Method for producing sic-containing film

Abstract

A method for producing a SiC-containing film, the method comprising the steps of: preparing XpHnSim-C≡C-SiqHrXs (in the formula, X is each independently a halogen element selected from the group consisting of F, Cl, Br, and I, m is an integer of 0 to 4, n and p are each an integer of 0 to 2m＋1 and satisfy n＋p=2m＋1, q is an integer of 1 to 4, and r and s are each an integer of 0 to 2q＋1 and satisfy r＋s=2q＋1) as a raw material gas; and supplying the raw material gas and a silane gas into a chamber in which a workpiece having a film-forming surface is accommodated, and forming a SiC-containing film on the film-forming surface by thermal chemical vapor deposition or atomic layer deposition.

Description

Method for producing SiC-containing film

[0001] The present invention relates to a method for producing a SiC-containing film.

[0002] SiC films (films containing silicon carbide) are materials that are expected to be used in semiconductor elements such as next-generation compound semiconductors, next-generation electronic elements, electronic elements capable of high-speed and high-temperature operation, and photovoltaic power generation elements, together with or as a replacement for Si films, GaAs films, GaN films, etc.

[0003] For example, Patent Document 1 discloses a method for producing an organic insulating film used as an insulating film in a semiconductor device, characterized in that the method uses a plasma CVD film formation method and uses an organosilane gas having a carbon triple bond, an oxidizing agent, and an inert gas as the gases used during film formation. It describes that the organosilanes used are disilylacetylene, bistrimethylsilylacetylene, and trimethylsilylacetylene, and that the films obtained using these are SiCH films or SiCNH films that have Si—H bonds but no Si—OH bonds.

[0004] Furthermore, Patent Document 2 discloses a method for producing a gas-barrier plastic molded article, which includes a film-forming step of forming a gas-barrier thin film by a heating element CVD method in which a raw material gas is brought into contact with a heating element that generates heat, the raw material gas is decomposed to generate chemical species, and the chemical species reach the surface of a plastic molded article. The method includes the step of forming a gas-barrier thin film by a heating element CVD method in which a raw material gas is brought into contact with a heating element that generates heat, the raw material gas is decomposed to generate chemical species, and the chemical species reach the surface of a plastic molded article. ３ An organic silane compound represented by Si-CnX (where n is 2 or 3 and X is SiH ３ , H or NH ２ The document discloses a method for producing a gas-barrier plastic molded article, which uses a material containing one or more metal elements selected from the group consisting of Mo, W, Zr, Ta, V, Nb, and Hf as the heating element, and sets the heating temperature of the heating element to 1550 to 2400° C. The document also discloses that the organosilane compound used is vinylsilane, disilabutane, disilylacetylene, or 2-aminoethylsilane, and that the film obtained using these compounds is a SiOCH film having Si—H bonds.

[0005] Japanese Patent Application Laid-Open No. 2007-088017 International Publication No. 2012 / 091097 Pamphlet

[0006] According to the findings of the present inventors, the SiC-containing film is expected to be used not only as the low-dielectric-constant insulating film or gas barrier film described above, but also as a coating material for graphite members, carbon fibers, SiC fibers, etc., a buried layer around wiring or around each element in a semiconductor device, a fine multilayer structure film or various protective films in large-scale integrated circuits used in semiconductors, an interlayer insulating film, an etching stopper film, a barrier insulating film, a waveguide or its protective film, an electrode material, etc.

[0007] In Patent Document 1, plasma CVD is used, which has a relatively low utilization efficiency of source gas, and therefore productivity is poor from an industrial perspective. Furthermore, with plasma CVD, control of the film composition ratio tends to become difficult as the film formation surface increases in area, and film formation on the backside of a structure or deep portions that are not irradiated with plasma is difficult, limiting its applicability to various applications. Furthermore, Patent Document 1 aims to obtain a SiCH or SiCNH film, and the resulting film contains Si—H bonds and C—H bonds.

[0008] Patent Document 2 provides a gas barrier plastic molded body having high gas barrier properties, but since it uses heating element CVD at a high temperature of 1550 to 2400°C, productivity is poor from an industrial point of view in terms of the film formation temperature.

[0009] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a manufacturing method and the like that can form a SiC-containing film while keeping the film formation temperature low.

