Compositions for carbon doping silicon-containing films and methods of using the same

Abstract

Disclosed herein are compositions and methods of using the same in the fabrication of electronic devices.Disclosed are compounds, compositions and methods for depositing silicon-containing films (such as, but not limited to, carbon-doped silicon oxide) with low dielectric constant (<4.0) and high oxygen ash resistance.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Application No. 15 / 654,426 filed on July 19, 2017 and U.S. Provisional Application No. 62 / 367,260 filed on July 27, 2016. The disclosures of U.S. Application No. 15 / 654,426 and U.S. Provisional Application No. 62 / 367,260 are hereby incorporated by reference herein.

[0003] The subject matter of the present disclosure is related to Patent Cooperation Treaty Application No. PCT / US2016 / 016514, filed on February 4, 2016. The disclosure of Application No. PCT / US2016 / 016514 is incorporated herein by reference. Background Art

[0004] Described herein are compositions and methods for making electronic devices. More specifically, described herein are compounds and compositions and methods 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 films, carbon-doped silicon nitride films, and carbon-doped silicon oxynitride films.

[0005] There is a need in the art to provide compositions and methods of using the same for depositing high carbon content (e.g., carbon content of about 10 atomic % or greater 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 / 022496 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 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.

[0008] PCT Application No. WO14134476A1 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 yH 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, and n has a value between 2 and 5, and the second precursor comprises a reducing 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" U.S. Application No. 2014287596A describes a method of manufacturing a semiconductor device, which includes forming a film containing silicon, oxygen and carbon on a substrate by performing a predetermined number of cycles, the cycle including: providing a precursor gas containing silicon, carbon and halogen elements and having Si-C bonds, and a first catalytic gas to the substrate; and providing 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." U.S. Patent No. 9,343,290B describes a method of manufacturing a semiconductor device, which includes 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 an ozone gas to the substrate. In the process 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 process 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 desired etching resistance and low dielectric constant.

[0012] U.S. Publication No. 2015 / 0044881A describes a method for forming a film containing carbon added at a high concentration, which is formed 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 providing a precursor gas containing at least two silicon atoms per 1 mol, containing carbon and halogen elements, and having Si-C bonding to the substrate, and providing 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 use of 1,2-bis[(dimethylamino)dimethylsilyl]ethane and ozone to grow carbosiloxane films. 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 use of H2 plasma on polysilsesquioxane deposited by spin coating techniques. H2 plasma provides a 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 improved 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 on carbon-doped silicon oxide PECVD films. There is no improvement in k after H2 plasma treatment, indicating no bulk modification.

[0017] The disclosures of previously identified patents, patent applications, and publications are incorporated herein by reference. Summary of the invention

[0018] The compositions and methods described herein overcome the problems of the prior art by providing compositions or formulations for depositing conformal silicon-containing films having one or more of the following properties: i) a specific heat of silicon oxide as measured in dilute hydrofluoric acid (e.g., in 1:99 dilute HF); ) an etch rate at least 0.5 times lower, and a carbon content of about 10 atomic weight percent (atomic %) or more as measured by X-ray spectroscopy (XPS); ii) a lower sensitivity of the dielectric constant and wet etch rate in dilute HF (dHF) to damage during an oxygen ashing process or exposure to an oxygen plasma, the oxygen ashing resistance being able to be improved by O2 ashing followed by The desired properties that can be achieved by the present invention are described in more detail in the following examples.

[0019] 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).

[0020] In one aspect, a composition for depositing a silicon-containing film comprises: (a) at least one linear or cyclic silicon precursor compound listed in Tables 1 and 2 having one Si-C-Si or two Si-C-Si bonds.

[0021] Table 1. Silicon precursors with one Si-C-Si bond

[0022]

[0023] Table 2. Silicon precursors with two Si-C-Si bonds

[0024]

[0025]

[0026] In at least one aspect of the present invention, (b) at least one solvent is included. In certain embodiments of the compositions described herein, exemplary solvents may include, but are not limited to, ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, siloxanes, tertiary amino ethers, and combinations thereof. In certain embodiments, the difference between the boiling point of the silicon compound and the boiling point of the solvent is 40°C or less, less than about 30°C, and in some cases less than about 20°C, preferably less than 10°C.

[0027] In another aspect, there is provided 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, comprising:

[0028] placing the substrate in a reactor;

[0029] heating the reactor to one or more temperatures in the range of about 25°C to about 550°C;

[0030] introducing into a reactor a precursor comprising at least one compound selected from the group consisting of the silicon precursors listed in Tables 1 and 2, and combinations thereof;

[0031] 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

[0032] The carbon-doped silicon nitride film is treated with an oxygen source at one or more temperatures in the range of from about 25° C. to 1000° C. or from about 100° C. to 400° C. under conditions sufficient to transform the carbon-doped silicon nitride film into the film. In certain embodiments, the carbon-doped silicon oxide film or the carbon-doped silicon oxynitride film has a carbon content of about 10 atomic weight percent (atomic %) or greater as measured by XPS, and an etch rate at least 0.5 times lower than thermal silicon oxide as measured in dilute hydrofluoric acid.

[0033] If desired, the present invention also includes treating the carbon-doped silicon-containing film with hydrogen or hydrogen / inert plasma at 25°C to 600°C.

[0034] One aspect of the present invention relates to a composition comprising:

[0035] (a) at least one linear or cyclic silicon precursor compound having one Si-C-Si or two Si-C-Si bonds, selected from 1,1,1,3,3,3-hexachloro-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro- 2-ethyl-1,3-disilacyclopropane, 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,1,3-trichloro-1,3-disilacyclobutane, 1,1,3-tribromo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1 ,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bromo-1,3-dimethyl-1,3-disilacyclobutane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5,5 5-octachloro-1,5-dimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-3,3-dimethyl-1,3,5-trisilapentane, 1,1,3,5,5,5-pentachloro-1,3,5-trimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-1,3,5-trisilapentane, 1,1,5,5-tetrachloro-1,3,5-trisilapentane; and;

[0036] (b) at least one solvent.

[0037] Another aspect of the present invention relates to a method for forming a carbon-doped silicon oxide film having a carbon content ranging from 15 atomic % to 30 atomic % by a thermal ALD process, the method comprising:

[0038] a) placing one or more substrates comprising surface features into a reactor;

[0039] 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;

[0040] c) introducing into the reactor at least one silicon precursor having two Si-C-Si bonds, which is selected from the group consisting of 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,1,3-trichloro-1,3-disilacyclobutane, 1,1,3-tribromo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bromo-1,3-dimethyl-1,3 -disilacyclobutane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5,5-octachloro-1,5-dimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-3,3-dimethyl-1,3,5-trisilapentane, 1,1,3,5,5,5-pentachloro-1,3,5-trimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-1,3,5-trisilapentane, 1,1,5,5-tetrachloro-1,3,5-trisilapentane;

[0041] d) purging with inert gas;

[0042] e) providing a nitrogen source into the reactor to react with the surface to form a carbon-doped silicon nitride film;

[0043] f) purging with an inert gas to remove reaction by-products;

[0044] g) repeating steps c to f to provide a desired thickness of carbon-doped silicon nitride;

[0045] h) treating the resulting 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 to a carbon-doped silicon oxide film; and

[0046] i) providing a post-deposition treatment of exposing the carbon-doped silicon oxide film to a plasma comprising hydrogen.

