WO2024080237A1 - シリコン含有膜前駆体、シリコン含有膜形成用の組成物、硫黄含有シロキサンの製造方法、及びシリコン含有膜の製造方法 - Google Patents

シリコン含有膜前駆体、シリコン含有膜形成用の組成物、硫黄含有シロキサンの製造方法、及びシリコン含有膜の製造方法 Download PDF

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WO2024080237A1
WO2024080237A1 PCT/JP2023/036524 JP2023036524W WO2024080237A1 WO 2024080237 A1 WO2024080237 A1 WO 2024080237A1 JP 2023036524 W JP2023036524 W JP 2023036524W WO 2024080237 A1 WO2024080237 A1 WO 2024080237A1
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silicon
carbon atoms
sulfur
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siloxane
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元輝 平
恵英 上野
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Sumitomo Seika Chemicals Co Ltd
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Sumitomo Seika Chemicals Co Ltd
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Priority to JP2024551494A priority patent/JPWO2024080237A1/ja
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
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    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H10P14/6339—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD
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    • H10P14/668—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials
    • H10P14/6681—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials the precursor containing a compound comprising Si
    • H10P14/6684—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H10P14/6686—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6921—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon
    • H10P14/69215—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material being a silicon oxide, e.g. SiO2
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    • H10P14/69—Inorganic materials
    • H10P14/694—Inorganic materials composed of nitrides
    • H10P14/6943—Inorganic materials composed of nitrides containing silicon
    • H10P14/69433—Inorganic materials composed of nitrides containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz

Definitions

  • the technical field of this disclosure relates to sulfur-containing siloxanes and methods for producing silicon-containing films using such compounds.
  • silicon-containing thin films are produced in various forms, such as silicon films, silicon oxide films, silicon nitride films, silicon carbonitride films, and silicon oxynitride films, through various deposition processes, and are used in a variety of fields.
  • silicon oxide films and silicon nitride films have excellent barrier properties and oxidation resistance, and therefore function as insulating films, intermetal dielectric materials, seed layers, spacers, hard masks, trench isolation, diffusion barriers, etch stop layers, and protective film layers in device fabrication.
  • Patent Document 1 proposes a method for forming a uniform silicon oxide film by using the aminosilane compound bisdiethylaminosilane (BDEAS) as a silicon source in an atomic layer deposition (ALD) method.
  • BDEAS aminosilane compound bisdiethylaminosilane
  • ALD atomic layer deposition
  • Patent Document 2 proposes a method for forming a uniform silicon oxide film at a high deposition rate by atomic layer deposition (ALD) using the aminosilane compound 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane as a silicon source.
  • ALD atomic layer deposition
  • Patent Document 3 also proposes a method for forming a uniform silicon oxide film at high temperatures using the atomic layer deposition (ALD) method and the aminosilane compound dimethylaminotrimethylsilane (DMATMS) as a silicon source.
  • ALD atomic layer deposition
  • DMATMS aminosilane compound dimethylaminotrimethylsilane
  • the bisdiethylaminosilane described in Patent Document 1 can form a silicon oxide film by atomic layer deposition (ALD) at 200 to 400°C
  • the 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane described in Patent Document 2 can form a silicon oxide film by atomic layer deposition (ALD) at 100 to 300°C
  • the temperature range is low, and if the film is formed at a high temperature of 500°C or higher, there is a risk that the film forming material will decompose and the film will not be formed uniformly.
  • the dimethylaminotrimethylsilane described in Patent Document 3 can form a silicon oxide film by the ALD method at 500 to 650°C, which is higher than the bisdiethylaminosilane described in Patent Document 1 and the 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane described in Patent Document 2, but it is difficult to say that the high temperature conditions are yet sufficient.
  • the present disclosure was conceived under these circumstances, and its main objective is to provide a siloxane compound that can be used as a new silicon-containing film precursor that can be formed by atomic layer deposition (ALD) even under high temperature conditions in the formation of silicon-containing films.
  • ALD atomic layer deposition
  • aminosilane compounds in which an amino group is bonded to a silicon atom have been commonly used as precursors for forming silicon-containing films (silicon-containing film precursors), but the inventors have found, after extensive research, that it is useful to use a thiosilane compound in which a sulfur atom is bonded to a silicon atom as a silicon-containing film precursor in order to obtain the desired effects.
