porous and has a density of about 1.7 grams per cubic centimeter (g / cc) or less and an etch rate of 0.20 Å / s or less in dilute 0.5 wt % hydrogen fluoride.

[0031] In one aspect, a composition for depositing a silicon-containing film includes (a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane and (b) mesitylene. In some embodiments, the composition can be delivered via direct liquid injection into a reactor chamber for silicon-containing films using conventional direct liquid injection equipment and methods. The concentration of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in a solvent can range from 1% to 90% by weight, preferably 10% to 80% by weight, and most preferably 15% to 60% by weight, depending on the solvent selected.

[0032] Mesitylene is an optimal solvent for the composition since it has a normal boiling point very similar to that of 1,1,3,3-tetrachloro-1,3-disilacyclobutane (165°C and 167°C, respectively). The two components of the composition have similar boiling points and similar vapor pressure curves over the temperature range of interest. The similar volatility of the chlorosilane chemicals and the solvent ensures that the composition of the vapor stream and the composition of the liquid blended product remain constant even as the blended product is depleted during vapor phase delivery. This consistency of the liquid and gas phase composition of the blended product is important to ensure a reliable and robust deposition process. Mesitylene is also hydrophobic and therefore can be easily dried by practical known methods such as treatment with molecular sieves to produce a solvent containing less than 10 ppm water, preferably less than 5 ppm water. Such low levels of water are important primarily because they minimize the amount of acidic by-products, such as HCl, formed when chlorosilanes, such as 1,1,3,3-tetrachloro-1,3-disilacyclobutane, are dissolved in the solvent. Eliminating or reducing traces of HCl in the final blended product is important to obtain a formulated product that is compatible with common container construction materials, such as stainless steel.

[0033] In another aspect, a method for depositing a film selected from a carbon-doped silicon oxide film and a carbon-doped silicon oxynitride film on at least a surface of a substrate includes the steps of placing the substrate in a reactor; heating the reactor to one or more temperatures ranging from about 25° C. to about 550° C.; introducing a formulation including (a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane-disilacyclobutane as a precursor and (b) mesitylene into the reactor; introducing a nitrogen source into the reactor to react with at least a portion of the precursor to form the carbon-doped silicon nitride film; and treating the carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about 25° C. to 1000° C. or from about 100° C. to 400° C. under conditions sufficient to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film or a carbon-doped silicon oxynitride film. In certain embodiments, the carbon-doped silicon oxide or silicon oxynitride film has a carbon content of about 10 atomic weight percent (at.%) or greater, as measured by XPS, and an etch rate of about 0.5 times or less than that of thermal silicon oxide, as measured in dilute hydrofluoric acid. If desired, the invention further comprises treating the carbon-doped silicon-containing film with a hydrogen or hydrogen / inert plasma at 25°C to 600°C.

[0034] In certain embodiments, silicon-containing film comprises silicon and nitrogen.In these embodiments, the silicon-containing film deposited using the method described herein is formed in the presence of a nitrogen-containing source.The nitrogen-containing source may be introduced into the reactor in the form of at least one nitrogen source and / or may be present incidentally in other precursors used in the deposition process.

[0035] Suitable nitrogen-containing or nitrogen source gases can include, for example, ammonia, ammonia plasma, hydrazine, monoalkylhydrazines, symmetrical or asymmetrical dialkylhydrazines, organic amines such as methylamine, ethylamine, ethylenediamine, ethanolamine, piperazine, N,N'-dimethylethylenediamine, imidazolidine, cyclotrimethylenetriamine, and combinations thereof.

[0036] In another aspect, a method is provided for forming a carbon-doped silicon oxide film having a carbon content in the range of 15 atomic % to 30 atomic % via a thermal ALD process, the method comprising: a) placing one or more substrates including surface features in a reactor; b) heating the reactor to one or more temperatures ranging from ambient temperature to about 550° C., and optionally maintaining the reactor at a pressure of 100 torr or less; c) introducing a composition to the reactor comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene; d) purging with an inert gas; and e) providing a nitrogen source to the reactor to remove the 1,1, f) purging with an inert gas to remove reaction by-products; g) repeating steps c-f to provide a carbon-doped silicon nitride film of a desired thickness; h) treating the resulting carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to about 1000° C., or from about 100° C. to about 400° C. to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film; and exposing the carbon-doped silicon oxide film to a plasma comprising hydrogen after deposition.

