Composition for carbon-doped silicon-containing film and method of using the same

Abstract

A composition and a method of using the composition in the manufacture of electronic devices are disclosed. Disclosed are methods for depositing low dielectric constant (llt; 4.0) and high oxygen ashing resistance silicon-containing films, such as, but not limited to, carbon doped silicon oxides.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 341,635, filed on May 13, 2022. Field of the Invention

[0003] Compositions and methods for making electronic devices are described herein. More specifically, compounds and compositions and methods containing the compounds are described herein for depositing low dielectric constant (<4.0) and high oxygen ash resistance silicon-containing films such as, but not limited to, carbon-doped silicon oxide, carbon-doped silicon nitride, carbon-doped silicon oxynitride. Background of the Invention

[0005] There is a need in the art to provide a composition and method of using the composition to deposit high carbon content (eg, about 10 at. % or more carbon content as measured by X-ray photoelectron spectroscopy (XPS)) doped silicon-containing films for certain applications in the electronics industry.

[0006] US Patent No. 8,575,033 describes a method for depositing a silicon carbide film on a substrate surface. The method includes using a gas phase carbosilane precursor and may employ a plasma enhanced atomic layer deposition process.

[0007] U.S. Publication No. 2013 / 022496A teaches a method for forming a dielectric film having Si-C bonds on a semiconductor substrate by atomic layer deposition (ALD), comprising: (i) adsorbing a precursor on the surface of the substrate; (ii) reacting the adsorbed precursor and a reaction 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.

[0008] PCT Publication No. WO14134476 A1 describes methods for depositing films comprising SiCN and SiOCN. Some methods include exposing a substrate surface to first and second precursors, the first precursor having the formula (X y H 3-y Si) z CH 4-z 、(X y H 3-y Si)(CH2)(SiX p H 2-p )(CH2)(SiX y H 3-y ) or (X y H 3-y Si)(CH2) n (SiX y H 3-y), wherein X is a halogen, y has a value between 1 and 3, z has a value between 1 and 3, p has a value between 0 and 2, n has a value between 2 and 5, and the second precursor comprises a reduced amine. Certain methods further comprise exposing the substrate surface to an oxygen source to provide a film comprising carbon-doped silicon oxide.

[0009] 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" US Publication No. 2014 / 287596A describes a method for manufacturing a semiconductor device, comprising forming a film containing silicon, oxygen and carbon on a substrate by performing a predetermined number of cycles, the cycle comprising: supplying a precursor gas containing silicon, carbon and a halogen element 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.

[0010] Hirose, Y., Mizuno, N., Yanagita, K., and Okubo, S. (2014) "Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium." US Patent No. 9,343,290B describes a method of manufacturing a semiconductor device, comprising forming an oxide film on a substrate by performing a predetermined number of cycles. The cycle includes supplying a precursor gas to the substrate; and supplying ozone gas to the substrate. In the action of supplying the precursor gas, the precursor gas is supplied to the substrate in a state where a catalytic gas is not supplied to the substrate, and in the action of supplying the ozone gas, the ozone gas is supplied to the substrate in a state where an amine-based catalytic gas is supplied to the substrate.

[0011] US Patent No. 9,349,586B discloses a thin film having desirable etching resistance and low dielectric constant.

[0012] US Publication No. 2015 / 0044881A describes a method for forming a film containing carbon added at a high concentration 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 and oxygen. The cycle includes supplying a precursor gas containing at least two silicon atoms per mole, carbon and a halogen element, and having a Si-C bond with the substrate, and supplying a modifying gas containing the predetermined element to the substrate.

[0013] Reference entitled "Highly Stable Ultrathin Carbosiloxane Films by Molecular Layer Deposition", Han, Z. et al., Journal of Physical Chemistry C, 2013, 117, 19967 teaches the growth of carbosiloxane films using 1,2-bis[(dimethylamino)dimethylsilyl]ethane and ozone. Thermal stability shows that the film is stable up to 40°C, with little thickness loss at 60°C.

[0014] Liu et al., Jpn. J. Appl. Phys., 1999, Vol. 38, 3482-3486, teach the application of H2 plasma on polysilsesquioxane deposited by spin coating technique. H2 plasma provides stable dielectric constant and improves film thermal stability and O2 ashing (plasma) treatment.

[0015] Kim et al., Journal of the Korean Physical Society, 2002, Vol. 40, 94, taught that H2 plasma treatment on PECVD carbon-doped silicon oxide films increased the leakage current density (4-5 orders of magnitude) while increasing the dielectric constant from 2.2 to 2.5. The carbon-doped silicon oxide film after H2 plasma was less damaged during the oxygen ashing process.

[0016] Posseme et al., Solid State Phenomena, 2005, Vol. 103-104, 337, teach different H2 / inert plasma treatments of carbon-doped silicon oxide PECVD films. After H2 plasma treatment, k did not increase, indicating no bulk modification.

[0017] 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 key 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 manufactured in high purity and 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

[0019] The compositions described herein meet these criteria. The compositions and methods described herein overcome the problems of the prior art by providing a composition or formulation for depositing a conformal silicon-containing film having one or more of the following properties: i) a dielectric constant of less than 4.0; ii) an etch rate as measured in dilute hydrofluoric acid (e.g., in a 1:99 dilution of HF); ) is the thermal silicon oxide etch rate (e.g., in a 1:99 diluted HF ) at most 0.5 times greater than ... ) quantifies oxygen ashing resistance. Oxygen ashing resistance is also exemplary when the film dielectric constant remains below 4.0 after an O2 ashing process. The desirable properties that can be achieved with the present invention are illustrated in more detail in the following examples.