[0047] In one aspect of the invention, the substrate comprises silicon or germanium doped silicon or boron doped silicon or a high-k material, and after depositing the carbon doped silicon oxide film of the invention, a film comprising silicon nitride or silicon oxide is deposited.

[0048] Another aspect of the invention relates to films having a k of less than about 4, a carbon content of at least about 10 atomic %, preferably 15 atomic % or greater, and most preferably 20 atomic % or greater, based on XPS measurements, and in another aspect, the films of the invention can be formed according to any of the methods of the invention. Since carbon content is an important factor for reducing wet etch rates and improving ashing resistance, the carbon content of the invention ranges from 10 atomic % to 40 atomic %, preferably 15 atomic % to 30 atomic %, and most preferably 20 atomic % to 35 atomic %, as measured by XPS.

[0049] Another aspect of the present invention relates to a stainless steel container containing the composition of the present invention.

[0050] The embodiments of the present invention can be used alone or in various combinations with each other. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 A comparison of the etch characteristics of 1,1,3,3,3-hexachloro-1,3-disilacyclopropane (HCDSP) and 1,1,3,3-tetrachloro-1,3-disilacyclobutane (TCDSB) carbon-doped silicon oxide films after plasma treatment followed by oxygen ashing is described, demonstrating that the carbon-doped silicon oxide film from TCDSB provides higher ashing resistance than the carbon-doped silicon oxide film from HCDSP. DETAILED DESCRIPTION

[0052] Described herein are silicon precursor compounds for depositing carbon-doped (e.g., carbon content of about 10 atomic % or greater as measured by XPS) silicon-containing films via deposition processes (e.g., but not limited to thermal atomic layer deposition processes), and compositions and methods comprising the silicon precursor compounds. Films deposited using the compositions and methods described herein exhibit extremely low etch rates, e.g., at least 0.5 times lower than the etch rate of thermal silicon oxide measured in dilute hydrofluoric acid (e.g., about 0.5% in dilute HF (0.5 wt%)). or lower or about or lower), or an etch rate at least 0.1 times lower than thermal silicon oxide, or an etch rate at least 0.05 times lower than thermal silicon oxide, or an etch rate at least 0.01 times lower than thermal silicon oxide, while exhibiting variability in other adjustable properties (such as but not limited to density, dielectric constant, refractive index, and elemental composition).

[0053] In certain embodiments, the silicon precursors and methods using the silicon precursors described herein impart one or more of the following features in the following manner. First, the reactive carbon-doped silicon nitride film thus deposited is formed using a silicon precursor and a nitrogen source comprising Si-C-Si bonds. Without wishing to be bound by any theory or explanation, it is believed that the Si-C-Si bonds from the silicon precursor remain in the resulting film thus deposited and provide 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 about 10 to about 15 atomic % carbon in some cases) as measured by XPS. Second, when the film thus deposited is exposed to an oxygen source (e.g., water) intermittently during the deposition process, as a post-deposition treatment, or as a 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 a carbon-doped silicon oxide film or a carbon-doped silicon oxynitride film. The nitrogen in the film thus deposited is released as one or more nitrogen-containing byproducts (e.g., ammonia or amine groups).

[0054] In this or other embodiments, the final membrane is porous and has a density of about 1.7 grams per cubic centimeter (g / cc) or less and a strength of 0.5 wt. % in dilute hydrogen fluoride. or lower etching rate.

[0055] In one aspect, a composition for depositing a silicon-containing film comprises: (a) at least one silicon precursor compound having one Si-C-Si or two Si-C-Si bonds selected from the group consisting of 1,1,1,3,3,3-hexachloro-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-di ... 3,3,3-hexachloro-2-ethyl-1,3-disilacyclopropane, 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,1,3-trichloro-1,3-disilacyclobutane, 1,1,3-tribromo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane 、1,1,3,3-tetrabromo-1,3-disilacyclobutane、1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane、1,3-bromo-1,3-dimethyl-1,3-disilacyclobutane、1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane、1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane、1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane、1,1,1,3,3,5,5,5-octachloro -1,5-dimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-3,3-dimethyl-1,3,5-trisilapentane, 1,1,3,5,5,5-pentachloro-1,3,5-trimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-1,3,5-trisilapentane, 1,1,5,5-tetrachloro-1,3,5-trisilapentane; and; (b) at least one solvent. In certain embodiments of the compositions described herein, exemplary solvents may include, but are not limited to, ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, tertiary amino ethers, siloxanes, and combinations thereof. In certain embodiments, the difference between the boiling point of the compound having one Si-C-Si or two Si-C-Si bonds and the boiling point of the solvent is 40°C or less. The weight % of the silicon precursor compound in the solvent can vary from 1 to 99 weight %, or 10 to 90 weight %, or 20 to 80 weight %, or 30 to 70 weight %, or 40 to 60 weight %, or 50 to 50 weight %. In some embodiments, the composition can be delivered to the reaction chamber for the silicon-containing film by direct liquid injection using conventional direct liquid injection equipment and methods.

[0056] 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 plasma containing hydrogen is used to improve film properties. In this embodiment, the method includes:

[0057] a. placing one or more substrates comprising surface features into a reactor;

[0058] 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;

[0059] c. Introducing into the reactor at least one silicon precursor having one Si-C-Si bond selected from 1,1,1,3,3,3-hexachloro-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2-ethyl-1,3-disilapropane;

[0060] d. purging with an inert gas to remove unreacted silicon precursor and to form a composition containing a purge gas and a silicon precursor;

[0061] e. providing a nitrogen source to the reactor to react with the surface to form a silicon carbonitride film;

[0062] f. purging with an inert gas to remove reaction by-products;

[0063] g. Repeat steps c to f to provide the desired thickness of carbon-doped silicon nitride;

[0064] h. providing a post-deposition treatment of 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. or from about 100° C. to 400° C. to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film in situ or in another chamber; and

[0065] i. providing a post-deposition treatment of exposing the carbon-doped silicon oxide film to a plasma comprising hydrogen to improve film characteristics to improve at least one film property;

[0066] j. Optionally, the carbon-doped silicon oxide film is post-deposition treated using a spike anneal at a temperature of 400° C. 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.