[0037] In another embodiment, a method for forming a carbon-doped silicon oxide film having a carbon content ranging from 15 atomic % to 30 atomic % via a thermal ALD process includes: a) placing one or more substrates including surface features in a reactor; b) heating the reactor to one or more temperatures ranging from ambient temperature to about 150° C., and optionally maintaining the reactor at a pressure of 100 torr or less; c) introducing a composition including 1,1,3,3-tetrachloro-1,3-disilacyclobutane, mesitylene, and a catalyst into the reactor; d) purging with an inert gas; e) supplying water vapor into the reactor to react with the 1,1,3,3-tetrachloro-1,3-disilacyclobutane in the presence of the catalyst to form a carbon-doped silicon oxide as-deposited film; and f) purging with an inert gas to remove reaction by-products, wherein steps c)-f) are repeated to obtain a carbon-doped silicon oxide film of a desired thickness.

[0038] In one embodiment of the method described herein, a carbon-doped silicon oxide film having a carbon content ranging from 5 atomic % to 20 atomic % is deposited using a thermal ALD process and a hydrogen-containing plasma, thereby improving the film properties. In this embodiment, the method includes: a. placing one or more substrates including surface features into a reactor; b. heating the reactor to one or more temperatures ranging from ambient temperature to about 550° C., and optionally maintaining the reactor at a pressure of about 100 torr or less; c. introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane as a silicon precursor and mesitylene into a reactor; d. purging with an inert gas, thereby removing unreacted silicon precursor, to form a composition comprising the purge gas and the silicon precursor; e. providing a nitrogen source into the reactor to react with the silicon precursor, thereby forming a carbon-doped silicon nitride film; f. purging with an inert gas to remove reaction by-products; g. repeating steps c to f to obtain a carbon-doped silicon nitride film of a desired thickness; h. post-deposition treating the carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to 1000° C. or from about 100° C. to 400° C. to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film, either in situ or in a separate chamber; i. exposing the carbon doped silicon oxide film after deposition to a hydrogen-containing plasma to improve film properties and improve at least one of the film properties; j. Optionally, post-deposition treating the carbon-doped silicon oxide film with a UV light source or spike anneal at a temperature between 400-1000° C. In this or other embodiments, the UV exposure step can be performed either during film deposition or after deposition is completed.

[0039] In one embodiment, the substrate includes at least one feature, which includes a patterned trench with an aspect ratio of 1:9 and an opening of 180 nm.

[0040] In another embodiment, disclosed is a method for depositing carbon-doped silicon oxide films having a carbon content in the range of 5 atomic % to 20 atomic % using a thermal ALD process and a hydrogen-containing plasma, thereby improving film properties. a. placing one or more substrates including surface features into a reactor; b. heating the reactor to one or more temperatures ranging from ambient temperature to about 550° C., and optionally maintaining the reactor at a pressure of about 100 torr or less; c. introducing into the reactor a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and a solvent selected from the group consisting of mesitylene, 2-methyl-nonane, 1,2,4,5-tetramethylpiperazine, ethoxy-benzene, and 1-ethyl-4-methyl-benzene; d. purging with an inert gas, thereby removing unreacted silicon precursor, to form a composition comprising the purge gas and the silicon precursor; e. providing a nitrogen source in the reactor to react with the surface to form a carbon doped silicon film; f. purging with an inert gas to remove reaction by-products; g. repeating steps c to f to obtain a carbon-doped silicon nitride film of a desired thickness; h. post-deposition treating the carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to 1000° C. or from about 100° C. to 400° C. to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film, either in situ or in a separate chamber; i. exposing the carbon-doped silicon oxide film after deposition to a hydrogen-containing plasma to improve at least one of the film's properties; j. Optionally, post-deposition treating the carbon-doped silicon oxide film with a UV light source or spike anneal at a temperature between 400-1000° C. In this or other embodiments, the UV exposure step can be performed either during film deposition or after deposition is completed.

[0041] In an embodiment of the method described herein, carbon-doped silicon oxide films having carbon content ranging from 15 atomic % to 30 atomic % are deposited using a thermal ALD process and a hydrogen-containing plasma, thereby improving film properties. In this embodiment, the method includes: a. placing one or more substrates including surface features into a reactor (e.g., in a conventional ALD reactor); b. heating the reactor to one or more temperatures ranging from ambient temperature to about 550° C., and optionally maintaining the reactor at a pressure of about 100 torr or less; c. introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene into a reactor; d. purging with an inert gas; e. providing a nitrogen source to the reactor to react with 1,1,3,3-tetrachloro-1,3-disilacyclobutane to form a carbon-doped silicon nitride film; f. purging with an inert gas to remove reaction by-products; g. repeating steps c to f to obtain a carbon-doped silicon nitride film of a desired thickness; h. post-deposition treating the carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to 1000° C. or from about 100° C. to 400° C. to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film, either in situ or in a separate chamber; i. exposing the carbon-doped silicon oxide film after deposition to a hydrogen-containing plasma to improve at least one of the film's physical properties; j. Optionally, post-deposition treating the carbon-doped silicon oxide film with a thermal anneal at a temperature between 400-1000° C. or a UV light source.

