SiC-containing film and method for producing same

Abstract

Provided are a novel production method and the like with which it is possible to efficiently and conformally form a SiC-containing film having a relatively high silicon atom content by means of a high-productivity production process. A method for producing a SiC-containing film, which comprises: a step (S1 step) for preparing, as a starting material gas, XpHnSim-C3 = C-SiqHrXs (in the formula, m is an integer of 0 to 4, n and p are integers of 0 to 2m + 1, and n + p = 2m + 1, q is an integer of 1 to 4, r and s are integers of 0 to 2q + 1, and r + s = 2q + 1, and X is each independently a halogen element selected from the group consisting of F, Cl, Br, and I); and a step (S2 step) in which the raw material gas is supplied into a chamber in which an object to be processed having a film formation surface is accommodated, and a SiC-containing film having Si and C as main components and having a ratio of the number of silicon atoms to the number of carbon atoms (Si / C) of 0.70 or more is formed on the film formation surface by a chemical vapor deposition method or an atomic layer deposition method using a thermal reaction.

Description

Technical Field

[0001] The present invention relates to a SiC-containing film and a method for producing the same. Background Art

[0002] SiC film (silicon carbide film) is a compound semiconductor with a larger band gap than Si and GaAs and high electron mobility. It is expected to be used as a material for semiconductor devices such as next-generation compound semiconductors, next-generation electronic components, high-speed and high-temperature electronic components, and solar power generation devices, or as a replacement material for these, along with Si films, GaAs films, and GaN films. However, SiC has over 200 polymorphs, and its physical properties vary significantly depending on the polymorph. Furthermore, the difficulty in controlling polymorphs currently limits its industrial application as a semiconductor device. For example, many SiC single crystal wafers currently on the market are manufactured by sublimation recrystallization. However, when crystal growth is carried out at a high temperature of 1000-2500°C, as in the sublimation recrystallization method, not only is the energy consumption cost high and the productivity low, but micropipes and small-angle grain boundaries are easily generated during the growth process, or mixed crystals labeled as 4H-SiC, 6H-Si, and 15R-SiC by the Ramsdell method are easily generated. These crystal mismatches will lead to a large number of defects, making it difficult to obtain SiC films with excellent crystal quality.

[0003] On the other hand, in the gas growth method, since the raw material gas can be flow-controlled, it is expected that high-quality crystal growth can be carried out continuously at high speed. However, in the prior art using organic silane materials such as SiH4 and hydrocarbon gases such as C3H8 as raw materials, it is necessary to react at high temperatures, which results in high energy costs. In addition, due to the variety of molecular species after decomposition, it is difficult to control the molecular species near the surface of the growing crystal. In this case, even if the SiC film (film containing silicon carbide) is not a single crystal, it has excellent mechanical strength, heat resistance, and corrosion resistance, and can obtain low dielectric constant and high thermal conductivity. Therefore, its application as a semiconductor element or in addition to a semiconductor element has been widely studied.

[0004] For example, Patent Document 1 discloses a method for forming an organic insulating film, characterized in that the film is used as an insulating film in a semiconductor device. The method employs a plasma CVD film formation method, using an organosilane gas having a carbon triple bond, an oxidant, and an inert gas. The method describes using disilylacetylene, bistrimethylsilylacetylene, and trimethylsilylacetylene as the organosilane, and states that the resulting film is a SiCH film or SiCNH film having Si-H bonds but no Si-OH bonds.

[0005] Patent Document 2 discloses a method for producing a gas-barrier plastic molded body, comprising a film-forming step in which a raw material gas is brought into contact with a heating element, the raw material gas is decomposed to generate chemical species, and the chemical species are allowed to reach the surface of the plastic molded body. A gas-barrier thin film is formed by a heating element CVD method. The method is characterized in that an organosilane compound represented by the general formula (Chemical Formula 1) H3Si-CnX (where n is 2 or 3 and X is SiH3, H, or NH2) is used as the raw material gas, and a material containing one or more metal elements selected from the group consisting of Mo, W, Zr, Ta, V, Nb, and Hf is used as the heating element, with the heating temperature of the heating element being set to 1550-2400°C. The method discloses that vinylsilane, disilbutane, disilylacetylene, or 2-aminoethylsilane is used as the organosilane compound, and that the film obtained using these is a SiOCH film having Si-H bonds.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2007-088017

[0009] Patent Document 2: International Publication No. 2012 / 091097 Pamphlet Summary of the Invention

[0010] Problems to be solved by the invention

[0011] According to the findings of the present inventors, SiC-containing films are not limited to the above-mentioned low-dielectric-constant insulating films and gas barrier films, and are expected to be used in coating materials such as graphite components, carbon fibers, and SiC fibers; embedded layers around wiring and components within semiconductor devices; fine multilayer structure films, various protective films, interlayer insulating films, etching stop films, barrier insulating films, waveguides and their protective films in large-scale integrated circuits used for semiconductors; and electrode materials.

