Method for manufacturing amorphous carbon-containing film and article

Abstract

The present invention provides a method for producing an amorphous carbon-containing film and an article that can form an amorphous carbon-containing film without using plasma or high temperatures. [Solution] A method for producing an amorphous carbon-containing film, comprising the step of bringing a substrate and a raw material gas containing a halogenated carbosilane into contact at a temperature of 300°C to 850°C in a non-plasma atmosphere to form an amorphous carbon-containing film on the surface of the substrate.

Description

[Technical Field]

[0001] This disclosure relates to a method for producing an amorphous carbon-containing film and to articles thereof. [Background technology]

[0002] Amorphous carbon-containing films, also known as diamond-like carbon films, possess properties such as heat resistance, high hardness, chemical stability, etching resistance, low friction, optical properties, and electrical properties. Therefore, they are used in various fields, including as protective films and sliding films for machinery and tools, moving parts, containers, medical devices, and optical components; as electrode and joint forming materials; and as hard mask materials in lithography processes. Amorphous carbon-containing films are generally formed by chemical or physical vapor deposition methods using hydrocarbon-containing precursors (U.S. Patent No. 7,842,622). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] U.S. Patent No. 7842622 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Most conventional formation processes utilize high-energy plasma and high-temperature processes for their reaction efficiency. However, this can lead to problems such as the generation of by-reactants and damage to the substrate due to the plasma or high temperatures. In recent years, these side effects from plasma and high temperatures have become more pronounced in increasingly precise and miniaturized equipment and processing processes.

[0005] This disclosure aims to provide a method for producing an amorphous carbon-containing film and an article that can form an amorphous carbon-containing film without using plasma or high temperatures. [Means for solving the problem]

[0006] As a result of intensive studies, the present inventor has found that the above problems can be solved by adopting the following configuration.

[0007] In one embodiment, the present invention A step of forming an amorphous carbon-containing film on the surface of the substrate by bringing the substrate into contact with a raw material gas containing a halogenated carbosilane at a temperature of 300°C or higher and 850°C or lower in a non-plasma atmosphere relates to a method for producing an amorphous carbon-containing film including this.

[0008] In one embodiment, it is preferable that the halogenated carbosilane has a halogenated silyl group.

[0009] In one embodiment, it is preferable that the halogenated carbosilane has a trichlorosilyl group.

[0010] In one embodiment, the composition formula of the halogenated carbosilane is preferably represented by the following formula (A). C a Si b X c H d (A) (In formula (A), X is a halogen atom. When there are a plurality of X, the plurality of X are the same or different from each other. a is an integer from 1 to 4. b is an integer from 2 to 2a + 2. c is an integer from 6 to 2a + 2b + 2. d is 2a + 2b - c + 2.)

[0011] In one embodiment, the halogenated carbosilane is preferably a compound represented by the following formula (1).

Chemical formula

[0012] In one embodiment, the silyl halide group is preferably a trichlorosilyl group.

[0013] In one embodiment, the halogen atom is preferably a chlorine atom.

[0014] In one embodiment, n is preferably 1 or 2.

[0015] In one embodiment, the number of hydrogen atoms in the carbosilane halide is preferably 2 or less.

[0016] In one embodiment, the carbon concentration in the amorphous carbon-containing film is preferably 85 atom% or more.

[0017] In one embodiment, the source gas preferably contains at least one carrier gas selected from the group consisting of N2, He, Ar, Kr, Xe, Ne and Rn.

[0018] In one embodiment, the carbosilane halide is preferably at least one selected from the group consisting of bis(trichlorosilyl)methane, dichlorobis(trichlorosilyl)methane, difluorobis(trichlorosilyl)methane, tris(trichlorosilyl)methane, 1,2-bis(trichlorosilyl)ethane, 1,1-bis(trichlorosilyl)ethane and 1,3-bis(trichlorosilyl)propane).

[0019] In another embodiment, the present invention is The main unit and At least a portion of the surface of the main body is an amorphous carbon-containing film formed by the method for manufacturing the amorphous carbon-containing film. Regarding articles that are equipped with...

[0020] In this specification, standard abbreviations for elements from the periodic table are used. Therefore, elements can be represented by these abbreviations. For example, C represents carbon, Si represents silicon, N represents nitrogen, H represents hydrogen, He represents helium, Ne represents neon, Ar represents argon, Kr represents krypton, Xe represents xenon, and Rn represents radon. The same applies to other elements.

[0021] In this specification, "CVD" means chemical vapor deposition or chemical vapor deposition, and "ALD" means atomic layer deposition. ALD is a type of CVD.