[0020] In a specific embodiment, the compositions described herein can be used in a method of depositing a carbon-doped silicon oxide film using thermal atomic layer deposition (ALD).

[0021] 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 mesitylene (boiling point 165°C), 2-methyl-nonane (boiling point 167°C), 1,2,4,5-tetramethylpiperazine (boiling point 166°C), ethoxybenzene (boiling point 171°C) and 1-ethyl-4-methylbenzene (boiling point 162°C).

[0022] 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.

[0023] In another aspect, a method of forming a carbon-doped silicon oxide film having a carbon content ranging from 15 at.% to 30 at.% by a thermal ALD process is disclosed, the method comprising: a) placing one or more substrates comprising 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 100 Torr or less; c) introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene into the reactor; d) purging with an inert gas; e) introducing a heat treatment agent into the reactor; and f) purging with an inert gas to remove reaction byproducts; g) repeating steps c to 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 approximately ambient temperature to about 1000° C. or, according to one embodiment, from about 100° C. to about 400° C. to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film; and exposing the carbon-doped silicon oxide film to a plasma comprising hydrogen.

[0024] In yet another aspect, a method for forming a carbon-doped silicon oxide film having a carbon content ranging from 15 at.% to 30 at.% by a thermal ALD process is disclosed, the method comprising: a) placing one or more substrates comprising surface features into a reactor; b) heating the reactor to one or more temperatures 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 the reactor; d) purging the reactor with an inert gas; e) providing 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 byproducts, and repeating steps c) to f) to provide a carbon-doped silicon oxide film of a desired thickness.

[0025] In yet another aspect, a stainless steel container containing the composition of the present invention is disclosed.

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

[0028] Figure 1An overlay of vapor pressure curves for 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene is shown;

[0029] Figure 2 Illustrated is 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 container during vapor pump delivery; square symbols indicate the concentration curve when the container is maintained at 70°C; circle symbols indicate the concentration curve when the container is maintained at 80°C.

[0030] Figure 3 Concentrations of common stainless steel metals are shown, and the graph shows an analysis of a 20 wt % solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene stored in a stainless steel commercial container; and

[0031] Figure 4 Shown is the growth per cycle (GPC) of film deposition for a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene. DETAILED DESCRIPTION OF THE INVENTION

[0033] Described herein are compositions and methods for depositing carbon-doped (e.g., having a carbon content of about 10 at.% or more as measured by XPS) silicon-containing films by 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 extremely low etch rates, such as at least 0.5 times lower than thermal silicon oxide etch rates measured in dilute hydrofluoric acid, for example, about 0.5% by weight in dilute HF (0.5 wt.%, i.e., 1:99 diluted HF). or lower or about or less, or at most 0.1 times the etch rate of thermal silicon oxide Or up to 0.05 times the etch rate of thermal silicon oxide Or up to 0.01 times the etch rate of thermal silicon oxide, while exhibiting variability in other tunable properties such as, but not limited to, density, dielectric constant, refractive index, and elemental composition.

[0034] In certain embodiments, the silicon precursors and methods of using the same as described herein impart one or more of the following features in the following manner. First, a reactive carbon-doped silicon nitride film deposited as is is formed using a silicon precursor and a nitrogen source comprising two Si-C-Si bonds. Without wishing to be bound by any theory or explanation, it is believed that some Si-C-Si bonds from the silicon precursor remain in the resulting as-deposited film and provide a high carbon content of at least 10 at.% or more (e.g., about 20 to about 30 at.%, about 10 to about 20 at.%, and in some cases, about 10 to about 15 at.% carbon) as measured by XPS. Secondly, 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 in combination thereof, at least a portion or all of the nitrogen content in the film is converted into oxygen to provide a film selected from carbon-doped silicon oxide or carbon-doped silicon oxynitride film. The nitrogen in the as-deposited film is released as one or more nitrogen-containing byproducts, such as ammonia or amine groups.

[0035] 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 in 0.5 wt. % dilute hydrofluoric acid of about or smaller.

[0036] In one aspect, a composition for depositing a silicon-containing film comprises: (a) 1,1,3,3-tetrachloro-1,3-disilacyclobutane; and (b) mesitylene. In some embodiments, the composition can be delivered to a reaction chamber for a silicon-containing film by direct liquid injection using conventional direct liquid injection equipment and methods. Depending on the selected solvent, the concentration of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in the solvent can range from 1 wt % to 90 wt %, preferably from 10 wt % to 80 wt %, and most preferably from 15 wt % to 60 wt %.

[0037] Mesitylene is the best solvent for the composition because its normal boiling point is 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 similarity in volatility of the chlorosilane chemistry and the solvent ensures that the composition of the vapor stream and the composition of the liquid formulated product remain constant as the formulated product is depleted during vapor phase delivery. This constancy of the liquid and vapor phase compositions of the formulated product is important to ensure a reliable, robust deposition process. Mesitylene is also hydrophobic and can therefore be easily dried by practical known methods, such as treatment with molecular sieves, to produce a solvent with less than 10 ppm water or preferably less than 5 ppm water. When chlorosilanes such as 1,1,3,3-tetrachloro-1,3-disilacyclobutane are dissolved in a solvent, it is critical to achieve such a low water content because this will minimize the amount of acidic byproducts (such as HCl) formed. Eliminating or reducing trace amounts of HCl in the final blended product is critical to obtaining a formulated product that is compatible with common container construction materials such as stainless steel.

