Method for producing sic-and-sio-containing film

Abstract

A method for producing a SiC-and-SiO-containing film, the method comprising: a step for preparing, as a material gas, XpHnSim-C≡C-SiqHrXs (in the formula, each X independently represents a halogen element selected from the group consisting of F, Cl, Br, and I, m represents an integer of 0-4, n and p each represent an integer of 0 to 2m+1, n+p=2m+1 is satisfied, q represents an integer of 1-4, r and s each represent an integer of 0 to 2q+1, and r+s=2q+1 is satisfied); and a film-formation step for supplying the material gas and an oxidizer into a chamber accommodating a treatment target body having a film-formation surface, and forming a SiC-and-SiO-containing film on the film-formation surface by atomic layer deposition or chemical vapor deposition through a thermal reaction, wherein in the film-formation step, the SiC-and-SiO-containing film is formed at a condition equal to or higher than 500°C.

Description

Method for producing SiC and SiO-containing films

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

[0002] SiC and SiO-containing films (films containing silicon carbide and silicon oxide) 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 ２The 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, SiC and SiO-containing films are expected to be used not only for the above-mentioned low-dielectric-constant insulating films and gas barrier films, but also for applications such as coating materials for graphite members, carbon fibers, SiC fibers, etc., 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, electrode materials, 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] In Patent Document 2, the object is to obtain a SiOCH film, and the obtained film contains Si—H bonds.

[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 efficiently form a SiC and SiO-containing film that suppresses the generation of C—H bonds.

[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 by using a specific compound as a precursor, it is possible to produce a SiC and SiO-containing film in which the formation of C—H bonds is suppressed, 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 the oxidizing agent into a chamber accommodating a workpiece having a film formation surface, and depositing a SiC and SiO-containing film on the film formation surface by chemical vapor deposition or atomic layer deposition using a thermal reaction, wherein the SiC and SiO-containing film is deposited under conditions of 500° C. or more in the film formation step. [2] A method for producing a SiC and SiO-containing film according to [1], wherein the SiC and SiO-containing film is substantially free of C—H bonds. [3] The oxidizing agent is O ３ and / or O ２[4-1] The method for producing a SiC and SiO-containing film according to any one of [1] to [3], wherein X is each independently F or Cl. [4-2] The method for producing a SiC and SiO-containing film according to any one of [1] to [4-1], wherein X is Cl. [5-1] The method for producing a SiC and SiO-containing film according to any one of [1] to [4-2], wherein m is 0, 1, 2, or 3. [5-2] The method for producing a SiC and SiO-containing film according to any one of [1] to [5-1], wherein m is 0, 1, or 2. [5-3] The method for producing a SiC and SiO-containing film according to any one of [1] to [5-2], wherein m is 0 or 1. [5-4] The method for producing a SiC and SiO-containing film according to any one of [1] to [5-3], wherein m is 1. [6-1] A method for producing a SiC and SiO-containing film according to any one of [1] to [5-4], wherein q is 1, 2, or 3. [6-2] A method for producing a SiC and SiO-containing film according to any one of [1] to [6-1], wherein q is 1 or 2. [6-3] A method for producing a SiC and SiO-containing film according to any one of [1] to [6-2], wherein q is 1. [7-1] A method for producing a SiC and SiO-containing film according to any one of [1] to [6-3], wherein n and r are each independently an integer of 0 to 9. [7-2] A method for producing a SiC and SiO-containing film according to any one of [1] to [7-1], wherein n and r are each independently an integer of 1 to 5. [7-3] A method for producing a SiC and SiO-containing film according to any one of [1] to [7-2], wherein n and r are each independently an integer of 1 to 3. [7-4] The method for producing a SiC and SiO-containing film according to any one of [1] to [7-3], wherein n and r are 3. [8-1] The method for producing a SiC and SiO-containing film according to any one of [1] to [7-4], wherein p and s are each independently an integer of 0 to 6. [8-2] The method for producing a SiC and SiO-containing film according to any one of [1] to [8-1], wherein p and s are each independently an integer of 0 to 3.[8-3] The method for producing a SiC and SiO-containing film according to any one of [1] to [8-2], wherein p and s are 0. [9-1] The source gas is H. ３ Si-C≡C-SiH ３ [9-2] The method for producing a SiC and SiO-containing film according to any one of [1] to [3], wherein the source gas is Cl ３ Si-C≡C-SiCl ３ [10-1] The method for producing a SiC and SiO-containing film according to any one of [1] to [9-2], wherein the film formation temperature in the film formation step is 500 to 1200°C. [10-2] The method for producing a SiC and SiO-containing film according to any one of [1] to [10-1], wherein the film formation temperature in the film formation step is 530 to 1000°C. [10-3] 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 550 to 800°C. [10-4] The method for producing a SiC and SiO-containing film according to any one of [1] to [10-3], wherein the film formation temperature in the film formation step is 580 to 700°C. [10-5] The method for producing a SiC and SiO-containing film according to any one of [1] to [10-4], wherein the film formation temperature in the film formation step is 600 to 700°C.

