Chlorosilyl-substituted silacycloalkanes and their use for forming films containing silicon and oxygen.

Abstract

A halidesilyl-substituted cyclic silicon precursor compound has a carbon-to-silicon ratio of at least 2:1 and is defined herein by formula I. A method for forming a film containing silicon and oxygen and having a carbon content in the range of 10 atomic% to 50 atomic% via a thermal ALD process is provided, comprising the steps of: placing one or more substrates having surface features in a reactor; heating the reactor to one or more temperatures in the range of ambient temperature to about 600°C and optionally maintaining the reactor at a pressure of 100 torr or less; introducing at least one silicon precursor according to formula I into the reactor; purging with an inert gas; and providing a nitrogen source to the reactor to react with the surface. The process includes the steps of: forming a carbon-doped silicon nitride film; purging with an inert gas to remove reaction byproducts; repeating the process to provide a carbon-doped silicon nitride film of a desired thickness; treating the obtained carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from approximately ambient temperature to about 1000°C, or from about 100°C to 400°C, to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film; and exposing the carbon-doped silicon oxide film to a hydrogen-containing plasma.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the interests of U.S. Provisional Patent Application No. 63 / 498,134, filed on 25 April 2023. The entire content of the identified Provisional Patent is incorporated herein by reference in full.

[0002] This specification describes compounds, compositions containing such compounds, and methods for using such compounds to manufacture electronic devices. More specifically, this specification describes compounds for depositing silicon-containing films having a dielectric constant (<6.0) and a low leakage current density and a high carbon content, such as, but not limited to, carbon-doped silicon oxide films, carbon-doped silicon nitride films, and carbon-doped silicon oxynitride films, as well as compositions incorporating such compounds and methods. [Background technology]

[0003] For low-k spacer applications, carbon-doped silicon-containing films, such as silicon oxide films, are required to achieve a low dielectric constant (k value). The higher the carbon content of such films, the greater the tunability. On the other hand, films with a certain nitrogen content have high resistance to high temperatures and oxygen ashing, making nitrogen content important for device integration. Furthermore, films with high nitrogen content generally have higher k values ​​than films with low nitrogen content. Therefore, there is a balance between the amounts of nitrogen and carbon in carbon-doped silicon-containing films to satisfy both electrical and integration step requirements. In this art, there is a need to provide compositions for depositing 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)), such as carbon-doped silicon oxide films, and methods for using such compositions, for numerous applications within the electronics industry.

[0004] U.S. Patent Application Publication No. 2018 / 0033614 discloses a silicon precursor having one or two Si-C-Si bonds and a method of incorporating the precursor for depositing a low-k carbon-doped silicon-containing film using atomic layer deposition that may include plasma.

[0005] U.S. Patent No. 8,575,033 describes a method of depositing a silicon carbide film on a substrate surface. This method includes the use of a vapor-phase carbosilane precursor and can employ a plasma-enhanced atomic layer deposition process.

[0006] U.S. Patent Application Publication No. 2013 / 022496(A) teaches a method of forming a dielectric film having Si-C bonds on a semiconductor substrate by atomic layer deposition (ALD). This method includes (i) a step of adsorbing a precursor on the surface of the substrate, (ii) a step of reacting the adsorbed precursor with a reaction gas on the surface, and (iii) a step of repeating steps (i) and (ii) to form a dielectric film having at least Si-C bonds on the substrate.

[0007] International Publication No. 14134476(A1) describes a method of depositing a film containing SiCN and SiOCN. The specific method includes exposing the substrate surface to a first and a second precursor. The first precursor has the formula (X y H 3-y Si)zCH 4-z 、(X y H 3-y Si)(CH2)(SiX p H 2-p )(CH2)(SiX y H 3-y )、or (X y H 3-y Si)(CH2) n (SiX y H 3-y )(where 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, and n has a value of 2 to 5), and the second precursor includes a reducing amine. The specific method also includes exposing the substrate surface to an oxygen source to provide a film containing carbon-doped silicon oxide.

[0008] Hirose, Y., Mizuno, K., Mizuno, N., Okubo, S., Okubo, S., Yanagida, K. and Yanagita, K. (2014) "Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium," U.S. Patent Application Publication No. 2014 / 287596(A), describes a method for manufacturing a semiconductor device, comprising forming a thin film containing silicon, oxygen, and carbon on a substrate by performing a predetermined number of cycles, the cycle comprising the steps of supplying a precursor gas containing silicon, carbon, and halogen elements and having Si-C bonds, and a first catalyst gas to the substrate, and supplying an oxidizing gas and a second catalyst gas to the substrate.

[0009] Hirose, Y., Mizuno, N., Yanagita, K. and Okubo, S. (2014) "Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium." U.S. Patent No. 9,343,290(B) describes a method for manufacturing a semiconductor device, comprising forming an oxide film on a substrate by performing a predetermined number of cycles. This cycle includes the steps of supplying a precursor gas to the substrate and supplying ozone gas to the substrate. In the step of supplying the precursor gas, the precursor gas is supplied to the substrate without a catalyst gas being supplied to the substrate, and in the step of supplying the ozone gas, the ozone gas is supplied to the substrate with an amine-based catalyst gas already supplied to the substrate.

[0010] U.S. Patent No. 9,349,586(B) discloses a thin film having desired etching resistance and low dielectric constant.

[0011] U.S. Patent Application Publication No. 2015 / 0044881(A) describes a method for forming a film containing carbon added at a high concentration with high controllability. A method for manufacturing a semiconductor device includes forming a film containing silicon, carbon, and a predetermined element on a substrate by performing a cycle a predetermined number of times. The predetermined element is one of nitrogen or oxygen. This cycle includes supplying a precursor gas containing at least two silicon atoms, carbon, and a halogen element per mole and having a Si-C bond to the substrate, and supplying a reforming gas containing the predetermined element to the substrate.