[0038] In another aspect, a method for depositing a film selected from a carbon-doped silicon oxide film and a carbon-doped silicon oxynitride film onto at least one surface of a substrate is provided, comprising: placing the substrate in a reactor; heating the reactor to one or more temperatures in the range of about 25°C to about 550°C; introducing a formulation comprising (a) 1,1,3,3-tetrachloro-1,3-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 a carbon-doped silicon nitride film; and treating the carbon-doped silicon nitride film with an oxygen source at one or more temperatures in the range of about 25°C to 1000°C or about 100°C to 400°C under conditions sufficient to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film or a carbon-doped silicon oxynitride film. In certain embodiments, the carbon-doped silicon oxide film or carbon-doped 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 at most 0.5 times the etch rate of thermal silicon oxide as measured in dilute hydrofluoric acid. If desired, the present invention further includes treating the carbon-doped silicon-containing film with hydrogen or hydrogen / inert plasma at 25° C. to 600° C.

[0039] In certain embodiments, the silicon-containing film comprises silicon and nitrogen. In these embodiments, the silicon-containing film deposited using the methods described herein is formed in the presence of a nitrogen-containing source. The nitrogen-containing source can be introduced into the reactor in the form of at least one nitrogen source and / or can be incidentally present in other precursors used in the deposition process.

[0040] Suitable nitrogen-containing or nitrogen source gases can include, for example, ammonia, ammonia plasma, hydrazine, monoalkylhydrazine, symmetrical or unsymmetrical dialkylhydrazine, organic amines such as methylamine, ethylamine, ethylenediamine, ethanolamine, piperazine, N,N'-dimethylethylenediamine, imidazolidine, cyclotrimethylenetriamine, and combinations thereof.

[0041] In another aspect, a method for forming a carbon-doped silicon oxide film having a carbon content ranging from 15 at.% to 30 at.% by a thermal ALD process is provided, the method comprising: a) placing one or more substrates comprising 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 comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene into the reactor; d) purging with an inert gas; e) introducing a heat-sensitive adhesive into the reactor; and The invention relates to a method for forming a carbon-doped silicon nitride film by providing a nitrogen source in a reactor to react with 1,1,3,3-tetrachloro-1,3-disilacyclobutane; f) purging with an inert gas to remove reaction byproducts; g) repeating steps c to f to provide a carbon-doped silicon nitride film of a desired thickness; h) treating the obtained carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from approximately ambient temperature to about 1000° C. or from about 100° C. to about 400° C. to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film; and exposing the carbon-doped silicon oxide film to a plasma containing hydrogen after deposition.

[0042] In yet another embodiment, a method for forming a carbon-doped silicon oxide film having a carbon content in a range of 15 at.% to 30 at.% by a thermal ALD process is provided, the method comprising: a) placing one or more substrates comprising surface features into a reactor; b) heating the reactor to one or more temperatures 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 the reactor; d) purging with an inert gas; e) providing water vapor into the reactor to react with 1,1,3,3-tetrachloro-1,3-disilacyclobutane in the presence of the catalyst to form an as-deposited carbon-doped silicon oxide film; and f) purging with an inert gas to remove reaction byproducts, wherein steps c) to f) are repeated to provide a carbon-doped silicon oxide film of a desired thickness.

[0043] In one embodiment of the method described herein, a carbon-doped silicon oxide film having a carbon content ranging from 5 at.% to 20 at.% is deposited using a thermal ALD process and a plasma containing hydrogen to improve the properties of the film. In this embodiment, the method comprises:

[0044] a. placing one or more substrates comprising surface features into a reactor;

[0045] b. heating the reactor to one or more temperatures in the range of ambient temperature to about 550° C., and optionally maintaining the reactor at a pressure of 100 Torr or less;

[0046] c. introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene as a silicon precursor into a reactor;

[0047] d. purging with an inert gas to remove unreacted silicon precursor and form a composition comprising a purge gas and a silicon precursor;

[0048] e. providing a nitrogen source to the reactor to react with the silicon precursor to form a carbon-doped silicon nitride film;

[0049] f. purging with an inert gas to remove reaction by-products;

[0050] g. Repeat steps c to f to provide a carbon-doped silicon nitride film of the desired thickness;

[0051] h. providing a post-deposition treatment of the carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from approximately ambient temperature to 1000° C. or from about 100° C. to 400° C. to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film in situ or in another chamber; and

[0052] i. providing a post-deposition exposure of the carbon-doped silicon oxide film to a plasma containing hydrogen to improve film properties, thereby improving at least one property of the film;

[0053] j. Optionally, the carbon-doped silicon oxide film is post-deposition treated with a spike anneal at a temperature of 400 to 1000° C. or with a UV light source. In this or other embodiments, the UV exposure step can be performed during film deposition or immediately after deposition is complete.

[0054] In one embodiment, the substrate includes at least one feature, wherein the feature comprises a patterned trench having an aspect ratio of 1:9 and an opening of 180 nanometers.

