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

Abstract

To provide compositions and methods of using the same for depositing high carbon content silicon-containing films.SOLUTION: Disclosed herein are compositions and methods of using the same for forming a silicon-containing film such as, without limitation, a carbon doped silicon oxide film, a carbon doped silicon nitride film, a carbon doped silicon oxynitride film in a deposition process. In one aspect, the composition comprises at least cyclic carbosilane having at least one Si-C-Si linkage and at least one anchoring group selected from a halide atom, an amino group, and combinations thereof.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] [Cross-references to related applications] This application claims priority to U.S. Provisional Patent Applications No. 62 / 113024 and No. 62 / 142546, filed on February 6, 2015, and April 3, 2015, respectively. The disclosures of these Provisional Patent Applications are incorporated herein by reference in their entirety. [Background technology]

[0002] This specification describes compositions and methods for the fabrication of electronic devices. More specifically, this specification describes, but is not limited to, compounds and compositions for the deposition of silicon-containing films, such as carbon-doped silicon oxide, carbon-doped silicon nitride, carbon-doped silicon oxynitride, or silicon carbide films, and methods comprising the same.

[0003] In this field, there is a need to provide compositions and methods for using silicon-containing films with high carbon content (e.g., carbon content of about 10 atomic percent or more as measured by X-ray photoelectron spectroscopy (XPS)) for several applications within the electronics industry.

[0004] U.S. Patent No. 8575033 describes a method for depositing a silicon carbide film on a substrate surface. The method involves the use of a gas-phase carbosilane precursor and can utilize a plasma atomic layer deposition process.

[0005] U.S. Patent Application Publication No. 2013 / 022496 provides a method for forming a dielectric film having Si-C bonds on a semiconductor substrate by atomic layer deposition (ALD), comprising the steps of (i) adsorbing a precursor onto the surface of the substrate, (ii) reacting the adsorbed precursor with 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.

[0006] U.S. Patent Application Publication 2014 / 302688 describes a method for forming a dielectric film on a patterned substrate, which may include combining a silicon- and carbon-containing precursor with a radical oxygen precursor in a plasma-free substrate processing region within a chemical vapor deposition chamber. The silicon- and carbon-containing precursor and the radical oxygen precursor react to deposit a fluid silicon-carbon-oxygen layer on the patterned substrate.

[0007] U.S. Patent Application Publication No. 2014 / 302690 describes a method for forming a low-k dielectric material on a substrate. The method may include the steps of: generating a radical precursor by introducing a non-excited precursor into a remote plasma region; and reacting the radical precursor with a gas-phase silicon precursor to deposit a fluid film on the substrate. The gas-phase silicon precursor may include at least one silicon- and oxygen-containing compound and at least one silicon- and carbon crosslinking agent. The fluid film can be cured to form a low-k dielectric material.

[0008] U.S. Patent Application Publication No. 2014 / 051264 describes a method for depositing an initial fluid dielectric film on a substrate. The method includes introducing a silicon-containing precursor into a deposition chamber containing the substrate. The method further includes generating at least one excitation precursor, for example, a radical nitrogen or oxygen precursor, in a remote plasma system located outside the deposition chamber. The excitation precursor is also introduced into the deposition chamber, where it reacts with the silicon-containing precursor in a reaction region to deposit an initial fluid film on the substrate. The fluid film can be processed, for example, in a vapor environment to form a silicon oxide film.

[0009] International Publication No. 14 / 134476 describes methods for depositing films containing SiCN and SiCON. Several methods involve exposing the substrate surface to a first precursor and a second precursor, the first precursor being of 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 of 1 to 3, z has a value of 1 to 3, p has a value of 0 to 2, n has a value of 2 to 5, and the second precursor contains a reducing amine. Some methods also include exposing the substrate surface to an oxygen source and providing a film containing SiCON.

[0010] In the literature titled "Highly Stable Ultrathin Carbosiloxane Films by Molecular Layer Deposition" in Journal of Physical Chemistry C, 2013, 117, 19967 by Han, Z et al., it teaches growing a carbosiloxane film using 1,2-bis[(dimethylamino)dimethylsilyl]ethane and ozone. The thermal stability shows that the film is stable below 40 °C and has little thickness loss at 60 °C.

Summary of the Invention

Problems to be Solved by the Invention

[0011] The compositions and methods described herein overcome the problems of the art by providing compositions or formulations for depositing silicon-containing films having one or more of the following properties: an etch rate of about 0.20 angstroms / second (Å / second) or less when measured in dilute hydrofluoric acid (HF) (e.g., a bath of 49% HF and Di water at a ratio of 1:99); and a carbon content of about 10 atomic percent (at.%) or more when measured by X-ray photoelectron spectroscopy (XPS). In one particular embodiment, the compositions described herein can be used in a method for depositing carbon-doped silicon oxide films using a thermal atomic layer deposition (ALD) process. [Means for solving the problem]

[0012] In one embodiment, a composition for depositing a silicon-containing film is the following formulas I and II [ka] A compound comprising at least one cyclic carbosilane precursor compound having and at least one anchor group, wherein X 1 , X 2 , X 3 , X 4 , X 5 and X 6 Each is independently a hydrogen atom; a halide atom selected from F, Cl, Br, and I; formula NR 1 R 2 An amino group having R in the formula 1 and R 2 These are, independently, hydrogen atoms, C1~C 10 Linear alkyl groups, C3-C 10 Branched alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Alkenyl group, C4~C 10 Aryl group, and C4~C 10 The amino group is selected from the group consisting of heterocyclic groups. In some embodiments of formula I, II, or both I and II, substituent X 1 , X 2 , X 3 , X 4, X 5 and X 6 Any one or more of these combine to form a substituted or unsubstituted, saturated or unsaturated cyclic group. In one particular embodiment of formulas I, II, or both I and II, substituent X 1 , X 2 , X 3 , X 4 , X 5 and X 6 Any one or more of these are either a halide atom or an amino group as described above. In some embodiments of Formula II, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 These cannot all be amino groups. In some embodiments of formula I or II, formula NR 1 R 2 R in an amino group having 1 and R 2 They bond together to form a ring. In one particular embodiment, R 1 and R 2 R is selected from linear or branched C3-C6 alkyl groups and bonded to form a cyclic ring. In alternative embodiments of formula I or II having an amino group, R 1 and R 2 They do not bond together to form a ring. In other embodiments of formulas I and II having an amino group, R 1 and R 2 They are different.

[0013] In some embodiments of formulas I and II, the composition for forming a silicon-containing film comprises at least one cyclic halocarbosilane compound, wherein the substituent X 1 , X 2 , X 3 , X 4 , X 5 , X 6 At least one of them is a halide atom selected from F, Cl, Br, and I as an anchor group, and substituent X 1 , X 2 , X 3, X 4 , X 5 , X 6 None of these are amino groups. Examples of cyclic chlorobosilanes include, but are not limited to, 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-iodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1,1-diiodo-1,3-disilacyclobutane, 1 Examples include 1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-tricilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-tricilacyclohexane, and 1,3,5-trichloro-1,3,5-tricilacyclohexane.

[0014] In some embodiments of formulas I and II, the composition for forming a silicon-containing film comprises at least one cyclic haloaminocarbosilane compound, wherein the substituent X 1 , X 2 , X 3 , X 4 , X 5 , X 6 At least one of them is a halide atom selected from F, Cl, Br, and I, and substituent X 1 , X 2 , X 3 , X 4 , X 5 , X 6At least one of them is an amino group as an anchor group. Exemplary cyclic haloaminocarbosilane compounds include, but are not limited to, 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane, and 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane.

[0015] In some embodiments of Formulas I and II, the composition for forming the silicon-containing film comprises at least one cyclic aminocarbosilane compound, wherein substituent X 1 , X 2 , X 3 , X 4 , X 5 , X 6 among which at least one is an amino group as an anchor group, and substituents X 1 , X 2 , X 3 , X 4 , X 5 , X 6 are not halide atoms. Exemplary cyclic aminocarbosilanes include, but are not limited to, 1,1,3,3-tetrakis(methylamino)-1,3-disilacyclobutane, 1,1,3,3-tetrakis(dimethylamino)-1,3-disilacyclobutane, 1,3-bis(dimethylamino)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(methylamino)-1,3-dimethyl-1,3-disilacyclobutane, and 1,3-bis(isopropylamino)-1,3-dimethyl-1,3-disilacyclobutane.