[0010] In addition to the objectives stated here, the present invention can also be positioned as another objective of achieving effects that cannot be obtained by conventional technologies, which are derived from the various components shown in the detailed description of the invention described below.

[0011] The present inventors have conducted extensive research to solve the above problems, and as a result have found that a SiC-containing film can be produced at a low film formation temperature by using a predetermined compound as a precursor, thereby completing the present invention.

[0012] That is, the present invention provides various specific embodiments as follows: [1] A source gas containing X ｐ H ｎ Si ｍ -C≡C-Si ｑ H ｒ X ｓ(wherein X is each independently a halogen element selected from the group consisting of F, Cl, Br, and I, m is an integer of 0 or more and 4 or less, n and p are each integers of 0 or more and 2m+1 or less and n+p=2m+1, q is an integer of 1 or more and 4 or less, r and s are each integers of 0 or more and 2q+1 or less and r+s=2q+1), and a step of supplying the source gas and silane gas into a chamber accommodating a workpiece having a film formation surface, and forming a SiC-containing film on the film formation surface by chemical vapor deposition or atomic layer deposition using a thermal reaction. [2] The manufacturing method according to [1], wherein the SiC-containing film is formed under conditions of 500°C or higher in the film formation step. [3] The manufacturing method according to [1] or [2], wherein the SiC-containing film is formed under conditions of 600°C or higher in the film formation step. [4] The method for producing a SiC and SiO-containing film according to any one of [1] to [3], wherein the silane gas contains trisilane. [5-1] The method for producing a SiC and SiO-containing film according to any one of [1] to [4], wherein X is each independently F or Cl. [5-2] The method for producing a SiC and SiO-containing film according to any one of [1] to [5-1], wherein X is Cl. [6-1] The method for producing a SiC and SiO-containing film according to any one of [1] to [5-2], wherein m is 0, 1, 2, or 3. [6-2] The method for producing a SiC and SiO-containing film according to any one of [1] to [6-1], wherein m is 0, 1, or 2. [6-3] The method for producing a SiC and SiO-containing film according to any one of [1] to [6-2], wherein m is 0 or 1. [6-4] The method for producing a SiC and SiO-containing film according to any one of [1] to [6-3], wherein m is 1. [7-1] A method for producing a SiC and SiO-containing film according to any one of [1] to [6-4], in which q is 1, 2, or 3. [7-2] A method for producing a SiC and SiO-containing film according to any one of [1] to [7-1], in which q is 1 or 2. [7-3] A method for producing a SiC and SiO-containing film according to any one of [1] to [7-2], in which q is 1.[8-1] The method for producing a SiC and SiO-containing film according to any one of [1] to [7-3], wherein n and r are each independently an integer of 0 or more and 9 or less. [8-2] The method for producing a SiC and SiO-containing film according to any one of [1] to [8-1], wherein n and r are each independently an integer of 1 or more and 5 or less. [8-3] The method for producing a SiC and SiO-containing film according to any one of [1] to [8-2], wherein n and r are each independently an integer of 1 or more and 3 or less. [8-4] The method for producing a SiC and SiO-containing film according to any one of [1] to [8-3], wherein n and r are 3. [9-1] The method for producing a SiC and SiO-containing film according to any one of [1] to [8-4], wherein p and s are each independently an integer of 0 or more and 6 or less. [9-2] The method for producing a SiC and SiO-containing film according to any one of [1] to [9-1], wherein p and s are each independently an integer of 0 or more and 3 or less. [9-3] The method for producing a SiC and SiO-containing film according to any one of [1] to [9-2], wherein p and s are 0. [10-1] The source gas is H. ３ Si-C≡C-SiH ３ [10-2] The method for producing a SiC and SiO-containing film according to any one of [1] to [4], wherein the source gas is Cl ３ Si-C≡C-SiCl ３[11-1] The method for producing a SiC and SiO-containing film according to any one of [1] to [10-2], wherein the film formation temperature in the film formation step is 300 to 1200°C. [11-2] The method for producing a SiC and SiO-containing film according to any one of [1] to [11-1], wherein the film formation temperature in the film formation step is 400 to 1000°C. [11-3] The method for producing a SiC and SiO-containing film according to any one of [1] to [11-2], wherein the film formation temperature in the film formation step is 500 to 800°C. [11-4] The method for producing a SiC and SiO-containing film according to any one of [1] to [11-3], wherein the film formation temperature in the film formation step is 600 to 800°C. [11-5] The method for producing a SiC and SiO-containing film according to any one of [1] to [11-3], wherein the film formation temperature in the film formation step is 500 to 600°C.