[0055] In another embodiment, a method for depositing a carbon-doped silicon oxide film having a carbon content ranging from 5 at.% to 20 at.% is disclosed, which uses a thermal ALD process and a plasma containing hydrogen to improve the properties of the film. In this embodiment, the method includes the following steps:

[0056] a. placing one or more substrates comprising surface features into a reactor;

[0057] b. heating the reactor to one or more temperatures in the range of ambient temperature to about 550° C., and optionally maintaining the reactor at a pressure of 100 Torr or less;

[0058] c. introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and a solvent selected from mesitylene, 2-methyl-nonane, 1,2,4,5-tetramethylpiperazine, ethoxybenzene and 1-ethyl-4-methylbenzene into a reactor;

[0059] d. purging with an inert gas to remove unreacted silicon precursor and form a composition comprising a purge gas and a silicon precursor;

[0060] e. providing a nitrogen source to the reactor to react with the surface to form a carbon-doped silicon film;

[0061] f. purging with an inert gas to remove reaction by-products;

[0062] g. Repeat steps c to f to provide a carbon-doped silicon nitride film of the desired thickness;

[0063] h. providing a post-deposition treatment of the carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from approximately ambient temperature to 1000° C. or from about 100° C. to 400° C. to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film in situ or in another chamber; and

[0064] i. providing a post-deposition exposure of the carbon-doped silicon oxide film to a plasma comprising hydrogen to improve at least one property of the film; and

[0065] j. Optionally, the carbon-doped silicon oxide film is post-deposition treated with a spike anneal at a temperature of 400 to 1000° C. or a UV light source. In this or other embodiments, the UV exposure step can be performed during film deposition or immediately after deposition is complete.

[0066] In an embodiment of the method described herein, a carbon-doped silicon oxide film having a carbon content ranging from 15 at.% to 30 at.% is deposited using a thermal ALD process and a plasma containing hydrogen to improve the properties of the film. In this embodiment, the method comprises:

[0067] a. placing one or more substrates comprising surface features into a reactor (e.g., into a conventional ALD reactor);

[0068] b. heating the reactor to one or more temperatures in the range of ambient temperature to about 550° C., and optionally maintaining the reactor at a pressure of 100 Torr or less;

[0069] c. introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene into a reactor;

[0070] d. Purge with inert gas;

[0071] 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;

[0072] f. purging with an inert gas to remove reaction by-products;

[0073] g. Repeat steps c to f to provide a carbon-doped silicon nitride film of the desired thickness;

[0074] h. providing a post-deposition treatment of the carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from approximately ambient temperature to 1000° C. or from about 100° C. to 400° C. to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film in situ or in another chamber;

[0075] i. providing a post-deposition exposure of the carbon-doped silicon oxide film to a plasma comprising hydrogen to improve at least one physical property of the film; and

[0076] j. Optionally, the carbon-doped silicon oxide film is post-deposition treated with thermal annealing at a temperature of 400 to 1000° C. or a UV light source.

[0077] In this or other embodiments, the UV exposure step may be performed during film deposition or once deposition is complete.

[0078] In yet another embodiment of the methods described herein, a 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:

[0079] a. placing one or more substrates comprising surface features into a reactor;

[0080] 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;

[0081] c. introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane, mesitylene and a catalyst into a reactor;

[0082] d. Purge with inert gas;

[0083] e. providing 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;

[0084] f. purging with an inert gas to remove reaction by-products;

[0085] g. Repeat steps c to f to provide a carbon-doped silicon oxide film of the desired thickness;

[0086] h. providing a post-deposition exposure of the film to a plasma comprising hydrogen to improve at least one property of the film; and

[0087] i. Optionally, the carbon-doped silicon oxide film is post-deposition treated with a spike anneal at a temperature of 400 to 1000° C. or a UV light source. In this or other embodiments, the UV exposure step can be performed during film deposition or once deposition is complete.

[0088] In this or other embodiments, the catalyst is selected from Lewis bases such as pyridine, piperazine, ammonia, triethylamine or other organic amines. The amount of Lewis base vapor is at least one equivalent of the amount of silicon precursor vapor during step c.

[0089] In certain embodiments, 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 hydrophobic thin layer prior to exposure to hydrogen plasma treatment. Suitable organoaminosilanes include, but are not limited to, diethylaminotrimethylsilane, dimethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, tert-butylaminotrimethylsilane, isopropylaminotrimethylsilane, diisopropylaminotrimethylsilane, pyrrolidinyltrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, ethylmethylaminodimethylsilane, tert-butylaminodimethylsilane, isopropylaminodimethylsilane, diisopropylaminodimethylsilane, pyrrolidinyldimethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)dimethylsilane, bis(ethylmethylamino)dimethylsilane, bis(diisopropylamino)dimethylsilane, bis(isopropylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane , dipyrrolidinodimethylsilane, bis(diethylamino)diethylsilane, bis(diethylamino)methylvinylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylmethylamino)methylvinylsilane, bis(diisopropylamino)methylvinylsilane, bis(isopropylamino)methylvinylsilane, bis(tert-butylamino)methylvinylsilane, dipyrrolidinodimethylvinylsilane, 2,6-dimethylpiperidinylmethylsilane, 2,6-dimethylpiperidinyldimethylsilane, 2,6-dimethylpiperidinyltrimethylsilane, tris(dimethylamino)phenylsilane, tris(dimethylamino)methylsilane, diisopropylaminosilane, di-sec-butylaminosilane, chlorodimethylsilane, chlorotrimethylsilane, dichloromethylsilane and dichlorodimethylsilane.

[0090] 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 to form a hydrophobic thin layer prior to exposure to hydrogen plasma treatment. Suitable alkoxysilanes or cyclic alkoxysilanes include, but are not limited to, diethoxymethylsilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxymethylsilane, 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 the organoaminosilane or alkoxysilane or cyclic alkoxysilane can be converted into a dense carbon-doped silicon oxide during plasma ashing, thereby further improving ashing resistance.