[0022] In this specification, "hydrocarbon group" includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. This "hydrocarbon group" includes saturated hydrocarbon groups and unsaturated hydrocarbon groups. "Linear hydrocarbon group" means a hydrocarbon group that does not contain a ring structure and consists only of a linear structure, and includes both linear hydrocarbon groups and branched hydrocarbon groups. "Alicyclic hydrocarbon group" means a hydrocarbon group that contains only an alicyclic structure as its ring structure and does not contain an aromatic ring structure, and includes both monocyclic alicyclic hydrocarbon groups and polycyclic alicyclic hydrocarbon groups (however, it is not necessary to consist only of an alicyclic structure, and it may contain a linear structure as part of it). "Aromatic hydrocarbon group" means a hydrocarbon group that contains an aromatic ring structure as its ring structure (however, it is not necessary to consist only of an aromatic ring structure, and it may contain an alicyclic structure or a linear structure as part of it). [Effects of the Invention]

[0023] According to this disclosure, amorphous carbon-containing films and articles comprising them can be efficiently manufactured without the use of plasma or high temperatures. In addition, according to this disclosure, it is also possible to design film deposition processes at low temperatures (e.g., below 450°C). [Brief explanation of the drawing]

[0024] [Figure 1] These are the results of crystal structure analysis by X-ray diffraction (XRD) of the films formed in Examples 1, 8, and 11-13, as well as the bare Si substrate. [Figure 2] This graph shows the atomic composition of amorphous carbon-containing films formed in Examples 1-2, 8, 11, 12-13, and 15-16. [Figure 3A] This shows the XPS results for an amorphous carbon-containing film formed on a Si substrate by chemical vapor deposition using the halogenated carbosilane of Example 1. [Figure 3B] This shows the XPS results for an amorphous carbon-containing film formed on a Si substrate by chemical vapor deposition using a halogenated carbosilane in Example 2. [Figure 3C] This shows the XPS results for an amorphous carbon-containing film formed on a Si substrate by chemical vapor deposition using a halogenated carbosilane in Example 8. [Figure 3D] This shows the XPS results for an amorphous carbon-containing film formed on a Si substrate by chemical vapor deposition using a halogenated carbosilane in Example 11. [Figure 3E] This shows the XPS results for an amorphous carbon-containing film formed on a Si substrate by chemical vapor deposition using a halogenated carbosilane in Example 12. [Figure 3F] This shows the XPS results for an amorphous carbon-containing film formed on a Si substrate by chemical vapor deposition using a halogenated carbosilane in Example 13. [Figure 3G] This shows the XPS results for an amorphous carbon-containing film formed on a Si substrate by chemical vapor deposition using a halogenated carbosilane in Example 15. [Figure 3H]This shows the XPS results for an amorphous carbon-containing film formed on a Si substrate by chemical vapor deposition using a halogenated carbosilane in Example 16. [Figure 3I] This shows the XPS results for an amorphous carbon-containing film formed on a Si substrate by chemical vapor deposition using a halogenated carbosilane in Example 20. [Figure 4] This graph shows the temperature dependence of the film thickness of an amorphous carbon-containing film. [Figure 5A] This is an SEM image of the region from the surface of the trench to a depth of 300 nm of the amorphous carbon-containing film formed on the trench in Example 12. [Figure 5B] This is an SEM image of the region around 3 μm deep from the surface of the trench in the amorphous carbon-containing film formed on the trench in Example 12. [Figure 5C] This is an SEM image of the region around 6 μm deep from the surface of the trench in the amorphous carbon-containing film formed on the trench in Example 12. [Modes for carrying out the invention]

[0025] The embodiments of this disclosure will be described below, but this disclosure is not limited to these embodiments and can be implemented with appropriate modifications. Furthermore, each of the configurations described below can be combined with each other.

[0026] Method for manufacturing amorphous carbon-containing films The method for producing an amorphous carbon-containing film according to this embodiment includes a step of forming an amorphous carbon-containing film on the surface of a substrate by contacting a substrate with a raw material gas containing a halide carbosilane in a non-plasma atmosphere at a temperature of 300°C to 850°C (hereinafter also referred to as the "contact step"). The production method may include a preliminary condition setting step as a preparation step for the contact step, in which the inside of a reactor containing the substrate is set to conditions suitable for the contact step. First, the raw material gas containing a halide carbosilane used in the production method will be described, and then each step will be described based on an embodiment that includes the optional preliminary condition setting step.