[0067] In one embodiment, the substrate includes at least one feature, wherein the feature includes a patterned trench having an aspect ratio of 1:9 and an opening of 180 nm.

[0068] In one embodiment of the method described herein, a thermal ALD process is used to deposit a carbon-doped silicon oxide film having a carbon content ranging from 15 atomic % to 30 atomic % and a plasma containing hydrogen is used to improve film properties. In this embodiment, the method includes:

[0069] a. placing one or more substrates comprising surface features into a reactor (eg, into a conventional ALD reactor);

[0070] 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;

[0071] c. Introducing into the reactor at least one silicon precursor having two Si-C-Si bonds, which is selected from 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,1,3-trichloro-1,3-disilacyclobutane, 1,1,3-tribromo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bromo-1,3-dimethyl-1,3 -disilacyclobutane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5,5-octachloro-1,5-dimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-3,3-dimethyl-1,3,5-trisilapentane, 1,1,3,5,5,5-pentachloro-1,3,5-trimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-1,3,5-trisilapentane, 1,1,5,5-tetrachloro-1,3,5-trisilapentane;

[0072] d. Purge with inert gas;

[0073] e. providing a nitrogen source to the reactor to react with the surface to form a carbon-doped silicon nitride film;

[0074] f. purging with an inert gas to remove reaction by-products;

[0075] g. Repeat steps c to f to provide the desired thickness of carbon-doped silicon nitride;

[0076] h. providing a post-deposition treatment of 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. or from about 100° C. to 400° C. to convert the carbon-doped silicon nitride film to a carbon-doped silicon oxide film in situ or in another chamber;

[0077] i. Providing a post-deposition treatment of exposing the carbon-doped silicon oxide film to a plasma comprising hydrogen to improve at least one physical property of the film.

[0078] j. Optionally, the carbon-doped silicon oxide film is post-deposition treated using a spike anneal at a temperature of 400° C. 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.

[0079] In yet a further embodiment of the methods described herein, the silicon-containing film is deposited using a thermal ALD process and a catalyst comprising ammonia or an organic amine. In this embodiment, the method includes:

[0080] a. placing one or more substrates comprising surface features into a reactor;

[0081] b. heating the reactor to one or more temperatures in the range of ambient temperature to about 150° C., and optionally maintaining the reactor at a pressure of 100 Torr or less;

[0082] c. introducing into the reactor at least one silicon precursor having one or two Si-C-Si bonds and a catalyst, the silicon precursor being selected from 1,1,1,3,3,3-hexachloro-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2 -ethyl-1,3-disilacyclopropane, 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,1,3-trichloro-1,3-disilacyclobutane, 1,1,3-tribromo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1 ,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bromo-1,3-dimethyl-1,3-disilacyclobutane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5 ,5-octachloro-1,5-dimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-3,3-dimethyl-1,3,5-trisilapentane, 1,1,3,5,5,5-pentachloro-1,3,5-trimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-1,3,5-trisilapentane, 1,1,5,5-tetrachloro-1,3,5-trisilapentane;

[0083] d. Purge with inert gas;

[0084] e. providing water vapor to the reactor to react with the precursor and the catalyst to form the carbon-doped silicon oxide film thus deposited;

[0085] f. purging with an inert gas to remove reaction by-products;

[0086] g. Repeat steps c to f to provide the desired thickness of carbon-doped silicon oxide;

[0087] h. providing a post-deposition treatment of exposing the processed film to a plasma comprising hydrogen to improve film properties, thereby improving at least one property of the film;

[0088] i. Optionally, the carbon-doped silicon oxide film is post-deposition treated using a spike anneal at a temperature of 400° C. 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.

[0089] 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 equivalent to the amount of silicon precursor vapor in step c.

[0090] In certain embodiments, the resulting carbon-doped silicon oxide film is exposed to a chlorosilane or an organoaminosilane having Si-Me or Si-H or both to form a hydrophobic thin layer prior to exposure to a 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(tert-butylaminodimethylsilane) bis(dimethylamino)methylvinylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylmethylamino)methylvinylsilane, bis(diisopropylamino)methylvinylsilane, bis(isopropylamino)methylvinylsilane, bis(tert-butylamino)methylvinylsilane, dipyrrolidinylmethylvinylsilane, 2,6-dimethylpiperidinylmethylsilane, 2,6-dimethylpiperidinyltrimethylsilane, tris(dimethylamino)phenylsilane, tris(dimethylamino)methylsilane, diisopropylaminosilane, di-sec-butylaminosilane, chlorodimethylsilane, chlorotrimethylsilane, dichloromethylsilane and dichlorodimethylsilane.

[0091] In another embodiment, the resulting carbon-doped silicon oxide film is exposed to a cyclic alkoxysilane or 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, 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 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.

[0092] In another embodiment, a container for depositing a silicon-containing film comprises 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 such 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), with appropriate valves and fittings to allow one or more precursors to be delivered to the reactor for CVD or ALD processes. In this or other embodiments, the silicon precursor is provided in a pressurizable container constructed of stainless steel, and the purity of the precursor is 98 wt % or greater or 99.5 % or greater, 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, the term "substantially free" when used in conjunction with Al 3+ Ion, Fe 2+ , Fe 3+ 、Ni 2 + Cr 3+ When relevant, it means less than about 5ppm (weight), preferably less than about 3ppm, and more preferably less than about 1ppm, and most preferably about 0.1ppm. In some embodiments, if necessary, such containers may also have a device for mixing the precursor with one or more other precursors. In these or other embodiments, the contents of the container may be premixed with other precursors. Alternatively, the silicon precursor and / or other precursors may be kept in a separate container or in a single container with a separator for keeping the silicon precursor and other precursors separated during storage.

[0093] 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 may be composed of and / or coated with various materials known in the art, including silicon (e.g., 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 (e.g., copper, tungsten, aluminum, cobalt, nickel, tantalum), metal nitrides such as (titanium nitride, tantalum nitride), metal oxides, III / V group metals or metalloids such as GaAs, InP, GaP and GaN and films of combinations thereof. These coatings may completely coat the semiconductor substrate, may be multiple layers of various materials, and may be partially etched to expose the underlying material layers. The surface may also have thereon a photoresist material that has been 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 pores, through holes, trenches and combinations 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 (eg, SADP, SAQP, or SAOP).

[0094] Deposition methods for forming silicon-containing films or coatings include deposition processes. 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 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 chemical process that deposits a film of material onto substrates of varying composition. 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 that is delivered to the reactor by direct evaporation, bubbling, or sublimation in the presence or absence of an inert gas. In some cases, the evaporated precursor may be delivered to the reactor by a plasma generator.