[0091] In another embodiment, a container for depositing a silicon-containing film comprising one or more silicon precursor compounds described herein. In a specific embodiment, the container comprises at least one pressurizable container (preferably a stainless steel pressurizable container having a design as disclosed in U.S. Patent Nos. US7334595; US6077356; US5069244; and US5465766, the disclosures of which are incorporated herein by reference). The container may comprise glass (borosilicate or quartz glass) or 316, 316L, 304 or 304L type stainless steel alloy (UNS designations S31600, S31603, S30400, S30403), which is equipped with suitable valves and fittings to allow one or more precursors to be delivered to a reactor for a CVD or ALD process. In this or other embodiments, the silicon precursor is provided in a pressurizable container composed of stainless steel, and the purity of the precursor is 98 wt% or more or 99.5 wt% or more, which is suitable for semiconductor applications. The silicon precursor compound is preferably substantially free of metal ions such as Al 3+ Ion, Fe 2+ , Fe 3+ 、Ni 2+ Cr 3+ As used herein, when referring to Al 3+ Ion, Fe 2+ , Fe 3+ 、Ni 2+ Cr 3+ When, the term "substantially free" refers to less than about 5ppm (weight), preferably less than about 3ppm, more preferably less than about 1ppm, and most preferably about 0.1ppm. In some embodiments, if necessary, this container can also have a device for mixing the precursor with one or more other precursors. In these or other embodiments, the contents of the container can be premixed with other precursors. Alternatively, the silicon precursor and / or other precursors can be stored in a separate container, or stored in a single container with a separation device for keeping the silicon precursor and other precursors separated during storage.

[0092] The silicon-containing film is deposited on at least one surface of a substrate (such as a semiconductor substrate). In the methods described herein, the substrate can be composed of and / or coated with a variety of materials known in the art, including silicon (such as crystalline silicon or amorphous silicon), silicon oxide, silicon nitride, amorphous carbon, silicon oxycarbide, 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 films of combinations thereof. These coatings can completely coat the semiconductor substrate, can be multiple layers of various materials, and can be partially etched to expose the underlying material layer. The surface can also have a photoresist material thereon, which has been exposed and developed with a pattern to partially coat the substrate. In some embodiments, the semiconductor substrate comprises at least one surface feature selected from a hole, a through hole, a groove and a combination thereof. Potential applications of silicon-containing films include, but are not limited to, low-k spacers for FinFETs or nanosheets, sacrificial hard masks for self-aligned patterning processes such as SADP, SAQP, or SAOP.

[0093] The deposition method for forming a silicon-containing film or coating is a deposition process. Examples of deposition processes suitable 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 deposition process" refers to any process in which a substrate is exposed to one or more volatile precursors, which 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 of a film of a material deposited on a substrate of different compositions. As used herein, the term "thermal atomic layer deposition process" refers to an atomic layer deposition process at a substrate temperature ranging from room temperature to 600° C. in the absence of an in-situ or remote plasma. Although the precursors, reagents, and sources used herein may sometimes be described as "gaseous", it should be understood that the precursor may be a liquid or solid, which may be delivered to the reactor by direct evaporation, bubbling, or sublimation with or without an inert gas. In some cases, the vaporized precursor may be passed through a plasma generator.

[0094] 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.

[0095] In certain embodiments, the method disclosed herein avoids the pre-reaction of the precursor by using an ALD or CCVD method that separates the precursor before and / or during the introduction into the reactor. In this regard, a deposition technique such as an ALD or CCVD process is used to deposit a silicon-containing film. In one embodiment, in a typical single-wafer ALD reactor, a semi-batch ALD reactor or a batch furnace ALD reactor, a film is deposited via an ALD process by alternately exposing the substrate surface to one or more silicon-containing precursors, an oxygen source, a nitrogen-containing source or other precursors or reagents. Film growth is carried out by self-limiting control of the surface reaction, the pulse length of each precursor or reagent, and the deposition temperature. However, once the substrate surface is saturated, film growth stops. In another embodiment, by moving or rotating the substrate to different sections of the reactor, each reactant including a silicon precursor and a reactive gas is exposed to the substrate, and each section is separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0096] Depending on the deposition method, in certain embodiments, the silicon precursors described herein and optional other silicon-containing precursors can 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 can be introduced into the reactor for a predetermined time period. In certain embodiments, the time period ranges from about 0.001 seconds to about 500 seconds.

[0097] In some embodiments, the silicon-containing film deposited using the methods described herein is formed in the presence of a catalyst in combination with an oxygen source, a reagent or an oxygen-containing precursor (i.e., water vapor). The oxygen source can be introduced into the reactor in the form of at least one oxygen source, and / or can be incidentally present in other precursors used in the deposition process. Suitable oxygen source gases can include, for example, water (H2O) (e.g., deionized water, purified water, distilled water, water vapor, water vapor plasma, oxygenated water, air, a composition comprising water and other organic liquids), oxygen (O2), oxygen plasma, ozone (O3), nitric oxide (NO), nitrogen dioxide (NO2), carbon monoxide (CO), plasma comprising water, plasma comprising water and argon, hydrogen peroxide, a composition comprising hydrogen, a composition comprising hydrogen and oxygen, carbon dioxide (CO2), air and combinations thereof. In some embodiments, the oxygen source comprises an oxygen source gas introduced into the reactor at a flow rate ranging from about 1 to about 10000 square centimeters (sccm) or from about 1 to about 1000sccm. The oxygen source can be introduced into the 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.