  • a thiosilane compound in which a sulfur atom is bonded to a silicon atom as a silicon-containing film precursor in order to obtain the desired effects.
  • a specific compound in which a sulfur atom is bonded to a silicon atom of a siloxane structure (-Si-O-) as a silicon-containing film precursor it is possible to form a film by atomic layer deposition (ALD) under higher temperature conditions, which has led to the completion of this disclosure.
  • ALD atomic layer deposition
  • R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 1 to R 8 may be bonded to each other to form a ring;
  • X 1 to X 3 are independently in each occurrence an oxygen atom or a sulfur atom;
  • n is an integer from 0 to 2.
  • the sulfur-containing siloxane has the formula (2): [In formula (2), R 1 to R 8 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; n is an integer from 0 to 2.
  • the sulfur-containing siloxane has the formula (3): Item 5.
  • R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 1 to R 8 may be bonded to each other to form a ring;
  • X 1 to X 3 are independently in each occurrence an oxygen atom or a sulfur atom;
  • n is an integer from 0 to 2.
  • a composition for forming a silicon-containing film comprising a sulfur-containing siloxane represented by the formula: [Item 9]
  • Formula (1) [In formula (1), R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 1 to R 8 may be bonded to each other to form a ring;
  • X 1 to X 3 are independently in each occurrence an oxygen atom or a sulfur atom;
  • n is an integer from 0 to 2.
  • Item 10 The method for producing a sulfur-containing siloxane according to Item 9, wherein in step (a), the raw material siloxane is reacted with a sulfurizing agent to synthesize the sulfur-containing siloxane.
  • the raw material siloxane has the following formula (4): [In formula (4), R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 1 to R 8 may be bonded to each other to form a ring; X 1 to X 3 are independently in each occurrence an oxygen atom or a sulfur atom; Y is a hydrogen atom or a halogen atom; n is an integer from 0 to 2. Item 11.
  • R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 1 to R 8 may be bonded to each other to form a ring;
  • X 1 to X 3 are independently in each occurrence an oxygen atom or a sulfur atom;
  • n is an integer from 0 to 2.
  • the silicon film obtained by the method of the present disclosure may exhibit a good shrinkage rate and/or a good etching rate. Therefore, according to the method of the present disclosure, it is possible to form a film that is uniform and has excellent film properties even under high temperature conditions, making it possible to fabricate high-performance semiconductor devices.
  • Example 1 shows a 1 H-NMR chart of 2,2,4,4,6,6,8,8-octamethyl-1,3,5-trioxa-7-thia-2,4,6,8-tetrasilacyclooctane obtained by the production method in Example 1 of the present disclosure.
  • 1 shows the relationship between the substrate temperature and the deposition rate in Example 2 and Comparative Examples 1 to 3 of the present disclosure.
  • the sulfur-containing siloxane of the present disclosure has at least one sulfur atom and has a cyclic structure.
  • R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 1 to R 8 may be bonded to each other to form a ring;
  • X 1 to X 3 are independently in each occurrence an oxygen atom or a sulfur atom;
  • n is an integer from 0 to 2. It is expressed as:
  • R 1 to R 8 in each occurrence are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., 1 to 3, 1 to 2, 1) (e.g., methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl), an alkenyl group having 2 to 5 carbon atoms (e.g., 2 to 4, 2 to 3, and 2) (e.g., vinyl or 2-propenyl), an alkynyl group having 2 to 5 carbon atoms (e.g., 2 to 4, 2 to 3, and 2) (e.g., ethynyl or propynyl), or an alkoxy group having 1 to 5 carbon atoms (e.g., 1 to 3, 1 to 2, and 1) (e.g., methoxy, ethoxy, propoxy).
  • an alkyl group having 1 to 5 carbon atoms e
  • the average number of carbon atoms in R 1 to R 8 may be 0.5 or more, 1 or more, 2 or more, or 3 or more, and is preferably at least 1.
  • the average number of carbon atoms in R 1 to R 8 may be 5 or less, 4 or less, 3 or less, 2 or less, or 1, and is preferably 3 or less, for example 2 or less.