[0012] On the other hand, from the perspective of controlling the various physical properties of SiC-containing films and improving their functionality, it is required to minimize the number of bonds other than Si-C bonds in SiC-containing films obtained by gas growth methods and CVD methods using organosilane-based materials. For example, when the ratio of silicon atoms in the raw gas is too high, the Si-Si bonds in the film will increase. In addition, when the ratio of carbon atoms in the raw gas is too high, there is a tendency for the number of C-C bonds in the film to increase. As a result, these impurity levels cause the band gap in the film to be unstable, thereby affecting the electrical and optical properties of the resulting film. In addition, it is also required to minimize the bonds between Si, C and other atoms, especially to obtain SiC-containing films without Si-H bonds or C-H bonds. In addition, in gas growth methods and CVD methods using organosilane-based materials, there is still room for improvement in further reducing temperatures, reducing energy costs, and improving productivity.

[0013] However, Patent Document 1 employs plasma CVD, which has low raw material gas utilization efficiency, resulting in poor industrial productivity. Furthermore, plasma CVD tends to be difficult to control the film composition ratio as the film formation surface area increases. Furthermore, film formation is difficult inside structures or at depths beyond the reach of the plasma, limiting its application in various environments. Furthermore, Patent Document 1 primarily aims to produce SiCH or SiCNH films, resulting in films containing both Si-H and C-H bonds.

[0014] On the other hand, although Patent Document 2 provides a gas barrier plastic molded body with high gas barrier properties, since it uses a heating element CVD at a high temperature of 1550 to 2400°C, the productivity is poor from an industrial perspective in terms of film forming temperature. In addition, even if the technology described in Patent Document 2 is applied to attempt to form a SiC-containing film on a Si substrate, it is easy to foresee that after the film is formed at a high temperature, thermal strain will occur during cooling, resulting in deterioration of the physical properties of the obtained film and mechanical damage. In addition, in Patent Document 2, the original purpose is to obtain a SiOCH film, and the obtained film contains Si-H bonds.

[0015] The present invention has been made in light of the above-mentioned problems. Specifically, the present invention aims to provide a novel manufacturing method, etc., capable of efficiently and conformally forming a SiC-containing film having a relatively high silicon atom content, using a highly productive manufacturing process, that is, without excessively increasing the film formation temperature, at a good film formation rate. Furthermore, another object of the present invention is to provide a SiC-containing film, etc., having a relatively high silicon atom content.

[0016] It should be noted that the present invention is not limited to the purposes described herein, and obtaining the effects determined by the various technical features shown in the specific embodiments described later, that is, the effects that cannot be obtained by the prior art, can also be considered as other purposes of the present invention.

[0017] Solutions for solving problems

[0018] The present inventors conducted intensive research to solve the above-mentioned technical problems and found that a SiC-containing film having a high silicon atom ratio can be produced by using a predetermined compound as a precursor, thereby completing the present invention.

[0019] That is, the present invention provides various specific aspects shown below. (1)

[0021] A method for manufacturing a SiC-containing film, comprising the following steps:

[0022] A step of preparing XpHnSim-C≡C-SiqHrXs (wherein, m is an integer from 0 to 4, n and p are integers from 0 to 2m+1, and satisfy n+p=2m+1, q is an integer from 1 to 4, r and s are integers from 0 to 2q+1, and satisfy r+s=2q+1, and X is independently a halogen element selected from F, Cl, Br, and I) as a raw material gas; and

[0023] The raw material gas is supplied into a chamber containing a workpiece having a film-forming surface, and a SiC-containing film is formed on the film-forming surface by a chemical vapor deposition method or an atomic layer deposition method utilizing a thermal reaction, wherein the SiC-containing film has Si and C as main components and a ratio of the number of silicon atoms to the number of carbon atoms (Si / C) is greater than 0.70. (2)

[0025] The method for producing a SiC-containing film according to (1), wherein:

[0026] In the film forming step, the SiC-containing film is formed in an inert gas atmosphere and / or a hydrogen atmosphere. (3)

[0028] The method for producing a SiC-containing film according to (1) or (2), wherein:

[0029] The SiC-containing film contains Si and C in a total amount of 50.0 atm % or more and 99.0 atm % or less. (4)

[0031] The method for producing a SiC-containing film according to any one of (1) to (3), wherein:

[0032] The SiC-containing film contains substantially no CH bonds. (5)

[0034] The method for producing a SiC-containing film according to any one of (1) to (4), wherein:

[0035] The SiC-containing film contains substantially no nitrogen atoms. (6)

[0037] The method for producing a SiC-containing film according to any one of (1) to (5), wherein:

[0038] The ratio (Si / C) of the SiC-containing film is 0.70 or more and 0.99 or less. (7)

[0040] The method for producing a SiC-containing film according to any one of (1) to (6), wherein:

[0041] In the film forming step, the SiC-containing film is formed at a temperature of 300° C. or higher. (8)

[0043] The method for producing a SiC-containing film according to any one of (1) to (7), wherein:

[0044] In the film forming step, the SiC-containing film is formed at a temperature of 1200° C. or lower. (9)

[0046] A SiC-containing film having Si and C as main components and a ratio of the number of silicon atoms to the number of carbon atoms (Si / C) of 0.70 or more. (10)

[0048] The SiC-containing film according to (9) is derived from XpHnSim-C≡C-SiqHrXs (wherein, m is an integer greater than or equal to 0 and less than or equal to 4, n and p are integers greater than or equal to 0 and less than or equal to 2m+1, and satisfy n+p=2m+1, q is an integer greater than or equal to 1 and less than or equal to 4, r and s are integers greater than or equal to 0 and less than or equal to 2q+1, and satisfy r+s=2q+1, and X is independently a halogen element selected from F, Cl, Br, and I). (11)

[0050] The SiC-containing film according to (9) or (10), containing Si and C in a total amount of 50.0 atm % or more and 99.0 atm % or less. (12)

[0052] The SiC-containing film according to any one of (9) to (11), which does not substantially contain a CH bond. (13)

[0054] The SiC-containing film according to any one of (9) to (12), which does not substantially contain nitrogen atoms. (14)

[0056] The SiC-containing film according to any one of (9) to (13), wherein

[0057] The ratio (Si / C) is 0.70 or more and 0.99 or less.

[0058] Effects of the Invention

[0059] According to the present invention, a SiC-containing film with a relatively high silicon atom content can be achieved. Furthermore, the present invention enables precise control of the flow rate of high-purity raw material gases and the generation of a relatively small number of reactive molecular species at relatively low temperatures. This is advantageous in controlling the growth of SiC single crystals using gas growth methods, and therefore has potential applications in the production and epitaxial growth of SiC single crystal wafers. Furthermore, because the present invention enables efficient and conformal deposition of such SiC-containing films using a highly productive manufacturing process, the resulting SiC-containing films are low-cost and offer excellent economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 1 is a flowchart showing the method for producing a SiC-containing film according to this embodiment.

[0061] Figure 2 1 is a schematic diagram showing an example of a film forming apparatus 100 for forming a SiC film according to the present embodiment.

[0062] Figure 3 It is a graph showing the IR measurement results of Examples 1 and 2.

[0063] Figure 4 It is a graph which shows the IR measurement results of Comparative Examples 1-4. DETAILED DESCRIPTION

[0064] The following describes the embodiments of the present invention in detail with reference to the accompanying drawings. However, the following embodiments are examples for explaining the present invention, and the present invention is not limited to these. That is, the present invention can be implemented with any changes within the scope of its main purpose. It should be noted that in this specification, unless otherwise specified, the positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings. In addition, the dimensional ratios of the drawings are not limited to the ratios shown in the drawings. On the other hand, in this specification, when "~" is used to describe numerical values or physical property values before and after it, the values before and after it are included. For example, the expression of the numerical range "1 to 100" includes both its lower limit "1" and upper limit "100". In addition, the expression of other numerical ranges is the same.

[0065] [Method for producing SiC-containing film]

[0066] Figure 1 1 is a flowchart showing the method for producing a SiC-containing film according to this embodiment. The method for manufacturing a SiC-containing film according to the present embodiment includes the following steps: a step of preparing XpHnSim-C≡C-SiqHrXs (wherein, m is an integer from 0 to 4, n and p are integers from 0 to 2m+1 and satisfy n+p=2m+1, q is an integer from 1 to 4, r and s are integers from 0 to 2q+1 and satisfy r+s=2q+1, and X is independently a halogen element selected from F, Cl, Br, and I) as a raw material gas (raw material gas preparation S1); and a step of supplying the raw material 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, wherein the SiC-containing film contains Si and C as main components and has a ratio of the number of silicon atoms to the number of carbon atoms (Si / C) of 0.70 or more (film formation step S2).