[0013] According to the present invention, a SiC-containing film can be produced at a low film-forming temperature, and therefore the resulting SiC-containing film is low cost and highly economical.

[0014] Fig. 1 is a flowchart showing a method for producing a SiC-containing film according to the present embodiment. Fig. 2 is a schematic diagram showing an example of a film formation apparatus 100 for a SiC-containing film according to the present embodiment. Fig. 3 is a chart showing the IR measurement results of Example 2.

[0015] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the following embodiments are merely examples for explaining the present invention, and the present invention is not limited to these. In other words, the present invention can be implemented with any modifications within the scope of the gist of the present invention. In this specification, positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings unless otherwise specified. Furthermore, the dimensional ratios of the drawings are not limited to the ratios shown. Meanwhile, in this specification, when a numerical value or physical property value is enclosed before and after "~", the values ​​before and after are used to include them. For example, the expression of a numerical range such as "1 to 100" includes both the lower limit "1" and the upper limit "100". The same applies to other numerical range expressions.

[0016] 1 is a flowchart showing a method for producing a SiC-containing film according to the present embodiment. ｐ H ｎ Si ｍ -C≡C-Si ｑ H ｒ X ｓ (wherein X is independently a halogen element selected from the group consisting of F, Cl, Br, and I; m is an integer of 0 to 4; n and p are each integers of 0 to 2m+1 and satisfy n+p=2m+1; q is an integer of 1 to 4; r and s are each integers of 0 to 2q+1 and satisfy r+s=2q+1) (source gas preparation S1); and (film formation step S2) supplying the source gas and silane gas into a chamber containing a workpiece having a film formation surface, and forming a SiC-containing film on the film formation surface by chemical vapor deposition or atomic layer deposition using a thermal reaction. Here, the silane gas is a gas different from the source gas. In this specification, to distinguish between the source gas and the silane gas, the source gas will also be referred to as a "first silane gas" and the silane gas will also be referred to as a "second silane gas."

[0017] (Source Gas Preparation Step S1) In the source gas preparation step S1, an organosilane having a silylacetylene structure is prepared as a source gas. Specifically, the organosilane used as the source gas has X ｐ H ｎ Si ｍ -C≡C-Si ｑ H ｒ X ｓ(In the formula, each X is independently a halogen element selected from the group consisting of F, Cl, Br, and I; m is an integer of 0 to 4; n and p are each integers of 0 to 2m+1, and satisfy the relationship n+p=2m+1; q is an integer of 1 to 4; r and s are each integers of 0 to 2q+1, and satisfy the relationship r+s=2q+1.) The organosilane represented by the above formula does not contain any carbon atoms other than the —C≡C— group (an alkynylene group having two carbon atoms) in the silylacetylene structure, making it easier to obtain a SiC-containing film with a relatively high silicon atom ratio. Furthermore, because the organosilane represented by the above formula is relatively safe and has a relatively low thermal decomposition temperature, by using it as a precursor to a SiC-containing film, a desired SiC-containing film can be formed at a good film formation rate without excessively increasing the film formation temperature, even without using a plasma CVD method. In the formula, when m or q is an integer of 3 or more, the silicon chain may be linear or branched. Here, in the formula, m is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably an integer of 0 to 1, and particularly preferably 1. Also, in the formula, q is preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and even more preferably 1. Furthermore, in the formula, n and r are each independently preferably an integer of 0 to 9, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, and particularly preferably 3. Also, in the formula, p and s are each independently preferably an integer of 0 to 6, more preferably an integer of 0 to 3, and even more preferably 0. As the halogen element for X, F or Cl is preferred, and Cl is more preferred. By containing or not containing X (halogen element) in the above formula, the film formation rate, film formation temperature, etc. can be adjusted. A specific example of a preferred organosilane is disilylacetylene (DSA:H) in which m=1, n=3, p=0, q=1, r=3, and s=0. ３ Si-C≡C-SiH ３ ), X is Cl, m=1, n=0, p=3, q=1, r=0, s=3, bistrichlorosilylacetylene (BTCSA:Cl ３Si-C≡C-SiCl ３ ) are listed.