  • R 1 to R 8 may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear.
  • R 1 to R 8 may or may not be bonded to each other to form a ring (when a ring is formed, one of R 1 to R 8 may form a ring with, for example, R 1 to R 8 bonded to the same silicon atom or an adjacent silicon atom).
  • bond here may mean that the bonds possessed by each of R 1 to R 8 (for example, bonds resulting from the elimination of a hydrogen atom from each of R 1 to R 8 ) are bonded to each other.
  • At least one of R 1 to R 8 may be a hydrocarbon group or an alkoxy group (e.g., a hydrocarbon group, particularly an alkyl group). All of R 1 to R 8 may be other than a hydrogen atom.
  • the number of R 1 to R 8 that is a hydrocarbon group or an alkoxy group may be 10 % or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 50% or more, based on the total number of R 1 to R 8.
  • the number of R 1 to R 8 that is a hydrocarbon group or an alkoxy group may be 100% or less, 95% or less, 85% or less, 75% or less, or 65% or less, based on the total number of R 1 to R 8 .
  • All of R 1 through R 8 may be hydrocarbon or alkoxy groups (eg, hydrocarbon groups, especially alkyl groups).
  • R 1 to R 8 may be the same or different, for example, they may be the same.
  • a preferred example is when all of R 1 to R 8 are alkyl groups, particularly methyl groups.
  • X 1 to X 3 are independently in each occurrence an oxygen atom or a sulfur atom.
  • At least one of X 1 to X 3 may be an oxygen atom.
  • the number of X 1 to X 3 which are oxygen atoms may be 20% or more, 40% or more, 60% or more, or 80 or more, preferably 40% or more, based on the total number of X 1 to X 3.
  • the number of X 1 to X 3 which are oxygen atoms may be 100% or less, 70% or less, or 40% or less, based on the total number of X 1 to X 3. All of X 1 to X 3 may be oxygen atoms.
  • n is an integer from 0 to 2, for example 0, 1 or 2, for example 0 or 1, 0 or 2, or 1 or 2, and in particular 1.
  • the molecular weight of the sulfur-containing siloxane may be 200 or more, 250 or more, 300 or more, 350 or more, 400 or more, 450 or more, 500 or more, 550 or more, or 600 or more, preferably 300 or more.
  • the molecular weight of the sulfur-containing siloxane may be 1000 or less, 900 or less, 800 or less, 700 or less, 600 or less, 500 or less, 400 or less, or 350 or less, preferably 400 or less.
  • the number of carbon atoms of the sulfur-containing siloxane may be 0 or more, 1 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 15 or more, or 20 or more, and is preferably 6 or more.
  • the number of carbon atoms of the sulfur-containing siloxane may be 50 or less, 40 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and is preferably 20 or less.
  • Examples of sulfur-containing siloxanes include: Formula (2): [In formula (2), R 1 to R 8 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; n is an integer from 0 to 2. Examples of the compound include compounds represented by the following formula:
  • sulfur-containing siloxanes in this disclosure include 2,2,4,4,6,6,8,8-octamethyl-1,3,5-trioxa-7-thia-2,4,6,8-tetrasilacyclooctane, 1,3-dioxa-5-thia-2,4,6-trisilacyclohexane, 2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-thia-2,4,6-trisilacyclohexane, 2,2,4,4,6,6-hexaethyl-1,3-dioxa-5-thia-2,4,6-trisilacyclohexane, 2,2,4,4,6,6-hexavinyl-1,3-dioxa-5-thia-2,4,6-trisilacyclohexane, and 2,2,4,4,6,6-hexapropyl-1,3-dioxa-5-thia-2,4,6- Trisilacyclohexan
  • the method for producing the sulfur-containing siloxane according to the present disclosure includes: The method may include a production method including: (a) a step of synthesizing a sulfur-containing siloxane from a raw material siloxane; and (b) a distillation step of isolating the sulfur-containing siloxane by distillation.
  • the synthesis step (a) may include reacting a starting siloxane with a sulfurizing agent.