[0067] (Raw Material Gas Preparation Step S1)

[0068] In this raw material gas preparation step S1, an organosilane having a silylacetylene structure is prepared as a raw material gas. Specifically, the organosilane used as the raw material gas is XpHnSim-C≡C-SiqHrXs (wherein, m is an integer from 0 to 4, n and p are integers from 0 to 2m+1, satisfying n+p=2m+1, q is an integer from 1 to 4, r and s are integers from 0 to 2q+1, satisfying r+s=2q+1, and X is independently a halogen element selected from F, Cl, Br, and I). The organosilane represented by the above formula has no carbon atoms other than the -C≡C- group (an alkynylene group having 2 carbon atoms) in the silylacetylene structure, making it easy to obtain a SiC-containing film having a high silicon atom ratio. In addition, the organosilane represented by the above formula is relatively safe and has a relatively low thermal decomposition temperature. Therefore, by using it as a precursor of a SiC-containing film, even without using a plasma CVD method, the desired SiC-containing film can be formed at a good film formation rate without excessively increasing the film formation temperature. Here, in the formula, m is preferably greater than or equal to 0 and less than 3, more preferably greater than or equal to 0 and less than 2, and further preferably greater than or equal to 0 and less than 1. In addition, in the formula, q is preferably greater than or equal to 1 and less than 3, more preferably greater than or equal to 1 and less than 2, and further preferably greater than or equal to 1. In addition, in the formula, n and r are each independently preferably greater than or equal to 0 and less than 9, more preferably greater than or equal to 1 and less than 5, and further preferably greater than or equal to 1 and less than 3. In addition, in the formula, p and s are each independently preferably greater than or equal to 0 and less than 6, more preferably greater than or equal to 0 and less than 3. As the halogen element of X, F and Cl are preferably, more preferably Cl. By containing or not containing X (halogen element) in the above formula, the film formation rate, film formation temperature, etc. can be adjusted. Specific examples of preferred organosilanes include disilylacetylene (DSA: H3Si-C≡C-SiH3) with m=1, n=3, p=0, q=1, r=3, and s=0; and bistrichlorosilylacetylene (BTCSA: Cl3Si-C≡C-SiCl3) with m=1, n=0, p=3, q=1, r=0, s=3, and X being Cl.

[0069] (Film Forming Step S2)

[0070] In the film forming step S2, the aforementioned raw material gas is used to form a SiC-containing film on the film forming surface of the workpiece. The SiC film mainly comprises Si and C, and has a ratio of silicon atoms to carbon atoms (Si / C) of 0.70 or greater. This will be described in further detail below.

[0071] Figure 2The present invention is a simplified schematic diagram showing an example of a film forming apparatus 100 containing a SiC film according to the present embodiment. The manufacturing apparatus 100 includes a chamber CMB (film forming chamber) for accommodating a workpiece having a film forming surface and forming a SiC film on the film forming surface. In the chamber CMB, a substrate serving as a workpiece fixed on a base (acceptor) is placed in the center. In addition, the chamber CMB includes a hot wall type and / or cold wall type heating device. The hot wall type heating device heats the entire chamber CMB and controls it to a specified temperature, and the cold wall type heating device controls the workpiece arranged in the chamber CMB to a specified temperature. Through these controls, the substrate can be heated from room temperature to 1200°C, for example, so that the desired film forming temperature can be set.

[0072] The raw gas supply line for introducing the above-mentioned raw material gases into the chamber CMB is connected to the upstream side of the chamber CMB via a mass flow controller MFC1 for flow control and a valve. It should be noted that when using multiple raw material gases, additional raw material gas supply lines can be connected to the chamber CMB via mass flow controllers and valves for flow control. Furthermore, on the upstream side of the chamber CMB, process gas supply lines for introducing inert gases such as Ar gas and hydrogen gas into the chamber CMB are connected to the chamber CMB via mass flow controllers MFC2, MFC3, and MFC4 for flow control and valves, respectively. In this example, the raw material gases are appropriately diluted with inert gases such as Ar gas before being introduced into the chamber CMB. Furthermore, hydrogen gas is appropriately mixed with inert gases such as Ar gas before being introduced into the chamber CMB.

[0073] On the other hand, the gas exhaust passage for discharging excess raw material gas, process gas, etc. is connected to the downstream side of the chamber CMB via the rotary pump RP and the valve. It should be noted that the pressure gauge for monitoring the pressure in the chamber CMB is connected to the gas exhaust passage, and the pressure in the chamber CMB can be adjusted by opening and closing the angle valve. In addition, the dilution gas supply passage is connected to the gas exhaust passage, and the various gases supplied to the chamber CMB are sucked into the dilution gas supply passage by the rotary pump RP and flow into the dilution gas supply passage, and are diluted to any proportion by the dilution gas as needed, and discharged to an external gas recovery mechanism not shown. It should be noted that the pressure in the chamber CMB can also be adjusted by the rotary pump RP and the angle valve. For example, the chamber CMB can be adjusted to a reduced pressure atmosphere.