[0012] The reference entitled "Highly Stable Ultrathin Carbosiloxane Films by Molecular Layer Deposition", Han, Z. et al., Journal of Physical Chemistry C, 2013, 117, 19967 teaches growing a carbosiloxane film using 1,2-bis[(dimethylamino)dimethylsilyl]ethane and ozone. The thermal stability indicates that the film is stable at 40°C or lower and there is little loss in thickness at 60°C.

[0013] Liu et al, Jpn. Appl. Phys., 1999, Vol. 38, 3482 - 3486 teaches the use of H2 plasma for polysilsesquioxane deposited by spin-on technology. The H2 plasma provides a stable dielectric constant and improves the thermal stability of the film and the O2 ashing (plasma) process.

[0014] Kim et al, Journal of the Korean Physical Society, 2002, Vol. 40, 94 teaches that H2 plasma treatment on a PECVD carbon-doped silicon oxide film improves the leakage current density (by 4 - 5 orders of magnitude) and the dielectric constant increases from 2.2 to 2.5. The carbon-doped silicon oxide film after H2 plasma has less damage during the oxygen ashing process.

[0015] Posseme et al, Solid State Phenomena, 2005, Vol. 103-104, 337, teach about different H2 / inert plasma treatments on carbon-doped silicon oxide PECVD films. k indicates no improvement after H2 plasma treatment, suggesting no bulk modification.

[0016] The patents, patent applications, and publications disclosed to date are incorporated herein by reference. [Overview of the project]

[0017] The compositions and methods described herein overcome the problems of the prior art by providing compositions or formulations for depositing conformal silicon-containing films using thermal atomic layer deposition (ALD). In one embodiment, the composition for depositing a silicon-containing film comprises (a) at least one halidesilyl-substituted cyclic silicon precursor, wherein formula I [ka] [In the formula, R 1~4 Each of these is independently a hydrogen atom, a linear or branched or cyclic C1-C atom. 10 Selected from the group consisting of alkyls and halides (i.e., F, Cl, Br, and I), X 1~5 These are halides, hydrogen, and C1-C 10 Independently selected from the group consisting of alkyls, provided that at least one X 1~5 It contains a precursor that is a halide. Preferably, R 1~4 X is independently selected from the group consisting of hydrogen or methyl. 1~5 This is independently selected from the group consisting of hydrogen, methyl, Cl, Br, or I.

[0018] In at least one aspect of the present invention, the composition further comprises (b) at least one solvent. In certain embodiments of the compositions described herein, exemplary solvents 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 precursor compound and the boiling point of the solvent is 40°C or less, less than about 30°C, possibly less than about 20°C, preferably less than 10°C.

[0019] Another aspect of the present invention relates to a method for forming a carbon-doped silicon oxide film having a carbon content in the range of 10 atomic% to 50 atomic% via a thermal ALD process, the method comprising: a. placing one or more substrates having surface features in a reactor; b. heating the reactor to one or more temperatures in the range of ambient temperature to about 600°C and optionally maintaining the reactor at a pressure of 100 torr or less; c. introducing a precursor comprising at least one compound selected from silicon precursors according to Formula 1 into the reactor; and d. purging with an inert gas to remove unreacted silicon precursor The process includes: e. a step of removing; f. a step of providing a nitrogen source to the reactor and reacting it with the surface to form a silicon carbonitride film; g. a step of purging with an inert gas to remove reaction byproducts; g. a step of repeating steps c to f to provide a silicon carbonitride film of a desired thickness; h. a step of treating the obtained silicon carbonitride film with an oxygen source at one or more temperatures ranging from approximately ambient temperature to 1000°C, or from about 100°C to 400°C, to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film; and i. a step of exposing the carbon-doped silicon oxide film to a hydrogen-containing plasma.

[0020] In another embodiment, a method is provided for depositing a film selected from films containing silicon and oxygen onto at least one surface of a substrate, comprising the steps of: placing the substrate in a reactor; heating the reactor to one or more temperatures in the range of about 25°C to about 600°C; introducing a precursor comprising at least one compound selected from silicon precursors according to Formula 1 into the reactor; 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; and treating the carbon-doped silicon nitride film with an oxygen source at one or more temperatures in the range of about 25°C to 1000°C or about 100°C to 400°C under conditions sufficient to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxynitride film. In certain embodiments, the carbon-doped silicon oxide film or carbon-doped silicon oxynitride film has a carbon content of approximately 10 atomic weight percent (atomic%) or more as measured by XPS, and its etching rate, as measured in dilute hydrofluoric acid, is at least 0.5 times lower than that of thermal silicon oxide.

[0021] If desired, the present invention further comprises the step of treating a carbon-doped silicon oxide or silicon oxynitride film with hydrogen or a hydrogen / inert plasma at a temperature of 25°C to 600°C.

[0022] A further aspect of the present invention relates to a film in which k is less than about 4 and the carbon content based on XPS measurement is at least about 10 atomic percent, and in another aspect, the film of the present invention can be formed according to any of the methods of the present invention.

[0023] Another aspect of the present invention relates to a stainless steel container for housing the composition of the present invention.

[0024] The embodiments of the present invention may be used individually or in various combinations with each other. [Brief explanation of the drawing]

[0025] (Not included in the original text) [Modes for carrying out the invention]

[0026] Described herein are silicon precursor compounds, compositions and methods comprising such compounds, for depositing silicon and oxygen-containing films (for example, having a carbon content of about 10 atomic% or more, preferably 15 atomic% or more, most preferably 20 atomic% or more, as measured by XPS; dielectric constant of 6.0 or less, preferably 3.5 or less, most preferably 3.0 or less) by a deposition process, such as a thermal atomic layer deposition process, but not limited to such processes. Since carbon content is an important factor for reducing the wet etching rate and increasing ashing resistance, the carbon content of the present invention is 10 atomic% to 50 atomic%, preferably 15 atomic% to 40 atomic%, as measured by XPS, most preferably 20 atomic% to 40 atomic%. Films deposited using the compositions and methods described herein exhibit extremely low etching rates, for example, at least 0.5 times lower than that of thermal silicon oxide measured in dilute hydrofluoric acid (e.g., about 0.20 Å / s or less or about 0.15 Å / s or less in dilute HF (0.5 wt%)), or at least 0.1 times lower than that of thermal silicon oxide, or at least 0.05 times lower than that of thermal silicon oxide, or at least 0.01 times lower than that of thermal silicon oxide, while exhibiting variability in other tunable properties, such as density, dielectric constant, refractive index, and elemental composition.