[0016] In another aspect, a method for depositing a film selected from a carbon-doped silicon oxide film and a carbon-doped silicon oxynitride film on at least one surface of a substrate, comprising: installing the substrate in a reactor; heating the reactor to one or more temperatures in the range of about 25 to about 700 °C; A step of introducing a precursor containing at least one compound selected from a cyclic halo-autobosilane compound, a cyclic halo-aminocarbosilane compound, and combinations thereof into a reactor, A step of introducing a nitrogen source into the reactor and reacting it with at least a portion of the precursor to form a carbon-doped silicon nitride film, A process of treating a carbon-doped silicon nitride film with an oxygen source at one or more temperatures in the range of approximately 25 to 1000°C or approximately 100 to 400°C, under conditions sufficient to convert the carbon-doped silicon nitride film into a film. A method is provided that includes the following: In some embodiments, the carbon-doped silicon oxide film or carbon-doped silicon oxynitride film has a carbon content of about 10 atomic percent (at.%) or more as measured by XPS and an etch rate of about 0.20 Å / second or less in diluted HF. [Brief explanation of the drawing]

[0017] [Figure 1] Figure 1 provides Fourier transform infrared (FTIR) spectra of films deposited using the precursor 1,3-dichloro-1,3-(dimethyl)amino-1,3-disilacyclobutane, as described in Example 11. [Figure 2] Figure 2 provides a comparison of FTIR spectra before (solid line) and after (dotted line) vacuum annealing, as described in Example 15. [Figure 3] Figures 3a-3c provide cross-sectional scanning electron microscope (SEM) images of deposited silicon-containing films, as described in Example 17. [Modes for carrying out the invention]

[0018] Described herein are cyclic carbosilane compounds, and compositions and methods comprising these compounds for depositing carbon-doped (e.g., carbon content of about 10 at% or more as measured by XPS) silicon nitride through deposition processes such as thermal atomic layer deposition processes, but not limited to these. Films deposited using the compositions and methods described herein exhibit extremely low etch rates (e.g., less than or equal to about 0.20 Å / sec or less or less than or equal to about 0.15 Å / sec in diluted HF), while exhibiting variability in other tunable properties such as density, dielectric constant, refractive index, and elemental composition, but not limited to these properties.

[0019] In some embodiments, the cyclic carbosilane precursors and methods using them described herein provide one or more of the features described below. First, the deposited reactive carbon-doped silicon nitride film is formed using a cyclic carbosilane precursor containing Si-C-Si bonds and a nitrogen source. The Si-C-Si bonds from the cyclic carbosilane precursor are thought to remain in the resulting deposited film and provide a high carbon content of at least 10 at.% when measured by XPS. Second, at least some or all of the nitrogen content in the film is converted to oxygen by exposing the deposited film to an oxygen source, such as water, intermittently during the deposition process, during post-deposition treatment, or a combination thereof, to provide a film selected from carbon-doped silicon oxide or carbon-doped silicon oxynitride films. The nitrogen in the deposited film is released as one or more nitrogen-containing byproducts, such as ammonia or amine groups. In this or other embodiment, the final film is porous and has a density of about 1.7 grams / cubic centimeter (g / cc) or less and a wet etch rate of 0.20 Å / second or less when measured in diluted HF.

[0020] In one embodiment, the composition is the following formulas I and II [ka] At least one cyclic carbosilane having, and at least one anchor group selected from a halide atom, an amino group, and combinations thereof, wherein X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are each independently a hydrogen atom; a halide atom selected from F, Cl, Br, and I; an amino group having the formula NR 1 R 2 , wherein R 1 and R 2 are independently selected from a hydrogen atom, a C1-C 10 linear alkyl group, a C3-C 10 branched alkyl group, a C3-C 10 cyclic alkyl group, a C3-C 10 alkenyl group, a C4-C 10 aryl group, and an amino group selected from the group consisting of a C4-C 10 heterocyclic group. In some embodiments of Formula I, II, or both I and II, the substituents X 1 , X 2 , X 3 , X 4 , X 5 and X 6 combine to form a substituted or unsubstituted, saturated or unsaturated cyclic group. In one particular embodiment of Formula I, II, or both I and II, any one or more of the substituents X 1 , X 2 , X 3 , X 4 , X 5 and X 6 is either a halide or an amino group as described above. In some embodiments of Formula II, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are not all amino groups. In some embodiments of Formula I or II, R 1 and R 2 in the amino group having the formula NR 1 R 2They bond together to form a ring. In one particular embodiment, R 1 and R 2 R is selected from linear or branched C3-C6 alkyl groups and bonded to form a cyclic ring. In alternative embodiments of formula I or II, R 1 and R 2 They do not bond together to form a ring. In other embodiments, R 1 and R 2 They are different.

[0021] As described herein, the cyclic carbosilane precursors having formulas I and II described herein include at least one anchor group. The term “anchor group” refers to an unstable group that can react with a hydroxyl or other reaction site on the substrate surface, for example, NH or NH2, but not limited to these. Examples of anchor groups include, but not limited to, halide atoms (e.g., Cl, Br, and I) and amino groups. The term “amino group” refers to a group of formula HNR 1 R 2 It represents an organic amino group having 1 to 10 carbon atoms, derived from an organic amine, where R 1 and R 2 As mentioned above, the example amino groups are not limited to secondary amines, such as dimethylamino(Me2N-), diethylamino(Et2N-), and diisopropylamino( i Secondary amino groups derived from Pr2N-; or primary amines, such as methylamino(MeNH-), ethylamino(EtNH-), isopropylamino( i PrNH-),sec-butylamino( s BuNH-), and tert-butylamino( t Examples include primary amino groups derived from BuNH-).

[0022] In the formulas described above and throughout the explanation, the term "alkyl" refers to a linear or branched functional group having 1 to 10 or 2 to 4 carbon atoms. Examples of linear alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, and hexyl. Examples of branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, and isohexyl. In some embodiments, the alkyl group may have one or more functional groups bonded thereto, such as, but not limited to, alkoxy groups, dialkylamino groups, or combinations thereof.

[0023] In the formulas described above and throughout the explanation, the term "cyclic alkyl" refers to a cyclic functional group having 3 to 10 or 4 to 10 carbon atoms. Examples of cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0024] In the formulas described above and throughout the explanation, the term "alkenyl group" refers to a group having one or more carbon-carbon double bonds and containing 2 to 10 or 2 to 6 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl groups and allyl groups.

[0025] In the above formula and throughout the explanation, the term "alkynyl group" refers to a group having one or more carbon-carbon triple bonds and containing 2 to 10 or 2 to 6 carbon atoms.

[0026] In the formulas described above and throughout the explanation, the term "aryl" refers to an aromatic cyclic functional group having 4 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Examples of aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, o-xylyl, 1,2,3-triazolyl, pyrrolyl, and furanyl, pyridadinyl, pyrimidinyl, and imidazolyl.

[0027] In some embodiments, the cyclic carbosilane precursors having either formula I or II described herein contain at least one halide atom as an anchor group and do not contain an amino group. Referring to formula I or II, these compounds have their substituent X as an anchor group. 1 , X 2 , X 3 , X 4 , X 5 , X 6 It comprises at least one halide atom selected from F, Cl, Br, and I, and substituent X 1 , X 2 , X 3 , X 4 , X 5 , X 6 None of these are amino groups. These precursors are referred to herein as cyclic halocbosilane compounds. Several examples of halocbosilane compounds are provided, for example, in Table I below.

[0028] [Table 1]

[0029] In some embodiments, the cyclic carbosilane precursors having either formula I or II described herein include at least an amino group and at least one halide atom as anchor groups. Referring to formula I or II, these compounds include a halide atom selected from F, Cl, Br, and I, and their substituent X as anchor groups. 1 , X 2 , X 3 , X 4 , X 5 , X 6 The compound has at least one amino group among them. These compounds are referred to herein as cyclic halo-aminocarbosilane compounds. Several examples of halo-aminocarbosilane compounds are provided, for example, in Table II below.

[0030] [Table 2]

[0031] In some embodiments, the cyclic carbosilane precursors having either formula I or II described herein contain at least one amino group as an anchor group and do not contain a halide atom. Referring to formula I or II, these compounds have their substituent X as an anchor group. 1 , X 2 , X 3 , X 4 , X 5 , X 6 It has at least one amino group, and substituent X 1 , X 2 , X 3 , X 4 , X 5 , X 6 None of these are halide atoms. These precursors are referred to herein as cyclic aminocarbosilane compounds. Several examples of aminocarbosilane compounds are provided, for example, in Table III below.