[0074] In a film formation process using the film formation apparatus 100, a workpiece having a film formation surface is first placed within the chamber CMB. Process gases such as inert gas and hydrogen are supplied as needed for purging. While the temperature is controlled to the specified film formation temperature, the organosilane, serving as the source gas, is introduced into the chamber CMB through the source gas supply passage. Furthermore, within the chamber CMB, a SiC-containing film is formed on the film formation surface at the specified film formation temperature using chemical vapor deposition or atomic layer deposition (ALD) utilizing a thermal reaction. Excess gases flowing into the chamber CMB are pumped by a rotary pump RP and an angle valve to maintain a specified pressure and then exhausted through the gas exhaust passage as described above.

[0075] The film forming atmosphere in the film forming process S2 is not particularly limited. However, from the perspective of safety, etc., since the above-mentioned organosilane is used as the raw material gas, it is preferably an inert gas atmosphere. In addition, from the perspective of generating a film with fewer defects by hydrogenation or promoting low-temperature film formation by hydrogen dissociation, it is preferably a hydrogen atmosphere. Taking these into consideration, the film forming atmosphere in the film forming process S2 can also be an inert gas and a hydrogen atmosphere. It should be noted that, in this specification, inert gas refers to He, Ne, Ar, Kr, N2. Among them, from the perspective of preventing nitriding reaction, He, Ne, Ar, Kr are preferred. It should be noted that the film forming atmosphere is also preferably a non-oxidizing atmosphere in the absence of O3, O2, CO, CO2, H2O, H2O2, N2O, etc.

[0076] The film forming temperature in the film forming step S2 is not particularly limited, but is preferably 300°C or higher. Since the above-mentioned organosilane is used as the raw material gas, even without using the plasma CVD method, the desired SiC-containing film can be formed at a good film forming rate without excessively increasing the film forming temperature. The film forming temperature is more preferably 400°C or higher, and further preferably 500°C or higher. On the other hand, the upper limit of the film forming temperature is not particularly limited, but is preferably 1200°C or lower, more preferably 1000°C or lower, and further preferably 800°C or lower. It should be noted that in this specification, the film forming temperature refers to the surface temperature of the film forming surface of the object to be processed, and refers to the value measured by a contact surface thermometer.

[0077] It should be noted that the film forming pressure in the film forming step S2 is not particularly limited and may be at normal pressure, pressurized, 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 perspectives of film density, uniformity, and conformality (uniform deposition of the film against uneven surfaces).

[0078] The film formation method in the film formation step S2 is not particularly limited, as long as it is a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method utilizing a thermal reaction. Specifically, thermal CVD, thermal ALD, and plasma ALD are examples. Of these, thermal CVD and thermal ALD are preferred from the perspectives of productivity and economic efficiency.

[0079] The flow rate of the raw material gas introduced in the film formation step S2 is not particularly limited, but is preferably 0.1 to 10 sccm, more preferably 0.5 to 5 sccm, and even more preferably 1 to 3 sccm. An introduction flow rate of 0.1 sccm or greater tends to result in efficient film formation. An introduction flow rate of 10 sccm or less tends to result in excellent film density, uniformity, and conformality.

[0080] 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.

[0081] The flow rate of the hydrogen gas introduced in the film forming step S2 is not particularly limited, but is preferably 0.1 to 10,000 sccm, more preferably 10 to 1,000 sccm, and even more preferably 50 to 200 sccm.

[0082] As the object to be processed, there is no particular limitation on the type of the object as long as it can form a SiC-containing film. In the above examples, a substrate is shown as the object to be processed, but for example, semiconductor products such as silicon wafers, quartz, glass, titanium, aluminum, SUS, and steel materials; electrode materials, optical materials, mechanical reinforcement materials, etc. can be listed, but are not particularly limited to these. In addition, as the film-forming surface, there is no particular limitation on the type of the object as long as it can form a SiC-containing film. In the above examples, the surface of the object to be processed is shown as the film-forming surface, but for example, the surface of a silicon wafer; SiO2 films, SiN films, GaN films, and polysilicon films formed on the surface of a silicon wafer; metal materials such as SUS and copper; precious metals such as platinum, ruthenium, iridium, and silver; transition metals such as tungsten, cobalt, nickel, and molybdenum can be listed, but are not particularly limited to these.