[0095] 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 yet another 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.

[0096] 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 of the precursor into the reactor. In this regard, a silicon-containing film is deposited using a deposition technique such as an ALD or CCVD process. In one embodiment, a film is deposited by an ALD process in a typical single wafer ALD reactor, a semi-batch ALD reactor or a batch furnace ALD reactor by exposing the substrate surface alternately 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, the film growth stops. In another embodiment, each reactant including a silicon precursor and a reactive gas is exposed to the 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.

[0097] Depending on the deposition method, in certain embodiments, the silicon precursors described herein and optionally 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 is in the range of about 0.001 to about 500 seconds.

[0098] In certain embodiments, the silicon-containing film deposited using the methods described herein is formed in the presence of a catalyst and an oxygen source, a reagent or precursor (i.e., water vapor) combination comprising oxygen. 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 may include, for example, water (H2O) (e.g., deionized water, purified water, distilled water, water vapor, water vapor plasma, oxygenated water, air, compositions 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, compositions comprising hydrogen, compositions comprising hydrogen and oxygen, carbon dioxide (CO2), air and combinations thereof. In certain embodiments, the oxygen source includes an oxygen source gas introduced into the reactor at a flow rate in the range of about 1 to about 10000 standard cubic centimeters (sccm) or about 1 to about 1000sccm. The oxygen source can be introduced for a time in the range of 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.

[0099] In embodiments where the film is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse duration greater than 0.01 seconds, and the oxygen source may have a pulse duration less than 0.01 seconds, and the water pulse duration may have a pulse duration less than 0.01 seconds.

[0100] 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 range from 0.01 seconds to 100 seconds.

[0101] 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 during the deposition process.

[0102] Suitable nitrogen-containing sources 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.

[0103] 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 greater than 0.01 seconds, and 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 a purge in between.

[0104] 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 in the range of about 10 to about 10000 sccm for about 0.1 to 1000 seconds, thereby purging unreacted materials and any byproducts that may remain in the reactor.

[0105] The respective steps of supplying precursors, oxygen sources, nitrogen-containing sources and / or other precursors, source gases and / or reagents may be performed by varying the time at which they are supplied to change the stoichiometric composition of the resulting film.

[0106] Energy is applied to at least one of the precursor, nitrogen-containing source, reducing agent, other precursors, or a combination thereof to cause a reaction and form a film or coating on the substrate. Such energy can be provided by, but is not limited to, heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma methods, and combinations thereof.

[0107] In certain embodiments, a secondary RF source may be used to change the plasma characteristics at the substrate surface. In embodiments where the deposition involves plasma, the plasma generation process may include a direct plasma generation process (wherein the plasma is generated directly in the reactor) or a remote plasma generation process (wherein the plasma is generated outside the reactor and supplied to the reactor).

[0108] 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 reactive gas is introduced into a reactor in sequence, 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 reactive gas is exposed to a substrate by moving or rotating the substrate to a different section 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.

[0109] Silicon precursors and / or other silicon-containing precursors can be delivered to a reaction chamber, such as a CVD or ALD reactor, in various ways. In one embodiment, a liquid delivery system can be used. In alternative embodiments, a combined liquid delivery and flash process unit can be used, such as a turbo evaporator manufactured by MSP Corporation, Shoreview, MN, so that low volatility materials can be delivered quantitatively (volumetrically), which results in repeatable transportation and deposition without thermal decomposition of the precursor. In a liquid delivery configuration, the precursors described herein can be delivered in pure liquid form, or alternatively can be used with a solvent formulation or a composition comprising a solvent formulation. Therefore, in certain embodiments, the precursor formulation can include one or more solvent components with suitable properties, such as suitable properties that can be desired and advantageous for forming a film on a substrate in a given end-use application.

[0110] In this or other embodiments, it should be understood that the steps of the methods described herein can be performed in various orders, can be performed sequentially or simultaneously (e.g., during at least a portion of another step), and in any combination thereof. The respective steps of supplying the precursor and nitrogen-containing source gas can be performed by varying the duration of supplying them to vary the stoichiometric composition of the resulting silicon-containing film.

[0111] In yet another embodiment of the methods described herein, the film or the film so deposited 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 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 under the same conditions using previously disclosed silicon precursors, films deposited using 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 that is lower than the wet etch rate of the film before the treatment step, or a density that is higher than the density before the treatment step. In a specific embodiment, the film so deposited is treated intermittently during the deposition process. These intermittent or in-deposition treatments may be performed, for example, after each ALD cycle, after a certain number of ALD cycles (e.g., 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).

[0112] In embodiments where the film is treated with a high temperature annealing step, the annealing temperature is at least 100° C. or 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 (e.g., H2O, N2O, NO2, or O2).

[0113] In embodiments where the film is treated with UV treatment, the film is exposed to a broad band UV, or a UV source having a wavelength in the range of about 150 nanometers (nm) to about 400 nm. In a specific embodiment, after the desired film thickness is achieved, the film so deposited is exposed to UV in a chamber different from the deposition chamber.

[0114] 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 contaminants from penetrating the film during subsequent plasma treatment. The passivation layer may be deposited using atomic layer deposition or cyclic chemical vapor deposition.

[0115] 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.

[0116] 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 reactive gas is introduced into a reactor in sequence, 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 reactive gas is exposed to a substrate by moving or rotating the substrate to a different section 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.

[0117] Throughout the specification, the term "ashing" refers to a process of removing photoresist or carbon hard mask using a plasma / inert gas plasma containing an oxygen source (e.g., O2), O2 plasma, CO2 plasma, CO plasma, H2 / O2 plasma, or a combination thereof in a semiconductor manufacturing process.

[0118] 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; The carbon content of the deep part (less than 5 atomic %) is within 5 atomic % of that before ashing; depth) and body (greater than The difference in dilute HF etching rate between films with a depth of less than The membrane is damaged.

[0119] 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, cyclodecane.

[0120] 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 trimethylbenzene.

[0121] 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 in a thermal ALD process. Exemplary catalysts include, but are not limited to, cyclic amine-based gases such as aminopyridine, picoline, lutidine, piperazine, piperidine, pyridine, or organic amine-based gases such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, and tert-butylamine.

[0122] 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, and 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.

[0123] Throughout the specification, the term "siloxane" refers to a siloxane having at least one Si-O-Si bond and a C4-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).

[0124] Throughout the specification, the term "step coverage" as used herein 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, the bottom step coverage being the ratio (in %) of the thickness at the bottom of the feature divided by the thickness at the top of the feature, and the intermediate step coverage being the ratio (in %) 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 more, or about 90% or more, 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.