[0032] [Table 3]

[0033] As described above, silicon-containing films are deposited on at least the surface of a substrate, such as a semiconductor substrate. In the methods described herein, the substrate may consist of and / or be coated with films of various materials well known in the art, such as silicon, silicon oxide, silicon nitride, amorphous carbon, silicon oxycarbide, silicon oxynitride, silicon carbide, germanium, germanium-doped silicon, metals (e.g., copper, tungsten, aluminum, cobalt, nickel, tantalum), metal nitrides, such as titanium nitride, tantalum nitride, metal oxides, group III / V metals or metalloids, such as GaAs, InP, GaP, and GaN, and 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. The surface can also have a photoresist material deposited thereon that exposes a pattern and partially coats and grows the substrate. In some embodiments, the semiconductor substrate includes at least one surface feature selected from the group consisting of holes, vias, trenches, and combinations thereof.

[0034] A deposition method used to form a silicon-containing film or coating is a deposition process. Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, chemical vapor deposition or atomic layer deposition processes. As used herein, the term “chemical vapor 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 a desired deposition. As used herein, the term “atomic layer deposition” refers to a self-limiting (e.g., constant amount of film material deposited in each reaction cycle) continuous surface chemistry that deposits films of material on substrates of varying compositions. While precursors, reagents, and sources used herein are sometimes described as “gaseous,” it is understood that precursors can be either liquids or solids, transported into the reactor with or without an inert gas, via direct vaporization, bubbling, or sublimation. In some cases, vaporized precursors can pass through a plasma generator.

[0035] 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.

[0036] In some embodiments, the methods disclosed herein prevent pre-reaction of one or more precursors by using an ALD or CCVD method to separate one or more precursors before and / or during introduction into the reactor. In this context, deposition techniques such as the ALD or CCVD process are used to deposit silicon-containing films. In one embodiment, the film is deposited by alternating exposure of the substrate surface to one or more silicon-containing precursors, an oxygen source, a nitrogen source, or other precursors or reactants through an ALD process in a typical single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor. Film growth proceeds by self-limiting control of the deposition temperature, the pulse length of each precursor or reactant, and the surface reaction. However, film growth stops when the substrate surface becomes saturated. In another embodiment, the substrate is moved or rotated to different areas of the reactor, thereby exposing the substrate to each reagent containing the cyclic carbosilane and the reaction gas, with each area separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0037] In some embodiments, depending on the deposition method, the cyclic carbosilane precursor described herein, and optionally other silicon-containing precursors, can be introduced into the reactor in a predetermined molar volume or about 0.1 to about 1000 micromoles. In this or other embodiments, the precursors can be introduced into the reactor for a predetermined period of time. In some embodiments, this period is in the range of about 0.001 to about 500 seconds.

[0038] In some embodiments, silicon-containing films deposited using the methods described herein are formed in the presence of oxygen using an oxygen source, an oxygen-containing reagent, or an oxygen-containing precursor. The oxygen source may be introduced into the reactor in the form of at least one oxygen source and / or may be incidentally present in other precursors used in the deposition process. Suitable oxygen source gases include water (H2O) (e.g., deionized water, purified water, distilled water, water vapor, water vapor plasma, oxygenated water, water and other organic liquid compositions), oxygen (O2), oxygen plasma, ozone (O3), nitric oxide (NO), nitrogen dioxide (NO2), carbon monoxide (CO), water-containing plasma, water and argon-containing plasma, hydrogen peroxide, hydrogen-containing compositions, hydrogen and oxygen-containing compositions, carbon dioxide (CO2), air, and combinations thereof. In some embodiments, the oxygen source includes an oxygen source gas introduced into the reactor at a flow rate ranging from about 1 to about 2000 standard cubic centimeters / minute (sccm) or about 1 to about 1000 sccm. The oxygen source can be introduced over a period of time ranging from approximately 0.1 to 100 seconds.

[0039] In embodiments in which a film is deposited by ALD or a periodic CVD process, the precursor pulse may have a pulse width of more than 0.01 seconds, the oxygen source may have a pulse width of less than 0.01 seconds, and the water pulse may have a pulse width of less than 0.01 seconds.

[0040] In some embodiments, an oxygen source flows continuously into the reactor while a precursor pulse and plasma are introduced sequentially. The precursor pulse may have a pulse width of more than 0.01 seconds, while the plasma interval may be in the range of 0.01 to 100 seconds.

[0041] In some embodiments, the silicon-containing film comprises silicon and nitrogen, and optionally oxygen. In these embodiments, the silicon-containing film deposited using the method described herein is formed in the presence of a nitrogen-containing source. The nitrogen-containing source may be introduced into the reactor in the form of at least one nitrogen source and / or may be incidentally present in other precursors used in the deposition process.

[0042] Suitable nitrogen-containing or nitrogen-source gases include, for example, ammonia, hydrazine, monoalkylhydrazine, symmetric or asymmetric dialkylhydrazine, nitrogen, NO, N2O, NO2, nitrogen and hydrogen-containing compositions, ammonia plasma, nitrogen plasma, ammonia and nitrogen-containing plasma, nitrogen and hydrogen-containing plasma, organic amine plasma, organic diamine plasma, and combinations thereof. In embodiments in which organic amine plasma or organic diamine plasma is used as the nitrogen-containing source, exemplary organic amino plasmas include, but are not limited to, diethylamine plasma, dimethylamine plasma, trimethylamine plasma, trimethylamine plasma, alkoxyamine plasma, methylamine, ethylamine, ethylenediamine, ethanolamine, piperazine, N,N'-dimethylethylediamine, imidazolidine, cyclotrimethylenetriamine, and combinations thereof.

[0043] In some embodiments, the nitrogen source is introduced into the reactor at a flow rate ranging from about 1 to about 2000 standard cubic centimeters / minute (sccm) or 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 in which films are deposited by ALD and periodic CVD processes using both nitrogen and oxygen sources, the precursor pulse can have a pulse width greater than 0.01 seconds, the nitrogen source can have a pulse width of less than 0.01 seconds, and the water pulse can have a pulse width of less than 0.01 seconds. In another embodiment, the purge interval between pulses can be as low as about 0 seconds, or pulses may be pulsed continuously without purging in between.

[0044] In some embodiments, one or more steps of the method are carried out in the presence of a catalyst. In these or other embodiments, the catalyst is selected from Lewis bases, such as pyridine, piperazine, ammonia, or other organic amines.

[0045] The deposition methods disclosed herein may include one or more purge gases. The purge gas used to purge unused reactants and / or reaction by-products is an inert gas that does not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2), and combinations thereof. In some embodiments, a purge gas such as Ar is supplied into the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 1000 seconds, thereby purging any unreacted material and any by-products that may remain in the reactor.

[0046] The continuous process of supplying precursors, oxygen sources, nitrogen sources, and / or other precursors, source gases, and / or reagents can be carried out by changing the supply time of these elements to alter the stoichiometric composition of the resulting film.

[0047] The reaction is induced by applying energy to at least one of a precursor, a nitrogen-containing source, a reducing agent, another precursor, or a combination thereof, thereby forming a film or coating on a substrate. Such energy can be provided by, but is not limited to, heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-rays, electron beams, photons, remote plasma methods, and combinations thereof.

[0048] In some embodiments, a secondary RF frequency source can be used to modify the plasma properties on the substrate surface. In embodiments in which deposition involves plasma, the plasma generation process may include a direct plasma generation process in which the plasma is generated directly in the reactor, or alternatively, a remote plasma generation process in which the plasma is generated outside the reactor and supplied into the reactor.

[0049] Cyclic carbosilane precursors and / or other silicon-containing precursors can be transported to a reaction chamber, such as a CVD or ALD reactor, in various ways. In one embodiment, a liquid transport system can be used. In an alternative embodiment, a combined liquid transport and flash evaporation process unit, such as a turbo evaporator from MSP Corporation (Shoreview, MN), can be used to enable quantitative transport of low-volatility materials, thereby resulting in reproducible transport and deposition without thermal decomposition of the precursor. In liquid transport formulations, the precursors described herein may be transported in liquid form, or alternatively, they may be used in a solvent formulation or a composition containing the same. Thus, in some embodiments, the precursor formulation may contain one or more solvent components with appropriate properties so as to be desirable and advantageous in a given end use for forming a film on a substrate.

[0050] In this or other embodiments, it is understood that the steps of the method described herein can be carried out in various orders, sequentially or simultaneously (for example, between at least part of another step), and in any combination thereof. The sequential step of supplying the precursor and nitrogen-containing source gases can be carried out by varying the time intervals at which they are supplied, thereby changing the stoichiometric composition of the resulting silicon-containing film.