[0083] [Containing SiC film]

[0084] The SiC-containing film of this embodiment is a SiC-containing film having Si and C as main components and a ratio of the number of silicon atoms to the number of carbon atoms (Si / C) of 0.70 or more. When using organosilane as a raw material gas to realize the SiC-containing film, how to increase the ratio of silicon atoms in the SiC-containing film becomes a problem. That is, in order to increase the ratio of silicon atoms in the SiC-containing film, it is necessary to use a silane compound with a high silicon atom content. However, for example, monosilane (SiH4) and disilane (Si2H6) with the simplest molecular structure belong to special high-pressure gases stipulated in Japan's High-Pressure Gas Safety Law, and their use is subject to very strict restrictions. From the perspective of safety management, there is a lack of utilization possibilities. On the other hand, although silane with a large proportion of hydrocarbon groups in the molecule is safer than monosilane (SiH4) and disilane (Si2H6), there is a tendency that the ratio of silicon atoms in the SiC-containing film decreases according to the proportion of hydrocarbon groups in the molecule. In addition, from the perspective of decomposition temperature, it is difficult to obtain a good process window (film formation temperature and film formation rate) in the application of thermal CVD, thermal ALD, and plasma ALD. In response to this situation, the present inventors have discovered that SiC-containing films having a high silicon atomic ratio, i.e., Si / C of 0.70 or greater, can be stably obtained by forming films using the above-mentioned organosilanes by chemical vapor deposition or atomic layer deposition utilizing a thermal reaction.

[0085] The SiC-containing film of this embodiment contains Si and C as main components. Here, "containing Si and C as main components" means that the total amount of Si and C contained is 50.0 atm% or more and 99.0 atm% or less relative to the total amount of the SiC-containing film. From the perspective of increasing the silicon atomic ratio in the film, the total amount of Si and C in the SiC-containing film is preferably 70.0 atm% or more and 99.0 atm% or less, more preferably 73.0 atm% or more and 95.0 atm% or less, and particularly preferably 75.0 atm% or more and 90.0 atm% or less.

[0086] The SiC-containing film of this embodiment is not particularly limited as long as the ratio (Si / C) is 0.70 or greater. The ratio (Si / C) is preferably 0.75 or greater, more preferably 0.78 or greater, and even more preferably 0.80 or greater. 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.

[0087] On the other hand, the SiC-containing film of this embodiment may contain O in addition to the aforementioned Si and C. In this case, it may be a SiCO film. Oxygen atoms may be supplied during the formation of the SiC-containing film, or surface oxidation may be performed when released into the atmosphere after film formation. The oxygen atom content of the SiC-containing film of this embodiment is not particularly limited, but is preferably 10.0 atm% to 30.0 atm% relative to the total amount of the SiC-containing film, more preferably 15.0 atm% to 28.0 atm%, and particularly preferably 18.0 atm% to 25.0 atm%.

[0088] It should be noted that the SiC-containing film of the present embodiment preferably does not substantially contain any other atoms other than the above-mentioned Si, C, and O. Here, substantially not containing means that the proportion of other atoms contained is less than 3.0atm%, preferably less than 1.0atm%, more preferably less than 0.5atm%, particularly preferably less than 0.1atm%, and most preferably 0.0atm% or below the detection limit relative to the total amount of the SiC-containing film. Here, as other atoms, for example, N (nitrogen atom) and F (fluorine atom) can be listed. N is a type of dopant that changes the Fermi level of the film, thereby changing the conductivity of the film. Although F is difficult to enter the film, once it enters the film, the dielectric constant of the film will decrease. Since the SiC-containing film does not substantially contain N and F, there is a tendency to easily control electrical and optical properties, and chemical stability and durability are significantly improved.

[0089] In addition, the SiC-containing film of this embodiment preferably contains substantially no CH bonds. Here, substantially no CH bonds means that no 1100 cm-1 bonds are detected in the measurement using a Fourier transform infrared spectrophotometer (FT-IR). -1 It should be noted that there is no peak at 1100cm -1 The peak is 1100cm -1 The peak height at 800 cm -1 The peak height at 5% is 5% or less. Since the SiC-containing film contains substantially no CH bonds, it is easy to control the electrical and optical properties, and there is a tendency for the heat resistance to be significantly improved.

[0090] Meanwhile, the 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 semiconductor and optical system applications, a thickness of 100 nm to 200 nm or less is generally preferred, with a more preferred range of 2 nm to 50 nm. Furthermore, in applications requiring mechanical strength or for use as structures, a thickness of 100 nm to 10 μm is generally preferred, with a more preferred range of 300 nm to 5 μm.