[0018] (Film Forming Step S2) In this film forming step S2, a SiC-containing film is formed on the film forming surface of the workpiece using the above-mentioned source gas and silane gas.

[0019] The silane gas in this embodiment (i.e., the second silane gas) is preferably a gas of a compound composed only of silicon and hydrogen. The compound is not particularly limited as long as it can be gasified, and is preferably Si ｘ H ２ｘ＋２ (x is an integer of 1 or more and 5 or less), and may be a chain molecule or a branched molecule. x is preferably an integer of 2 or more and 4 or less. Examples of such compounds include disilane (Si ２ H ６ ), trisilane (Si ３ H ８ ), tetrasilane (Si ４ H １０ The silane gas may be used alone or in combination of two or more.

[0020] FIG. 2 is a schematic diagram illustrating an example of a SiC-containing film formation apparatus 100 according to this embodiment. This manufacturing apparatus 100 includes a chamber CMB (film formation chamber) for accommodating a workpiece having a film formation surface and forming a SiC-containing film on the workpiece. A substrate, which is the workpiece and is fixed to a susceptor, is set in the center of the chamber CMB. The chamber CMB also includes a hot-wall and / or cold-wall heating device. The hot-wall heating device heats the entire chamber CMB to a predetermined temperature, while the cold-wall heating device controls the workpiece placed in the chamber CMB to a predetermined temperature. These controls allow the substrate to be heated, for example, from room temperature to 1200°C, thereby enabling the desired film formation temperature to be set.

[0021] A source gas supply path for introducing the source gas into the chamber CMB is connected to the upstream side of the chamber CMB via a mass flow controller MFC1 and a valve that controls the flow rate. When multiple source gases are used, an additional source gas supply path may be connected to the chamber CMB via a mass flow controller and a valve that controls the flow rate. Also, upstream of the chamber CMB, process gas supply paths for introducing an inert gas such as Ar gas or silane gas (second silane gas) into the chamber CMB are connected to the chamber CMB via mass flow controllers MFC2, MFC3, and MFC4 that control the flow rate and valves, respectively. In this example, the source gas is appropriately diluted with an inert gas such as Ar gas and introduced into the chamber CMB, and the silane gas (second silane gas) is also appropriately mixed with an inert gas such as Ar gas and introduced into the chamber CMB.

[0022] Meanwhile, a gas exhaust path for exhausting excess source gases, process gases, etc. is connected to the downstream side of the chamber CMB via a rotary pump R.P. and a valve. A pressure gauge for monitoring the pressure inside the chamber CMB is connected to the gas exhaust path, and the pressure inside the chamber CMB can be adjusted by opening and closing an angle valve. A dilution gas supply path is also connected to the gas exhaust path, and various gases supplied into the chamber CMB are sucked by the rotary pump R.P. and flow into the dilution gas supply path, where they are diluted to a desired ratio with the dilution gas as needed, and then discharged to an external gas recovery mechanism (not shown). The pressure inside the chamber CMB can also be adjusted using the rotary pump R.P. or an angle valve; for example, the chamber CMB can be adjusted to a reduced pressure atmosphere.

[0023] In the film formation process using this film formation apparatus 100, a substrate having a film formation surface is first placed in the chamber CMB. A process gas, such as an inert gas, is supplied and purged as necessary. While controlling the temperature to a predetermined film formation temperature, the aforementioned organosilanes, i.e., first and second silane gases, are introduced into the chamber CMB through the source gas supply path. Then, in the chamber CMB, a SiC-containing film is formed on the film formation surface by thermal chemical vapor deposition or atomic layer deposition at the desired film formation temperature. Excess gases flowing into the chamber CMB are sucked in by a rotary pump R.P. or angle valve to maintain a predetermined pressure, and are then exhausted through the gas exhaust path as described above.