[0027] In certain embodiments, one or more of the features described herein can be obtained by the silicon precursors and methods using said precursors in the following manner: Firstly, the as-deposited reactive carbon-doped silicon-containing film is at least one halidesilyl-substituted cyclic silicon precursor, wherein formula I [ka] [In the formula, R 1~4 Each of these is independently a hydrogen atom, a linear or branched or cyclic C1-C atom. 10 Selected from the group consisting of alkyls and halides (i.e., F, Cl, Br, and I), X 1~5 These are halides, hydrogen, and C1-C10 Independently selected from the group consisting of alkyls, provided that at least one X 1~5 It is formed using a precursor that follows the rule that [is a halide]. Preferably, R 1~4 X is independently selected from the group consisting of hydrogen or methyl. 1~5 This is independently selected from the group consisting of hydrogen, methyl, Cl, Br, or I.

[0028] While we do not wish to be bound by any theory or explanation, it is thought that some of the Si-CC-Si bonds from the halidesilyl-substituted cyclic silicon precursor remain in the resulting Azdepo film, resulting in a high carbon content of at least 10 to 50 atoms, preferably 15 to 40 atoms, and most preferably 20 to 40 atoms, as measured by XPS.

[0029] Secondly, according to some embodiments, when the Azdepo film is intermittently exposed to an oxygen source such as water during the deposition process, as a post-deposition treatment, or a combination thereof, at least some or all of the nitrogen content in the film is converted to oxygen, resulting in a film selected from carbon-doped silicon oxide films or carbon-doped silicon oxynitride films. The nitrogen in the Azdepo film is released as one or more nitrogen-containing byproducts such as ammonia or amine groups.

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

[0031] In one embodiment, the composition for depositing a silicon-containing film comprises at least one halidesilyl-substituted cyclic silicon precursor having a carbon-to-silicon ratio of at least 2:1, and formula I [ka] [In the formula, R 1~4 Each of these is independently a hydrogen atom, a linear or branched or cyclic C1-C atom. 10Selected from the group consisting of alkyls and halides (i.e., F, Cl, Br, and I), X 1~5 These are halides, hydrogen, and C1-C 10 Independently selected from the group consisting of alkyls, provided that at least one X 1~5 It contains a precursor that is a halide. Preferably, R 1~4 X is independently selected from the group consisting of hydrogen or methyl. 1~5 The element is independently selected from the group consisting of hydrogen, methyl, Cl, Br, or I. Exemplary compounds following formula I are listed in Table I, but are not limited to these. [Table 1-1] [Table 1-2]

[0032] In further embodiments, the composition further comprises (b) at least one solvent. In certain embodiments of the compositions described herein, exemplary solvents 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 a Si-CC-Si bond and the boiling point of the solvent is 40°C or less. The weight percent of the silicon precursor compound in the solvent may vary from 1 to 99% by weight, or 10 to 90% by weight, or 20 to 80% by weight, or 30 to 70% by weight, or 40 to 60% by weight, or 50 to 50% by weight. In some embodiments, the composition can be delivered by direct liquid injection into a reactor chamber for a silicon-containing membrane using conventional direct liquid injection apparatus and methods.

[0033] Another embodiment of the method described herein involves depositing a film containing silicon and oxygen having a carbon content in the range of 10 atomic% to 50 atomic%, preferably 15 atomic% to 40 atomic%, using a thermal ALD process. In this embodiment, the method is a. A step of placing one or more substrates having surface features into a reactor, b. A step of heating the reactor to one or more temperatures in the range from ambient temperature to approximately 600°C, and optionally maintaining the reactor at a pressure of 100 torr or less, c. A step of introducing at least one silicon precursor according to formula I into the reactor, d. A step of purging with an inert gas to remove unreacted silicon precursor, e. A step of providing a nitrogen source to the reactor and reacting it with the above surface to form a carbon-doped silicon nitride film, f. A step of purging with an inert gas to remove reaction by-products, g. A step of repeating steps c to f to provide a carbon-doped silicon nitride film of a desired thickness, h. A step of treating a carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from approximately ambient temperature to 1000°C, preferably in the range of about 100°C to 400°C, and converting the carbon-doped silicon nitride film to a carbon-doped silicon oxide film either in situ or in another chamber. i. A step of exposing a carbon-doped silicon oxide film to a hydrogen-containing plasma, j. Optionally, the process includes treating the carbon-doped silicon oxide film by spike annealing at a temperature of 400 to 1000°C or with a UV light source. In this embodiment or other embodiments, the UV exposure step may be performed either during film deposition or after deposition is complete.