[0091] As described in detail above, the method for producing a SiC-containing film according to this embodiment can efficiently and conformally form a SiC-containing film having a relatively high silicon atom content using a highly productive manufacturing process, that is, at a good film formation rate without excessively increasing the film formation temperature. The resulting SiC-containing film has a relatively high silicon atom content. Therefore, the SiC-containing film and the method for producing the same according to this embodiment have high productivity and low cost.

[0092] Example

[0093] Below by embodiment and comparative example, feature of the present invention is further specifically described, but the present invention is not limited by these at all.That is, as long as do not depart from the gist of the present invention, material, consumption, ratio, processing content, processing step etc. shown in following examples can suitably change.In addition, the value of various manufacturing conditions, evaluation result in following examples refers to the preferred upper limit value or preferred lower limit value in the embodiment of the present invention, and preferred range can be the scope determined by the combination of the value of described upper limit or lower limit and the value of following examples or the value between examples.

[0094] <Film Forming Equipment>

[0095] As a CVD device, use Figure 2 The apparatus shown is a thermal CVD apparatus manufactured by Japan Advanced Chemicals Co., Ltd. having a similar structure. The thermal CVD apparatus includes a tubular furnace having an inner diameter of 45 mm and a length of 500 mm as a film forming chamber.

[0096] [Example 1]

[0097] Using DSA (disilylacetylene: H3Si-C≡C-SiH3) as a precursor, a 105.3nm thick SiC film was formed on the surface of a silicon wafer substrate using the aforementioned film formation apparatus in an argon atmosphere for 10 minutes. The DSA flow rate was set to 0.8sccm, and the argon flow rate was set to 100sccm. The chamber pressure was set to 1.0 Torr, and the film formation temperature (substrate temperature) was set to 700°C.

[0098] [Example 2]

[0099] Using DSA as a precursor, a 215nm thick SiC-containing film was formed on the surface of a silicon wafer substrate using the aforementioned film formation apparatus in an argon and hydrogen atmosphere for 20 minutes. The DSA flow rate was set to 0.8sccm, and the argon and hydrogen flow rates were set to 100sccm. The chamber pressure was set to 1.0 Torr, and the film formation temperature (substrate temperature) was set to 700°C.

[0100] [Comparative Example 1]

[0101] Using vinylsilane (H₂C═CH₁-SiH₃) as a precursor, a 20.7 nm thick SiC-containing film was formed on the surface of a silicon wafer substrate in a hydrogen atmosphere using the aforementioned film formation apparatus for 20 minutes. The vinylsilane flow rate was set to 0.8 sccm, and the hydrogen flow rate was set to 100 sccm. The chamber pressure was set to 1.0 Torr, and the film formation temperature (substrate temperature) was set to 800°C.

[0102] [Comparative Example 2]

[0103] Using vinylsilane as a precursor, a 57nm thick SiC-containing film was formed on the surface of a silicon wafer substrate using the aforementioned film formation apparatus in an argon atmosphere for 10 minutes. The vinylsilane flow rate was set to 0.8sccm, and the argon flow rate was set to 100sccm. The chamber pressure was set to 1.0 Torr, and the film formation temperature (substrate temperature) was set to 900°C.

[0104] [Comparative Example 3]

[0105] Using vinylsilane as a precursor, a 51.3 nm thick SiC-containing film was formed on the surface of a silicon wafer substrate in a hydrogen atmosphere using the aforementioned film formation apparatus over a 15-minute film formation period. The vinylsilane flow rate was set to 0.8 sccm, and the hydrogen flow rate was set to 100 sccm. The chamber pressure was set to 1.0 Torr, and the film formation temperature (substrate temperature) was set to 900°C.

[0106] [Comparative Example 4]

[0107] Using vinylsilane as a precursor, a 70.1 nm thick SiC-containing film was formed on the surface of a silicon wafer substrate in a hydrogen atmosphere using the aforementioned film formation apparatus for 10 minutes. The vinylsilane flow rate was set to 0.8 sccm, and the hydrogen flow rate was set to 100 sccm. The chamber pressure was set to 1.0 Torr, and the film formation temperature (substrate temperature) was set to 1000°C.

[0108] Surface elemental analysis (XPS) of each of the obtained SiC-containing films was performed under the following conditions.

[0109] <XPS conditions>

[0110] Device: PHI 5000 VersaProbe III (manufactured by ULVAC-PHI.INC.)

[0111] X-ray source: Al, 100 μm, 25 W, 15 kV

[0112] Ion gun: 5V

[0113] Detection angle: 45 degrees.