[0051] In further embodiments of the methods described herein, the film or deposited film undergoes a processing step. The processing step can be performed during at least a portion of the deposition process, after the deposition process, and in combination thereof. Exemplary processing steps include, but are not limited to, treatment through thermal annealing, plasma treatment, ultraviolet (UV) light treatment, laser treatment, electron beam treatment, and combinations thereof, which affect one or more properties of the film. Films deposited with cyclic carbosilane precursors described herein have improved properties, but are not limited to, a wet etch rate lower than that of the film before the processing step, a density higher than that of the film before the processing step, or a reduction in one or more impurities in the film, compared to films deposited with previously disclosed carbosilane precursors under the same conditions. In one particular embodiment, the deposited film is intermittently processed during the deposition process. These intermittent or intermediate sedimentation processes can be performed, for example, after each ALD cycle, or at any specific number of ALD cycles, for example, but not limited to, every two (2) ALD cycles, every five (5) ALD cycles, or every ten (10) or more ALD cycles.

[0052] In embodiments in which the film is treated in a thermal annealing process, the annealing temperature is at least 100°C or higher than the deposition temperature. In this or other embodiments, the thermal annealing temperature is in the range of about 400°C to about 1000°C. In alternative embodiments, the annealing temperature is the same as or within ±100°C of the deposition temperature. In this or other embodiments, the thermal annealing process can be carried out in a vacuum (<760 Torr) or in an inert environment.

[0053] In embodiments in which the film is treated with UV, the film is exposed to a UV source having broadband UV, or alternatively, a wavelength in the range of about 150 nanometers (nm) to about 400 nm. In one particular embodiment, the deposited film is irradiated with UV in a chamber different from the deposition chamber after it has reached a desired film thickness.

[0054] In embodiments in which the film is treated with plasma, the plasma source is selected from the group consisting of nitrogen plasma, nitrogen and helium-containing plasma, nitrogen and argon-containing plasma, ammonia plasma, ammonia and helium-containing plasma, ammonia and argon-containing plasma, helium plasma, argon plasma, neon plasma, hydrogen plasma, hydrogen and helium-containing plasma, hydrogen and argon-containing plasma, organic amine plasma, organic diamine plasma, and combinations thereof. In one particular embodiment, the plasma contains an inert gas selected from the group consisting of helium, neon, argon, krypton, and combinations thereof.

[0055] In one particular embodiment, the method involves depositing a silicon-containing film selected from carbon-doped silicon oxide, carbon-doped silicon nitride, and carbon-doped silicon oxynitride films, and the following steps: A step of placing one or more substrates in the reactor, A process of heating the reactor to one or more temperatures in the range of approximately 25 to approximately 700°C, and optionally maintaining it at a pressure of 100 torr or less, A step of introducing at least one cyclic carbosilane selected from the group consisting of cyclic halo-carbosilanes and cyclic halo-aminocarbosilanes, A process of exposing carbon-doped silicon nitride to an oxygen source at one or more temperatures in the range of approximately ambient temperature (e.g., 25°C) to 1000°C, or approximately 100 to 400°C, to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film or a carbon-doped silicon oxynitride film. Includes.

[0056] In a further embodiment of the method described herein, the silicon-containing film is deposited using a thermal ALD process. In this embodiment, the method is A step of placing one or more substrates in the reactor, A process of heating a reactor to one or more temperatures in the range of approximately ambient temperature (e.g., 25°C) to approximately 700°C, and optionally maintaining a pressure of 100 torr or less; A step of introducing at least one cyclic carbosilane selected from the group consisting of cyclic halo-carbosilanes and cyclic halo-aminocarbosilanes, A step comprising providing an oxygen source and optionally a catalyst into a reactor and reacting them with a surface to form a deposited film, wherein the catalyst contains a Lewis base, An annealing step in which the deposited film is annealed at one or more temperatures higher than the heating temperature, wherein the annealing step is performed at one or more temperatures in the range of approximately 400 to approximately 1000°C. The process involves optionally performing a post-deposition treatment on the deposited film with an oxygen source at one or more temperatures in the range of approximately ambient temperature to approximately 1000°C, or approximately 100 to 400°C, to provide a film with a certain density. Optionally, a process in which the deposited film is exposed to a UV source, Optionally, a process is taken to post-deposit the film to be treated with a rare gas or hydrogen-containing plasma. Includes.

[0057] In yet another further embodiment of the method described herein, the silicon-containing film is deposited using a thermal ALD process with a nitrogen source containing an organic amine. In this embodiment, the method is A step of placing one or more substrates containing surface features into a reactor, A step of heating the reactor to one or more temperatures in the range of ambient temperature ~700°C, and optionally maintaining the reactor at a pressure of 100 torr or less, A step of introducing at least one cyclic carbosilane selected from the group consisting of cyclic halo-carbosilane, cyclic halo-aminocarbosilane, and cyclic aminocarbosilane into a reactor, The process includes providing a nitrogen source into the reactor and reacting it with a precursor to form a silicon carbonitride deposited film. Optionally, a step of post-deposit annealing of the deposited film, A step of converting a carbon-doped silicon nitride film to a carbon-doped silicon oxide film by post-deposition treatment with an oxygen source at one or more temperatures in the range of approximately ambient temperature ~1000°C or approximately 100~400°C, wherein the oxygen source is selected from the group consisting of water vapor, water plasma, oxygenated water, oxygenated water vapor, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxide, nitrous oxide, ozone, ozonated water, and combinations thereof. The process optionally includes a step of exposing the carbon-doped silicon oxide film to a UV light source. In this or other embodiments, the UV exposure step can be performed either during or after film deposition.

[0058] In yet another embodiment of the method described herein, carbon-doped silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride film, carbon-doped silicon nitride, or silicon carbide film is deposited using a plasma ALD process. In this embodiment, the method is A step of placing one or more substrates having surface features selected from holes, vias, trenches, or a combination thereof into a reactor, A step of heating the reactor to one or more temperatures in the range of ambient temperature ~700°C, and optionally maintaining the reactor at a pressure of 100 torr or less, A step of introducing at least one cyclic carbosilane selected from the group consisting of cyclic halo-bosilane, cyclic halo-aminocarbosilane, and cyclic aminocarbosilane into a reactor, A step comprising providing a plasma source in a reactor and reacting it with a precursor to form a silicon carbonitride film, wherein the plasma source is selected from the group consisting of nitrogen plasma, nitrogen and helium-containing plasma, nitrogen and argon-containing plasma, ammonia plasma, ammonia and helium-containing plasma, ammonia and argon-containing plasma, helium plasma, argon plasma, neon plasma, hydrogen plasma, hydrogen and helium-containing plasma, hydrogen and argon-containing plasma, organic amine plasma, organic diamine plasma, and combinations thereof, The process involves optionally performing post-deposit thermal annealing of the deposited film at one or more temperatures in the range of approximately 400 to 1000°C, A step of converting a carbon-doped silicon nitride film to a carbon-doped silicon oxide film by post-deposition treatment with an oxygen source at one or more temperatures in the range of approximately ambient temperature to approximately 1000°C or approximately 100°C to approximately 400°C, wherein the oxygen source is at least one selected from the group consisting of water vapor, water plasma, oxygenated water, oxygenated water vapor, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxide, and combinations thereof. Optionally, the process involves post-deposition irradiation of the film to be treated with a UV light source, The process optionally includes a step of post-depositing the film to be treated with a rare gas or hydrogen-containing plasma to improve at least one of the film's properties.

[0059] In yet another further embodiment of the method described herein, carbon-doped silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride film, carbon-doped silicon nitride, or silicon carbide is deposited using a plasma ALD process. In this embodiment, the method is A step of placing one or more substrates having surface features selected from holes, vias, trenches, or a combination thereof into a reactor, A step of heating the reactor to one or more temperatures in the range of 25 to approximately 650°C, and optionally maintaining the reactor at a pressure of 10 torr or less, A step of introducing at least one cyclic carbosilane selected from the group consisting of cyclic halo-carbosilane, cyclic halo-aminocarbosilane, and cyclic aminocarbosilane into a reactor, A step comprising providing a plasma source in a reactor and reacting it with the surface of a sample to form a silicon carbonitride film, wherein the plasma source is selected from the group consisting of nitrogen plasma, nitrogen and helium-containing plasma, nitrogen and argon-containing plasma, ammonia plasma, ammonia and helium-containing plasma, ammonia and argon-containing plasma, helium plasma, argon plasma, neon plasma, hydrogen plasma, hydrogen and helium-containing plasma, hydrogen and argon-containing plasma, organic amine plasma, organic diamine plasma, and combinations thereof, Optionally, a step of post-deposit thermal annealing of the deposited film, A process of post-depositing a carbon-doped silicon nitride film with an oxygen source at one or more temperatures in the range of approximately ambient temperature (e.g., 25°C) to approximately 1000°C, wherein the oxygen source is selected from the group consisting of water vapor, water plasma, oxygenated water, oxygenated water vapor, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxide, and combinations thereof. Optionally, the process involves post-deposition irradiation of the film to be treated with UV light, The process optionally includes a step of post-depositing the film to be treated with a plasma selected from noble gas or hydrogen-containing plasmas.