[0034] A further embodiment of the method described herein includes depositing a film containing silicon and oxygen having a carbon content in the range of 10 atomic% to 50 atomic%, preferably 15 atomic% to 40 atomic%, using a combination of thermal ALD and plasma ALD. In this embodiment, the method is a. A step of placing one or more substrates having surface features into a reactor, b. A step of heating the reactor to one or more temperatures in the range from ambient temperature to approximately 600°C, and optionally maintaining the reactor at a pressure of 100 torr or less, c. A step of introducing at least one silicon precursor according to formula I into the reactor, d. A step of purging with an inert gas to remove unreacted silicon precursors, e. A step of providing a nitrogen source to the reactor and reacting it with the above surface to form a carbon-doped silicon nitride film, f. A step of purging with an inert gas to remove reaction by-products, g. A step of introducing an oxygen source to form carbon-doped silicon oxynitride, h. A step of purging with an inert gas to remove reaction by-products, i. Optionally, a step of exposing the film to a plasma source containing hydrogen, j. A step of purging with an inert gas to remove reaction by-products, Includes. To obtain the desired film thickness, steps c to j are repeated multiple times.

[0035] In one embodiment, the surface features of the substrate include a pattern trench with an aspect ratio of 1:9 and an aperture of 180 nm.

[0036] In yet another embodiment of the method described herein, a film containing silicon and oxygen having a carbon content in the range of 10 atomic% to 50 atomic%, preferably 15 atomic% to 40 atomic%, is deposited using a thermal ALD process with a catalyst containing ammonia or an organic amine. In this embodiment, the method is a. A step of placing one or more substrates having surface features into a reactor, b. A step of heating the reactor to one or more temperatures within the range of ambient temperature up to approximately 150°C, and optionally maintaining the reactor at a pressure of 100 torr or less, c. A step of introducing at least one silicon precursor according to formula I into the reactor, d. A step of purging with an inert gas to remove unreacted silicon precursors, e. A step of supplying steam to the reactor and reacting it with the catalyst and the precursor to form a carbon-doped silicon oxide film, f. A step of purging with an inert gas to remove reaction by-products, g. A step of repeating steps c to f to provide the carbon-doped silicon oxide film of the desired thickness, h. A step of exposing the carbon-doped silicon oxide film to a hydrogen-containing plasma, i. Optionally, the process includes treating the carbon-doped silicon oxide film by spike annealing at a temperature of 400 to 1000°C or with a UV light source. In this embodiment or other embodiments, the UV exposure step may be performed either during film deposition or after deposition is complete.

[0037] In this embodiment 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 1 equivalent relative to the amount of silicon precursor vapor generated in the reactor during step c.

[0038] In certain embodiments, the resulting carbon-doped silicon oxide film is exposed to an organic aminosilane or chlorosilane having Si-Me, Si-H, or both, before being exposed to hydrogen plasma treatment to form a hydrophobic thin layer. Suitable organic aminosilanes are not limited to these, but include diethylaminotrimethylsilane, dimethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, t-butylaminotrimethylsilane, isopropylaminotrimethylsilane, diisopropylaminotrimethylsilane, pyrrolidinotrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, ethylmethylaminodimethylsilane, t-butylaminodimethylsilane, isopropylaminodimethylsilane, diisopropylaminodimethylsilane, pyrrolidinodimethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)dimethylsilane, bis(ethylmethylamino)dimethylsilane, bis(diisopropylamino)dimethylsilane, bis(isopropylamino)dimethylsilane, bis(tert-butylamino)dimethyl Examples include rusilane, dipyrrolidinodimethylsilane, bis(diethylamino)diethylsilane, bis(diethylamino)methylvinylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylmethylamino)methylvinylsilane, bis(diisopropylamino)methylvinylsilane, bis(isopropylamino)methylvinylsilane, bis(tert-butylamino)methylvinylsilane, dipyrrolidinomethylvinylsilane, 2,6-dimethylpiperidinomethylsilane, 2,6-dimethylpiperidinodimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, tris(dimethylamino)phenylsilane, tris(dimethylamino)methylsilane, diisopropylaminosilane, di-sec-butylaminosilane, chlorodimethylsilane, chlorotrimethylsilane, dichloromethylsilane, and dichlorodimethylsilane.

[0039] In another embodiment, the resulting carbon-doped silicon oxide film is exposed to an alkoxysilane or cyclic alkoxysilane having Si-Me, Si-H, or both, before being exposed to hydrogen plasma treatment to form a hydrophobic thin layer. Suitable alkoxysilanes or cyclic alkoxysilanes include, but are not limited to, diethoxymethylsilane, dimethoxymethylsilane, diethoxydimethylsilane, dimethoxydimethylsilane, 2,4,6,8-tetramethylcyclotetrasiloxane, or octamethylcyclotetrasiloxane. While we do not wish to be bound by any theory or explanation, it is thought that thin layers formed by organic aminosilanes or alkoxysilanes or cyclic alkoxysilanes may be converted to high-density carbon-doped silicon oxide during the plasma ashing process, further enhancing ashing resistance.

[0040] In another embodiment, a vessel for depositing a silicon-containing film comprises one or more silicon precursor compounds as described herein. In one particular embodiment, the vessel includes at least one pressurized vessel (preferably made of stainless steel having a design as disclosed in U.S. Patent Nos. 7,334,595, 6,077,356, 5,069,244, and 5,465,766 (these disclosures are incorporated herein by reference)). The vessel may include either glass (borosilicate glass or quartz glass) or a 316, 316L, 304, or 304L type stainless steel alloy (UNS designations S31600, S31603, S30400, S30403) and is fitted with appropriate valves and fittings to enable the delivery of one or more precursors to a reactor for a CVD or ALD process. In this embodiment or other embodiments, the silicon precursor is supplied in a pressurized vessel made of stainless steel, and the purity of the precursor is 98% by weight or 99.5% by weight or higher, which is suitable for semiconductor applications. The silicon precursor compound is preferably Al 3+ Ions, Fe 2+ Fe 3+ Ni 2+ , Cr 3+It is substantially free of metal ions such as Al. 3+ Ions, Fe 2+ Fe 3+ Ni 2+ , Cr 3+ The term “substantially absent” in relation to means less than about 5 ppm (by weight), preferably less than about 3 ppm, more preferably less than about 1 ppm, and most preferably about 0.1 ppm. In certain embodiments, such vessels may also have means for mixing the precursor with one or more additional precursors, if desired. In these embodiments or other embodiments, the contents of the vessel(s) may be pre-mixed with additional precursors. Alternatively, the silicon precursor and / or other precursors may be maintained during storage in separate vessels or in a single vessel having separation means for maintaining the silicon precursor and other precursors separately.