[0027] (raw material gas) The raw material gas contains a halogenated carbosilane. A halogenated carbosilane is a compound containing at least a carbon atom, a silicon atom, and a halogen atom, and containing a Si-C bond. Halogenated carbosilanes have been mainly used to form silicon-containing films. The inventors have found that, by changing the perspective, even halogenated carbosilanes can form amorphous carbon-containing films by contacting them with a substrate at a predetermined temperature in a non-plasma atmosphere. This disclosure is based on such novel findings. The raw material gas may contain only halogenated carbosilanes, or it may contain other components besides halogenated carbosilanes. The raw material gas may contain one or more halogenated carbosilanes.

[0028] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among these, fluorine atoms and chlorine atoms are preferred halogen atoms, with chlorine atoms being more preferred.

[0029] Although the specific structure of the halogenated carbosilane is not particularly limited, it is preferable that the halogenated carbosilane has a silyl halogenated group. A silyl halogenated group is a group in which some or all of the hydrogen atoms of a silyl group (-SH3) are replaced with halogen atoms. Therefore, examples of silyl halogenated groups include monohalogenosilyl groups, dihalogenosilyl groups, and trihalogenosilyl groups. Among the silyl halogenated groups, trihalogenosilyl groups are preferred, and trichlorosilyl groups are more preferred.

[0030] The structure of the halogenated carbosilane is preferably one in which some or all of the hydrogen atoms of the hydrocarbon are replaced with the silyl halogenated group. Examples of hydrocarbons include chain hydrocarbons having 1 to 10 carbon atoms, alicyclic hydrocarbons having 3 to 10 carbon atoms, aromatic hydrocarbons having 6 to 12 carbon atoms, or combinations thereof.

[0031] Examples of chain hydrocarbons having 1 to 10 carbon atoms include linear or branched alkanes such as methane, ethane, propane, 2-methylpropane, 2,2-dimethylpropane, n-butane, 2-methylbutane, and n-pentane; alkenes such as ethylene, propene, 1-butene, and 2-butene; and alkynes such as acetylene, propyne, 1-butyne, and 2-butyne.

[0032] Examples of alicyclic hydrocarbons having 3 to 10 carbon atoms include monocyclic alicyclic saturated hydrocarbons such as cyclopentane, cyclobutane, and cyclohexane; polycyclic alicyclic saturated hydrocarbons such as norbornane, adamantane, and tricyclodecane; monocyclic alicyclic unsaturated hydrocarbons such as cyclopentene, cyclobutene, cyclopentene, and cyclohexene; and polycyclic alicyclic unsaturated hydrocarbons such as norbornene and tricyclodecene.

[0033] Examples of aromatic hydrocarbons with 6 to 12 carbon atoms include benzene, naphthalene, and other arenes.

[0034] The hydrocarbons are preferably chain-like hydrocarbons having 1 to 10 carbon atoms, more preferably chain-like saturated hydrocarbons having 1 to 8 carbon atoms, even more preferably linear saturated hydrocarbons having 1 to 6 carbon atoms, and particularly preferably linear saturated hydrocarbons having 1 to 4 carbon atoms.

[0035] The compositional formula of the aforementioned halogenated carbosilane is preferably represented by the following formula (A). C a Si b X c H d (A) (In formula (A), X is a halogen atom. If there are multiple X atoms, they are either identical or different from one another. a is an integer between 1 and 4. b is an integer between 2 and 2a+2. c is an integer between 6 and 2a+2b+2. d is 2a + 2b - c + 2.

[0036] The halogen atom represented by X can preferably be the aforementioned halogen atom.

[0037] a is preferably an integer from 1 to 3, more preferably 1 or 2, and even more preferably 1. b is preferably an integer between 2 and 4, and more preferably 2 or 3. c is preferably an integer between 6 and 10, and more preferably an integer between 6 and 9. d is preferably an integer between 0 and 4, more preferably an integer between 0 and 2, and even more preferably 0 or 1.

[0038] In particular, it is preferable to combine the hydrocarbon and the silyl halogen group such that the structure of the halogenated carbosilane satisfies the compositional formula represented by formula (A), more preferably to combine the linear saturated hydrocarbon having 1 to 6 carbon atoms with the trihalogenosilyl group, and even more preferably to combine the linear saturated hydrocarbon having 1 to 4 carbon atoms with the trichlorosilyl group.