[0013] According to the present invention, it is possible to produce a SiC and SiO-containing film in which the formation of C—H bonds is suppressed.

[0014] Fig. 1 is a flowchart showing a method for manufacturing a SiC and SiO-containing film according to this embodiment. Fig. 2 is a schematic diagram showing an example of a film forming apparatus 100 for forming a SiC and SiO-containing film according to this embodiment. Fig. 3 is a chart showing the IR measurement results of Examples 1 to 4.

[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] In this embodiment, the SiC and SiO-containing film refers to a film in which Si—C bonds and Si—O bonds exist. In this specification, the “SiC and SiO-containing film” is also referred to as a SiCO-containing film.

[0017] 1 is a flowchart showing a method for producing a SiCO-containing film according to the present embodiment. ｐ H ｎ Si ｍ -C≡C-Si ｑ H ｒ X ｓ (wherein X's are 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 n+p=2m+1; q is an integer of 1 to 4; r and s are each integers of 0 to 2q+1, and r+s=2q+1), and the method includes a step of supplying the source gas and an oxidizing agent into a chamber containing a substrate having a deposition surface, and depositing a SiC- and SiO-containing film on the deposition surface by chemical vapor deposition or atomic layer deposition using a thermal reaction (film deposition step S2). The method for producing a SiCO-containing film of this embodiment suppresses the generation of C—H bonds.

[0018] (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 has no carbon atoms other than the —C≡C— group (an alkynylene group having two carbon atoms) in the silylacetylene structure, and therefore tends to make it easier to obtain a SiCO-containing film with a relatively high silicon atom ratio. In addition, the organosilane represented by the above formula is relatively safe and has a relatively low thermal decomposition temperature, so by using it as a precursor for a SiCO-containing film, it tends to be possible to form a desired SiCO-containing film 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 ), bistrichlorosilylacetylene (BTCSA:Cl) in which X is Cl, m=1, n=0, p=3, q=1, r=0, and s=3３ Si-C≡C-SiCl ３ ) are listed.

[0019] (Film Forming Step S2) In this film forming step S2, a SiCO-containing film is formed on the film forming surface of the workpiece using the above-mentioned source gas.

[0020] FIG. 2 is a schematic diagram illustrating an example of a SiCO-containing film forming apparatus 100 according to this embodiment. This manufacturing apparatus 100 includes a chamber CMB (film forming chamber) for accommodating a workpiece having a film forming surface and forming a SiCO-containing film on the workpiece surface. 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 forming temperature to be set.

[0021] A source gas supply path that introduces the source gas into the chamber CMB is connected to the upstream side of the chamber CMB via a mass flow controller MFC1 that controls the flow rate and a valve. When multiple source gases are used, a separate 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, a process gas supply path that introduces an inert gas such as Ar gas as a process gas and an oxidizer into the chamber CMB is connected to the chamber CMB via mass flow controllers MFC2, MFC3, MFC4, and MFC5 that control the flow rate and a valve. 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 oxidizer 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. The source gas, organosilane, is introduced into the chamber CMB through the source gas supply path while controlling the temperature to a predetermined film formation temperature. The oxidizer may be introduced simultaneously with the source gas or after the source gas is introduced and purged. Then, in the chamber CMB, a SiCO-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 then discharged through the gas exhaust path as described above. The introduction of the source gas and oxidizer, film formation, and discharge of excess gases may be repeated.

[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 ２Among these, from the viewpoint of preventing the nitriding reaction, He, Ne, Ar and Kr are preferred, and Ar is more preferred.

[0025] The film formation temperature in the film formation step S2 is 500°C or higher. Because the above-described organosilane is used as the source gas, a desired SiCO-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 530°C or higher, and even more preferably 550°C or higher. Furthermore, increasing the film formation temperature tends to increase the SiC content. In the manufacturing method of this embodiment, the amount of SiC and SiO in the film can be controlled by controlling the film formation temperature. From the viewpoint of increasing the SiC content, the film formation temperature is preferably 580°C or higher, 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, even more preferably 800°C or lower, and even more preferably 700°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 500 to 1200° C., 530 to 1000° C., 550 to 800° C., 580 to 700° C., or 600 to 700° C. In this specification, the film formation temperature refers to the surface temperature of the film formation surface of the object to be treated, 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 rate of the source gas introduced in the film-forming step S2 is not particularly limited, but is 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 150 sccm or less tends to provide excellent film density, uniformity, and conformality.