[0114] Sample shape: Cut the sample into 1-2 cm squares and fix them to the sample holder with copper tape.

[0115] Pre-drying: No

[0116] Sputter: None

[0117] X-ray irradiation method: Area (HP: 1400×200μm)

[0118] Time Per Step: 50 (ms)

[0119] Cycles: 1

[0120] Analysis: Multipak software was used for smoothing, semiquantitative value calculation, and peak fitting. No offset correction was performed at this time.

[0121] The presence or absence of CH bonds in each of the obtained SiC-containing films was measured under the following conditions.

[0122] <Presence or absence of CH bond>

[0123] FT-IR device: Thermo SCIENTIC NICOLET iS10

[0124] The presence or absence of 1100 cm -1 The peak at 1100 cm is used to determine whether there is a CH bond. -1 The peak height at 800 cm -1 The peak height at is less than 5%.

[0125] The evaluation results are shown in Table 1. In addition, the IR measurement results are shown in Table 1. Figure 3 and Figure 4 shown.

[0126] [Table 1]

[0127]

[0128] Industrial applicability

[0129] The SiC-containing film and its manufacturing method of the present invention can efficiently realize a conformal SiC-containing film with a relatively high silicon atom content ratio in a high-productivity manufacturing process, and thus can be widely and effectively applied to, for example, low-dielectric-constant insulating films, gas barrier films, graphite components, carbon fibers, SiC fibers and other covering materials; embedded layers around wiring and components within semiconductor devices; fine multilayer structure films, various protective films, interlayer insulating films, etching stop films, barrier insulating films, waveguides and their protective films used in large-scale integrated circuits of semiconductors; and various applications requiring SiC-containing films, such as electrode materials.

[0130] Description of Reference Numerals

[0131] 100···Film forming apparatus including SiC film.

Claims

1. A method for producing a SiC-containing film, comprising the following steps: A step of preparing XpHnSim-C≡C-SiqHrXs as a raw material gas, wherein m is an integer from 0 to 4, n and p are integers from 0 to 2m+1, and satisfy n+p=2m+1, q is an integer from 1 to 4, r and s are integers from 0 to 2q+1, and satisfy r+s=2q+1, and X is independently a halogen element selected from F, Cl, Br, and I; and The raw material gas is supplied into a chamber containing a workpiece having a film-forming surface, and a SiC-containing film is formed on the film-forming surface by a chemical vapor deposition method or an atomic layer deposition method utilizing a thermal reaction, wherein the SiC-containing film has Si and C as main components and a ratio of the number of silicon atoms to the number of carbon atoms (Si / C) is greater than 0.

70.

2. The method for producing a SiC-containing film according to claim 1, wherein: In the film forming step, the SiC-containing film is formed in an inert gas atmosphere and / or a hydrogen atmosphere.

3. The method for producing a SiC-containing film according to claim 1, wherein: The SiC-containing film contains Si and C in a total amount of 50.0 atm % or more and 99.0 atm % or less.

4. The method for producing a SiC-containing film according to claim 1, wherein: The SiC-containing film contains substantially no CH bonds.

5. The method for producing a SiC-containing film according to claim 1, wherein: The SiC-containing film contains substantially no nitrogen atoms.

6. The method for producing a SiC-containing film according to claim 1, wherein: The ratio (Si / C) of the SiC-containing film is 0.70 or more and 0.99 or less.

7. The method for producing a SiC-containing film according to claim 1, wherein: In the film forming step, the SiC-containing film is formed at a temperature of 300° C. or higher.

8. The method for producing a SiC-containing film according to claim 1, wherein: In the film forming step, the SiC-containing film is formed at a temperature of 1200° C. or lower.

9. A SiC-containing film comprising Si and C as main components, wherein the ratio of the number of silicon atoms to the number of carbon atoms (Si / C) is 0.70 or more.

10. The SiC-containing film according to claim 9, which is derived from XpHnSim-C≡C-SiqHrXs, wherein m is an integer from 0 to 4, n and p are integers from 0 to 2m+1, and satisfy n+p=2m+1, q is an integer from 1 to 4, r and s are integers from 0 to 2q+1, and satisfy r+s=2q+1, and X is independently a halogen element selected from F, Cl, Br, and I. The SiC-containing film according to claim 9 , comprising Si and C in a total amount of 50.0 atm % to 99.0 atm %. The SiC-containing film according to claim 9 , comprising substantially no CH bonds. The SiC-containing film according to claim 9 , comprising substantially no nitrogen atoms.

14. The SiC-containing film according to claim 9, wherein The ratio (Si / C) is 0.70 or more and 0.99 or less.

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