[0039] The aforementioned halogenated carbosilane is preferably a compound represented by the following formula (1). [ka] (in formula (1) Y 1 , Y 2 , Y 3 and Y 4 Each of these is independently a silyl halide group, a halogen atom, or a hydrogen atom. 2 and Y 3 If there are multiple Y 2 and Y 3 They are either identical or different from each other. 1 , Y 2 , Y 3 and Y 4 At least two of the group consisting of are silyl halogenated groups. n is an integer between 1 and 4.

[0040] Y 1 , Y 2 , Y 3 and Y 4 The silyl halide group and halogen atom represented by the above can preferably be the silyl halide group and halogen atom described above.

[0041] n is preferably an integer between 1 and 3, more preferably 1 or 2, and even more preferably 1.

[0042] Y 1 , Y 2 , Y 3 and Y 4 The number of silyl halide groups in the compound is preferably between two and four, and more preferably two or three.

[0043] The number of hydrogen atoms in the aforementioned carbosilane halogen is preferably two or less, more preferably zero or one, and even more preferably zero.

[0044] Examples of the aforementioned halogenated carbosilanes include bis(trichlorosilyl)methane (a compound represented by the following formula (1-1)) and dichlorobis(trichlorosilyl)methane (the following formula Compounds represented by (1-2), difluorobis(trichlorosilyl)methane (compounds represented by formula (1-3) below), tris(trichlorosilyl)methane (compounds represented by formula (1-4) below), 1,2-bis(trichlorosilyl)ethane (compounds represented by formula (1-5) below), 1,1-bis(trichlorosilyl)ethane (compounds represented by formula (1-6) below), chlorotris(trichlorosilyl)methane (compounds represented by formula (1-7) below), chlorobis(trichlorosilyl)methane (compounds represented by formula (1-8) below), 1,2-dichloro-1,2-bis(trichlorosilyl)ethane (below Examples include compounds represented by formulas (1-9), tetra(trichlorosilyl)methane (compound represented by formula (1-10) below), 1,3-bis(trichlorosilyl)propane (compound represented by formula (1-11) below), 1,1,1,3,3,3,-hexachloro-2,2-dimethyl-1,3-disilapropane (compound represented by formula (1-12) below), 1,1,1,3,3,3,-hexachloro-2-ethyl-1,3-disilapropane (compound represented by formula (1-13) below), and 1,1,1,4,4,4,-hexachloro-2-methyl-1,4-disilabutane (compound represented by formula (1-14) below).

[0045] [ka]

[0046] The halogenated carbosilane is preferably at least one selected from the group consisting of bis(trichlorosilyl)methane (compound represented by formula (1-1)), dichlorobis(trichlorosilyl)methane (compound represented by formula (1-2)), difluorobis(trichlorosilyl)methane (compound represented by formula (1-3)), tris(trichlorosilyl)methane (compound represented by formula (1-4)), 1,2-bis(trichlorosilyl)ethane (compound represented by formula (1-5)), 1,1-bis(trichlorosilyl)ethane (compound represented by formula (1-6)), and 1,3-bis(trichlorosilyl)propane (compound represented by formula (1-11)).

[0047] (Method for synthesizing carbosilane halogens) Carbosilane halides can be synthesized by known methods. Commercially available carbosilane halides may also be used.

[0048] (Preliminary condition setting process) In this process, the reactor containing the substrate is set to conditions suitable for the contact process. The type of substrate on which the amorphous carbon-containing film is deposited is selected as appropriate according to the final application.

[0049] In some embodiments, the substrate is made from an oxide used as an insulating material in Si substrates, MIM, DRAM, or FeRam technology (e.g., HfO2-based materials, TiO2-based materials, ZrO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.), or a nitride-based film used as an oxygen barrier between copper and a low-k film. (For example, TaN) can be selected. Other substrates can be used in the manufacture of semiconductors, photocells, LCD-TFTs, or flat panel devices. Examples of such substrates include, but are not limited to, solid substrates such as metal nitride-containing substrates (e.g., TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); insulators (e.g., SiO2, Si3N4, SiON, HfO2, Ta2O5, ZrO2, TiO2, Al2O3, and barium strontium titanate); or other substrates containing some of these materials in combination. The actual substrate used may also depend on the specific embodiment of the source gas used.

[0050] The reactor can be any enclosed vessel or chamber of the device in which chemical vapor deposition is performed. Specific examples, but are not limited to, parallel-plate reactors, cold-wall reactors, hot-wall reactors, single-wafer reactors, multi-wafer reactors, or other types of deposition systems.