[0029] The flow rate of the oxidizing agent introduced in the film-forming step S2 is not particularly limited, but is preferably 0.1 to 100 sccm, more preferably 0.5 to 50 sccm, and even more preferably 5 to 40 sccm. When the introduction flow rate is 0.1 sccm or more, film formation tends to proceed efficiently. When the introduction flow rate is 100 sccm or less, the film tends to have excellent density, uniformity, and conformality.

[0030] The oxidizing agent is not limited as long as it is used in the oxidation reaction and is gaseous, but oxygen and / or ozone can be preferably used.

[0031] 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. The flow rate of the inert gas introduced is the total amount of the inert gas introduced into the chamber.

[0032] The type of the object to be treated is not particularly limited as long as it is capable of forming a SiCO-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 SiCO-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.

[0033] [SiCO-Containing Film] The SiCO-containing film of this embodiment contains, as main components, Si, C, and O. Here, "containing, as main components, Si, C, and O" means that the total amount of Si, C, and O is 50.0 atm % or more and 99.0 atm % or less with respect to the total amount of the SiCO-containing film.

[0034] The Si / C ratio in the SiCO-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.

[0035] On the other hand, the SiCO-containing film of this embodiment contains O in addition to Si and C. Oxygen atoms may be supplied during the formation of the SiCO-containing film, or the surface may be oxidized when the film is exposed to the atmosphere after formation. The oxygen atom content of the SiCO-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%, based on the total amount of the SiCO-containing film.

[0036] It is preferable that the SiCO-containing film of this embodiment substantially does not contain any other atoms other than the above-mentioned Si, C, and O. Here, "substantially does not contain" means that the content of other atoms is less than 3.0 atm% of the total amount of the SiCO-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 dielectric constant of the film decreases. The SiCO-containing film substantially free of N and F facilitates control of electrical and optical properties and tends to significantly improve chemical stability and durability.

[0037] Furthermore, it is preferable that the SiCO-containing film of this embodiment is substantially free of C—H bonds. Here, "substantially free of C—H bonds" 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 SiCO-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.

[0038] On the other hand, the film thickness of the SiCO-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 monoatomic layer 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.

[0039] The SiCO-containing film of this embodiment can be produced, for example, according to the above-mentioned [Method for producing a SiCO-containing film].

[0040] 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.

[0041] <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.

[0042] [Example 1] DSA (disilylacetylene: H) was used as a precursor. ３ Si-C≡C-SiH ３ ) as an oxidizing agent, and ozone (O ３ ) was used, and under an argon atmosphere, the above-mentioned film formation apparatus was used, with one cycle consisting of supplying DSA for 3 seconds, purging DSA for 5 seconds, supplying ozone and reacting for 3 seconds, and purging for 5 seconds, and this cycle was repeated 50 times. The SiOC-containing film thickness on the surface of the silicon wafer substrate was 13.6 nm. The flow rates of DSA, ozone, and argon were 50 sccm, respectively. The chamber pressure was 0.5 Torr, and the film formation temperature (substrate temperature) was 560°C.

[0043] Example 2: DSA was used as a precursor and O was used as an oxidizing agent. ３ In an argon atmosphere, the above film forming apparatus was used to supply DSA for 3 seconds, purging DSA for 5 seconds, and O ３One cycle of supply and reaction for 3 seconds and purging for 5 seconds was repeated 50 times. The thickness of the SiOC-containing film on the surface of the silicon wafer substrate was 40.4 nm. The flow rate of DSA was 50 sccm, and O ３ The flow rate of argon was 50 sccm, the pressure inside the chamber was 0.5 Torr, and the film formation temperature (substrate temperature) was 580°C.

[0044] Example 3: DSA was used as a precursor and O was used as an oxidizing agent. ３ In an argon atmosphere, the above film forming apparatus was used to supply DSA for 3 seconds, purging DSA for 5 seconds, and O ３ One cycle of supply and reaction for 3 seconds and purging for 5 seconds was repeated 50 times. The thickness of the SiOC-containing film on the surface of the silicon wafer substrate was 108.0 nm. The flow rate of DSA was 50 sccm, and O ３ The flow rate of argon was 50 sccm, the pressure inside the chamber was 0.5 Torr, and the film formation temperature (substrate temperature) was 600°C.

[0045] Example 4: DSA was used as a precursor and O was used as an oxidizing agent. ３ In an argon atmosphere, the above film forming apparatus was used to supply DSA for 3 seconds, purging DSA for 5 seconds, and O ３ One cycle of supply and reaction for 3 seconds and purging for 5 seconds was repeated 50 times. The thickness of the SiOC-containing film on the surface of the silicon wafer substrate was 84.0 nm. The flow rate of DSA was 50 sccm, and O ３ The flow rate of argon was 50 sccm, the pressure inside the chamber was 0.5 Torr, and the film formation temperature (substrate temperature) was 620°C.