  • the raw material siloxane has the following formula (4): [In formula (4), R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 1 to R 8 may be bonded to each other to form a ring; X 1 to X 3 are independently in each occurrence an oxygen atom or a sulfur atom; Y is a hydrogen atom or a halogen atom; n is an integer from 0 to 2.
  • the compound may be represented by the formula:
  • Y is a hydrogen atom or a halogen atom.
  • examples of Y include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the siloxane compound in which Y is a hydrogen atom may be used as is in the synthesis step (a), or Y may be substituted with a halogen using a halogenating agent before carrying out the synthesis step (a).
  • the halogenating agent may be a fluorinating agent, a chlorinating agent, a brominating agent, or an iodinating agent.
  • chlorinating agents such as N-chlorosuccinimide and N-chlorophthalimide are preferably used.
  • the molecular weight of the raw siloxane may be 150 or more, 200 or more, 250 or more, 300 or more, 350 or more, 400 or more, 450 or more, 500 or more, or 550 or more, and is preferably 250 or more.
  • the molecular weight of the raw siloxane may be 1000 or less, 900 or less, 800 or less, 700 or less, 600 or less, 500 or less, 400 or less, 350 or less, or 300 or less, and is preferably 350 or less.
  • the sulfurizing agent is a sulfur compound capable of replacing Y in -SiY with sulfur, and examples of sulfides that can be used include lithium sulfide, sodium sulfide, and hydrogen sulfide.
  • step (a) either of the following methods can be applied to this reaction: first dissolving the raw material siloxane (e.g., raw material siloxane (4)) in an organic solvent and then adding the sulfurizing agent; or dissolving the sulfurizing agent in an organic solvent and then adding the raw material siloxane (e.g., raw material siloxane (4)).
  • the amount of sulfurizing agent used is usually 0.2 to 3.0 moles, preferably 0.4 to 2.0 moles, per 1.0 mole of raw siloxane (e.g., raw siloxane (4)).
  • the reaction may be carried out at temperatures between -20°C and 100°C, preferably between -10°C and 60°C.
  • the reaction time is usually in the range of 0.5 to 30 hours.
  • Solvents that can be used in the present disclosure include, for example, hydrocarbons such as hexane, cyclohexane, heptane, nonane, and decane; halogenated hydrocarbons such as dichloroethane, dichloromethane, and chloroform; aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and trichlorobenzene; ethers such as diethyl ether, tetrahydrofuran (THF), and ethylene glycol dimethyl ether, and mixtures thereof.
  • hydrocarbons such as hexane, cyclohexane, heptane, nonane, and decane
  • halogenated hydrocarbons such as dichloroethane, dichloromethane, and chloroform
  • aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and trichlorobenz
  • ethers such as diethyl ether and tetrahydrofuran (THF) are preferred, with tetrahydrofuran (THF) being particularly preferred.
  • THF tetrahydrofuran
  • the amount of solvent used is usually 0.1 to 50 times the mass of the raw siloxane compound.
  • step (a) if solids such as by-product salts are present in the reaction liquid, filtration may be performed after completion of the reaction, if necessary.
  • a dry inert gas for example, nitrogen or argon
  • the filtration temperature is not uniquely determined, but can be from 10°C to the boiling point of the solvent used. It is preferable to perform the filtration in the range of 20°C to 65°C.
  • step (b) the sulfur-containing siloxane is isolated by distillation, for example, vacuum distillation.
  • the sulfurizing agent and the organic solvent can be easily removed, and the sulfur-containing siloxane can be purified to a sufficiently high purity.
  • the sulfur-containing siloxane according to the present disclosure can be used as an intermediate for forming a silicon-containing film on a substrate.
  • the method for forming a silicon-containing film according to the present disclosure can be chemical vapor deposition, particularly atomic layer deposition.
  • the method for forming a silicon-containing film according to the present disclosure includes: (c) applying to the substrate a compound represented by the following formula (1):
  • R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 1 to R 8 may be bonded to each other to form a ring
  • X 1 to X 3 are independently in each occurrence an oxygen atom or a sulfur atom
  • n is an integer from 0 to 2.
  • the method may be a chemical vapor deposition method (particularly an atomic layer deposition method).