[0041] A silicon-containing film is deposited on at least one surface of a substrate, such as a semiconductor substrate. In the method described herein, the substrate may be composed of and / or coated with various materials well known in the art, such as silicon, metals such as crystalline or amorphous silicon, silicon oxide, silicon nitride, amorphous carbon, silicon oxycarbide, silicon oxynitride, silicon carbide, germanium, germanium-doped silicon, boron-doped silicon, copper, tungsten, aluminum, cobalt, nickel, and tantalum, metal nitrides such as titanium nitride and tantalum nitride, metal oxides, Group III / V metals or metalloids such as GaAs, InP, GaP, and GaN, and combinations thereof. These coatings may completely coat the semiconductor substrate, be multiple layers of various materials, or be partially etched to expose the underlying layers of the material. The surface may also have a photoresist material on it that is exposed in a pattern and developed to partially coat the substrate. In certain embodiments, the semiconductor substrate comprises at least one surface feature selected from the group consisting of pores, vias, trenches, and combinations thereof. Potential applications of silicon-containing films include, but are not limited to, low-k spacers for FinFETs or nanosheets, and sacrificial hard masks for self-aligned patterning processes (such as SADP, SAQP, or SAOP).

[0042] Deposition methods used to form silicon-containing films include, but are not limited to, atomic layer deposition processes, cyclic chemical vapor deposition processes, or chemical vapor 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., constant amount of film material deposited in each reaction cycle) and sequential surface chemistry process for depositing films of material on substrates of various compositions. As used herein, the term “thermal atomic layer deposition process” refers to an atomic layer deposition process at substrate temperatures ranging from room temperature to 600°C, without the use of in situ plasma or remote plasma. Although precursors, reagents, and sources used herein may be described as “gaseous,” it is understood that precursors may be either liquids or solids transported to the reactor by direct vaporization, bubbling, or sublimation, with or without an inert gas. In some cases, vaporized precursors may pass through a plasma generator.

[0043] 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.

[0044] In certain embodiments, the methods disclosed herein avoid preliminary reactions of the precursor(s) by using an ALD or CCVD method to separate the precursor(s) before and / or during introduction into the reactor. In this context, deposition techniques such as ALD or CCVD processes are used to deposit silicon-containing films. In one embodiment, the film is deposited via an ALD process in a typical single-wafer ALD reactor, semi-batch ALD reactor, or batch furnace ALD reactor by alternately exposing the substrate surface to one or more silicon-containing precursors, an oxygen source, a nitrogen-containing feed source, or other precursors or reagents. Film growth proceeds by self-limiting control of the surface reaction, the pulse length of each precursor or reagent, and the deposition temperature. However, film growth stops when the substrate surface becomes saturated. In another embodiment, each reactant, including silicon precursors and reactive gases, is exposed to the substrate by moving or rotating the substrate to different sections of the reactor, each section being separated by an inert gas curtain, i.e., a space ALD reactor or roll-to-roll ALD reactor.

[0045] Depending on the deposition method, in certain embodiments, the silicon precursor described herein and optionally other silicon-containing precursors may be introduced into the reactor in a predetermined molar volume, or about 0.1 to about 1000 micromoles. In this embodiment or other embodiments, the precursors may be introduced into the reactor over a predetermined period of time. In certain embodiments, the period of time is in the range of about 0.001 to about 500 seconds.

[0046] In certain embodiments, silicon-containing films deposited using the method described herein are formed in the presence of a catalyst and a combination of an oxygen source, an oxygen-containing reagent or precursor, i.e., water vapor. The oxygen source may be introduced into the reactor in the form of at least one oxygen source and / or may be incidentally present in other precursors used in the deposition process. Suitable oxygen source gases may include, for example, water (H2O) (e.g., deionized water, pure water, distilled water, water vapor, water vapor plasma, oxygenated water, air, water-containing compositions, and other organic liquids), oxygen (O2), oxygen plasma, ozone (O3), nitric oxide (NO), nitrogen dioxide (NO2), carbon monoxide (CO), water-containing plasma, water-containing plasma, hydrogen peroxide, hydrogen-containing compositions, hydrogen-containing compositions, carbon dioxide (CO2), air, and combinations thereof. In certain embodiments, the oxygen source comprises an oxygen source gas introduced into the reactor at a flow rate ranging from about 1 to about 10,000 square cubic centimeters (sccm) or about 1 to about 1,000 sccm. The oxygen source can be introduced over a time 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.

[0047] In embodiments in which the film is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse duration of more than 0.01 seconds, the oxygen source may have a pulse duration of less than 0.01 seconds, and the water pulse may have a pulse duration of less than 0.01 seconds.

[0048] In certain embodiments, an oxygen source flows continuously into the reactor while the precursor pulse and plasma are introduced sequentially. The precursor pulse can have a pulse duration of more than 0.01 seconds, and the plasma duration can be in the range of 0.01 seconds to 100 seconds.

[0049] In certain embodiments, the silicon-containing film comprises silicon and nitrogen. In these embodiments, the silicon-containing film deposited using the method described herein is formed in the presence of a nitrogen-containing source. The nitrogen-containing source may be introduced into the reactor in the form of at least one nitrogen source and / or may be incidentally present in other precursors used in the deposition process.

[0050] Suitable nitrogen-containing gases or nitrogen source gases include, for example, ammonia, hydrazine, monoalkylhydrazine, symmetric or asymmetric dialkylhydrazine, organic amines such as methylamine, ethylamine, ethylenediamine, ethanolamine, piperazine, N,N'-dimethylethylenediamine, imidazolidine, cyclotrimethylenetriamine, and combinations thereof.

