Film formation method

Abstract

To provide a film deposition method which can form a film of high density on an object to be processed at an excellent film deposition rate under a low-temperature condition.SOLUTION: A film deposition method for forming a film on an object to be processes includes: a raw material gas supply process of supplying a raw material gas into a processing container in which the object to be processed is provided to adsorb the raw material gas on the object to be processed, and then purging the inside of the processing container with a first purge gas; and a reaction gas supply process of supplying a reaction gas into the processing container after the raw material gas supply process to oxidize the raw material gas adsorbed on the object of processing, and then purging the inside of the processing container with a second purge gas. For example, the raw material gas and a first catalytic gas are supplied to the processing container in the raw material gas supply process, the reaction gas and a second catalytic gas are supplied to the processing container in the reaction gas supply process, and non-aromatic amine gases of the same kind or different kinds are used as the first catalytic gas and second catalytic gas.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a film formation method, and more particularly to a film formation method capable of forming a film, such as an SiO2 film, on an object to be processed. [Background technology]

[0002] In recent years, there has been a growing need for lower deposition temperatures in fields such as electronics (primarily semiconductors and liquid crystals), pharmaceuticals, and organic chemicals for food products, as well as in other sectors such as substrates made of materials with low heat resistance, and deposition methods that reduce thermal effects and maintain material properties. Examples of methods that enable deposition at low temperatures include plasma CVD (Chemical Vapor Deposition), plasma ALD (Atomic Layer Deposition), vacuum deposition, sputtering, plating, thermal CVD, and thermal ALD.

[0003] Among these film deposition methods, plasma-based deposition methods can achieve reactions equivalent to those in high-temperature regions by utilizing plasma energy. However, this method has the problem that plasma-active species can damage the thin film. Furthermore, it can have unexpected effects on the deposition equipment. Therefore, when adopting a plasma-based deposition method, it is necessary to confirm in advance what kind of effects may occur.

[0004] Furthermore, in the case of vacuum deposition and sputtering, it is difficult to deposit films on the fine pattern formation surface of the substrate. Therefore, these film deposition methods cannot be used in the manufacture of highly integrated semiconductor devices.

[0005] Therefore, it is conceivable to employ thermal ALD, which can suppress damage, form thin films with good film quality, and offer high controllability of film deposition. However, this deposition method has the problem that, in the low-temperature range, it is often not possible to exceed the activation energy required for the reaction of the chemical species necessary to obtain the target compound. Consequently, it becomes necessary to add energy other than thermal energy (for example, plasma and UV (Ultraviolet) energy) to promote the chemical reaction and advance the deposition process. However, as mentioned above, plasma damages thin films. Similarly, UV also causes damage, so thermal ALD has the problem of being unsuitable for film deposition in the low-temperature range.

[0006] To address these problems, for example, Patent Document 1 discloses a technique for forming films at low temperatures using thermal ALD. More specifically, it describes how an SiO2 film can be formed on an organic substrate at low temperatures by using NH3 as a catalyst and an alkoxysilane such as TMOS (tetramethoxysilane) or TEOS (triethoxysilane) as a raw material gas under atmospheric pressure. However, the film formation method disclosed in Patent Document 1 requires a long supply time of 3 to 4 minutes per cycle for the alkoxysilane raw material gas. Therefore, the film formation method in Patent Document 1 has the problem of low productivity.

[0007] Furthermore, Patent Document 2 describes that an SiO2 film can be formed on a substrate at low temperatures by using pyridine as a catalyst and HCDS (hexachlorodisilane), which has high reaction activity, as a raw material gas. However, with the film formation method disclosed in Patent Document 2, if the film formation temperature is 67°C or lower, there is a problem in that salt is generated in the reactor due to the chlorine atoms contained in HCDS. In addition, if a surrounding metal film is formed, there is a problem in that it corrodes and damages the metal film.

[0008] Patent Document 3 describes that by using pyrimidine as a catalyst ligand and a precursor containing silicon and oxygen, it is possible to form a SiO2 film at a low temperature on a substrate. However, Patent Document 3 states that the SiO2 film grows with a film thickness variation of 1 Å to 6 Å per cycle. This means that the film formation of the SiO2 film per cycle varies within the range of 1 Å to 6 Å in film thickness. Therefore, the film formation method disclosed in Patent Document 3 has a problem of poor film thickness controllability of the SiO2 film.

[0009] Non-Patent Document 1 describes that by using TEOS (tetrakisethoxysilane) as a silicon precursor, H2O as an oxidizing agent, and ammonia as a catalyst, a SiO2 film can be formed at room temperature on ZrO2 and BaTiO3 particles. However, Non-Patent Document 1 does not describe forming a SiO2 film on a silicon substrate, and it is difficult to apply the film formation method described in Non-Patent Document 1 to semiconductor devices. Also, the supply time of ammonia is 9,400 seconds per cycle, and the film formation method in Non-Patent Document 1 has a problem of low productivity and is not industrially viable.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Documents

[0011]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0012] The present invention has been made in view of the above problems, and an object thereof is to provide a film forming method capable of forming a high-density film on an object to be processed at a good film forming rate at low temperature and applicable to industrial production.