[0126] Example

[0127] General film deposition

[0128] Film deposition was performed in a laboratory scale atomic layer deposition (ALD) reactor using silicon precursors and ammonia (ammonia as nitrogen source). The ALD cycle steps and process conditions are provided in Table 3 below:

[0129] Table 3: ALD cycle steps and process conditions

[0130]

[0131]

[0132] During the deposition process, steps 3 to 10 are repeated for multiple cycles up to 2000 times to obtain the desired thickness of the carbon-doped silicon nitride film as deposited. The resulting as-deposited film is annealed in situ (annealing performed on the as-deposited film in the reactor) or ex situ (annealing performed externally or in a separate chamber) to convert the film into a carbon-doped silicon oxide film. Typical annealing conditions performed are as follows: moisture annealing at a vacuum of 30 Torr; air annealing at ambient temperature (e.g., 25° C.) or on a hot plate at about 300° C.

[0133] The carbon-doped silicon oxide film was treated using a standard hydrogen-containing plasma. The H2 plasma treatment parameters were:

[0134] a. H2 plasma only:

[0135] Plasma frequency = 13.56 MHz

[0136] H2 flow rate = 135 sccm

[0137] Chamber pressure = 2 Torr

[0138] Time = 5 minutes

[0139] b.H2 / Ar plasma

[0140] Plasma frequency = 13.56 MHz

[0141] H2 flow rate = 65 sccm

[0142] Ar flow rate = 65 sccm

[0143] Chamber pressure = 2 Torr

[0144] Time = 5 minutes

[0145] Refractive index and thickness were measured directly after deposition using an ellipsometer at 632.8 nm. Bulk film composition was characterized using X-ray photoelectron spectroscopy (XPS) a few nanometers (2-5 nm) below the surface to eliminate the effects of adventitious carbon. Film density was characterized using X-ray reflectometry (XRR).

[0146] The wet etch rate process was performed at two different concentrations of dilute hydrofluoric acid (dHF): 1:199 of 49% HF and deionized water and 1:99 of 49% HF and deionized water. The more diluted HF concentration improves the measurement accuracy of the damaged layer. During this process, the thermal silicon oxide film was etched simultaneously to ensure the consistency of the etching solution.

[0147] The oxygen ashing process was carried out at room temperature using a commercial plasma ashing instrument PVA TePLAM4L. The process parameters were as follows: power = 100-200 W; He / O2 = 1:3; pressure = 600 mTorr. The film dielectric constant (k) was calculated from the CV curve measured using an MDC 802b MercuryProbe connected to a HP4284LCR meter. The measurement was carried out in positive contact mode, and the liquid metal (mercury) was used to form two conductive contacts.

[0148] Example 1: Low dielectric constant and high oxygen ashing resistance of carbon-doped silicon oxide films deposited by thermal ALD.

[0149] The carbon doped silicon oxide films were deposited using a thermal ALD process at 300°C using 1,1,3,3-tetrachlorodisilacyclobutane (TCDSB) and 1,1,1,3,3,3-hexachloro-1,3-disilapropane (HCDSP) and ammonia as described in Table 3.

[0150] After deposition, the films were then further treated ex situ at 300 °C in air for 3 h.

[0151] Table 4. Film composition of carbon-doped silicon oxide films deposited from 1,1,3,3-tetrachloro-1,3-bicyclobutane and ammonia measured by XPS after annealing

[0152]

[0153] Table 4 shows the film composition comparison between films deposited from HCDSP and TCDSB. The TCDSB film has a relatively large carbon content compared to HCDSP, demonstrating that TCDSM is a better silicon precursor that introduces more carbon than HCDSP.

[0154] The dHF etch rate for the thermal silicon oxide reference etch rate is The etching rates of HCDSP and TCDSB films are successively and

[0155] The TDCSB film etch rate is below the detection limit of our measurements. The lower TDCSB film dilute HF etch rate (>5x lower) is consistent with the higher carbon content in the film.

[0156] The film dielectric constant of carbon-doped silicon oxide films deposited from HCDSP or TCDSB is greater than 5.

[0157] Using the conditions described above, the carbon-doped silicon oxide films deposited from the HCDSP or TCDSB films were further treated with hydrogen plasma using a 300 mm commercial PEALD tool using H2 / Ar plasma. After plasma treatment, the dielectric constants of the HCDSP and TCDSB films were reduced to 3.5 and 3.4, respectively, demonstrating that plasma containing hydrogen is an effective way to reduce the dielectric constant.

[0158] The films were then exposed to standard oxygen ashing followed by a dilute HF dip to determine damage. Figure 1 , Figure 1 The film thickness removed is shown as a function of the time of immersion in dilute HF.

[0159] The HCDSP and TCDSB films show fast etch rates at the beginning and then slow down, indicating surface damage from oxygen ashing. Oxygen ashing oxidizes the carbon in the film, thus causing fast etch rates. The etch rate curves show that for the TCDSB film The damaged layer and the HCDSP membrane This indicates that under the same etching conditions, the oxygen ashing resistance of the TCDSB film is higher than that of the HCDSP film.

[0160] Example 2. Step coverage of carbon-doped silicon oxide films from 1,1,3,3-tetrachloro-1,3-disilacyclobutane

[0161] As described in Table 3, a carbon-doped silicon oxide film was deposited on the patterned structure from 1,1,3,3-tetrachloro-1,3-disilacyclobutane and ammonia at 300°C and then treated ex-situ at 300°C for 3 hours in an air environment.

[0162] Scanning electron microscopy (SEM) was performed on a trench structure with an aspect ratio of 1:9 and a trench opening of 180 nm.

[0163] Table 5. Surface coverage of carbon-doped silicon oxide films deposited from 1,1,3,3-tetrachloro-1,3-disilacyclobutane

[0164]

[0165] As shown in Table 5, the step coverage of the carbon-doped silicon oxide film deposited from 1,1,3,3-tetrachloro-1,3-disilacyclobutane is >99%.

[0166] Example 3. Deposition of silicon-containing films using 1,1,3,3-tetrachloro-1,3-disilacyclobutane by thermal ALD deposition

[0167] The silicon-containing film was deposited from 1,1,3,3-tetrachloro-1,3-disilacyclobutane and ammonia at a substrate temperature of 500°C and stored in ambient.

[0168] Film characteristics, such as XPS and wet etch rate in dilute HF, were obtained approximately one week after film deposition. The results of these tests are provided in Table 6.

[0169] Table 6. Film composition and WER of ALD films

[0170] Temperature(℃) ％O ％N ％C ％Cl %Si dHF WER relative to thermal oxide 500 20.1 18.1 23.9 0.4 37.6 0.12

[0171] Referring to Table 6, XPS data show that carbon-doped silicon oxide has very little chlorine content (e.g., less than 0.5 atomic %). The film deposited at 500°C has a higher nitrogen content than that at 300°C while maintaining a similar amount of carbon in the film. It is believed that at the lower deposition temperature of 300°C, the method can provide more Si-NH2 or Si-NH-Si fragments that are easily oxidized. On the other hand, deposition at a higher temperature of 500°C can provide sufficient energy to form stronger Si-NH2 that is more resistant to oxidation. x network.