[0060] In yet another further embodiment of the method described herein, carbon-doped silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, or carbon-doped silicon nitride film is deposited using a thermal ALD process and inert plasma to improve the properties of the film. In this embodiment, the method is A step of placing one or more substrates containing surface features into a reactor, A step of heating the reactor to one or more temperatures in the range of 25 to approximately 700°C, and optionally maintaining the reactor at a pressure of 100 torr or less, A step of introducing at least one cyclic carbosilane selected from the group consisting of cyclic halo-carbosilane, cyclic halo-aminocarbosilane, and cyclic aminocarbosilane into a reactor, A step of providing a nitrogen source into the reactor and reacting it with the surface to form a silicon carbonitride film, A step of providing a plasma selected from inert plasma and hydrogen plasma, comprising the step of the inert plasma comprising at least one selected from helium, neon, argon, krypton and combinations thereof, Optionally, a process of post-depositing and annealing the film, The process involves optionally performing a post-deposition treatment of a carbon-doped silicon nitride film with an oxygen source at one or more temperatures in the range of approximately ambient temperature ~1000°C or approximately 100~400°C to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film, Optionally, the process involves post-deposition irradiation of the film to be treated with a UV light source, The process includes a step of post-depositing the film to be treated with a noble gas or hydrogen-containing plasma to improve at least one of the film's properties.

[0061] In yet another further embodiment of the method described herein, carbon-doped silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, or carbon-doped silicon nitride film is deposited using a thermal ALD process. In this embodiment, the method is A step of installing one or more substrates including surface features, A step of heating the reactor to one or more temperatures in the range of 25 to approximately 700°C, and optionally maintaining the reactor at a pressure of 100 torr or less, A step of introducing at least one cyclic carbosilane selected from the group consisting of cyclic halo-carbosilane, cyclic halo-aminocarbosilane, and cyclic aminocarbosilane into a reactor, A step of providing a nitrogen source into the reactor and reacting it with the surface to form a silicon carbonitride film, A step of providing an oxygen source to convert silicon carbonitride to carbon-doped silicon oxynitride, wherein the oxygen source includes at least one selected from the group consisting of water vapor, oxygen, nitrous oxide, ethylene glycol, ozone, oxygen plasma, nitrous oxide plasma, carbon dioxide (CO2), carbon monoxide (CO), CO2 plasma, CO plasma, O2 plasma, and combinations thereof, Optionally, the process involves post-deposit annealing of the deposited film in a vacuum (<760 Torr) or inert environment at one or more temperatures in the range of approximately 400 to approximately 1000°C. The process involves optionally performing a post-deposition treatment of a carbon-doped silicon nitride film with an oxygen source at one or more temperatures in the range of approximately 25 to 1000°C or approximately 100 to 400°C to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film, Optionally, the process involves post-deposition irradiation of the film to be treated with a UV light source, The process includes a step of post-depositing the film to be treated with a noble gas or hydrogen-containing plasma to improve at least one of the film's properties. [Examples]

[0062] Examples of typical membrane deposition Unless otherwise specified, film deposition was performed in a laboratory-scale atomic layer deposition (ALD) reactor using a cyclic carbosilane precursor and ammonia as the nitrogen source. The steps and process conditions of the ALD cycle are shown in Table IV below.

[0063] [Table 4]

[0064] During deposition, process steps 3-10 were repeated for a maximum of 2000 cycles to obtain the desired thickness of the deposited carbon-doped silicon nitride film. The resulting deposited film was then converted to a carbon-doped silicon oxide film by either in-situ annealing (annealing performed on the deposited film inside the reactor) or out-of-situ annealing (annealing in an external chamber or another chamber). Typical annealing conditions performed were as follows: vapor annealing under a vacuum of 200 mTorr, oxygen annealing at 2 Torr, or air annealing on a hot plate at ambient temperature (e.g., 25°C) or approximately 300°C.

[0065] Reflectance and thickness were directly measured after deposition using an ellipsometer at 632.8 nm. To eliminate the effect of accidental carbon deposits, the bulk film composition was characterized using X-ray photoelectron spectroscopy (XPS) several nanometers (2–5 nm) below the surface. Film density was characterized using X-ray reflectance (XRR).

[0066] A wet etching rate process was performed under diluted HF (dHF, 49% HF and DI water in a 1:99 ratio). During the process, a thermal oxide film was etched and simultaneously used to verify the etching solution concentration. The typical WER for thermal oxides is 0.55 Å / sec.

[0067] Example 1: Synthesis of 1-chloro-1,3-disilacyclobutane In a nitrogen-filled glove box, 1,3-disilacyclobutane (15.0 g, 0.170 mol) was rapidly added to a stirred mixture of copper(I) chloride (5.61 g, 0.0567 mol) in Et2O (50 mL). The mixture was stirred and reacted for 30 minutes, during which time the solids turned dark gray / brown and a gaseous byproduct (presumably H2) was produced. The reaction mixture was filtered to remove the solids, and the solvent and unreacted initial materials were removed by distillation at a pressure of 1 atm. This procedure was repeated a total of five times, and the crude compound was purified by vacuum distillation to obtain 20.4 grams (g) of 1-chloro-1,3-disilacyclobutane in solution. The 1-chloro-1,3-disilacyclobutane in solution was analyzed by gas chromatography (GC-TCD), mass spectrometry (GC-MS), and 1 Identification was performed by 1H NMR analysis. Gas chromatography analysis was performed on the product eluate using a TCD equipped with a 0.53 mm diameter × 30 m Supleco column containing 3 μm thick SPB-5 medium and an HP-5890 series II GC. GC-MS showed the following peaks: 122 (M+), 107 (M-15), 93, 85, 81, 58, and 43.

[0068] Example 2: Synthesis of 1,3-dichloro-1,3-disilacyclobutane In a nitrogen-filled glove box, copper(II) chloride (89.6 g, 0.666 mol) and copper(I) iodide (1.51 g, 0.00793 mol) were mixed and slowly added to a stirred solution of 1,3-disilacyclobutane (14.0 g, 0.159 mol) in Et2O (300 mL) at room temperature over 2 hours. The reaction mixture was vented through a diaphragm with a needle to release excess pressure. After 6 hours, the venting needle was removed, and the gray reaction mixture was stirred overnight. Solid matter was removed by filtration, and the filtrate was concentrated under reduced pressure (to 80 Torr). 20.4 g of a pale yellow crude product was obtained, and GC-MS determined that it contained a mixture of two isomers (cis and trans) of 1,3-dichloro-1,3-disilacyclobutane as the main component. GC-MS showed the following peaks: 156(M-1), 141, 119, 105, 93, 78, 63, 58, and 43.

[0069] Example 3: Synthesis of 1-bromo-1,3-disilacyclobutane and 1,3-dibromo-1,3-disilacyclobutane In a nitrogen-containing glove box, 1,3-disilacyclobutane (1.0 g, 0.011 mol) was added to a stirred mixture of copper(I) bromide (1.6 g, 0.011 mol) in diethyl ether (5 g) in a scintillation vial, and the reaction was carried out by stirring overnight. The solution released a gaseous byproduct (presumably H2), and GC-MS of the solution determined that it contained a mixture of 1-bromo-1,3-disilacyclobutane (m / z=166(M+), 151(M-15), 137, 123, 109, 85, 69, 59, 43) and 1,3-dibromo-1,3-disilacyclobutane (m / z=246(M+), 231(M-15), 216, 202, 189, 159, 137, 109, 69, 58, 43).