[0051] The deposition methods disclosed herein may involve one or more purge gases. The purge gas used to remove unconsumed reactants and / or reaction by-products is an inert gas that does not react with the precursors. Examples of purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2), and mixtures 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 10,000 sccm for about 0.1 to about 1,000 seconds, thereby purging unreacted material and any by-products that may remain in the reactor.

[0052] Each step of supplying the precursor, oxygen source, nitrogen-containing supply source, and / or other precursor, supply gas, and / or reagent may be performed by varying the supply time in order to change the stoichiometric composition of the resulting membrane.

[0053] Energy is applied to at least one of a precursor, a nitrogen-containing source, a reducing agent, another precursor, or a combination thereof to induce a reaction and form 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.

[0054] In certain embodiments, a secondary RF frequency source can be used to modify the plasma properties on the substrate surface. In embodiments using plasma for deposition, the plasma generation process may include a direct plasma generation process in which the plasma is generated directly within the reactor, or a remote plasma generation process in which the plasma is generated outside the reactor and supplied to the reactor.

[0055] Silicon precursors and / or other silicon-containing precursors can be delivered to a reaction chamber, such as a CVD or ALD reactor, by various means. In one embodiment, a liquid delivery system can be utilized. In an alternative embodiment, a unit combining liquid delivery and a flash vaporization process may be used to enable volumetric delivery of low-volatility materials, such as a turbo vaporizer manufactured by MSP Corporation (Shoreview, MN), which results in reproducible transport and deposition of the precursor without thermal decomposition. In liquid delivery formulations, the precursors described herein may be delivered in neat liquid form or used in a solvent formulation or a composition containing a solvent formulation. Thus, in certain embodiments, the precursor formulation may contain solvent components of a preferred property that may be desirable and advantageous in a given end-use application for forming films on a substrate.

[0056] In this embodiment or other embodiments, it will be understood that the steps of the method described herein may be performed in various orders, sequentially or simultaneously (for example, between at least some of the steps of another step), and in any combination thereof. Each step of supplying the precursor and the nitrogen-containing source gas may be performed by varying the duration of the time they are supplied in order to change the stoichiometric composition of the resulting silicon-containing membrane.

[0057] In further embodiments of the methods described herein, the film or Azdepo film is subjected to a processing step. The processing step can be performed during at least part of the deposition process, after the deposition process, and in combination thereof. Exemplary processing steps include, but are not limited to, high-temperature thermal annealing; plasma treatment; ultraviolet (UV) treatment; laser treatment; electron beam treatment; and combinations thereof, for affecting one or more properties of the film. Films deposited with one or two Si-CC-Si bonded silicon precursors as described herein have improved properties when compared with films deposited with previously disclosed silicon precursors under the same conditions, for example, having a lower wet etching rate than the film before the processing step, or a higher density than the film before the processing step. In a particular embodiment, the Azdepo film is intermittently processed during the deposition process. These intermittent or intermediate deposition processes can be carried out, for example, after each ALD cycle, after a specific number of ALD cycles, for example, but not limited to, one ALD cycle, two ALD cycles, five ALD cycles, or ten or more ALD cycles.

[0058] In embodiments in which the film is treated in a high-temperature annealing process, the annealing temperature is at least 100°C higher than the deposition temperature. In this embodiment or other embodiments, the annealing temperature is in the range of about 400°C to about 1000°C. In this embodiment or other embodiments, the annealing process can be carried out in a vacuum (<760 Torr), an inert environment, or an oxygen-containing environment (such as H2O, N2O, NO2, or O2).

[0059] In embodiments where the film is treated with UV, the film is exposed to a broadband UV source or a UV source having wavelengths in the range of approximately 150 nanometers (nm) to approximately 400 nm. In a particular embodiment, the Azdepo film is exposed to UV in a chamber different from the deposition chamber after it has reached a desired film thickness.

[0060] In embodiments where the film is treated with plasma, a passivation layer, such as SiO2 or carbon-doped SiO2, is deposited to prevent chlorine and nitrogen contamination from penetrating the film during subsequent plasma treatment. The passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

[0061] In embodiments where the film is treated with plasma, the plasma source is selected from the group consisting of hydrogen plasma, plasma containing hydrogen and helium, and plasma containing hydrogen and argon. Hydrogen plasma reduces the dielectric constant of the film while maintaining little change in the bulk carbon content, thereby increasing its resistance to damage during subsequent plasma ashing processes.

[0062] Throughout this specification, the term "ashing" refers to the process in semiconductor manufacturing processes of removing a photoresist or carbon hard mask using a plasma containing an oxygen source, such as an O2 / inert gas plasma, O2 plasma, CO2 plasma, CO plasma, H2 / O2 plasma, or a combination thereof.

[0063] 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 film properties after oxygen ashing being: film dielectric constant less than 4.5; carbon content in the bulk (at depths greater than 50 Å into the film) less than 5 atomic percent, as before ashing; and damage to the film less than 50 Å is observed by the difference in diluted HF etching rates between the film near the surface (depths less than 50 Å) and the bulk (depths greater than 50 Å).

[0064] Throughout this specification, the term "alkyl hydrocarbon" refers to a straight-chain or branched-chain C1-C1 20 Hydrocarbons, cyclic C6-C 20 This refers to hydrocarbons. Examples of hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

[0065] Throughout this specification, the term "aromatic hydrocarbons" refers to C6-C6 20 This refers to aromatic hydrocarbons. Examples of aromatic hydrocarbons n include toluene and mesitylene, but are not limited to these.

[0066] Throughout this specification, the term “catalyst” refers to a Lewis base in the vapor phase that can catalyze the surface reaction between a hydroxyl group and a Si-Cl bond during a thermal ALD process. Examples of catalysts include, but are not limited to, cyclic amine gases such as aminopyridine, picoline, lutidine, piperazine, piperidine, and pyridine, or at least one of the organic amine gases methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, and tert-butylamine.