[0051] The substrate can be heated to a temperature sufficient to obtain the desired amorphous carbon-containing film with a sufficient growth rate and desired physical state and composition. The temperature inside the reactor (temperature of the substrate surface) should be set within the range of 300°C to 850°C. The temperature is preferably within the range of 300°C to 750°C, more preferably within the range of 350°C to 700°C, and even more preferably within the range of 350°C to 650°C.

[0052] The temperature inside the reactor (temperature of the substrate surface) can be set according to the type of halogenated carbosilane. When the halogenated carbosilane is bis(trichlorosilyl)methane, 1,2-bis(trichlorosilyl)ethane, 1,1-bis(trichlorosilyl)ethane, or 1,3-bis(trichlorosilyl)propane, the temperature is preferably 800°C to 850°C. When the halogenated carbosilane is tris(trichlorosilyl)methane, the temperature is preferably 500°C to 600°C. When the halogenated carbosilane is dichlorobis(trichlorosilyl)methane, the temperature is preferably 450°C to 500°C.

[0053] During heating of the substrate, an inert gas may be introduced into the reactor to stabilize the pressure inside the reactor. The inert gas is not limited, but at least one selected from the group consisting of N2, He, Ar, Kr, Xe, Ne, and Rn can be mentioned.

[0054] The flow rate of the inert gas can be set as appropriate, preferably between 1 sccm and 100 sccm, and more preferably between 10 sccm and 50 sccm.

[0055] Carbosilane halides can be prepared in their pure form (e.g., liquid or low-melting-point solid).

[0056] (contact process) In this process, the raw material gas containing carbosilane halogens, which was introduced into the reactor in the introduction step, is brought into contact with the substrate in a non-plasma atmosphere at a temperature of 300°C to 850°C to form an amorphous carbon-containing film on the surface of the substrate. The substrate temperature is maintained in this process at the same temperature as in the preliminary condition setting step.

[0057] Contact between the source gas and the substrate can be brought into contact by introducing a source gas containing vaporized carbosilane halogens into the reactor. Pure (single) carbosilane halogens or blended (multiple) carbosilane halogens may be supplied to the vaporizer in liquid form and vaporized there before being introduced into the reactor. Alternatively, the carbosilane halogens can be vaporized by passing a carrier gas through a container containing the carbosilane halogens, or by bubbling a carrier gas through the carbosilane halogens.

[0058] In the contact process, an amorphous carbon-containing film can be formed simply by introducing a raw material gas containing a halogenated carbosilane, without the need to introduce oxidizing gases (such as oxygen gas or water) or catalytic gases (such as amines).

[0059] The pressure inside the reactor is preferably in the range of 0.01 Torr to 50 Torr, more preferably in the range of 0.1 Torr to 20 Torr, and even more preferably in the range of 0.5 Torr to 10 Torr.

[0060] In this process, an amorphous carbon-containing film can be formed simply by bringing a raw material gas containing a carbosilane halide into contact with a substrate within a predetermined temperature range, without the need for a plasma atmosphere, which is commonly used in conventional methods. In this process, the thermal decomposition of the carbosilane halide proceeds, and carbon is deposited on the substrate to form an amorphous carbon-containing film. Because a non-plasma atmosphere is used, the generation of by-reactants and damage to the substrate during the deposition process can be suppressed as much as possible.

[0061] The thickness of the amorphous carbon-containing film obtained by this manufacturing method can be appropriately set according to the intended application. The lower limit of the thickness of the amorphous carbon-containing film may be 1 nm, 5 nm, 10 nm, or 15 nm. The upper limit of the thickness may be 5 μm, 3 μm, 1 μm, or 500 nm.

[0062] The carbon concentration in the amorphous carbon-containing film obtained by this manufacturing method is preferably 85 atom% or higher. The lower limit of the carbon concentration is more preferably 86 atom%, even more preferably 87 atom% and particularly preferably 88 atom%. The upper limit of the carbon concentration is preferable as it is higher, but may be 99.5 atom% or 99 atom%. By simply contacting the substrate with a halogenated carbosilane at a predetermined temperature, an amorphous carbon-containing film with a high carbon concentration can be formed even in a non-plasma atmosphere.

[0063] The amorphous carbon-containing film may contain chlorine, oxygen, nitrogen, silicon, etc., in addition to carbon. The chlorine concentration is preferably 5 atom% or less, and more preferably 4 atom% or less. The oxygen concentration is preferably 5 atom% or less, and more preferably 4 atom% or less. The nitrogen concentration is preferably 2 atom% or less, and more preferably 1 atom% or less. The silicon concentration is preferably 6 atom% or less, more preferably 5 atom% or less, even more preferably 4 atom% or less, and particularly preferably 3 atom% or less. The lower limit of the concentrations of chlorine, oxygen, nitrogen, and silicon is preferable as much as possible. In any case, the lower limit of the concentration may be 0.1 atom%, 0.2 atom% or 0.3 atom%.