[0024] The film formation atmosphere in the film formation step S2 is not particularly limited, but an inert gas atmosphere is preferable from the viewpoint of safety, etc., since the above-mentioned organic silane is used as a raw material gas. In consideration of this, the film formation atmosphere in the film formation step S2 can also be an inert gas atmosphere. In this specification, the inert gas refers to He, Ne, Ar, Kr, N ２ Among these, from the viewpoint of preventing nitriding reaction, He, Ne, Ar, and Kr are preferable, and Ar is more preferable. ３ , O ２ , CO, CO ２ , H ２ O, H ２ O ２ , N ２ It is also preferable to carry out the treatment in a non-oxidizing atmosphere in which O or the like is not present.

[0025] The film formation temperature in the film formation step S2 is not particularly limited, but is preferably 300°C or higher. Because the above-described organosilane is used, a desired SiC-containing film can be formed at a good film formation rate without excessively increasing the film formation temperature, even without using a plasma CVD method. The film formation temperature is more preferably 400°C or higher, even more preferably 500°C or higher, and even more preferably 600°C or higher. On the other hand, the upper limit of the film formation temperature is not particularly limited, but is preferably 1200°C or lower, more preferably 1000°C or lower, and even more preferably 800°C or lower. The temperature range may be defined by appropriately combining the above-described lower and upper limits of the film formation temperature. For example, the film formation temperature may be 300 to 1200°C, 400 to 1000°C, 500 to 800°C, or 600 to 800°C. Alternatively, the film formation temperature may be 500 to 600°C. In this specification, the film formation temperature refers to the surface temperature of the film formation surface of the object to be processed, and refers to a value measured with a contact surface thermometer.

[0026] The film formation pressure in the film formation step S2 is not particularly limited, and may be normal pressure, increased pressure, or reduced pressure. For example, the reduced pressure condition is preferably 0.05 Torr to 760 Torr, and more preferably 0.05 Torr to 10 Torr, from the viewpoints of film density, uniformity, conformality (uniform film deposition ability over unevenness), etc.

[0027] The film formation mode in the film formation step S2 is not particularly limited as long as it is a chemical vapor deposition (CVD) method using a thermal reaction or an atomic layer deposition (ALD) method. Specific examples include thermal CVD, thermal ALD, and plasma ALD. Among these, thermal CVD and thermal ALD are preferred from the viewpoints of productivity, economy, and the like.

[0028] The flow rates of the source gas and silane gas introduced in the film-forming step S2 are not particularly limited, but are preferably 0.1 to 150 sccm, more preferably 0.5 to 100 sccm, even more preferably 1 to 90 sccm, still more preferably 10 to 80 sccm, and even more preferably 20 to 80 sccm. An introduction flow rate of 0.1 sccm or more tends to allow film formation to proceed efficiently. An introduction flow rate of 10 sccm or less tends to provide excellent film density, uniformity, and conformality.

[0029] The flow rate of the inert gas introduced in the film-forming step S2 is not particularly limited, but is preferably 1 to 500 sccm, more preferably 10 to 300 sccm, and even more preferably 50 to 100 sccm.

[0030] The type of the object to be treated is not particularly limited as long as it is capable of forming a SiC-containing film. In the above example, a substrate is shown as the object to be treated, but examples thereof include semiconductor products such as silicon wafers, quartz, glass, titanium, aluminum, SUS, and steel materials, electrode materials, optical materials, and mechanically reinforcing materials, but are not particularly limited to these. Furthermore, the type of the film formation surface is not particularly limited as long as it is capable of forming a SiC-containing film. In the above example, the surface of the object to be treated is shown as the film formation surface, but examples thereof include the surface of a silicon wafer, SiO formed on the surface of a silicon wafer, and the like. ２ Examples of the material include, but are not limited to, metal materials such as SUS and copper, precious metals such as platinum, ruthenium, iridium, and silver, and transition metals such as tungsten, cobalt, nickel, and molybdenum.

[0031] [SiC-Containing Film] The SiC-containing film of this embodiment contains Si and C as its main components. Here, "containing Si and C as its main components" means that the total amount of Si and C is 50.0 atm% or more and 99.0 atm% or less relative to the total amount of the SiC-containing film. From the viewpoint of increasing the proportion of silicon atoms in the film, the SiC-containing film contains a total amount of Si and C of preferably 70.0 atm% or more and 99.0 atm%, more preferably 73.0 atm% or more and 95.0 atm%, and particularly preferably 75.0 atm% or more and 90.0 atm% or less.