[0067] Throughout this specification, the term "organic amine" refers to C1-C 20 Hydrocarbons, cyclic C6-C 20 This refers to primary, secondary, and tertiary amines having hydrocarbons. Examples of organic amines include, but are not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, and tert-butylamine.

[0068] Throughout this specification, the term "siloxane" refers to a compound containing at least one Si-O-Si bond and C4-C 20This refers to a linear, branched, or cyclic liquid compound having carbon atoms. Examples of siloxanes include, but are not limited to, tetramethyldisiloxane, hexamethyldisiloxane (HMDSO), 1,1,1,3,3,5,5,5-octamethyltrisiloxane, and octamethylcyclotetrasiloxane (OMCTS).

[0069] Throughout this specification, the term “step coverage” as used herein is defined as the ratio (percent) of two thicknesses of a deposited film on a structured or feature-containing substrate having either or both vias and / or trenches, where bottom step coverage is the ratio (%) of the thickness at the bottom of a feature divided by the thickness at the top of the feature, and middle step coverage is the ratio (%) of the thickness at the sidewall of a 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, which indicates that the film is conformal.

[0070] Throughout this specification, the term “silicon-oxygen film” refers to a carbon-doped silicon oxide film or a carbon-doped silicon oxynitride film.

[0071] Throughout this specification, the term “ALD or ALD-like” refers to a process that includes, but is not limited to, the following: a) each reactant, including a silicon precursor and a reactive gas, is sequentially introduced into a reactor such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) each reactant, including a silicon precursor and a reactive gas, is exposed to a substrate by moving or rotating the substrate to different sections of the reactor, each section being separated by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor.

[0072] The following examples illustrate specific aspects of the present invention and do not limit the scope of the appended claims. [Examples]

[0073] Example 1. Synthesis of 1,1-dichloro-3-trichlorosilyl-1-silacyclopentane 1,1-Dichloro-1-Silacyclopenta-3-ene (19.8 g, 130 mmol) and trichlorosilane (21.9 g (162.0 mmol)) were placed in a 250 mL round-bottom flask, to which 0.10 mL of a xylene solution (2 wt% Pt) of Karstedt catalyst was added. The reaction mixture turned yellowish-brown, and this was heated at 80-90°C for 4 hours. The resulting reaction mixture was subjected to fractional distillation (65°C / 500 mTorr) to obtain 32.1 g of the desired product as a colorless liquid. Its purity was measured at 98% by GC-TCD analysis. GC-MS analysis of the product showed the following mass peaks: m / z = 288 (M+), 262, 253, 225, 211, 187, 175, 153, 139, 135, 127, 117, 115, 99, 90, 63, 53.

[0074] Example 2. Synthesis of 1,1-dichloro-3-(dichloromethylsilyl)silacyclopentane A mixture of 1,1-dichloro-1-silacyclopenta-3-ene (0.95 g, 0.01 mol) and an equimolar amount of MeHSiCl2 was heated in a sealed stainless steel tube in the presence of Karstedt catalyst (0.1 mL) at 120°C for 2 hours. GC-MS analysis of the resulting mixture showed 1,1-dichloro-3-(dichloromethylsilyl)silacyclopentane as the main product. GC-MS showed the following peaks: m / z = 268 (M), 253, 240, 125, 117, 105, 98, 90, 79, 63.

[0075] Example 3. Synthesis of 1,1-dichloro-3-(chlorodimethylsilyl)silacyclopentane A mixture of 1,1-dichloro-1-silacyclopenta-3-ene (0.95 g, 0.01 mol) and an equimolar amount of MeHSiCl2 was heated in a sealed stainless steel tube in the presence of Karstedt catalyst (0.1 mL) at 120°C for 2 hours. GC-MS analysis of the resulting mixture showed 1,1-dichloro-3-(chlorodimethylsilyl)silacyclopentane as the main product. GC-MS showed the following peaks: m / z = 233 (M-15), 125, 117, 105, 93, 85, 78, 63.

[0076] Example 4.1 Synthesis of 1,1-dichloro-3-(dichlorosilyl)silacyclopentane A mixture of 1,1-dichloro-1-silacyclopenta-3-ene (0.95 g, 0.01 mol) and an equimolar amount of H2SiCl2 was heated in a sealed stainless steel tube in the presence of Karstedt catalyst (0.1 mL) at 120°C for 2 hours. GC-MS analysis of the resulting mixture showed 1,1-dichloro-3-(dichlorosilyl)silacyclopentane as the main product. GC-MS showed the following peaks: m / z = 220 (M-35), 1192, 153, 125, 117, 105, 99, 91, 83, 63.

[0077] Example 5. Silicon-containing film deposition using thermal ALD process Silicon-containing films were deposited at 300°C and 550°C using the ALD method with the following steps: [Table 2]

[0078] As shown in Tables IIa and IIb, the films were deposited at 300°C and 550°C using the process described above. The same method was performed using the precursor bis(trichlorosilyl)methane (BTCSM), and the films were compared. The film compositions using the precursor 1,1-dichloro-3-trichlorosilyl-1-silacyclopentane had a higher carbon content than the films deposited using (BTCSM) at both temperatures. The film compositions deposited using 1,1-dichloro-3-trichlorosilyl-1-silacyclopentane are shown below.

[0079] [Table 3]

[0080] [Table 4]

[0081] While the present invention has been described with reference to specific embodiments, those skilled in the art will understand that various modifications can be made without departing from the scope of the invention, and that elements may be replaced with equivalents. Furthermore, many modifications can be made without departing from the essential scope of the invention to adapt specific situations or materials to the teachings of the invention. Thus, the present invention is not limited to the specific embodiments disclosed as the best mode intended for carrying out the invention, and the invention is intended to include all embodiments that fall within the scope of the appended claims.