[0064] The amorphous carbon-containing film formed by this manufacturing method is not particularly limited in its applications and can be used in a variety of applications, such as hard mask layers for patterning in semiconductor device manufacturing, electrode and junction formation, thin film deposition for micro-electromechanical systems (MEMS), substrates for growing carbon nanotubes and graphene, and low-friction coatings for moving parts of electronic devices. [Examples]

[0065] Examples are provided below to illustrate the application of the disclosures herein, but it should be understood that not all of the advantages of the processes described herein can be encompassed in any particular embodiment or group of embodiments of the present invention. While specific embodiments and examples are disclosed below, it will be understood by those skilled in the art that the present invention includes obvious modifications and extensions beyond the specifically disclosed embodiments and / or uses of the present invention. Therefore, it should be understood that the scope of the disclosed invention should not be limited by the specific embodiments described below.

[0066] (Carbosilane halogenates) The following compound represented by the formula below was used as the halogenated carbosilane for forming amorphous carbon-containing films. Hereafter, each halogenated carbosilane may be abbreviated. BTCSM: Bis(trichlorosilyl)methane 1,2-BTCSE: 1,2-bis(trichlorosilyl)ethane 1,1-BTCSE:1,1-Bis(trichlorosilyl)ethane 1,3-BTCSP: 1,3-Bis(trichlorosilyl)propane DCBTCSM: Dichlorobis(trichlorosilyl)methane TTCSM: Tris(trichlorosilyl)methane

[0067] [ka]

[0068] <Formation of amorphous carbon-containing film> (Example 1) BTCSM was used as the carbosilane halogen to form an amorphous carbon-containing film on a silicon wafer substrate. Specifically, a Si substrate cleaned with a 1 volume % HF solution was placed in a fluidized bed reactor. BTCSM and N2 carrier gas were mixed (35 sccm N2 flow, 2 sccm BTCSM flow), and vapor deposition was carried out at a substrate surface temperature of 800°C and 5 Torr for 60 minutes to produce an amorphous carbon-containing film with a thickness of 12.8 nm.

[0069] (Example 2) An amorphous carbon-containing film with a thickness of 23 nm was formed using the same method as in Example 1, except that the vapor phase deposition time was set to 120 minutes.

[0070] (Example 3) An amorphous carbon-containing film with a thickness of 1.7 nm was formed using the same method as in Example 1, except that the substrate surface temperature was set to 700°C.

[0071] (Example 4) An amorphous carbon-containing film with a thickness of 0.9 nm was formed using the same method as in Example 1, except that the substrate surface temperature was set to 600°C.

[0072] (Example 5) An amorphous carbon-containing film with a thickness of 1.1 nm was formed using the same method as in Example 1, except that 1,2-BTCSE was used as the carbosilane halogen and the substrate surface temperature was set to 600°C.

[0073] (Example 6) An amorphous carbon-containing film with a thickness of 1.4 nm was formed in the same manner as in Example 1, except that 1,2-BTCSE was used as the carbosilane halogen and the substrate surface temperature was set to 700°C.

[0074] (Example 7) An amorphous carbon-containing film with a thickness of 5.2 nm was formed using the same method as in Example 1, except that 1,2-BTCSE was used as the carbosilane halogen and the substrate surface temperature was set to 800°C.

[0075] (Example 8) An amorphous carbon-containing film with a thickness of 14.1 nm was formed using the same method as in Example 1, except that 1,2-BTCSE was used as the carbosilane halogen and the substrate surface temperature was set to 850°C.

[0076] (Example 9) An amorphous carbon-containing film with a thickness of 0.9 nm was formed in the same manner as in Example 1, except that 1,1-BTCSE was used as the carbosilane halogen and the substrate surface temperature was set to 700°C.

[0077] (Example 10) An amorphous carbon-containing film with a thickness of 1.1 nm was formed in the same manner as in Example 1, except that 1,1-BTCSE was used as the carbosilane halogen and the substrate surface temperature was set to 800°C.

[0078] (Example 11) An amorphous carbon-containing film with a thickness of 14.3 nm was formed in the same manner as in Example 1, except that 1,1-BTCSE was used as the carbosilane halogen and the substrate surface temperature was set to 850°C.