[0098] In embodiments where the film is deposited by an ALD or cyclic CVD process, the pulse duration of the precursor pulse may be greater than 0.01 seconds, the pulse duration of the oxygen source may be less than 0.01 seconds, and the water pulse duration may be less than 0.01 seconds.

[0099] In certain embodiments, the oxygen source flows continuously into the reactor while the precursor pulse and plasma are sequentially introduced. The precursor pulse may have a pulse duration greater than 0.01 seconds, while the plasma duration may be in the range of 0.01 seconds to 100 seconds.

[0100] In certain embodiments, the silicon-containing film comprises silicon and nitrogen. In these embodiments, the silicon-containing film deposited using the methods described herein is formed in the presence of a nitrogen-containing source. The nitrogen-containing source can be introduced into the reactor in the form of at least one nitrogen source and / or can be incidentally present in other precursors used in the deposition process.

[0101] Suitable nitrogen-containing or nitrogen source gases may include, for example, ammonia, hydrazine, monoalkylhydrazine, symmetrical or unsymmetrical dialkylhydrazine, organic amines such as methylamine, ethylamine, ethylenediamine, ethanolamine, piperazine, N,N'-dimethylethylenediamine, imidazolidine, cyclotrimethylenetriamine, and combinations thereof.

[0102] In certain embodiments, the nitrogen source is introduced into the reactor at a flow rate ranging from about 1 to about 10,000 square 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 greater 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 another embodiment, the purge duration between pulses can be as low as 0 seconds, or continuous pulses without intermediate purges.

[0103] The deposition method disclosed herein may involve one or more purge gases. The purge gas used to purge unconsumed reactants and / or reaction byproducts is an inert gas that does not react with the precursor. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2) and combinations thereof. In certain embodiments, a purge gas such as Ar is supplied to the reactor at a flow rate ranging from about 10 to about 10000 sccm for about 0.1 to 1000 seconds to purge unreacted materials and any byproducts that may remain in the reactor.

[0104] The corresponding steps of supplying precursors, oxygen sources, nitrogen-containing sources and / or other precursors, source gases and / or reagents can be performed to change the stoichiometric composition of the resulting film by changing the time of supplying the precursors, oxygen sources, nitrogen-containing sources and / or other precursors, source gases and / or reagents.

[0105] Energy is applied to at least one of the precursor, nitrogen-containing source, reducing agent, other precursors, or a combination thereof to initiate a reaction and form a film or coating on the substrate. Such energy may 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.

[0106] In certain embodiments, a secondary RF frequency source may be used to alter the plasma characteristics at the substrate surface. In embodiments where deposition involves plasma, the plasma generation process may include a direct plasma generation process, where the plasma is generated directly in the reactor, or alternatively a remote plasma generation process, where the plasma is generated external to the reactor and supplied to the reactor.

[0107] Throughout the specification, the term "ALD or ALD-like" refers to a process including but not limited to the following processes: a) each reactant including a silicon precursor and a reaction gas is sequentially introduced into a reactor, such as a single wafer ALD reactor, a semi-batch ALD reactor or a batch furnace ALD reactor; b) each reactant including a silicon precursor and a reaction gas is exposed to a substrate by moving or rotating the substrate to different sections of the reactor, and each section is separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0108] 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 optional embodiment, a combined liquid delivery and flash process unit can be used, for example, a turbo evaporator manufactured by MSP Corporation of Shoreview, MN, to enable quantitative delivery of low-volatility materials, which results in reproducible delivery and deposition without thermal decomposition of the precursor. In the liquid delivery mode, the precursors described herein can be delivered in neat liquid form, or alternatively can be used in a solvent formulation or composition comprising the precursor. Therefore, in certain embodiments, the precursor formulation can include a solvent component of suitable properties, such as may be desirable and advantageous for forming a film on a substrate in a given end-use application.

[0109] In this or other embodiments, it should be understood that the steps of the methods described herein can be performed in a variety of orders, can be performed sequentially or simultaneously (e.g., during at least a portion of another step), and in any combination thereof. The respective steps of supplying the precursor and nitrogen-containing source gas can be performed by changing the duration of supplying them to change the stoichiometric composition of the resulting silicon-containing film.

[0110] In still further embodiments of the methods described herein, the film or the as-deposited film is subjected to a treatment step. The treatment step may 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) light treatment; laser; electron beam treatment, and combinations thereof to affect one or more properties of the film. When compared to films deposited with previously disclosed silicon precursors under the same conditions, 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 lower wet etch rate than the film prior to the treatment step or a higher density than prior to the treatment step. In a specific embodiment, the as-deposited film is treated intermittently during the deposition process. These intermittent or mid-deposition treatments may be performed, for example, after each ALD cycle, after a certain number of ALD cycles, such as, but not limited to, one (1) ALD cycle, two (2) ALD cycles, five (5) ALD cycles, or after every ten (10) or more ALD cycles.

[0111] In embodiments where the film is treated with a high temperature annealing step, the annealing temperature is at least 100° C. or more above the deposition temperature. In this or other embodiments, the annealing temperature is in the range of 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 (such as H2O, N2O, NO2, or O2).

[0112] In embodiments where the film is UV treated, the film is exposed to broadband UV, or a UV source having a wavelength range of about 150 nanometers (nm) to about 400 nm. In a specific embodiment, after the desired film thickness is achieved, the as-deposited film is exposed to UV in a chamber different from the deposition chamber.