[0032] The Si / C ratio in the SiC-containing film of this embodiment is preferably 0.70 or more, more preferably 0.75 or more, even more preferably 0.78 or more, and even more preferably 0.80 or more. The upper limit of the ratio (Si / C) is not particularly limited, but is preferably 1.10 or less, more preferably 1.00 or less, even more preferably 0.99 or less, and particularly preferably 0.98 or less.

[0033] On the other hand, the SiC-containing film of this embodiment may contain O in addition to the above-mentioned Si and C, in which case it may be a SiCO film. Oxygen atoms may be supplied during the formation of the SiC-containing film, or the surface may be oxidized when the film is exposed to the atmosphere after formation. The content of oxygen atoms in the SiC-containing film of this embodiment is not particularly limited, but is preferably 10.0 atm% to 30.0 atm%, more preferably 15.0 atm% to 28.0 atm%, and particularly preferably 18.0 atm% to 25.0 atm%, relative to the total amount of the SiC-containing film.

[0034] It is preferable that the SiC-containing film of this embodiment is substantially free of other atoms other than the above-described Si, C, and O. Here, "substantially free" means that the content of other atoms is less than 3.0 atm% relative to the total amount of the SiC-containing film, preferably 1.0 atm% or less, more preferably less than 0.5 atm%, particularly preferably less than 0.1 atm%, and most preferably 0.0 atm% or below the detection limit. Examples of other atoms include N (nitrogen atom) and F (fluorine atom). N is a type of dopant that changes the Fermi level of the film and alters the film's conductivity. F is difficult to incorporate into the film, but when it enters the film, the film's dielectric constant decreases. The SiC-containing film being substantially free of N and F facilitates control of electrical and optical properties and also tends to significantly improve chemical stability and durability.

[0035] Furthermore, the SiC-containing film of this embodiment preferably does not substantially contain C—H bonds. Here, "substantially does not contain" means that the C—H bonds are not present at 1100 cm as measured by a Fourier transform infrared spectrophotometer (FT-IR). －１ This means that there is no peak at 1100 cm －１ There is no peak at 1100 cm －１ The height of the peak at －１ When the SiC-containing film is substantially free of C—H bonds, it becomes easier to control the electrical and optical properties, and the heat resistance tends to be significantly improved.

[0036] On the other hand, the film thickness of the SiC-containing film of this embodiment can be appropriately set depending on the application and required performance, and is not particularly limited. For example, in the case of applications in semiconductors and optical systems, a monolayer film thickness of 200 nm or less is generally preferred, and a thickness of 2 nm to 50 nm is more preferred. Furthermore, in the case of applications requiring mechanical strength or use as a structure, a thickness of 100 nm to 10 μm is generally preferred, and a thickness of 300 nm to 5 μm is more preferred.

[0037] The SiC-containing film of this embodiment can be produced, for example, according to the above-mentioned [Method for producing a SiC-containing film].

[0038] The features of the present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. That is, the materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Furthermore, the values ​​of various production conditions and evaluation results in the following examples represent preferred upper or lower limits in the embodiments of the present invention, and preferred ranges may be defined by combining the above-mentioned upper or lower limits with the values ​​in the following examples or values ​​between the examples.

[0039] <Film Formation Apparatus> A thermal CVD apparatus manufactured by Japan Advanced Chemicals Co., Ltd. was used as the CVD apparatus, having a configuration equivalent to that shown in Fig. 2. This thermal CVD apparatus was equipped with a tubular furnace having an inner diameter of 45 mm and a length of 500 mm as a film formation chamber.

[0040] [Example 1] First silane gas: DSA (disilylacetylene: H ３ Si-C≡C-SiH ３ ) and a second silane gas: trisilane. Using the above-described film formation apparatus, under an argon atmosphere, a cycle of supplying DSA for 10 seconds and then supplying trisilane for 10 seconds was repeated 60 times to form a SiC-containing film on the surface of a silicon wafer substrate. The flow rates of DSA, trisilane, and argon were 0.5 sccm, 50 sccm, and 80 sccm, respectively. The chamber pressure was 1.3 Torr, and the film formation temperature (substrate temperature) was 500°C. Trisilane was diluted with argon to form a 0.96% trisilane gas.