[0079] (Example 12) An amorphous carbon-containing film with a thickness of 14.7 nm was formed using the same method as in Example 1, except that DCBTCSM was used as the carbosilane halogen and the substrate surface temperature was set to 450°C.

[0080] (Example 13) An amorphous carbon-containing film with a thickness of 47 nm was formed using the same method as in Example 12, except that the substrate surface temperature was set to 500°C. (Example 14) An amorphous carbon-containing film with a thickness of 3.5 nm was formed using the same method as in Example 12, except that the substrate surface temperature was set to 400°C.

[0081] (Example 15) An amorphous carbon-containing film with a thickness of 23.7 nm was formed using the same method as in Example 1, except that TTCSM was used as the carbosilane halogen and the substrate surface temperature was set to 500°C.

[0082] (Example 16) An amorphous carbon-containing film with a thickness of 50.2 nm was formed using the same method as in Example 15, except that the substrate surface temperature was set to 600°C.

[0083] (Example 17) An amorphous carbon-containing film with a thickness of 4.1 nm was formed using the same method as in Example 15, except that the substrate surface temperature was set to 300°C.

[0084] (Example 18) An amorphous carbon-containing film with a thickness of 3.1 nm was formed in the same manner as in Example 1, except that 1,3-BTCSP was used as the carbosilane halogen and the substrate surface temperature was set to 750°C.

[0085] (Example 19) An amorphous carbon-containing film with a thickness of 7.5 nm was formed using the same method as in Example 18, except that the substrate surface temperature was set to 800°C.

[0086] (Example 20) An amorphous carbon-containing film with a thickness of 13.6 nm was formed using the same method as in Example 18, except that the substrate surface temperature was set to 850°C.

[0087] <Rating> (Confirmation that it is an amorphous film) The crystalline structure of the films formed in Examples 1, 8, and 11-13, as well as the bare Si substrate, was evaluated by X-ray diffraction (XRD). Specifically, measurements were taken using an X-ray diffractometer (Rigaku Corporation, "SmartLab") with the following conditions: 2θ scan: 3-80°, step: 0.02°, speed: 10° / min, and receiving slit: 0.1 mm. The results are shown in Figure 1. In films with a crystalline structure, specific peaks are observed because the constituent atoms have a regular arrangement. In each measurement sample, peaks similar to those of the bare Si substrate were confirmed between 2θ of 50° and 60°, while no other characteristic peaks were observed. From this, it was concluded that the films formed in Examples 1, 8, and 11-13 are amorphous films.

[0088] (atomic composition) The atomic composition of amorphous carbon-containing films formed in Examples 1-2, 8, 11, 12-13, 15-16, and 20 was measured using an X-ray photoelectron spectrometer (Thermo Fisher Scientific, product name: "K-Alpha"). The results are shown in Figure 2. Figure 2 is a graph showing the atomic composition of amorphous carbon-containing films formed in Examples 1-2, 8, 11, 12-13, 15-16, and 20. From Figure 2, it can be seen that all amorphous carbon-containing films showed high carbon concentrations exceeding 85 atoms.

[0089] (Depth profiling using XPS) The depth profiles of the amorphous carbon-containing films formed in Examples 1-2, 8, 11-13, 15-16, and 20 were evaluated using an X-ray photoelectron spectroscopy (XPS) system (Thermo Fisher Scientific, product name: "K-Alpha"). Figures 3A-3I show the XPS results for the amorphous carbon-containing films formed on Si substrates by chemical vapor deposition using carbosilane halides in Examples 1-2, 8, 11-13, 15-16, and 20. Figures 3A-3I highlight the achievement of a uniform composition in the amorphous carbon-containing films.

[0090] (Temperature dependence of film thickness of amorphous carbon-containing films) Using the three types of halogenated carbosilanes described in Examples 1, 3-20, the change in film thickness was evaluated when amorphous carbon-containing films were formed by vapor deposition at different temperatures and for the same duration. Figure 4 is a graph showing the temperature dependence of the film thickness of the amorphous carbon-containing films. When vapor deposition was performed at different temperatures and for the same duration, a tendency was observed for the film thickness to increase with increasing temperature.

[0091] (4-terminal resistance measurement) For the amorphous carbon-containing films formed in Examples 2 and 13, a 4-terminal resistance measuring device was used. The resistance was measured using a Keithley 2400 SMU (product name: "2400 SMU"). The results are shown in Table 1 below. It was found that samples produced at low temperatures using DCBTCSM had lower resistivity compared to samples produced at high temperatures using BTCSM.