[0042] In this or other embodiments, the UV exposure step can be performed either during film deposition or after deposition is completed.

[0043] In yet another further embodiment of the methods described herein, the silicon-containing film is deposited using a thermal ALD process with a catalyst comprising ammonia or an organic amine. In this embodiment, the method comprises: a. placing one or more substrates including surface features into a reactor; b. heating the reactor to one or more temperatures ranging from ambient temperature to about 150° C., and optionally maintaining the reactor at a pressure of 100 torr or less; c. introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane, mesitylene, and a catalyst into a reactor; d. purging with an inert gas; e. supplying water vapor to the reactor to react with 1,1,3,3-tetrachloro-1,3-disilacyclobutane in the presence of a catalyst to form a carbon-doped silicon oxide as-deposited film; f. purging with an inert gas to remove reaction by-products; g. Repeating steps c to f to obtain a carbon-doped silicon oxide film of a desired thickness; h. after deposition, exposing the film to a hydrogen-containing plasma to improve at least one of the film's properties; i. optionally post-deposition treating the carbon-doped silicon oxide film with a UV light source or spike anneal at a temperature between 400-1000° C. In this or other embodiments, the UV exposure step can be performed either during film deposition or after deposition is completed.

[0044] In this or other embodiments, the catalyst is selected from Lewis bases such as pyridine, piperazine, ammonia, triethylamine or other organic amines, and the amount of Lewis base vapor is at least 1 equivalent relative to the amount of silicon precursor vapor in step c.

[0045] In a particular embodiment, the resulting carbon-doped silicon oxide film is exposed to an organoaminosilane or chlorosilane having Si-Me or Si-H or both to form a thin hydrophobic layer prior to exposure to hydrogen plasma treatment. Suitable organoaminosilanes include, but are not limited to, diethylaminotrimethylsilane, dimethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, t-butylaminotrimethylsilane, isopropylaminotrimethylsilane, diisopropylaminotrimethylsilane, pyrrolidinotrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, ethylmethylaminodimethylsilane, t-butylaminodimethylsilane, isopropylaminodimethylsilane, diisopropylaminodimethylsilane, pyrrolidinodimethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)dimethylsilane, bis(ethylmethylamino)dimethylsilane, bis(diisopropylamino)dimethylsilane, bis(isopropylamino)dimethylsilane, bis(tert-butyl ... Silane, dipyrrolidinodimethylsilane, bis(diethylamino)diethylsilane, bis(diethylamino)methylvinylsilane, bis(dimethylamino)methylvinylsilane bis(ethylmethylamino)methylvinylsilane, bis(diisopropylamino)methylvinylsilane, bis(isopropylamino)methylvinylsilane, bis(tert-butylamino)methylvinylsilane, dipyrrolidinomethylvinylsilane, 2,6-dimethylpiperidinomethylsilane, 2,6-dimethylpiperidinodimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, tris(dimethylamino)phenylsilane, tris(dimethylamino)methylsilane, diiso-propylaminosilane, di-sec-butylaminosilane, chlorodimethylsilane, chlorotrimethylsilane, dichloromethylsilane, and dichlorodimethylsilane.

[0046] In another embodiment, the resulting carbon-doped silicon oxide film is exposed to an alkoxysilane or cyclic alkoxysilane having Si-Me or Si-H or both before being exposed to hydrogen plasma treatment to form a thin hydrophobic layer. Suitable alkoxysilanes or cyclic alkoxysilanes include, but are not limited to, diethoxymethylsilane, dimethoxymethylsilane, diethoxydimethylsilane, dimethoxydimethylsilane, 2,4,6,8-tetramethylcyclotetrasiloxane, or octamethylcyclotetrasiloxane. Without wishing to be bound by any theory or explanation, it is believed that the thin layer formed by organic aminosilane or alkoxysilane or cyclic alkoxysilane can be converted to high density carbon-doped silicon oxide during plasma ashing process, further enhancing ashing resistance.

[0047] In another embodiment, the vessel for depositing silicon-containing film comprises one or more silicon precursor compounds as described herein.In a particular embodiment, the vessel comprises at least one pressurizable vessel (preferably made of stainless steel with a design as disclosed in US Pat. No. 7,334,595, US Pat. No. 6,077,356, US Pat. No. 5,069,244, and US Pat. No. 5,465,766 (the disclosures of which are incorporated herein by reference)).The vessel can comprise either glass (borosilicate glass or quartz glass) or type 316, 316L, 304, or 304L stainless steel alloy (UNS designation S31600, S31603, S30400, S30403), equipped with appropriate valves and fittings that allow one or more precursors to be delivered to the reactor for CVD or ALD process. In this or other embodiments, the silicon precursor is provided in a pressurizable vessel constructed from stainless steel, and the purity of the precursor is 98% by weight or greater, or 99.5% by weight or greater, which is suitable for semiconductor applications. The silicon precursor compound is preferably Al 3+ Ion, Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+As used herein, Al is substantially free of metal ions such as 3+ Ion, Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+ The term "substantially free" in relation to means less than about 5 ppm (by weight), preferably less than about 3 ppm, more preferably less than about 1 ppm, and most preferably about 0.1 ppm. In certain embodiments, such vessels may also have means for mixing the precursor with one or more additional precursors, if desired. In these or other embodiments, the contents of the vessel(s) may be premixed with the additional precursors. Alternatively, the silicon precursor and / or other precursors may be maintained in separate vessels or a single vessel having a separation means for keeping the silicon precursor and other precursors separate during storage.