  • the substrate temperature may be 100 to 800°C, preferably 100 to 750°C. From the viewpoint of the film properties obtained, the substrate temperature may be 200°C or higher, 300°C or higher, 400°C or higher, 500°C or higher, 600°C or higher, or 700°C or higher, for example, 250°C or higher, preferably 300°C or higher, 400°C or higher, or 500°C or higher.
  • the film formation temperature may be the temperature of at least one of steps (c) to (f), for example, the temperature of the substrate when it comes into contact with the sulfur-containing siloxane composition in step (c).
  • the silicon-containing film obtained from the sulfur-containing siloxane of the present disclosure is stable even at high temperatures, and the sulfur-containing siloxane of the present disclosure can be suitably used in a method for producing a silicon-containing film that employs a high substrate temperature.
  • the pressure during gas injection in steps (c) and (e) is 0.05 to 100 Torr, preferably 0.05 to 50 Torr.
  • the sulfur-containing siloxane composition may contain an inert gas such as nitrogen or argon as a carrier gas.
  • step (e) when forming a silicon oxide film having Si-O bonds, one or more gases selected from oxygen, ozone, and nitric oxide can be used as the reactive gas.
  • one or more gases selected from nitrogen, ammonia, nitrous oxide, nitric oxide, and nitrogen dioxide can be used.
  • the formation of the silicon-containing film is preferably carried out after replacing the atmosphere with an inert gas such as nitrogen or argon.
  • an inert gas such as nitrogen or argon.
  • the sulfur-containing siloxanes disclosed herein are suitable for use in the manufacture of silicon-containing films (silicon oxide films, silicon nitride films, etc.) by chemical vapor deposition (particularly atomic layer deposition).
  • the lower limit of the ALD window may be 300°C, preferably 350°C.
  • the upper limit of the ALD window may be 800°C, preferably 750°C.
  • the ALD window generally refers to the temperature range between the vaporization temperature of a silicon-containing film precursor compound and the thermal decomposition temperature of the silicon-containing film precursor compound, and in this specification, the ALD window can be defined as the temperature range from the point at which the deposition rate is maximum to the point at which it is minimum when the deposition temperature is on the horizontal axis and the deposition rate is on the vertical axis.
  • Example 1 Synthesis of 2,2,4,4,6,6,8,8-octamethyl-1,3,5-trioxa-7-thia-2,4,6,8-tetrasilacyclooctane
  • 1.98 g (0.043 mol) of lithium sulfide and 317 g of tetrahydrofuran were added to a 500 mL flask equipped with a thermometer, a condenser, and a motor stirrer.
  • 10.9 g (0.031 mol) of 1,7-dichloro-octamethyltetrasiloxane was slowly added dropwise while stirring at room temperature. After the addition, the mixture was stirred for 6 hours while maintaining the temperature at 20 to 26°C.
  • Tetrahydrofuran was then removed by vacuum distillation at an internal temperature of 50 to 60°C. Then, in a nitrogen-substituted glove box, solid matter, mainly lithium chloride produced as a by-product, was removed by vacuum filtration to obtain a solution containing 2,2,4,4,6,6,8,8-octamethyl-1,3,5-trioxa-7-thia-2,4,6,8-tetrasilacyclooctane. Thereafter, distillation was performed under reduced pressure at an internal temperature of 68° C. and 1.9 Torr to obtain 2,2,4,4,6,6,8,8-octamethyl-1,3,5-trioxa-7-thia-2,4,6,8-tetrasilacyclooctane in high purity.
  • Example 2 Formation of silicon-containing film using 2,2,4,4,6,6,8,8-octamethyl-1,3,5-trioxa-7-thia-2,4,6,8-tetrasilacyclooctane]
  • a silicon substrate was placed in a vacuum apparatus and heated to a predetermined temperature of 500 to 750°C.
  • the siloxane composition containing 2,2,4,4,6,6,8,8-octamethyl-1,3,5-trioxa-7-thia-2,4,6,8-tetrasilacyclooctane and a carrier gas obtained in Example 1 was injected at a pressure of 0.05 to 100 Torr and adsorbed onto the heated silicon substrate.
  • argon gas was introduced to purge the unadsorbed sulfur-containing siloxane composition and by-products from the apparatus.