Means for Solving the Problems

[0013] The above conventional problems are solved by the invention described below. That is, in order to solve the above problems, the film forming method according to the present invention is a film forming method for forming a film on an object to be processed, including a step (A) of providing the object to be processed in a processing container; a raw material gas supply step (B) of supplying a raw material gas into the processing container, adsorbing the raw material gas on the object to be processed, and then purging the inside of the processing container with a first purge gas; a reaction gas supply step (C) of supplying a reaction gas into the processing container after the raw material gas supply step (B), oxidizing the raw material gas adsorbed on the object to be processed, and then purging the inside of the processing container with a second purge gas, wherein the supply of the raw material gas in the raw material gas supply step (B) is a step (b1) of supplying a first catalyst gas into the processing container together with the raw material gas; a step (b2) of supplying a first catalyst gas into the processing container, purging with a third purge gas, and then supplying the raw material gas; or any one of a step (b3) of supplying only the raw material gas into the processing container, and the supply of the reaction gas in the reaction gas supply step (C) is a step (c1) of supplying a second catalyst gas into the processing container together with the reaction gas; a step (c2) of supplying a second catalyst gas into the processing container before supplying the reaction gas, and then purging with a fourth purge gas; or any one of a step (c3) of supplying only the reaction gas into the processing container, When the raw material gas supply step (B) is the step (b3), the reaction gas supply step (C) does not include the step (c3), The first catalyst gas and the second catalyst gas are characterized by being the same or different non-aromatic amine gases.

[0014] In the above configuration, it is preferable that the acid dissociation constant pKa of the non-aromatic amine gas at 25 ° C is within the range of 9.5 or more and 14 or less.

[0015] In the above configuration, the non-aromatic amine gas may be at least one selected from the group consisting of pyrrolidine gas, piperidine gas, tetramethylguanidine gas, 1-methylpiperidine gas, and gases of their derivatives.

[0016] In the above configuration, it is preferable that the raw material gas is a Group 4 element gas of the periodic table having no halogen ligand and / or a silicon gas having no halogen ligand.

[0017] In the above configuration, the raw material gas is represented by the general formula Am-M-B(4-m) (where A and B are each independently any one selected from the group consisting of an RO group, an RRN group, a CpR group, a CqHqN group (q = 4 or 5), and a hydrogen atom. Also, R, R, R, and R are each independently a CrHr group (r ≧ 0). M is Ti, Zr, Hf, or Si. Cp is a cyclopentadienyl ligand. 0 ≦ m ≦ 4.). 1 O group, R 2 R 3 N group, CpR 4 group, C q H 2q N group (q = 4 or 5) and a hydrogen atom. Also, R 1 , R 2 , R 3 and R 4 are each independently any one selected from the group consisting of a CrHr group (r ≧ 0). M is Ti, Zr, Hf, or Si. Cp is a cyclopentadienyl ligand. 0 ≦ m ≦ 4.). r H 2r+1 group (r ≧ 0). M is Ti, Zr, Hf, or Si. Cp is a cyclopentadienyl ligand. 0 ≦ m ≦ 4.).

[0018] In the above configuration, it is preferable that the raw material gas is at least one gas selected from the group consisting of Si(OMe)4, Si(NMe2)(OMe)3, Si(NMe2)2(OMe)2, Si(NMe2)3(OMe), Si(NMe2)(OEt)3, Si(NMe2)2(OEt)2, Si(NMe2)3(OEt), Si(NEt2)(OMe)3, Si(NEt2)(OEt)3, SiH(NMe2)3, SiH2(NEt2)2, SiH2(NHt-Bu)2, Si(pyrrolidine)(OMe)3, Si(pyrrolidine)2(OMe)2, and Si(pyrrolidine)3(OMe).

[0019] In the above configuration, it is preferable that the reaction gas is an oxidizing gas having oxygen atoms.

[0020] In the above configuration, it is preferable that the oxidizing gas is at least one gas selected from the group consisting of water, hydrogen peroxide, formic acid, and aldehyde.

[0021] In the above configuration, it is preferable that the supply of the raw material gas and / or the first catalyst gas in the raw material gas supply step is carried out so that the pressure in the processing vessel is within the range of 13 Pa or more and 40,000 Pa or less, and that the supply of the reaction gas and / or the second catalyst gas in the reaction gas supply step is carried out so that the pressure in the processing vessel is within the range of 13 Pa or more and 40,000 Pa or less.