[0092] [Table 1]

[0093] (SEM imaging of amorphous carbon-containing films) An amorphous carbon-containing film was formed in a trench (CD: 300 nm; depth 6 μm; aspect ratio 20:1) formed on the surface of a Si substrate using the same procedure as in Example 12 (DCBTCSM). Cross-sectional observations were performed perpendicular to the trench formation direction using a scanning electron microscope (SEM) (HITACHI Corporation, product name: "SU9000") in the region from the trench surface to a depth of 300 nm, the region around a depth of 3 μm, and the region around a depth of 6 μm (magnification: 150,000x). Figure 5A is an SEM image of the region from the trench surface to a depth of 300 nm, Figure 5B is an SEM image of the region from the trench surface to a depth of 3 μm, and Figure 5C is an SEM image of the region from the trench surface to a depth of 6 μm. The thickness of the amorphous carbon-containing film was measured at three or more arbitrary points in each region and the average value was calculated. Note that in the diagram, there are some discrepancies between the film thickness measurement points (areas between the two arrows) and the measured values. However, the order of the measurement points and the order of the measured values ​​are consistent, so the values ​​should be read based on that relationship. For example, there are four measurement points in the upper part of Figure 5A. The corresponding measured values ​​from left to right are 11.6 nm, 10.3 nm, 10.9 nm, and 10.3 nm. Furthermore, Table 2 below shows the average film thickness and step coverage for each region.

[0094] [Table 2]

[0095] Figures 5A to 5C and Table 2 show that a conformal amorphous carbon-containing film was formed with a significant thickness in the trenches by DCBTCSM.

Claims

1. A process of forming an amorphous carbon-containing film on the surface of a substrate by bringing a substrate and a source gas containing a carbosilane halogenate into contact at a temperature of 300°C to 850°C under a non-plasma atmosphere. A method for producing an amorphous carbon-containing film, including [the specified component].

2. The method for producing an amorphous carbon-containing film according to claim 1, wherein the halogenated carbosilane has a halogenated silyl group.

3. The method for producing an amorphous carbon-containing film according to claim 1, wherein the halogenated carbosilane has a trichlorosilyl group.

4. The method for producing an amorphous carbon-containing film according to claim 1, wherein the compositional formula of the halogenated carbosilane is represented by the following formula (A). C ａ Yes ｂ X ｃ H ｄ (A) (In formula (A), X is a halogen atom. If there are multiple X atoms, they are either identical or different from each other. 'a' is an integer between 1 and 4. b is an integer between 2 and 2a+2. c is an integer between 6 and 2a + 2b + 2. d is 2a + 2b - c + 2.

5. The method for producing an amorphous carbon-containing film according to claim 1, wherein the halogenated carbosilane is a compound represented by the following formula (1). 【Chemistry 1】 (In formula (1) Y １ 、 Y ２ 、 Y ３ and Y ４ are each independently a silyl halide group, a halogen atom or a hydrogen atom. Y ２ and Y ３ When there are a plurality of Y ２ and Y ３ they may be the same as or different from each other. Y １ 、 Y ２ 、 Y ３ and Y ４ At least two selected from the group consisting of are silyl halide groups. n is an integer between 1 and 4.

6. The method for producing an amorphous carbon-containing film according to claim 5, wherein the silyl halogenated group is a trichlorosilyl group.

7. The method for producing an amorphous carbon-containing film according to claim 5, wherein the halogen atom is a chlorine atom.

8. The method for producing an amorphous carbon-containing film according to claim 5, wherein n is 1 or 2.

9. The method for producing an amorphous carbon-containing film according to claim 1, wherein the number of hydrogen atoms in the halogenated carbosilane is two or less.

10. The method for producing an amorphous carbon-containing film according to claim 1, wherein the carbon concentration in the amorphous carbon-containing film is 85 atom% or more.

11. The aforementioned raw material gas is N ２ A method for producing an amorphous carbon-containing film according to claim 1, comprising at least one carrier gas selected from the group consisting of He, Ar, Kr, Xe, Ne, and Rn.

12. The method for producing an amorphous carbon-containing film according to claim 1, wherein the halogenated carbosilane is at least one selected from the group consisting of bis(trichlorosilyl)methane, dichlorobis(trichlorosilyl)methane, difluorobis(trichlorosilyl)methane, tris(trichlorosilyl)methane, 1,2-bis(trichlorosilyl)ethane, 1,1-bis(trichlorosilyl)ethane, and 1,3-bis(trichlorosilyl)propane.

Images