[0048] The silicon-containing film is deposited on at least the surface of a substrate, such as a semiconductor substrate. In the methods described herein, the substrate may be composed of and / or coated with various materials well known in the art, such as silicon, e.g., crystalline or amorphous silicon, silicon oxide, silicon nitride, amorphous carbon, silicon oxide carbide, silicon oxynitride, silicon carbide, germanium, germanium-doped silicon, boron-doped silicon, metals such as copper, tungsten, aluminum, cobalt, nickel, tantalum, metal nitrides such as titanium nitride, tantalum nitride, metal oxides, III / V metals or metalloids such as GaAs, InP, GaP and GaN, and combinations thereof. These coatings may completely coat the semiconductor substrate, or may be multiple layers of various materials, and may be partially etched to expose the underlying layers of materials. The surface may also have a photoresist material thereon that is exposed in a pattern and developed to partially coat the substrate. In certain embodiments, the semiconductor substrate comprises at least one surface feature selected from the group consisting of pores, vias, trenches, and combinations thereof. Potential applications of the silicon-containing film include, but are not limited to, low-k spacers for FinFETs or nanosheets, sacrificial hardmasks for self-aligned patterning processes (such as SADP, SAQP, or SAOP).

[0049] The deposition method used to form the silicon-containing film or coating is a deposition process. Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, chemical vapor deposition or atomic layer deposition processes. As used herein, the term "chemical vapor phase deposition process" refers to any process in which a substrate is exposed to one or more volatile precursors that react and / or decompose on the substrate surface to produce the desired deposition. As used herein, the term "atomic layer deposition process" refers to a self-limiting (e.g., the amount of film material deposited in each reaction cycle is constant) sequential surface chemistry that deposits a film of material on a substrate of various compositions. As used herein, the term "thermal atomic layer deposition process" refers to an atomic layer deposition process at substrate temperatures ranging from room temperature to 600°C without in situ or remote plasma. Although the precursors, reagents, and sources used herein may be described as "gaseous", it is understood that the precursors may be either liquids or solids that are transported into the reactor by direct vaporization, bubbling, or sublimation, with or without an inert gas. In some cases, the vaporized precursors may be passed through a plasma generator.

[0050] In one embodiment, the silicon-containing film is deposited using an ALD process. In another embodiment, the silicon-containing film is deposited using a CCVD process. In a further embodiment, the silicon-containing film is deposited using a thermal ALD process. As used herein, the term "reactor" includes, but is not limited to, a reaction chamber or a deposition chamber.

[0051] In certain embodiments, the methods disclosed herein avoid pre-reaction of the precursor(s) by using ALD or CCVD methods that separate the precursor(s) before and / or during introduction into the reactor. In this regard, deposition techniques such as ALD or CCVD processes are used to deposit silicon-containing films. In one embodiment, the film is deposited via an ALD process in a typical single-wafer ALD reactor, semi-batch ALD reactor, or batch furnace ALD reactor by alternately exposing the substrate surface to one or more silicon-containing precursors, oxygen sources, nitrogen-containing sources, or other precursors or reagents. Film growth proceeds by self-limiting control of surface reactions, pulse length of each precursor or reagent, and deposition temperature. However, film growth stops when the surface of the substrate is saturated. In another embodiment, each reactant, including the silicon precursor and reactive gas, is exposed to the substrate by moving or rotating the substrate to different parts of the reactor, each part being separated by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor.

[0052] Depending on the deposition method, in certain embodiments, the silicon precursors described herein and optionally other silicon-containing precursors may be introduced into the reactor at a predetermined molar volume, or from about 0.1 to about 1000 micromoles. In this or other embodiments, the precursors may be introduced into the reactor for a predetermined period of time. In certain embodiments, the period of time ranges from about 0.001 to about 500 seconds.