[0046] Example 5: DSA was used as a precursor and oxygen (O ２ ) was used, and under an argon atmosphere, DSA was supplied for 3 seconds using the above film formation apparatus, DSA was purged for 5 seconds, and O ２One cycle of supply and reaction for 3 seconds and purging for 5 seconds was repeated 50 times. The thickness of the SiOC-containing film on the surface of the silicon wafer substrate was 19.3 nm. The flow rate of DSA was 50 sccm, and O ２ The flow rate of argon was 50 sccm, the pressure inside the chamber was 0.5 Torr, and the film formation temperature (substrate temperature) was 580°C.

[0047] Example 6: DSA was used as a precursor and O was used as an oxidizing agent. ２ In an argon atmosphere, the above film forming apparatus was used to supply DSA for 3 seconds, purging DSA for 5 seconds, and O ２ One cycle of supply and reaction for 3 seconds and purging for 5 seconds was repeated 50 times. The thickness of the SiOC-containing film on the surface of the silicon wafer substrate was 35.8 nm. The flow rate of DSA was 50 sccm, and O ２ The flow rate of argon was 50 sccm, the pressure inside the chamber was 0.5 Torr, and the film formation temperature (substrate temperature) was 600°C.

[0048] Example 7: DSA was used as a precursor and O was used as an oxidizing agent. ２ In an argon atmosphere, the above film forming apparatus was used to supply DSA for 3 seconds, purging DSA for 5 seconds, and O ２ One cycle of supply and reaction for 3 seconds and purging for 5 seconds was repeated 50 times. The thickness of the SiOC-containing film on the surface of the silicon wafer substrate was 74.6 nm. The flow rate of DSA was 50 sccm, and O ２ The flow rate of argon was 50 sccm, the pressure inside the chamber was 0.5 Torr, and the film formation temperature (substrate temperature) was 620°C.

[0049] Comparative Example 1: DSA was used as a precursor and O was used as an oxidizing agent. ３ In an argon atmosphere, the above film forming apparatus was used to supply DSA for 3 seconds, purging DSA for 5 seconds, and O ３One cycle of supply and reaction for 3 seconds and purging for 5 seconds was repeated 50 times. No SiOC-containing film was observed on the surface of the silicon wafer substrate. The flow rate of DSA was 50 sccm, and O ３ The flow rate of argon was 50 sccm, the pressure inside the chamber was 0.5 Torr, and the film formation temperature (substrate temperature) was 100°C.

[0050] Comparative Example 2: DSA was used as a precursor and O was used as an oxidizing agent. ３ In an argon atmosphere, the above film forming apparatus was used to supply DSA for 3 seconds, purging DSA for 5 seconds, and O ３ One cycle of supply and reaction for 3 seconds and purging for 5 seconds was repeated 50 times. No SiOC-containing film was observed on the surface of the silicon wafer substrate. The flow rate of DSA was 50 sccm, and O ３ The flow rate of argon was 50 sccm, the pressure inside the chamber was 0.5 Torr, and the film formation temperature (substrate temperature) was 200°C.

[0051] The presence or absence of C—H bonds in each of the obtained SiCO-containing films was measured under the following conditions. <Presence or absence of C—H bonds> FT-IR device: Thermo SCIENTIC NICOLET iS10 1100 cm in the obtained spectrum －１ The presence or absence of a C—H bond was determined from the presence or absence of a peak at 1100 cm. －１ The height of the peak at －１ This means that the peak height is 5% or less of the peak height in the sample.

[0052] The evaluation results are shown in Table 1. The IR measurement results of Examples 1 to 4 are shown in FIG.

[0053] The SiCO-containing film and method for producing the same of the present invention can be widely and effectively used in various applications requiring a SiCO-containing film, such as low-dielectric-constant insulating films, gas barrier films, coating materials such as graphite members, carbon fibers, and SiC fibers, embedded 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.

[0054] 100 ...SiCO-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's are 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 inclusive and satisfy n+p=2m+1; q is an integer of 1 to 4 inclusive; r and s are each integers of 0 to 2q+1 inclusive and satisfy r+s=2q+1), and a step of supplying the source gas and the oxidizing agent into a chamber containing a workpiece having a film formation surface, and depositing a SiC and SiO-containing film on the film formation surface by chemical vapor deposition or atomic layer deposition using a thermal reaction, wherein the SiC and SiO-containing film is deposited at 500° C. or higher in the film formation step.

2. The method for producing a SiC and SiO-containing film according to claim 1, wherein the SiC and SiO-containing film is substantially free of C—H bonds.

3. The oxidizing agent is O ３ and / or O ２ The method for producing a SiC and SiO-containing film according to claim 1 or 2, wherein

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