[0070] Example 4: Synthesis of 1,1,3,3-tetrabromo-1,3-disilacyclobutane Under nitrogen protection, acetyl bromide (209 g, 1.70 mol) was combined with 1,1,3,3-tetraethoxy-1,3-disilacyclobutane (75 g, 0.28 mol) in the presence of AlBr3 (1.9 g, 0.0071 mol) and stirred at room temperature for approximately one month. Unreacted acetyl bromide and ethyl acetate byproducts were removed under reduced pressure. The remaining wet solid was stirred in pentane (30 mL) and then collected by vacuum filtration. The crude solid was purified by vacuum sublimation in a flask (90°C, 150 mTorr) to obtain 59 g of colorless crystalline solid, which was determined to be 1,1,3,3-tetrabromo-1,3-disilacyclobutane by GC-MS. GC-MS analysis revealed the following peaks: 404(M+), 376, 323, 297, 267, 243, 229, 202, 188, 165, 149, 135, 109, 81, 55, and 42. The melting point (mp) was 117°C and the boiling point (bp) was 252°C. The structure was confirmed by analyzing the single crystal using X-ray diffraction.

[0071] Example 5: Synthesis of 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane Under nitrogen protection, a solution of diethylamine (29.5 g, 0.403 mol) in hexane (80 mL) was added dropwise via a funnel to a stirred solution of triethylamine (44.4 g, 0.439 mol) and 1,1,3,3-tetrachloro-1,3-disilacyclobutane (40.0 g, 0.177 mol) in hexane (400 mL) at -20°C. The resulting white slurry was warmed to room temperature and stirred overnight. The white solid was removed by filtration and washed twice with hexane (30 mL). The combined filtrate was concentrated under reduced pressure at room temperature until its volume remained unchanged. The crude product was heated to 100°C and then vacuum-transported into a cooling trap at -78°C to obtain 28.6 g of a colorless liquid, which was determined by GC-MS to be a mixture of isomers (cis and trans) of 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane. GC-MS showed the following peaks: 298(M-1), 283, 269, 255, 239, 226, 212, 198, 184, 170, 157, 143, 134, 121, 106, 93, 72, 58, and 42. Bp = 283°C.

[0072] Example 6: Synthesis of 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane Under nitrogen protection, a solution of dimethylamine (2.11 M, 500 mL, 1.06 mol) in THF was added dropwise to a stirred solution of Et3N (119 g, 1.18 mol) and 1,1,3,3-tetrachloro-1,3-disilacyclobutane (120.8 g, 0.535 mol) in hexane (1.5 L) at -20°C. The resulting white slurry was warmed to room temperature and stirred overnight. The white solid was removed by filtration and washed twice with hexane (100 mL). The solvent was removed under reduced pressure at room temperature until the volume remained unchanged. The crude product was purified by vacuum distillation in a flask (80°C, 150 mTorr) and collected in a cooling trap (-15°C) to obtain 77 g of colorless crystalline solid. This solid was determined by GC-MS to be a mixture of isomers (cis and trans) of 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane. GC-MS showed the following peaks: 243 (M+), 228 (M-15), 208, 199, 185, 171, 157, 143, 121, 106, 93, 72, 63, and 43. Mp = 6~41°C; bp = 230°C. Single crystals of the trans isomer were grown from a concentrated pentane solution at -35°C and their structure was confirmed by X-ray diffraction analysis.

[0073] Synthesis of 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane Under nitrogen protection, acetyl chloride (115 g, 1.46 mol) was added dropwise via a funnel to a stirred mixture of iron(III) chloride (0.47 g, 0.0029 mol) and 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane (120 g, 0.587 mol) at room temperature. The mixture was stirred and allowed to react for 14 days. The volatiles were transported away from the iron catalyst under vacuum, and then purified by vacuum distillation (12 Torr / 70°C) to obtain 98 g of a colorless liquid, which was determined by GC-MS to be a mixture of isomers (cis and trans) of 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane. GC-MS showed the following peaks: 184 (M-1), 169, 149, 133, 93, 79, 71, and 63.

[0074] Example 8: Deposition of silicon-containing films by thermal ALD deposition using the cyclic carbosilane precursor 1,1,3,3-tetrachloro-1,3-disilacyclobutane Without post-deposition treatment, silicon-containing films were deposited at substrate temperatures of 300°C and 500°C using 1,1,3,3-tetrachloro-1,3-disilacyclobutane as a cyclic carbosilane precursor and ammonia, using the process steps described herein as shown in Table IV. After initial reflectance and thickness measurements, the samples were stored at room temperature and measured intermittently. The reflectance and thickness of the deposited films are summarized in Table V. Table VI shows that the reflectance of the film deposited at 300°C decreased over time, from 1.65 to 1.53 after 24 hours, indicating an oxidation process due to the ambient environment at room temperature. No further decrease in reflectance was observed after 24 hours. Other film properties, such as XPS and wet etch rates in diluted HF, were measured approximately one week after film deposition. The results of these tests are shown in Table VII.

[0075] [Table 5]

[0076] [Table 6]

[0077] [Table 7]

[0078] Referring to Table VII, XPS data show that carbon-doped silicon oxide films deposited from cyclic carbosilane and ammonia have low chlorine content (e.g., less than 0.5 at.%). Small amounts of nitrogen were detected in films deposited at 300°C, whereas films deposited at 500°C had significantly higher nitrogen content. It is thought that at lower deposition temperatures of 300°C, the process may provide more Si-NH2 or Si-NH-Si fragments that are susceptible to oxidation. On the other hand, deposition at higher temperatures of 500°C provides Si-NH2 that are more resistant to oxidation. x It can provide enough energy to form a network.

[0079] Example 9: ALD deposition of carbon-doped silicon-containing films using 1,1,3,3-tetrachloro-1,3-disilacyclobutane, followed by in-situ annealing in various environments. Using the process steps described in Table IV, a Si-containing film was deposited at 300°C from 1,1,3,3-tetrachloro-1,3-disilacyclobutane as a cyclic carbosilane precursor and ammonia.

[0080] After deposition, the reflectance and thickness were measured, and the samples from each deposition were separated into three (3) parts. Each part was thermally annealed at 300°C under either ambient air, oxygen (O2), or water (H2O) vapor, as described above. The reflectance and thickness were measured after 1 hour of annealing and after another 2-hour additional annealing treatment. The results are given in Table VIII below.

[0081] [Table 8]

[0082] The film deposition growth rate was 0.2 Å / cycle. Table VIII shows the change in reflectivity under different annealing conditions. The decrease in reflectivity after annealing indicates that the film was converted to a silicon oxycarbide (SiO:C) film. The process was nearing completion after 1 hour of annealing, as indicated by the small change in reflectivity during additional annealing.

[0083] The wet etch rate of the film in 1:99 HF after post-deposition annealing was undetectable (<0.01 Å / sec), while the thermal oxide film showed an etch rate of 0.55 Å / sec. The film was then exposed to diluted HF with a higher concentration of HF in solution (49% HF:DI water in a 10:90 ratio). After exposure to the higher HF acid concentration, no etching of the film was detected (<0.01 Å / sec), while the comparative thermal oxide film showed an etch rate of 5.5 Å / sec.

[0084] Example 10: Film composition of carbon-doped silicon-containing film deposited by thermal ALD Using the process steps described in Table IV, a silicon-containing film was deposited at 300°C from 1,1,3,3-tetrachloro-1,3-disilacyclobutane as a cyclic carbosilane precursor and ammonia. After deposition, the reflectance and thickness were measured, and the film was then separated into three (3) parts. Each part was annealed in situ at 300°C for 3 consecutive hours under either O2, water vapor, or air, as described above. The film reflectance of the deposited film was 1.64 after it was removed from the reactor. After post-deposition treatment outside the situ, the reflectance decreased to 1.55–1.57, consistent with the results in Table VIII. The composition and density of the deposited film are summarized in Table IX.

[0085] [Table 9]

[0086] Example 11: Carbon-doped silicon-containing film by thermal ALD deposition using ammonia and water process Si-containing films were deposited from the cyclic halo-aminocarbosilane precursor 1,3-dichloro-1,3-(dimethyl)amino-1,3-disilacyclobutane using the process steps described in Table X. In each ALD cycle, SiCNH x The surface was converted to SiCOH, thus eliminating the need for post-deposition treatment.

[0087] [Table 10]

[0088] During deposition, process steps 3-13 were repeated multiple times to obtain the desired film thickness. The resulting film had a growth rate of 0.27 Å / cycle and a reflectance of 1.58. The IR spectrum of the sample was obtained and is shown in Figure 1. Figure 1 shows that the deposited film is mostly SiO:C, with a composition of 24.3%C, 5.0%N, 41.0%O, and 33.6%Si. The resulting film had an undetectable wet etch rate or a WER of less than 0.01 Å / sec in diluted HF.