[0053] In certain embodiments, the silicon-containing films deposited using the methods described herein are formed in the presence of an oxygen source, an oxygen-containing reagent or precursor, i.e., a catalyst in combination with water vapor. The oxygen source may be introduced into the reactor in the form of at least one oxygen source and / or may be incidentally present in other precursors used in the deposition process. Suitable oxygen source gases include, for example, water (H 2 O) (e.g., deionized water, pure water, distilled water, water vapor, water vapor plasma, oxygenated water, air, compositions containing water, and other organic liquids), oxygen (O 2 ), oxygen plasma, ozone (O3 ), nitric oxide (NO), nitrogen dioxide (NO 2 ), carbon monoxide (CO), plasma containing water, plasma containing water and argon, hydrogen peroxide, composition containing hydrogen, composition containing hydrogen and oxygen, carbon dioxide (CO 2 ), air, and combinations thereof. In certain embodiments, the oxygen source comprises an oxygen source gas introduced into the reactor at a flow rate ranging from about 1 to about 10,000 sccm or from about 1 to about 1000 sccm. The oxygen source can be introduced for a time ranging from about 0.1 to about 100 seconds. The catalyst is selected from Lewis bases such as pyridine, piperazine, trimethylamine, tert-butylamine, diethylamine, trimethylamine, ethylenediamine, ammonia, or other organic amines.

[0054] In embodiments in which the film is deposited by an ALD or cyclic CVD process, the precursor pulse can have a pulse duration greater than 0.01 seconds, the oxygen source can have a pulse duration less than 0.01 seconds, and the water pulse can have a pulse duration less than 0.01 seconds.

[0055] In certain embodiments, the oxygen source flows continuously into the reactor while the precursor pulse and plasma are introduced in sequence. The precursor pulse can have a pulse duration greater than 0.01 seconds, and the plasma duration can range from 0.01 seconds to 100 seconds.

[0056] In certain embodiments, silicon-containing film comprises silicon and nitrogen.In these embodiments, the silicon-containing film deposited using the method described herein is formed in the presence of a nitrogen-containing source.The nitrogen-containing source may be introduced into the reactor in the form of at least one nitrogen source and / or may be present incidentally in other precursors used in the deposition process.

[0057] Suitable nitrogen-containing or nitrogen source gases can include, for example, ammonia, hydrazine, monoalkylhydrazines, symmetrical or asymmetrical dialkylhydrazines, organic amines such as methylamine, ethylamine, ethylenediamine, ethanolamine, piperazine, N,N'-dimethylethylenediamine, imidazolidine, cyclotrimethylenetriamine, and combinations thereof.

[0058] In certain embodiments, the nitrogen source is introduced into the reactor at a flow rate ranging from about 1 to about 10,000 standard cubic centimeters (sccm) or from about 1 to about 1000 sccm. The nitrogen-containing source can be introduced for a time ranging from about 0.1 to about 100 seconds. In embodiments where the film is deposited by an ALD or cyclic CVD process using both a nitrogen source and an oxygen source, the precursor pulse can have a pulse duration longer than 0.01 seconds, the nitrogen source can have a pulse duration less than 0.01 seconds, and the water pulse duration can have a pulse duration less than 0.01 seconds. In yet other embodiments, the purge duration between pulses can be as short as 0 seconds, or pulsed continuously with no purge in between.

[0059] The deposition methods disclosed herein may involve one or more purge gases. Purge gases used to purge away unconsumed reactants and / or reaction by-products are inert gases that do not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N 2 ), helium (He), neon, hydrogen (H 2 In one particular embodiment, a purge gas, such as Ar, is fed into the reactor at a flow rate in the range of about 10 to 10,000 sccm for about 0.1 to about 1000 seconds, thereby purging unreacted materials and any by-products that may remain in the reactor.

[0060] Each step of supplying the precursor, oxygen source, nitrogen-containing source, and / or other precursors, source gases, and / or reagents may be performed by varying the time for which they are supplied to vary the stoichiometry of the resulting film.

[0061] Energy is applied to at least one of the precursors, nitrogen-containing sources, reducing agents, other precursors, or combinations thereof to induce a reaction and form a film or coating on the substrate. Such energy can be provided by, but is not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma methods, and combinations thereof.

[0062] In certain embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments in which deposition involves a plasma, the plasma generation process may include a direct plasma generation process, in which the plasma is generated directly within the reactor, or a remote plasma generation process, in which the plasma is generated outside the reactor and fed into the reactor.

[0063] Throughout this specification, the term "ALD or ALD-like" refers to processes including, but not limited to, a) where reactants including silicon precursor and reactive gas are introduced sequentially into a reactor, such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) where reactants including silicon precursor and reactive gas are exposed to the substrate by moving or rotating the substrate to different sites in the reactor, each site being separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0064] Silicon precursors and / or other silicon-containing precursors can be delivered to a reaction chamber, such as a CVD or ALD reactor, in a variety of ways. In one embodiment, a liquid delivery system can be utilized. In an alternative embodiment, a combined liquid delivery and flash evaporation process unit, such as a turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, can be used to enable volumetric delivery of low volatility materials, resulting in reproducible transport and deposition without thermal decomposition of the precursor. In a liquid delivery formulation, the precursors described herein can be delivered in pure liquid form or can be used in a solvent formulation or a composition that includes a solvent formulation. Thus, in certain embodiments, the precursor formulation can include a solvent component(s) of suitable properties that may be desirable and advantageous in a given end use application for forming a film on a substrate.