  • ozone was injected as a reactive gas at a pressure of 0.05 to 100 Torr to form an atomic layer of silicon oxide derived from 2,2,4,4,6,6,8,8-octamethyl-1,3,5-trioxa-7-thia-2,4,6,8-tetrasilacyclooctane deposited on the substrate.
  • argon gas was introduced to purge the unadsorbed ozone and by-products. The above cycle was repeated to obtain a silicon oxide film.
  • Comparative Example 1 Formation of silicon-containing film using bis(diethylaminosilane) A silicon substrate was placed in a vacuum apparatus and heated to a predetermined temperature of 100 to 750°C. An aminosilane composition containing bisdiethylaminosilane and a carrier gas was injected at a pressure of 0.05 to 100 Torr and adsorbed onto the heated silicon substrate. Argon gas was then introduced to purge the unadsorbed aminosilane composition and by-products from within the apparatus. Ozone was then injected as a reactive gas at a pressure of 0.05 to 100 Torr to form an atomic layer of silicon oxide derived from bisdiethylaminosilane deposited on the substrate. Argon gas was then introduced to purge the unreacted ozone gas and by-products. The above cycle was repeated to obtain a silicon oxide film.
  • Ozone was then injected as a reactive gas at a pressure of 0.05 to 100 Torr to form an atomic layer of silicon oxide derived from 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane deposited on the substrate.
  • Argon gas was then introduced to purge the unreacted ozone gas and by-products. The above cycle was repeated to obtain a silicon oxide film.
  • Comparative Example 3 Formation of silicon-containing film using 2,4,6,8-tetramethylcyclotetrasiloxane A silicon substrate was placed in a vacuum apparatus and heated to a predetermined temperature of 200 to 750°C. A siloxane composition containing 2,4,6,8-tetramethylcyclotetrasiloxane and a carrier gas was injected at a pressure of 0.05 to 100 Torr and adsorbed onto the heated silicon substrate. Next, argon gas was introduced to purge the unadsorbed aminosiloxane composition and by-products from within the apparatus.
  • ozone was injected as a reactive gas at a pressure of 0.05 to 100 Torr to form an atomic layer of silicon oxide derived from 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane deposited on the substrate.
  • argon gas was introduced to purge the unreacted ozone gas and by-products. The above cycle was repeated to obtain a silicon oxide film.
  • Table 1 Specific deposition methods are shown in Table 1 below.
  • Figure 2 shows the relationship between substrate temperature and deposition rate. In the measurement of each plot in Figure 2, the siloxane supply time that maximizes the deposition rate was selected.
  • Table 2 shows the deposition rate in Example 2 when 50 cycles were repeated at a substrate temperature of 725°C, which is the maximum temperature of the ALD window, and at 750°C, which is outside the ALD window.
  • the ALD window here refers to the temperature range from the point where the deposition rate is maximum to the point where it is minimum in Figure 2.
  • Table 3 also summarizes the temperature range of the ALD window for Example 1 and Comparative Examples 1 and 2. The layer thickness was measured with an ellipsometer.
  • Table 4 shows the shrinkage rate when a film was formed near the upper limit of the ALD window (700°C for the Example, 550°C for Comparative Example 1) and then annealed at 800°C for 30 minutes.
  • Table 5 shows the etching rate when a film was formed near the upper limit of the ALD window (700°C for the Example, 500°C for Comparative Example 1) and then immersed in 0.5% hydrofluoric acid for 60 seconds. The etching rate was calculated by measuring the film thickness before and after immersion in 0.5% hydrofluoric acid with an ellipsometer, calculating the amount of film thickness reduction, and dividing the result by the immersion time.
  • Example 2 the supply time of the 2,2,4,4,6,6,8,8-octamethyl-1,3,5-trioxa-7-thia-2,4,6,8-tetrasilacyclooctane composition was examined to form an atomic layer of silicon oxide derived from the 2,2,4,4,6,6,8,8-octamethyl-1,3,5-trioxa-7-thia-2,4,6,8-tetrasilacyclooctane compound. It was confirmed that the deposition rate reached its maximum at a substrate temperature of 725°C for 6 seconds or more, resulting in ALD film formation.
  • the sulfur-containing siloxane disclosed herein is useful for atomic deposition methods that form films at high temperatures.

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