[0089] Example 12: Thermal ALD deposition of carbon-doped Si-containing films and post-deposition in air, followed by in-situ annealing. Using the process steps described in Table IV, silicon-containing films were deposited at 300°C from a cyclic halo-aminocarbosilane 1,1,3,3-tetrachloro-1,3-disilacyclobutane precursor and ammonia. The deposited films were subjected to the characterization process described above and repeated out-of-situ post-deposition annealing. Annealing was performed at 300°C on a hot plate in ambient air. Changes in reflectance and thickness at different annealing times are reported in Table XI.

[0090] [Table 11]

[0091] Referring to Table XI, after annealing in the ambient environment, the reflectivity of the film decreased from 1.64 to 1.55, indicating a conversion from a silicon nitride film to a silicon oxide film.

[0092] Example 13: Carbon-doped Si-containing film by thermal ALD deposition and in-situ post-treatment with an oxygen source. Using the process steps described in Table XII, silicon-containing films were deposited at 300°C from a cyclic halocbosilane 1,1,3,3-tetrachloro-1,3-disilacyclobutane precursor and ammonia.

[0093] [Table 12]

[0094] Process steps 3-11 were repeated multiple times to obtain the desired film thickness. After the ALD cycle was completed, while the film was still in the chamber, steam was introduced into the reactor to deposit a silicon oxycarbide (SiOC) film. The resulting film had a composition of 39.0%O, 2.6%N, 25.1%C, and 33.2%Si as measured by XPS, and a density of 1.55 g / cc as measured by XRR.

[0095] Example 14: Post-deposition UV treatment of carbon-doped silicon-containing films As described in Example 10, multiple silicon-containing films were deposited from the cyclic halocbosilane precursor 1,1,3,3-tetrachlorodisilacyclobutane. The films were deposited using ammonia as the nitrogen source, followed by in-situ thermal annealing in ambient air on a hot plate for 3 hours. Both deposition and annealing temperatures were 300°C. The films were UV-annealed to remove trapped water and final hydroxyls. UV annealing was performed using a fusion UV system with a broadband UV bulb mounted on an Applied Materials Precision-5000 system. The samples were held under a helium gas stream at one or more pressures below 10 Torr and one or more temperatures below 400°C. Thickness and reflectance were measured on a Woollam ellipsometer system before and after UV annealing. Dielectric constant was determined using Hg probe technique on a medium resistivity p-type wafer.

[0096] [Table 13]

[0097] [Table 14]

[0098] Table XIII shows a comparison of dielectric constant and shrinkage upon UV irradiation, and Table XIV shows the corresponding density and composition. Samples irradiated with UV for 3 minutes were damaged during the procedure and therefore density measurements could not be obtained, as indicated by (Not Applicable) in Table XIV. UV irradiation for more than 1 minute resulted in significantly lower dielectric constant and some film shrinkage, leading to higher film density, although the carbon content within the film did not appear to be affected.

[0099] Example 15: Post-deposition vacuum annealing of carbon-doped silicon-containing films As described in Example 10, a silicon-containing film was deposited from a cyclic halocbosilane 1,1,3,3-tetrachlorodisilacyclobutane precursor. An ammonia process was used, followed by an out-of-situ annealing step on a hot plate in ambient air for 3 hours to deposit the film. Both the deposition and annealing temperatures were 300°C. The film was then vacuum-annealed at 600°C for 1 hour (<0.001 Torr) to remove the final hydroxyl groups within the film. The film thickness shrank by 9–10%, and the reflectance decreased from 1.55 to 1.50. The IR spectrum of the film shown in Figure 2 decreased at 870 cm⁻¹ after vacuum annealing. -1 This shows the Si-OH band.

[0100] Example 16: PEALD of carbon-doped silicon-containing film A silicon-containing film was deposited using a commercial PEALD reactor at a substrate temperature of 300°C with cyclic halocbosilane 1,1,3,3-tetrachlorodisilacyclobutane, ammonia, and an inert gas. Film density was improved using an inert plasma. The deposition process, shown in Table XV, is as follows:

[0101] [Table 15]

[0102] Process steps 3-6 were repeated multiple times to obtain the desired film thickness, after which step 7 was performed. The resulting film had a film density of 1.82 g / cc, a composition of 29.5% O, 14% N, 20.8% C, 34.6% Si, and 1.1% Cl as measured by XPS, and a wet etch rate of 0.19 Å / sec as measured in diluted HF. The high oxygen content within the film is thought to be due to exposure to ambient air.

[0103] Example 17: Step coverage ratio of carbon-doped silicon-containing film As described in Example 10, a silicon-containing film was deposited from the cyclic halocbosilane precursor 1,1,3,3-tetrachlorodisilacyclobutane on a Si-patterned wafer with surface features. The structural aspect ratio of the surface features is 1:10, with an aperture of 1 micron and a depth of 10 microns. As shown in Figures 3a-3c, cross-sections were made from the deposited film and observed with a scanning electron microscope. The aspect ratio of the surface features is 1:10 (1 micron aperture), with the top of the (upper) structure shown in 3a, the sidewall of the (intermediate) structure shown in 3b, and the bottom of the (bottom) structure shown in 3c. The SEM image of the cross-section shows approximately 100% surface coverage of the film.

[0104] Example 18: Plasma densification treatment during ALD deposition of carbon-doped silicon-containing films At a substrate temperature of 300°C, silicon-containing films were deposited in each ALD cycle using the cyclic halo-bosilane precursor 1,1,3,3-tetrachlorodisilacyclobutane, ammonia, and an inert plasma densification process. This demonstrated that intermittent film processing can improve several properties of the resulting films, such as density. The deposition process is shown in Table XVI below.

[0105] [Table 16]

[0106] Process steps 3-8 in Table XVI were repeated 1000 times to obtain a silicon-containing film of the desired thickness. The obtained film contained 7.1% O, 48.0% N, 5.3% C, 39.3% Si, and 0.3% Cl as measured by XPS, and had a relatively high density of 2.6 g / cc. The high oxygen content within the film is thought to be due to exposure to ambient air.

[0107] Example 19: Carbon-doped silicon-containing film deposited using ethylenediamine in a thermal ALD process At a temperature of 300°C, silicon-containing films were deposited using 1,1,3,3-tetrachloro-1,3-disilacyclobutane as a cyclic carbosilane precursor and ethylenediamine. The precursor was transported using vapor suction at a source temperature of 70°C, and the nitrogen source was transported at 30°C using vapor suction.

[0108] [Table 17]

[0109] Process steps 3-14 were repeated multiple times to obtain the desired film thickness. The resulting film had a reflectance of 1.56. The film density was 1.55 g / cc. The film composition, as measured by XRR and XPS, was 33.7% C, 6.4% N, 24.4% N, 34.3% O, and 1.2% Cl. The high oxygen content within the film is thought to be due to exposure to ambient air. The carbon content in the ethylenediamine process (33.7% C) was higher than that in the ammonia process (24.7%).

[0110] Comparative Example 1: Silicon-containing film deposited using SiCl4 and ammonia Using the process steps described in Table IV, silicon-containing films were deposited at 300°C using tetrasilicon chloride (SiCl4) instead of the cyclic carbosilane precursor and ammonia as the nitrogen source. The resulting films had a thickness of 250 nm and a reflectance of 1.70.

[0111] After being immersed in diluted HF for 15 seconds, the film was completely etched, which can be interpreted as an extremely high etching rate of over 16.7 Å / second.

[0112] Comparative Example 2: Carbon-doped silicon-containing film deposited using bis(trichlorosilyl)methane and ammonia Silicon-containing films were deposited at 300°C and 500°C using the process steps described in Table IV, with precursor bis(trichlorosilyl)methane, linear carbosilane, and ammonia as the nitrogen source. The films were exposed to diluted HF for approximately one week after deposition, and their wet etch rates were measured. Tables XVIII and XIX show the film composition data, reflectance, and wet etch rate (WER). Compared to the cyclic carbosilane in Example 9, films deposited using linear carbosilane showed extremely high WER and extremely low carbon content.