[0065] In this or other embodiments, it is understood that the steps of the methods described herein may be performed in various orders, sequentially or simultaneously (e.g., between at least a portion of another step), and any combination thereof. Each step of supplying a precursor and a nitrogen-containing source gas may be performed by varying the duration of time for which they are supplied to vary the stoichiometric composition of the resulting silicon-containing film.

[0066] In further embodiments of the methods described herein, the film or as-deposited film is subjected to a treatment step. The treatment step can be performed during at least a portion of the deposition step, after the deposition step, and combinations thereof. Exemplary treatment steps include, but are not limited to, treatment by high temperature thermal annealing; plasma treatment; ultraviolet (UV) radiation treatment; laser; electron beam treatment, and combinations thereof, to affect one or more properties of the film. Films deposited with silicon precursors having one or two Si-C-Si bonds described herein have improved properties, such as, but not limited to, a wet etch rate lower than the wet etch rate of the film before the treatment step, or a density higher than the density before the treatment step, when compared to films deposited with silicon precursors previously disclosed under the same conditions. In a particular embodiment, the as-deposited film is intermittently treated during the deposition process. These intermittent or intermediate deposition treatments can be performed, for example, after each ALD cycle, after a certain number of ALD cycles, such as, but not limited to, every 1 ALD cycle, 2 ALD cycles, 5 ALD cycles, or every 10 or more ALD cycles.

[0067] In embodiments where the film is subjected to a high temperature annealing step, the annealing temperature is at least 100° C. higher than the deposition temperature. In this or other embodiments, the annealing temperature ranges from about 400° C. to about 1000° C. In this or other embodiments, the annealing process can be performed in a vacuum (<760 Torr), an inert environment, or an oxygen-containing environment (H 2 O, N 2 O, NO 2 Or O 2 etc.)

[0068] In embodiments in which the film is subjected to a UV treatment, the film is exposed to broadband UV, or a UV source having a wavelength in the range of about 150 nanometers (nm) to about 400 nm. In one particular embodiment, the as-deposited film is exposed to UV in a chamber separate from the deposition chamber after the desired film thickness is reached.

[0069] In embodiments where the film is treated with plasma, SiO 2 or carbon-doped SiO 2 A passivation layer, such as SiO 2 , is deposited to prevent chlorine and nitrogen contamination from penetrating the film during subsequent plasma processing. The passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

[0070] In embodiments where the film is treated with a plasma, the plasma source is selected from the group consisting of a hydrogen plasma, a hydrogen and helium-containing plasma, and a hydrogen and argon-containing plasma. The hydrogen plasma lowers the dielectric constant of the film while keeping the carbon content in the bulk nearly unchanged, making it more resistant to damage from subsequent plasma ashing processes.

[0071] Throughout this specification, the term "ALD or ALD-like" refers to processes including, but not limited to, a) where reactants including silicon precursor and reactive gas are introduced sequentially into a reactor, such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) where reactants including silicon precursor and reactive gas are exposed to the substrate by moving or rotating the substrate to different sites in the reactor, each site being separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0072] Throughout this specification, the term "ashing" refers to 2 / inert gas plasma, O 2 Plasma, CO 2 Plasma, CO plasma, H 2 / O 2 It refers to the process of removing photoresist or carbon hard masks in semiconductor manufacturing processes using plasmas containing an oxygen source, such as oxygen plasmas or combinations thereof.

[0073] Throughout this specification, the term "damage resistance" refers to film properties after an oxygen ashing process. Good or high damage resistance is defined as the following film properties after oxygen ashing: film dielectric constant less than 4.5; carbon content in the bulk (film depth greater than 50 Å) within 5 atomic % as before ashing. Films less than 50 Å are damaged, as observed by the difference in dilute HF etch rate between the film near the surface (depth less than 50 Å) and the bulk (depth greater than 50 Å).

[0074] Throughout this specification, the term "alkyl hydrocarbon" refers to straight or branched chain C 1 ~C 20 Hydrocarbons, cyclic C 6 ~C 20 Refers to a hydrocarbon. Exemplary hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

[0075] Throughout this specification, the term "aromatic hydrocarbon" refers to 6 ~C 20 Refers to aromatic hydrocarbons. Exemplary aromatic hydrocarbons n include, but are not limited to, toluene and mesitylene.