[0172] Example 4. In-situ annealing of carbon-doped silicon oxide films deposited from 1,1,3,3-tetrachloro-1,3-disilacyclobutane

[0173] The carbon-doped silicon oxide film was deposited at 300 °C using 1,1,3,3-tetrachloro-1,3-disilacyclobutane and ammonia as described in Table 3. The film was treated with in-situ H2O vapor using the following parameters:

[0174] H2O vapor pumping; H2O tank temperature = 50°C; chamber pressure = 30 Torr; T = 300°C.

[0175] The film growth per cycle is / cycle. The refractive index of the obtained film was 1.55, and the density was 1.55 g / cc. The film composition measured by XPS was O=39.0%, N=2.6%, C=25.1% and Si=33.2%. No chlorine was detected in the film.

[0176] Example 5. Oxygen ashing resistance of carbon-doped silicon oxide films deposited by thermal ALD deposition using 1,1,3,3-tetrachloro-1,3-disilacyclobutane and ammonia followed by thermal annealing and plasma treatment

[0177] The carbon-doped silicon oxide films were deposited at 300°C using 1,1,3,3-tetrachloro-1,3-disilacyclobutane and ammonia as described in Table 3, and then heat treated in air at 300°C. The carbon-doped silicon oxide films were further heated in nitrogen at 200-400°C, 5 Torr for 1 hour prior to the H2 / Ar plasma treatment described previously.

[0178] The films were then exposed to oxygen ashing followed by dilute HF etching to determine the thickness of the damage.

[0179] The film dielectric constants are shown in Table 7, while the thickness of O2 ashing damage is shown in Table 8.

[0180] Table 7. Dielectric constants of carbon-doped silicon oxide films treated by H2 / Ar plasma.

[0181]

[0182] Table 8. Damage thickness of carbon-doped silicon oxide films after exposure to O2 ashing.

[0183]

[0184]

[0185] The additional annealing before the H2 / Ar plasma treatment showed a lower dielectric constant (k = 2.8-3.2) than the sample treated with H2 / Ar plasma only (k = 3.6). The oxygen ashing damage thickness of the film was

[0186] Example 6. Carbon doping of silicon oxide film using 1,1,3,3-tetrachloro-1,3-disilacyclobutane and ammonia at 300°C followed by high temperature annealing

[0187] A 300 mm commercial cross-flow reactor was used to deposit carbon-doped silicon oxide films in ALD mode using 1,1,3,3-tetrachloro-1,3-disilacyclobutane (as silicon precursor) and ammonia at 300° C. ALD steps 2 to 8 shown in Table 9 were repeated to obtain the desired thickness.

[0188] Table 9. ALD steps for carbon-doped silicon oxide film deposition

[0189]

[0190]

[0191] The deposited sample was placed in an environment and converted into a carbon-doped silicon oxide film. The growth per cycle (GPC) of the film was / cycle.

[0192] As described above, the carbon-doped silicon oxide film is further treated at 300° C. in a nitrogen atmosphere for 1 hour and then subjected to a hydrogen-containing plasma treatment (H 2 plasma only or H 2 / Ar plasma).

[0193] After the plasma treatment, the films were exposed to O2 ashing and then to dilute HF to determine the thickness of the damage. The dielectric constant and damage thickness after O2 ashing are shown in Table 10.

[0194] Table 10. Dielectric constants and damage thickness of carbon-doped silicon oxide films after O2 ashing

[0195]

[0196] This process demonstrates a carbon-doped silicon oxide film with high oxygen resistance and low k before and after oxygen ashing treatment. The low damage thickness after oxygen ashing and low k (k<4.0) indicate high oxygen resistance.

[0197] Example 7. Step coverage of silicon-containing films after plasma treatment

[0198] Carbon doped silicon oxide films were deposited using a 300 mm commercial cross-flow reactor in ALD mode using 1,1,3,3-tetrachloro-1,3-disilacyclobutane and ammonia at 300°C followed by H2 / Ar plasma treatment as described in Example 6. The substrate used was a patterned wafer with an aspect ratio of 1:9 and an opening of 180 nm.

[0199] Transmission electron microscopy (TEM) was used to determine the surface coverage. Table 11 shows the film thickness at various locations in the structure.

[0200] Table 11. Thickness of carbon-doped silicon oxide deposited from 1,1,3,3-tetrachloro-1,3-disilacyclobutane followed by H2 / Ar plasma treatment

[0201]

[0202] Membrane stage coverage >97%.

[0203] Example 8. Chemical Treatment of Carbon-Containing Films Deposited from 1,1,3,3-Tetrachloro-1,3-Disilacyclobutane and Ammonia

[0204] The carbon doped silicon oxide films deposited from 1,1,3,3-tetrachloro-1,3-disilacyclobutane and ammonia at 300°C as described in Table 9 were annealed at 300°C in an inert atmosphere for 1 hour and then exposed to a chemical treatment using diethylaminotrimethylsilane. The chemical treatment parameters were:

[0205] T = 300°C; time = 5 minutes and 25 minutes; chamber pressure = 1 Torr

[0206] As a control, the films were only annealed at 300 °C without any chemical exposure.

[0207] After treatment, the film dielectric constants were measured and are shown in Table 12.

[0208] Table 12. Dielectric constants of films treated with diethylaminotrimethylsilane

[0209] Temperature(℃) Time (minutes) Dielectric constant (k) No chemical treatment, only annealing at 300℃ 25 5.5 300 5 2.9 300 25 2.7

[0210] The chemical treatment showed an improvement in the film dielectric constant from 5.5 to less than 3.0.

[0211] Example 9. Deposition of Carbon-Containing Silicon Films Using 1,1,3,3-Tetrachlorodimethylcyclobutane and Ammonia in Octane

[0212] A 20 wt% solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in octane was used for film deposition. Chemicals were delivered using direct liquid injection (pot temperature = 60°C, Ar flow through evaporator was 100 sccm. Liquid flow rate was ~200 mg / min). Evaporator temperature was 70°C.

[0213] The deposition process includes the following steps:

[0214] Table 13. Steps for Depositing Silicon-Containing Films Using 1,1,3,3-Tetrachloro-1,3-Disilacyclobutane Solutions

[0215]

[0216] Steps 3 to 4 were repeated 5 times, and steps 3 to 8 were repeated multiple times to obtain the desired thickness before proceeding to step 5. The film composition analyzed by XPS was:

[0217] Si=35.7%; O=36.5%; C=23.0%; N=4.5%; Cl=0.3%.