[0113] In embodiments where the film is treated with plasma, a passivation layer such as SiO2 or carbon-doped SiO2 is deposited to prevent chlorine and nitrogen contamination from penetrating the film during subsequent plasma treatment. The passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

[0114] In embodiments where the film is treated with plasma, the plasma source is selected from hydrogen plasma, plasma containing hydrogen and helium, plasma containing hydrogen and argon. Hydrogen plasma reduces the film dielectric constant and improves damage resistance to subsequent plasma ashing processes while still keeping the carbon content in the bulk almost unchanged.

[0115] Throughout the specification, the term "ALD or ALD-like" refers to a process including but not limited to the following processes: a) each reactant including a silicon precursor and a reaction gas is sequentially introduced into a reactor, such as a single wafer ALD reactor, a semi-batch ALD reactor or a batch furnace ALD reactor; b) each reactant including a silicon precursor and a reaction gas is exposed to a substrate by moving or rotating the substrate to different sections of the reactor, and each section is separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0116] Throughout the specification, the term "ashing" refers to the process of removing photoresist or carbon hard mask using plasma in a semiconductor manufacturing process, wherein the plasma contains an oxygen source such as O2 / inert gas plasma, O2 plasma, CO2 plasma, CO plasma, H2 / O2 plasma or a combination thereof.

[0117] Throughout this specification, the term "damage resistance" refers to the film properties after the oxygen ashing process. Good or high damage resistance is defined as the following film properties after oxygen ashing: film dielectric constant below 4.5; carbon content in the bulk (more than 1% in the film) Depth) within 5at.% before ashing; through near surface (less than depth) and body (greater than The difference in dilute HF etching rate between films with depths of less than The membrane is damaged.

[0118] Throughout the specification, the term "alkyl hydrocarbon" refers to a linear or branched C1 to C 20 Hydrocarbons, cyclic C6 to C 20 Hydrocarbons. Exemplary hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

[0119] Throughout the specification, the term "aromatic hydrocarbons" refers to C6 to C 20 Aromatic hydrocarbons. Exemplary aromatic hydrocarbons include, but are not limited to, toluene and mesitylene.

[0120] Throughout the specification, the term "catalyst" refers to a Lewis base in the gas phase that can catalyze the surface reaction between hydroxyl groups and Si-Cl bonds during the thermal ALD process. Exemplary catalysts include, but are not limited to, at least one cyclic amine-based gas such as aminopyridine, picoline, lutidine, piperazine, piperidine, pyridine or an organic amine-based gas, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, and tert-butylamine.

[0121] Throughout the specification, the term "organic amine" refers to an organic amine having a C1 to C 20 Hydrocarbons, cyclic C6 to C 20 Primary amines, secondary amines, tertiary amines of hydrocarbons. Exemplary organic amines include, but are not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, and tert-butylamine.

[0122] Throughout the specification, the term "siloxane" refers to a siloxane having at least one Si-O-Si bond and C4 to C 20 A linear, branched or cyclic liquid compound of 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).

[0123] Throughout this specification, when the term "an etch rate that is at most x times the etch rate of thermal silicon oxide" is used, the value x is calculated by dividing the etch rate of the target silicon-containing film in 1:99 dilute HF by the etch rate of thermal silicon oxide in 1:99 dilute HF (e.g., ) calculation, both etching rates were measured under the same conditions.

[0124] As used throughout this specification, the term "step coverage" is defined as the percentage of two thicknesses of a deposited film in a structured or feature substrate having a via or trench or both, wherein the bottom step coverage is the ratio (in percentage) of the thickness at the bottom of the feature divided by the thickness at the top of the feature, and the intermediate step coverage is the ratio (in percentage) 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 a step coverage of about 80% or greater or about 90% or greater, indicating that the film is conformal.

[0125] The following examples illustrate certain aspects of the invention but do not limit the scope of the appended claims. Example

[0126] Example 1. A formulated product consisting of 20 wt. % 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene.

[0127] The formulation was prepared by dissolving 20% ​​by weight of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in mesitylene. Figure 1 An overlay of the vapor pressure curves of 1,1,3,3-tetrachloro-1,3-disilacyclobutane and mesitylene is shown, showing their similarity over the temperature range of interest.

[0128] Figure 2 The normalized concentrations of common stainless steel constituent metals such as iron, chromium, nickel, and manganese in a 20 wt% 1,1,3,3-tetrachloro-1,3-disilacyclobutane solution in mesitylene aged for the equivalent of 2 years at room temperature in a stainless steel container are shown. The fact that these common stainless steel metals do not increase systematically over time provides strong support that the formulated product consisting of a low water mesitylene component is compatible with stainless steel containers.

[0129] Figure 3 Plotted is 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 container as it is consumed during the vapor draw delivery process.

[0130] Concentration consistency was achieved 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 consisted of 200 grams of material in a 500 ml stainless steel vessel. The vessel was heated to 80°C and vapor extraction was used to deliver the chemicals. Film deposition was performed in a lab-scale atomic layer deposition (ALD) reactor using silicon precursors and ammonia as the nitrogen source. The ALD steps and process conditions are provided in Table 3 below:

[0131] Table 3: ALD cycle steps and process conditions

[0132]

[0133]

[0134] During the deposition process, repeat step 3 to 10 more cycles to obtain the desired thickness of as-deposited carbon-doped silicon nitride.

[0135] Gas chromatography was performed occasionally between runs to check solution concentrations.