[0076] Throughout this specification, the term "catalyst" refers to a Lewis base in the vapor phase that can catalyze the surface reaction of hydroxyl groups with Si-Cl bonds during a thermal ALD process. Exemplary catalysts include, but are not limited to, at least one of cyclic amine-based gases such as aminopyridine, picoline, lutidine, piperazine, piperidine, pyridine, or organic amine-based gases, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, and tert-butylamine.

[0077] Throughout this specification, the term "organic amine" refers to 1 ~C 20 Hydrocarbons, cyclic C 6~C 20 Refers to primary, secondary, and tertiary amines with hydrocarbons. Exemplary organic amines include, but are not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, and tert-butylamine.

[0078] As used herein, the term "siloxane" refers to a linear, branched, or cyclic liquid compound having at least one Si-O-Si bond and C4 to C20 carbon atoms. Exemplary siloxanes include, but are not limited to, tetramethyldisiloxane, hexamethyldisiloxane (HMDSO), 1,1,1,3,3,5,5,5-octamethyltrisiloxane, and octamethylcyclotetrasiloxane (OMCTS).

[0079] Throughout this specification, when the term "etch rate that is x times or less than the etch rate of thermal silicon oxide" is used, the value x is calculated by dividing the etch rate of the subject silicon-containing film in 1:99 dilute HF by the etch rate of thermal silicon oxide in 1:99 dilute HF (e.g., 0.45 Å / s), both etch rates being measured under the same conditions.

[0080] Throughout this specification, the term "step coverage" as used herein is defined as the ratio (percentage) of two thicknesses of a deposited film on a structured or characterized substrate having either a via or a trench or both, where bottom step coverage is the ratio (%) of the thickness at the bottom of the feature divided by the thickness at the top of the feature, and intermediate step coverage is the ratio (%) of the thickness at the sidewall of the feature divided by the thickness at the top of the feature. Films deposited using the methods described herein exhibit step coverage of about 80% or greater, or about 90% or greater, indicating that the film is conformal.

[0081] The following examples illustrate certain aspects of the invention and are not intended to limit the scope of the appended claims. EXAMPLES

[0082] Example 1. A blended product consisting of 20% by weight 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene. The formulation was prepared by dissolving 20 wt.% 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene. Figure 1 shows the overlay of the vapor pressure curves of 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene, indicating their similarity over the temperature range of interest.

[0083] Figure 2 shows the normalized concentrations of common stainless steel constituent metals such as Fe, Cr, Ni, and Mn in a 20 wt% solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene aged at room temperature for the equivalent of 2 years in a stainless steel container. The lack of a systematic increase in these common stainless steel metals over time provides strong support for the compatibility of a formulated product made from low moisture mesitylene components with stainless steel containers.

[0084] FIG. 3 shows the normalized concentration of the chlorosilane component, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, as a function of the volume percent remaining in the vessel when it is depleted during the vapor draw delivery process.

[0085] Concentration consistency was performed by depositing silicon-containing films using a 20 wt% solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene and ammonia in thermal ALD mode. The vessel contained only 200 g of material in a 500 ml stainless steel vessel. The vessel was heated to 80° C. and a vapor draw was used to deliver the chemicals. Film deposition was performed in a laboratory-scale atomic layer deposition (ALD) reactor using a silicon precursor and ammonia as the nitrogen source ammonia. The ALD steps and process conditions are shown in Table 3 below. [Table 1]

[0086] During deposition, steps 3 through 10 are repeated for multiple cycles to obtain the desired thickness of as-deposited carbon-doped silicon nitride.

[0087] Gas chromatography assays were performed at intervals throughout the run to verify solution concentrations.

[0088] As shown in Figure 4, the film growth was consistent with GPC of 0.39 Å / cycle ± 0.03 Å / cycle. GC assays were taken from the reservoir during the deposition. Tables 4 and 5 represent assays taken at intervals during the deposition with the reservoir heated to temperatures of 80°C and 70°C, respectively. As shown in the tables, the precursor concentration is constant throughout the deposition in both cases.

[0089] [Table 2]

[0090] [Table 3]

[0091] Although the invention has been described with reference to specific embodiments, those skilled in the art will recognize that various changes can be made and equivalents substituted for elements thereof without departing from the scope of the invention. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but the invention is intended to include all embodiments falling within the scope of the appended claims.

Claims

1. A composition for depositing a silicon-containing film, comprising: (a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane, (b) mesitylene.