[0113] [Table 18]

[0114] [Table 19]

[0115] Comparative Example 3: Carbon-doped silicon-containing film deposited using bis(trichlorosilyl)methane and ammonia, followed by off-site post-deposition treatment. Using the process steps described in Table IV, silicon-containing films were deposited at 300°C using bis(trichlorosilyl)methane as a substitute for cyclic carbosilane and ammonia. The deposited films were then annealed in situ at 300°C for 3 hours in the ambient environment. The resulting films had a composition of 57.9%O, 2.4%N, 11.9%C, and 27.7%Si. The WER of the films in diluted HF was 0.17 Å / sec. Compared to films deposited with cyclic carbosilane precursors, such as those in Examples 9 and 10, under the same experimental conditions, the carbon content was extremely low and the WER was extremely high.

[0116] Comparative Example 4: Plasma densification treatment during ALD deposition of carbon-doped silicon-containing films using bis(trichlorosilyl)methane (BTCSM) Using bis(trichlorosilyl)methane and ammonia as a nitrogen source, a Si-containing film was deposited by performing an in-situ inert plasma densification process at the end of the ALD deposition. The process temperature was 300°C. The deposition process is described in Table XXI as follows.

[0117] [Table 20]

[0118] Process steps 3-6 were repeated multiple times, followed by step 7, to obtain a silicon-containing film of the desired thickness. The deposited film had a WER of over 9 Å / sec at diluted HF, which was significantly higher than that of the silicon-containing film from cyclic carbosilane in Example 16 under the same deposition conditions.

[0119] The present invention includes the following embodiments. (1) A composition for depositing a silicon-containing film, 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-iodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1,1-diiodo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane A cyclic halocbosilane selected from the group consisting of clobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-tricilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-tricilacyclohexane, and 1,3,5-trichloro-1,3,5-tricilacyclohexane, A cyclic haloaminocarbosilane selected from the group consisting of 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane, and 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane, A cyclic aminocarbosilane selected from the group consisting of 1,1,3,3-tetrakis(methylamino)-1,3-disilacyclobutane, 1,1,3,3-tetrakis(dimethylamino)-1,3-disilacyclobutane, 1,3-bis(dimethylamino)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(methylamino)-1,3-dimethyl-1,3-disilacyclobutane, and 1,3-bis(iso-propylamino)-1,3-dimethyl-1,3-disilacyclobutane. A composition comprising at least one precursor selected from the group consisting of the following.

[0120] (2) A method for depositing a carbon-doped silicon-containing film selected from carbon-doped silicon oxide films and carbon-doped silicon oxynitride films, The process of placing the substrate in the reactor, A step of heating the reactor to one or more temperatures in the range of approximately 25 to approximately 700°C, A step of introducing at least one cyclic carbosilane precursor selected from the group consisting of cyclic halo-bosilane, cyclic halo-aminocarbosilane, cyclic aminocarbosilane, and combinations thereof, A step of introducing a nitrogen source under conditions sufficient to react with the at least one cyclic carbosilane precursor to form a carbon-doped silicon nitride film, Optionally, the silicon carbonitride film is exposed to an oxygen source and converted to a film at one or more temperatures in the range of approximately 100 to 1000°C. Methods that include...

[0121] (3) The method according to (2), further comprising treating the silicon-containing film with at least one selected from the group consisting of thermal annealing, plasma, ultraviolet light irradiation, laser irradiation, electron beam irradiation, and combinations thereof. (4) The cyclic carbosilane is 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-iodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1,1-diiodo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disila The method according to (2), comprising a cyclic halocbosilane selected from the group consisting of cyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-tricilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-tricilacyclohexane, and 1,3,5-trichloro-1,3,5-tricilacyclohexane.

[0122] (5) The method according to (2), wherein the cyclic carbosilane comprises a cyclic haloaminocarbosilane selected from the group consisting of 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane, and 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane. (6) The method according to (2), wherein the cyclic carbosilane comprises a cyclic aminocarbosilane selected from the group consisting of 1,1,3,3-tetrakis(methylamino)-1,3-disilacyclobutane, 1,1,3,3-tetrakis(dimethylamino)-1,3-disilacyclobutane, 1,3-bis(dimethylamino)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(methylamino)-1,3-dimethyl-1,3-disilacyclobutane, and 1,3-bis(iso-propylamino)-1,3-dimethyl-1,3-disilacyclobutane. (7) The method according to (2), wherein the film contains approximately 10 atomic percent or more of carbon when measured by XPS. (8) The method according to (2), wherein the film includes wet etching of about 0.15 Å / second or less when measured with dilute hydrofluoric acid.

[0123] (9) A method for depositing a silicon-containing film selected from silicon carbide films and carbon-doped silicon nitride films, The process of placing the semiconductor substrate in the reactor, A step of heating the reactor to one or more temperatures in the range of approximately 25 to approximately 700°C, and optionally maintaining the reactor at a pressure of 100 torr or less, A step of introducing at least one cyclic carbosilane selected from the group consisting of cyclic halo-carbosilane, cyclic halo-aminocarbosilane, and combinations thereof, A step of introducing a nitrogen-containing plasma source into the reactor under conditions sufficient to react with the carbosilane precursor and form the film; Methods that include...

[0124] (10) The method according to (9), wherein the nitrogen-containing plasma source is selected from the group consisting of nitrogen plasma, nitrogen and helium-containing plasma, nitrogen and argon-containing plasma, ammonia plasma, ammonia and helium-containing plasma, ammonia and argon-containing plasma, helium plasma, argon plasma, neon plasma, hydrogen plasma, hydrogen and helium-containing plasma, hydrogen and argon-containing plasma, organic amine plasma, organic diamine plasma, and combinations thereof. (11) The method according to (9), further comprising treating the silicon-containing film with at least one selected from the group consisting of thermal annealing, plasma treatment, ultraviolet light irradiation, laser irradiation, electron beam irradiation, and combinations thereof. (12) The method according to (9), further comprising exposing the film to an oxygen source in the reactor to convert the silicon-containing film into a silicon oxide film or a carbon-doped silicon oxide film. (13) The method according to (12), wherein the oxygen source is selected from the group consisting of water vapor, water plasma, oxygenated water, oxygenated water vapor, oxygen, oxygen plasma, oxygen and helium-containing plasma, oxygen and argon-containing plasma, nitrogen oxide-containing plasma, carbon dioxide-containing plasma, hydrogen peroxide, organic peroxide, and combinations thereof.

[0125] (14) The cyclic carbosilane is 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-iodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1,1-diiodo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disila The method according to (12), comprising a cyclic halocbosilane selected from the group consisting of cyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-tricilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-tricilacyclohexane, and 1,3,5-trichloro-1,3,5-tricilacyclohexane. (15) The method according to (12), wherein the cyclic carbosilane comprises a cyclic haloaminocarbosilane selected from the group consisting of 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane, and 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane.

Claims

1. 1. A method for depositing a carbon-doped silicon-containing film selected from a carbon-doped silicon nitride film and a carbon-doped silicon oxynitride film, comprising: a) placing a substrate in a reactor; b) heating the reactor to one or more temperatures in the range of 25 to 700° C.; c) 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-iodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1,1-diiodo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1 introducing at least one cyclic halolocalbosilane selected from the group consisting of 1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-trisilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-trisilacyclohexane, and 1,3,5-trichloro-1,3,5-trisilacyclohexane; d) introducing a nitrogen-containing plasma source into said reactor under conditions sufficient to react with said at least one cyclic halolocalvosilane and form said carbon-doped silicon nitride film; e) optionally exposing the carbon-doped silicon nitride film to an oxygen source to convert the carbon-doped silicon nitride film to the carbon-doped silicon oxynitride film at one or more temperatures in the range of 100-1000° C.; Including, the nitrogen-containing plasma is selected from the group consisting of nitrogen plasma, nitrogen and helium-containing plasma, nitrogen and argon-containing plasma, ammonia plasma, ammonia and helium-containing plasma, ammonia and argon-containing plasma, organic amine plasma, and organic diamine plasma; method.

2. 2. The method of claim 1, wherein the method is a plasma enhanced atomic layer deposition method, whereby steps c through d are repeated iteratively to form the carbon-doped silicon-containing film in layers.

3. The method of claim 1 , wherein a plasma is selected as the oxygen source during step e.

4. The method of claim 3 , wherein the oxygen source is selected from the group consisting of a water vapor plasma, an oxygen plasma, and a plasma comprising water and an inert gas.

5. 10. The method of claim 1, wherein the carbon-doped silicon-containing film comprises a carbon content of 10 atomic percent or greater as measured by XPS.

6. 2. The method of claim 1, wherein the carbon-doped silicon-containing film comprises a wet etch rate of 0.15 Å / sec or less as measured in dilute hydrofluoric acid, the dilute hydrofluoric acid being a 1:99 bath of 49% HF and DI water.

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