Claims

1. A halidesilyl-substituted cyclic silicon precursor compound having at least a carbon-to-silicon ratio of 2:1, wherein formula I 【Chemistry 1】 [In the formula, R １～４ Each of these is independently a hydrogen atom, a linear or branched or cyclic carbon atom. １ ~C １０ Selected from the group consisting of alkyl and halide, X １～５ These are independently halide, hydrogen, and C １ ~C １０ Selected from the group consisting of alkyls, provided that at least one X １～５ [is halide] Precursor compound.

2. R １～４ each of which is independently selected from the group consisting of hydrogen or methyl, and X １～５ each of which is independently selected from the group consisting of hydrogen, methyl, Cl, Br and I, the precursor compound according to claim 1.

3. A precursor compound according to claim 1, selected from the group consisting of 1,1-dichloro-3-trichlorosilyl-1-silacyclopentane, 1,1-dichloro-3-dichlorosilyl-1-silacyclopentane, 1,1-dichloro-3-dichloromethylsilyl-1-silacyclopentane, 1,1-dichloro-3-dichloroethylsilyl-1-silacyclopentane, 1,1-dichloro-3-dichlorofluorosilyl-1-silacyclopentane, 1,1-dichloro-3-dichloroiodosilyl-1-silacyclopentane, 1,1-dichloro-3-chlorosilyl-1-silacyclopentane, and 1,1-dichloro-3-iodosilyl-1-silacyclopentane.

4. A composition comprising the precursor compound described in claim 1, and further comprising a solvent comprising at least one member selected from the group consisting of ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, siloxanes, and tertiary amino ethers.

5. The composition according to claim 4, wherein the difference between the boiling point of the precursor compound and the boiling point of the solvent is about 40°C or less.

6. The composition according to claim 4, wherein the solvent comprises at least one member selected from the group consisting of heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, cyclodecane, toluene, and mesitylene.

7. A method for forming a film containing silicon and oxygen, having a carbon content in the range of 10 atomic% to 50 atomic% via a thermal ALD process, a. A step of placing one or more substrates having surface features into a reactor, b. A step of heating the reactor to one or more temperatures in the range from ambient temperature to about 600°C, and optionally maintaining the reactor at a pressure of 100 torr or less, c. A step of introducing at least one silicon precursor containing the precursor compound described in claim 1 into the reactor, d. A step of purging the reactor with an inert gas, e. A step of providing a nitrogen source to the reactor and reacting it with the surface to form a carbon-doped silicon nitride film, f. A step of purging the reactor with an inert gas to remove reaction by-products, g. A step of repeating steps c to f to provide the carbon-doped silicon nitride film of a desired thickness, h. A step of treating the obtained carbon-doped silicon nitride film with an oxygen source at one or more temperatures ranging from approximately ambient temperature to 1000°C, or from approximately 100°C to 400°C, to convert the carbon-doped silicon nitride film into a carbon-doped silicon oxide film, i. A step of exposing the carbon-doped silicon oxide film to a hydrogen-containing plasma, Methods that include...

8. The method according to claim 7, wherein the precursor compound is selected from the group consisting of 1,1-dichloro-3-trichlorosilyl-1-silacyclopentane, 1,1-dichloro-3-dichlorosilyl-1-silacyclopentane, 1,1-dichloro-3-dichloromethylsilyl-1-silacyclopentane, 1,1-dichloro-3-dichloroethylsilyl-1-silacyclopentane, 1,1-dichloro-3-dichlorofluorosilyl-1-silacyclopentane, 1,1-dichloro-3-dichloroiodosilyl-1-silacyclopentane, 1,1-dichloro-3-chlorosilyl-1-silacyclopentane, and 1,1-dichloro-3-iodosilyl-1-silacyclopentane.

9. A film formed according to the method of claim 7, wherein k is less than about 6.0 and the carbon content is at least about 15.0 atomic percent.

10. A stainless steel container for containing the precursor compound described in claim 1.

11. A method for forming a carbon-doped silicon oxide film having a carbon content in the range of 20 atomic% to 40 atomic% via a thermal ALD process, a. A step of placing one or more substrates having surface features into a reactor, b. A step of heating the reactor to one or more temperatures in the range from ambient temperature to approximately 150°C, and optionally maintaining the reactor at a pressure of 100 torr or less. c. A step of introducing at least one precursor containing the precursor compound described in claim 1 and a catalyst into the reactor, d. A step of purging the reactor with an inert gas, e. A step of supplying steam to the reactor and reacting it with the at least one precursor and catalyst to form a carbon-doped silicon oxide film, f. A step of purging the reactor with an inert gas to remove reaction by-products, g. A step of repeating steps c to f to provide the carbon-doped silicon oxide film of the desired thickness, Methods that include...

12. The method according to claim 11, further comprising the step of treating the carbon-doped silicon oxide film by thermal annealing at a temperature of 500 to 1000°C.

13. The method according to claim 11, further comprising the step of exposing the carbon-doped silicon oxide film to a hydrogen-containing plasma.

14. The method according to claim 11, wherein the precursor compound is selected from the group consisting of 1,1-dichloro-3-trichlorosilyl-1-silacyclopentane, 1,1-dichloro-3-dichlorosilyl-1-silacyclopentane, 1,1-dichloro-3-dichloromethylsilyl-1-silacyclopentane, 1,1-dichloro-3-dichloroethylsilyl-1-silacyclopentane, 1,1-dichloro-3-dichlorofluorosilyl-1-silacyclopentane, 1,1-dichloro-3-dichloroiodosilyl-1-silacyclopentane, 1,1-dichloro-3-chlorosilyl-1-silacyclopentane, and 1,1-dichloro-3-iodosilyl-1-silacyclopentane.

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