[0218] The deposited film was further annealed at 300 °C for 1 h in an inert environment followed by H2 / Ar plasma treatment.

[0219] The treated films were exposed to standard O2 ashing and immersed in dilute HF to determine the thickness of the damage. For films treated sequentially with H2 plasma only and H2 / Ar plasma, the damage thickness after O2 ashing was and

[0220] Example 10. High Carbon Content Silicon Oxide Film from In-Situ Processing

[0221] A 20 wt% solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in octane was used for film deposition. Chemicals were delivered using direct liquid injection (pot temperature = 60°C, Ar flow through the evaporator was 100 sccm. Liquid flow rate was ~200 mg / min). The evaporator temperature was 70°C.

[0222] The deposition process includes the following steps:

[0223] Table 14. Steps for Depositing Silicon-Containing Films Using 1,1,3,3-Tetrachloro-1,3-Disilacyclobutane Solutions

[0224]

[0225] Steps 3 to 4 were repeated 5 times, and steps 3 to 6 were repeated multiple times to obtain the desired thickness before proceeding to step 5. Steps 8, 9, and 10 were optional for comparison.

[0226] Table 15. Film properties of carbon-doped silicon oxide films processed in situ using 1,1,3,3-tetrachloro-1,3-disilacyclobutane.

[0227]

[0228] The resulting films had the film properties in Table 15. For the as-deposited films without annealing, the film etch rate was very low, i.e., 0.12 times that of thermal oxide. After additional treatment (N2 drying or N2 drying and plasma), the etch rate dropped to a level below our detection limit.

[0229] The film density of the as-deposited films was 1.34 g / cc with slight densification using either additional N2 drying or N2 drying and H2 plasma treatment. In all cases, the films had high carbon content of 25-29% and low Cl content (<2%).

[0230] Example 11. Low dielectric constant carbon-doped silicon oxide film deposited from 1,1,3,3-tetrachloro-1,3-disilacyclobutane and water / pyridine

[0231] Film deposition was performed using 1,1,3,3-tetrachloro-1,3-disilacyclobutane and H2O. Pyridine was used as a reaction catalyst. Chemicals (tank temperature = 70°C) were delivered as Ar swept through the precursor tank. The water temperature was 17°C (vapor pressure = 15 Torr), and water vapor was delivered with steam pumping, and the pyridine temperature was 25-35°C (vapor pressure = 15-25 Torr), and pyridine vapor was delivered with steam pumping. The main N2 flow rate was 200 sccm, and the Ar flow rate was 50 sccm.

[0232] The deposition process included the steps described in Table 16.

[0233] Table 16. Deposition steps for depositing Si-containing films from 1,1,3,3-tetrachloro-1,3-disilacyclobutane and water / pyridine.

[0234]

[0235]

[0236] Repeat steps 3 to 6 500 times to obtain the desired thickness.

[0237] The refractive index of the film deposited as such was 1.53, and the GPC was / cycle. The film composition measured by XPS is: Si = 35.3%, O = 34.0%, C = 28.9%, N = 0.6% and Cl = 1.3%. The film density is 1.8 g / cc, and the dilute etch rate is

[0238] The film was then subjected to a standard ex situ H2 / Ar plasma treatment at 300° C. as described previously. The film dielectric constant was measured to be 3.6 before and after plasma treatment, which is an improvement from the as-deposited film (k=6.1).

[0239] Example 12. High Carbon Content Silicon Oxide Film from In-Situ Processing

[0240] A 20 wt% solution of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in octane was used for film deposition. Chemicals were delivered using direct liquid injection (pot temperature = 60°C, Ar flow through the evaporator was 100 sccm. Liquid flow rate was ~200 mg / min). The evaporator temperature was 70°C.

[0241] The deposition process included the steps described in Table 17.

[0242] Table 17. Deposition steps for depositing silicon-containing films using 1,1,3,3-tetrachloro-1,3-disilacyclobutane solution

[0243]

[0244] Steps 3 to 4 were repeated 5 times, and steps 3 to 8 were repeated multiple times to obtain the desired thickness before proceeding to step 5. For some wafers, step 9 was optional to allow comparison between H2O in-situ annealing and conversion in ambient.

[0245] Table 18 shows similar film compositions measured by XPS for both carbon doped silicon oxide converted in ambient and carbon doped silicon oxide with in situ H2O treatment.

[0246] Table 18. Comparison of film compositions of carbon-doped silicon oxide

[0247] Si O C N Cl Environmental transformation 34.69 41.4 21.82 1.74 0.35 <![CDATA[In-situ H2O]]> 35.2 38.22 23.49 2.82 0.27

[0248] Example 13. High temperature annealing of carbon-doped silicon oxide film

[0249] Using a 300 mm commercial cross-flow reactor, carbon-doped silicon oxide films were deposited using 1,1,3,3-tetrachloro-1,3-disilacyclobutane and ammonia in ALD mode at 300° C. The ALD steps shown in Table 8 were repeated to obtain the desired thickness.

[0250] The thus deposited carbon-doped silicon oxide film was annealed at 500° C. to 800° C. in an inert atmosphere for 1 hour.

[0251] The film dielectric constants are shown in Table 19.

[0252] Table 19. Dielectric Constants of Si-Containing Films Deposited Using 1,1,3,3-Tetrachloro-1,3-Disilacyclobutane and Ammonia After Thermal Annealing

[0253] Annealing temperature(℃) Dielectric constant (k) after annealing (before oxygen ashing) No annealing (room temperature) 5.7 500℃ 2.6 600℃ 2.3 700℃ 2.6 800℃ 3.9

[0254] High temperature annealing is effective in reducing the film dielectric constant.

[0255] Comparative Example 1: Effect of Hydrogen Plasma Treatment and Oxygen Ashing on Carbon-Doped Silicon Oxide Films Deposited by PECVD Using Diethoxymethylsilane

[0256] A carbon-doped silicon oxide film was deposited using diethoxymethylsilane (DEMS) at 300° C. using a 200 mm commercial PECVD tool. The process parameters were as follows: power = 500 W; pressure = 9 Torr; Si precursor flow = 500 sccm; He flow = 300 sccm;

[0257] The films thus deposited had the compositions shown in Table 20.

[0258] Table 20. Film composition of carbon-doped silicon oxide films using DEMSPECVD process measured by XPS

[0259]

[0260] The film density was 1.48 g / cc. The WER in dilute HF (1:99 of 49% HF and DI water) as deposited (before H2 plasma) is in Table 21. The film shows very high dilute HF etch resistance as indicated by the low etch rate.