[0136] like Figure 4 As shown, the film growth and / cycle / cycle. GC analysis was performed on the container between depositions. Tables 4 and 5 show the analysis performed at intervals during the deposition process when the solution container was heated to 80°C and 70°C, respectively. As shown in the tables, in either case, the precursor concentration was consistent throughout the deposition process.

[0137] Table 4. Solution concentrations of vessels heated and maintained at 80°C. Analyses were performed between runs. Starting weight was 200 grams.

[0138] Materials used (%) Silicon precursor concentration (wt%) 0％ 20.00％ 39％ 19.85％ 44％ 19.95％ 65％ 19.76％ 83％ 19.86％

[0139] Table 5. Solution concentrations of vessels heated and maintained at 70°C. Analyses were performed between runs. Starting weight was 200 grams.

[0140] Materials used (%) Silicon precursor concentration (wt%) 0％ 20.00％ 12％ 20.15％ 14％ 20.52％ 29％ 20.44％ 46％ 20.21％ 62％ 20.12％ 67％ 19.81％ 78％ 20.35％

[0141] Although the present invention has been described with reference to specific embodiments, it will be appreciated by those skilled in the art that various changes may be made without departing from the scope of the present invention, and that equivalent replacements may be made to its elements. In addition, many modifications may be made without departing from the basic scope of the present invention to adapt specific situations or materials to the teachings of the present invention. Therefore, it is intended that the present invention is not limited to the specific embodiments disclosed as the best mode for implementing the present invention, but that the present invention will include all embodiments falling within the scope of the appended claims.

Claims

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

2. The composition of claim 1, comprising less than 5 ppm of at least one selected from Al 3+ , Fe 2+ , Fe 3+ 、Ni 2+ and Cr 3+ of metal ions.

3. A method for forming a carbon-doped silicon oxide film by a thermal ALD process, the method comprising: a) placing one or more substrates into a reactor, each substrate comprising a surface including a surface feature; 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 to f to provide a carbon-doped silicon nitride film of desired thickness; h) treating the resulting carbon-doped silicon nitride film with an oxygen source at one or more temperatures in the range of approximately ambient temperature to about 1000° C. to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film; and i) exposing the carbon-doped silicon oxide film to plasma containing hydrogen.

4. A film formed according to the method of claim 3 having a k of less than about 4 and a carbon content of at least about 10 at. %.

5. A film formed by the method of claim 3, wherein the etching rate of the film in 1:99 dilute HF is at most 0.5 times the etching rate of thermal silicon oxide.

6. The film of claim 5, wherein the etch rate is at most 0.1 times the etch rate of thermal silicon oxide.

7. The film of claim 5, wherein the etch rate is at most 0.05 times the etch rate of thermal silicon oxide.

8. The film of claim 5, wherein the etch rate is at most 0.01 times the etch rate of thermal silicon oxide.

9. A film formed by the method of claim 3, having, after exposing the film to an oxygen ashing process: or smaller damage layer.

10. The film of claim 9, wherein after exposing the film to an oxygen ashing process, the damaged layer is or smaller.

11. The film of claim 9, wherein after exposing the film to an oxygen ashing process, the damaged layer is or smaller.

12. The film of claim 9, wherein after exposing the film to an oxygen ashing process, the damaged layer is or smaller.

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

14. A method for forming a carbon-doped silicon oxide film having a carbon content in the range of 15 at.% to 30 at.% by a thermal ALD process, the method comprising: a. placing one or more substrates comprising surface features into a reactor; b. heating the reactor to one or more temperatures in the range of 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 the reactor; d. purging the reactor with an inert gas; e. providing 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 film; and f. purging the reactor with an inert gas to remove any reaction by-products, wherein Steps c to f are repeated to provide the carbon-doped silicon oxide film with a desired thickness.

15. The method of claim 14, further comprising treating the carbon-doped silicon oxide film with thermal annealing at a temperature of 300 to 700°C. 16 . The method of claim 14 , further comprising treating the carbon-doped silicon oxide film with hydrogen plasma containing hydrogen.

17. The method of claim 3, wherein the composition is introduced into the reactor by vapor extraction or bubbling.

18. The method of claim 14, wherein the composition is introduced into the reactor by vapor extraction or bubbling.

19. A method of depositing a carbon-doped silicon oxide film having a carbon content in the range of 5 at.% to 20 at.% using a thermal ALD process and a plasma containing hydrogen, the method comprising the steps of: a. placing one or more substrates including a surface into a reactor; a. heating the reactor to one or more temperatures from ambient temperature to about 550° C., and optionally maintaining the reactor at a pressure of 100 Torr or less; b. introducing a composition comprising 1,1,3,3-tetrachloro-1,3-disilacyclobutane and a solvent selected from mesitylene, 2-methyl-nonane, 1,2,4,5-tetramethylpiperazine, ethoxybenzene and 1-ethyl-4-methylbenzene into the reactor to form a film on the surface; c. purging the reactor with an inert gas to remove any unreacted composition; d. introducing a nitrogen source into the reactor to react with the film to form a carbon-doped silicon nitride film; e. purging the reactor with an inert gas to remove any reaction byproducts; f. Repeating steps b to e to provide the carbon-doped silicon nitride film of the desired thickness; g. treating the carbon-doped silicon nitride film with an oxygen source at one or more temperatures in the range of from approximately ambient temperature to 1000° C. to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film in situ or in another chamber; and h. exposing the carbon-doped silicon oxide film to a plasma comprising hydrogen; and i. Optionally treating the carbon-doped silicon oxide film with a spike annealing at a temperature of 400 to 1000° C. or a UV light source.

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

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