[0041] [Example 2] Using the first silane gas (DSA) and the second silane gas (trisilane) as precursors, and using the above-mentioned film formation apparatus under an argon atmosphere, a cycle of supplying DSA for 10 seconds and then supplying trisilane for 10 seconds was repeated 60 times to form a SiC-containing film on the surface of a silicon wafer substrate. The flow rate of DSA was 0.5 sccm, the flow rate of trisilane was 50 sccm, and the flow rate of argon was 80 sccm. The pressure in the chamber was 1.3 Torr, and the film formation temperature (substrate temperature) was 600°C. Trisilane was used as a gas diluted with argon to a trisilane concentration of 0.96%.

[0042] Comparative Example 1: Using only DSA as a precursor, the above-mentioned film-forming apparatus was used in an argon atmosphere, and DSA was supplied for 10 seconds 60 times to form a SiC-containing film on the surface of a silicon wafer substrate. The flow rate of DSA was 0.5 sccm, and the flow rate of argon was 80 sccm. The pressure in the chamber was 1.3 Torr, and the film-forming temperature (substrate temperature) was 500°C.

[0043] [Comparative Example 2] Using only DSA as a precursor, the above-mentioned film formation apparatus was used in an argon atmosphere, and DSA was supplied for 10 seconds 60 times to form a SiC-containing film on the surface of a silicon wafer substrate. The flow rate of DSA was 0.5 sccm, and the flow rate of argon was 80 sccm. The pressure in the chamber was 1.3 Torr, and the film formation temperature (substrate temperature) was 600°C.

[0044] Comparative Example 3: Using only trisilane as a precursor, a SiC-containing film was formed on the surface of a silicon wafer substrate using the above-described film formation apparatus under an argon atmosphere by repeating the supply of trisilane for 10 seconds 60 times. The flow rate of trisilane was 50 sccm, and the flow rate of argon was 80 sccm. The chamber pressure was 1.3 Torr, and the film formation temperature (substrate temperature) was 500°C.

[0045] The presence or absence of film formation in each of the examples and comparative examples was confirmed visually.

[0046] For Example 2, the presence or absence of Si—C bonds in the SiC-containing film was measured under the following conditions: <Presence or absence of Si—C bonds> FT-IR device: Thermo SCIENTIC NICOLET iS10 700 cm in the obtained spectrum －１ The presence or absence of Si—C was determined based on the presence or absence of the peak.

[0047] The evaluation results are shown in Table 1. The IR measurement results of Example 2 are shown in FIG.

[0048] The SiC-containing film and method for producing the same of the present invention can be widely and effectively used in various applications requiring a SiC-containing film, such as low-dielectric-constant insulating films, gas barrier films, coating materials such as graphite members, carbon fibers, and SiC fibers, buried layers around wiring and around each element in semiconductor devices, fine multilayer structure films and various protective films in large-scale integrated circuits used in semiconductors, interlayer insulating films, etching stopper films, barrier insulating films, waveguides and their protective films, and electrode materials.

[0049] 100 ... SiC-containing film forming apparatus

Claims

1. X as raw material gas ｐ H ｎ Si ｍ -C≡C-Si ｑ H ｒ X ｓ (wherein X is each independently a halogen element selected from the group consisting of F, Cl, Br, and I; m is an integer of 0 to 4; n and p are each integers of 0 to 2m+1 and satisfy n+p=2m+1; q is an integer of 1 to 4; r and s are each integers of 0 to 2q+1 and satisfy r+s=2q+1), and a method of manufacturing a SiC-containing film, comprising the steps of: supplying the source gas and silane gas into a chamber containing a workpiece having a film formation surface; and depositing a SiC-containing film on the film formation surface by chemical vapor deposition or atomic layer deposition using a thermal reaction.

2. The manufacturing method according to claim 1, wherein the SiC-containing film is formed under conditions of 500° C. or higher in the film forming step.

3. The manufacturing method according to claim 1, wherein the SiC-containing film is formed under conditions of 600° C. or higher in the film forming step.

4. The manufacturing method according to any one of claims 1 to 3, wherein the silane gas includes trisilane.

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