[0261] Table 21. WER in dilute HF (1:99, 0.5 wt%) of carbon-doped silicon oxide from as-deposited PECVD DEMS (before H2 plasma). Thermal silicon oxide reference etch rate is

[0262]

[0263] The film was then treated with H2 plasma at 300 W and 300°C for 5 minutes. After the H2 plasma treatment, the sample was exposed to oxygen ashing. Both the hydrogen plasma treatment and the oxygen ashing treatment were the same as described previously.

[0264] Table 22 shows the dielectric constant measurements of the PECVD DEMS samples.

[0265] Table 22. PECVD DEMS dielectric constants after H2 plasma treatment and H2 plasma followed by oxygen ashing

[0266]

[0267] The dielectric constant increased from 3.2 to 3.7 after H2 plasma, indicating higher damage thickness. Oxygen ashing further increased the film dielectric constant to 5.5. Dilute HF (1:99 49% HF and DI water) characterization after H2 plasma followed by oxygen ashing is listed in Table 17.

[0268] Table 23. WER in dilute HF (1:99) of carbon-doped silicon oxide from PECVD DEMS after H2 plasma followed by oxygen ashing. Thermal silicon oxide reference etch rate is

[0269]

[0270] The carbon-doped silicon oxide film clearly shows greater than The film etch rate of the film after oxygen ashing is much higher (>10x) than the as-deposited film. The high film dielectric constant after exposure to oxygen ashing is consistent with the thick damage layer from oxygen ashing.

[0271] Comparative Example 2. Silicon-containing film control without post-deposition treatment.

[0272] As described in Table 3, the carbon doped silicon oxide films were deposited using a thermal ALD process using 1,1,3,3-tetrachloro-1,3-disilacyclobutane and ammonia at 300°C. After deposition, the films were then annealed at room temperature in air at 300°C for 3 hours. Standard oxygen ashing was performed on the carbon doped silicon oxide films. Dilute HF was used to determine the thickness of the damage, as shown in Table 24.

[0273] Table 24. Dilute HF etch rates of carbon-doped silicon oxide films after exposure to oxygen ashing

[0274]

[0275] With the film thus deposited Compared with the surface The etch rate of 0.040 nm shows a very high etch rate, indicating that carbon is removed. The carbon removal is consistent with a damaged film due to oxygen ashing.

[0276] Example 10. Preparation of 1,1,3,3-tetrachloro-1,3-disilacyclobutane

[0277] Table 25 summarizes the solubility of 1,1,3,3-tetrachloro-1,3-disilacyclobutane in various solvents as a potential formulation for vapor delivery by direct liquid injection since 1,1,3,3-tetrachloro-1,3-disilacyclobutane is a solid at room temperature.

[0278]

[0279] Although the present invention has been described with reference to certain embodiments, it will be appreciated by those skilled in the art that various changes may be made and elements thereof may be replaced with equivalents without departing from the scope of the present invention. In addition, many modifications may be made to adapt specific circumstances or materials to the teachings of the present invention without departing from the essential scope of the present invention. Therefore, the present invention is not intended to be limited to the specific embodiments disclosed as the best mode for carrying out the present invention, but the present invention will include all embodiments falling within the scope of the appended claims.

Claims

1. A method for forming a carbon-doped silicon oxide film having a carbon content ranging from 15 atomic % to 30 atomic % 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 a temperature in the range of from ambient temperature to 550° C., and optionally maintaining the reactor at a pressure of 100 Torr or less; c) introducing into the reactor at least one silicon precursor having two Si-C-Si bonds, the silicon precursor being selected from the group consisting of 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,1,3-trichloro-1,3-disilacyclobutane, 1,1,3-tribromo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilacyclobutane, Pentane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5,5-octachloro-1,5-dimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-3,3-dimethyl-1,3,5-trisilapentane, 1,1,3,5,5,5-pentachloro-1,3,5-trimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-1,3,5-trisilapentane, 1,1,5,5-tetrachloro-1,3,5-trisilapentane; d) purging with inert gas; e) providing a nitrogen source into the reactor to react with the surface 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 provide a desired thickness of carbon-doped silicon nitride; h) treating the resulting carbon-doped silicon nitride film with an oxygen source at a temperature ranging from ambient temperature to 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 a plasma containing hydrogen after deposition.

2. The method of claim 1, wherein the silicon precursor is delivered in pure liquid form, or is used in a solvent formulation or a composition comprising a solvent formulation.

3. The method of claim 1, wherein the film formed has a dielectric constant of less than 4 and a carbon content of at least 10 atomic %.

4. The method of claim 1, wherein the formed film has an etch rate at least 0.5 times lower than thermal silicon oxide.

5. The method of claim 1, wherein the formed film has an etch rate at least 0.1 times lower than thermal silicon oxide.

6. The method of claim 1, wherein the formed film has an etch rate at least 0.05 times lower than thermal silicon oxide.

7. The method of claim 1, wherein the formed film has an etch rate at least 0.01 times lower than thermal silicon oxide.

8. The method of claim 1, wherein the formed film has a or smaller damage layer.

9. The method of claim 1, wherein the formed film has a or smaller damage layer.

10. The method of claim 1, wherein the formed film has a or smaller damage layer.

11. The method of claim 1, wherein the formed film has a or smaller damage layer.

12. The method according to claim 1, wherein step h) is treating the obtained carbon-doped silicon nitride film with an oxygen source at a temperature ranging from 100°C to 400°C to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film.

13. A method for forming a carbon-doped silicon oxide film having a carbon content ranging from 15 atomic % to 30 atomic % 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 a temperature ranging from ambient temperature to 150° C., and optionally maintaining the reactor at a pressure of 100 Torr or less; c) introducing a precursor having at least two Si-C-Si bonds and a catalyst into the reactor, the precursor being selected from 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,1,3-trichloro-1,3-disilacyclobutane, 1,1,3-tribromo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilacyclobutane Pentane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,1,3,3,5,5,5-octachloro-1,5-dimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-3,3-dimethyl-1,3,5-trisilapentane, 1,1,3,5,5,5-pentachloro-1,3,5-trimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-1,3,5-trisilapentane, 1,1,5,5-tetrachloro-1,3,5-trisilapentane; d) purging with inert gas; e) supplying water vapor into the reactor to react with the precursor and the catalyst to form the thus deposited carbon-doped silicon oxide film; f) purging with an inert gas to remove reaction by-products; g) Repeating steps c to f to provide the desired thickness of carbon-doped silicon oxide.

14. The method of claim 13, further comprising post-deposition treating the carbon-doped silicon oxide film with thermal annealing at a temperature from 300 to 700°C.

15. The method of claim 13, further comprising subjecting the carbon-doped silicon oxide film to a hydrogen plasma treatment using plasma containing hydrogen.

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