2. A 3+ , Fe 2+ , Fe 3+ , Ni 2+ , and Cr 3+ 2. The composition of claim 1, comprising less than 5 ppm of at least one metal ion selected from the group consisting of:

3. 1. A method for forming a carbon-doped silicon oxide film via a thermal ALD process, comprising: a) placing one or more substrates in a reactor, each substrate having a surface including surface features; b) heating the reactor to one or more temperatures ranging from ambient temperature to about 550° C., and optionally maintaining the reactor at a pressure of 100 torr or less; c) introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene into the reactor to form a film on the surface; d) purging the reactor with an inert gas; e) introducing a nitrogen source into the reactor to react with the film to form a carbon-doped silicon nitride film; f) purging the reactor with an inert gas to remove reaction by-products; g) repeating steps c-f to provide a carbon doped silicon nitride film of a desired thickness; h) treating the resulting carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to about 1000° C. to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film; i) exposing the carbon doped silicon oxide film to a plasma comprising hydrogen.

4. 4. A film formed according to the method of claim 3, wherein k is less than about 4 and the carbon content is at least about 10 atomic percent.

5. 4. A film formed according to the method of claim 3 having an etch rate in 1:99 dilute HF that is no more than 0.5 times the etch rate of thermal silicon oxide.

6. 6. The film of claim 5, wherein the etch rate is less than or equal to 0.1 times the etch rate of thermal silicon oxide.

7. 6. The film of claim 5, wherein the etch rate is less than or equal to 0.05 times the etch rate of thermal silicon oxide.

8. 6. The film of claim 5, wherein the etch rate is less than or equal to 0.01 times the etch rate of thermal silicon oxide.

9. 4. A film formed by the method of claim 3 having a damage layer of 50 Å or less after exposing the film to an oxygen ashing process.

10. 10. The film of claim 9, wherein the damage layer is less than or equal to 20 Å after exposing the film to an oxygen ashing process.

11. 10. The film of claim 9, wherein the damage layer is less than or equal to 10 Å after exposing the film to an oxygen ashing process.

12. 10. The film of claim 9, wherein the damage layer is less than or equal to 5 Å after exposing the film to an oxygen ashing process.

13. A stainless steel container containing the composition of claim 1 or 2.

14. 1. A method for forming a carbon-doped silicon oxide film having a carbon content ranging from 15 atomic % to 30 atomic % via a thermal ALD process, comprising: a. placing one or more substrates including surface features into a reactor; b. heating the reactor to one or more temperatures ranging from ambient temperature to about 150° C., and optionally maintaining the reactor at a pressure of 100 torr or less; c. introducing into the reactor a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane, mesitylene, and a catalyst; d. purging the reactor with an inert gas; e. supplying water vapor to the reactor to react with 1,1,3,3-tetrachloro-1,3-disilacyclobutane in the presence of the catalyst to form a carbon-doped silicon oxide film; f. purging the reactor with an inert gas to remove any reaction by-products. Steps c through f are repeated to obtain a desired thickness of said carbon-doped silicon oxide film.

15. 15. The method of claim 14, further comprising the step of treating the carbon-doped silicon oxide film with a thermal anneal at a temperature of 300-700°C.

16. 15. The method of claim 14, further comprising treating the carbon doped silicon oxide film with a hydrogen plasma containing hydrogen.

17. 4. The method of claim 3, wherein the composition is introduced into the reactor via vapor draw or bubbling.

18. 15. The method of claim 14, wherein the composition is introduced into the reactor via vapor draw or bubbling.

19. 1. A method for depositing a carbon-doped silicon oxide film having a carbon content ranging from 5 atomic % to 20 atomic % using a thermal ALD process and a hydrogen-containing plasma, comprising: a. placing one or more substrates including a surface into a reactor; b. heating the reactor to one or more temperatures ranging from ambient temperature to about 550° C., and optionally maintaining said reactor at a pressure of about 100 torr or less; c. introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and a solvent selected from the group consisting of mesitylene, 2-methyl-nonane, 1,2,4,5-tetramethylpiperazine, ethoxy-benzene, and 1-ethyl-4-methyl-benzene into the reactor to form a film on the surface; d. purging the reactor with an inert gas to remove any unreacted components; e. introducing a nitrogen source into the reactor to react with the film to form a carbon-doped silicon nitride film; f. purging the reactor with an inert gas to remove any reaction by-products; g. repeating steps b through e to provide a carbon-doped silicon nitride film of a desired thickness; h. treating said carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from about ambient temperature to 1000° C. to convert said carbon-doped silicon nitride film to a carbon-doped silicon oxide film, either in situ or in a separate chamber; i. exposing the carbon doped silicon oxide film to a plasma comprising hydrogen; j) optionally treating the carbon doped silicon oxide film with either a spike anneal at a temperature between 400-1000° C. or a UV light source.

20. A composition for depositing a silicon-containing film, comprising: (a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane, (b) a solvent selected from the group consisting of mesitylene, 2-methyl-nonane, 1,2,4,5-tetramethylpiperazine, ethoxy-benzene, and 1-ethyl-4-methyl-benzene.

Images