[0022] In the above configuration, it is preferable that the temperature inside the processing vessel in the raw material gas supply step and / or the reaction gas supply step is 200°C or lower. [Effects of the Invention]

[0023] The present invention provides a film formation method that can form a film with good film quality on an object to be processed at a low temperature, and is applicable to industrial production. [Brief explanation of the drawing]

[0024] [Figure 1] This is a schematic diagram illustrating a film deposition apparatus according to an embodiment of the present invention. [Figure 2] This is a flowchart illustrating the film deposition method according to this embodiment. [Figure 3] This is a schematic diagram illustrating how the raw material gas is adsorbed onto the substrate when the raw material gas and the first catalyst gas are supplied simultaneously in this embodiment. [Figure 4] This is a schematic diagram illustrating how the raw material gas is adsorbed onto the substrate when only the raw material gas is supplied in this embodiment. [Figure 5] This schematic diagram illustrates how OH groups are introduced to adsorbed molecules adsorbed on the substrate surface when the reaction gas and the second catalyst gas are supplied simultaneously in this embodiment. [Figure 6] This is a schematic diagram illustrating how OH groups are introduced to adsorbed molecules adsorbed on the substrate surface when only the reaction gas is supplied in this embodiment. [Figure 7] This diagram shows the deposition sequence of the SiO2 film in this Example 1. [Figure 8] This diagram shows the deposition sequence of the SiO2 film in this second embodiment. [Figure 9] This diagram shows the deposition sequence of the SiO2 film in this third embodiment. [Figure 10] This figure shows the deposition sequence of the SiO2 film in this 4th embodiment. [Figure 11] This graph shows the correlation between the number of cycles and the thickness of the SiO2 film when TMOS gas is used as the source gas. [Figure 12] This graph shows the relationship between the temperature inside the processing vessel and the deposition rate of the SiO2 film in various film deposition methods. [Figure 13] This graph shows the correlation between the number of cycles and the thickness of the SiO2 film when 3DMAS gas is used as the source gas. [Figure 14] This graph shows the relationship between the temperature inside the processing vessel and the deposition rate of the SiO2 film in various film deposition methods. [Figure 15]This graph shows the relationship between the pressure inside the processing vessel and the deposition rate of the SiO2 film in various film deposition methods. [Figure 16] This graph shows the relationship between the pressure inside the processing vessel and the deposition rate of the SiO2 film in various film deposition methods. [Figure 17] This diagram shows the deposition sequence of the SiO2 film in this Example 18. [Figure 18] This graph shows the relationship between the supply time of the reaction gas (pulse time) and the deposition rate of the SiO2 film. [Figure 19] This is a schematic diagram showing the film deposition apparatus related to the comparative example. [Modes for carrying out the invention]

[0025] (Film forming equipment) A film deposition apparatus according to one embodiment of the present invention will be described below. The film deposition apparatus according to this embodiment can be used, for example, in a substrate processing step, which is one step in the manufacturing process of a semiconductor manufacturing apparatus.

[0026] First, the configuration of the film deposition apparatus according to this embodiment will be explained based on Figure 1. Figure 1 is a schematic diagram representing the film deposition apparatus according to this embodiment.

[0027] As shown in Figure 1, the film deposition apparatus 1 comprises at least a processing container 11 for containing the substrate W as the object to be processed, a raw material gas supply unit 12 for supplying raw material gas, a first catalyst gas supply unit 13 for supplying a first catalyst gas, a second catalyst gas supply unit 14 for supplying a second catalyst gas, a reaction gas supply unit 15 for supplying reaction gas, a purge gas supply passage 25 for supplying purge gas, and a discharge passage 26 for discharging the atmosphere inside the processing container 11.

[0028] The processing container 11 has a sealed structure that allows its interior to be isolated from the outside air. The processing container 11 is also configured to accommodate the substrate W in a horizontal position using a boat or the like. The processing container 11 may also include a heating mechanism capable of heating the substrate W to a predetermined temperature. The heating mechanism is not particularly limited, and known devices such as heaters can be used.

[0029] The raw material gas supply unit 12 has the function of supplying raw material gas to the processing container 11. Liquid raw material is stored in the raw material gas supply unit 12. The raw material gas supply unit 12 is also provided with a carrier gas supply passage 17A for introducing carrier gas. The carrier gas supplied from the carrier gas supply passage 17A can be flow-controlled by an MFC (Mass Flow Controller). Details of the raw material gas and carrier gas will be described later.

[0030] A raw material gas supply passage 21 is provided between the raw material gas supply unit 12 and the processing container 11. This makes it possible to supply the raw material gas, which is the vaporized raw material stored in the raw material gas supply unit 12, to the processing container 11. In addition, needle valves 21a and on-off valves 21b are sequentially provided in the raw material gas supply passage 21 from the upstream side.

[0031] The first catalyst gas supply unit 13 has the function of supplying the first catalyst gas to the processing container 11. For example, the first catalyst in liquid form is stored in the first catalyst gas supply unit 13. The first catalyst gas supply unit 13 is also provided with a carrier gas supply passage 17B for introducing a carrier gas. The carrier gas supplied from the carrier gas supply passage 17B can be flow-controlled by an MFC. Details of the first catalyst gas and carrier gas will be described later.

[0032] A first catalyst gas supply passage 22 is provided between the first catalyst gas supply unit 13 and the processing container 11. This makes it possible to supply the first catalyst gas, which is formed by the vaporization of the liquid first catalyst stored in the first catalyst gas supply unit 13, to the processing container 11. In addition, a needle valve 22a and an on-off valve 22b are sequentially provided in the first catalyst gas supply passage 22 from the upstream side.

[0033] The second catalyst gas supply unit 14 has the function of supplying the second catalyst gas to the processing container 11. For example, the second catalyst in liquid form is stored in the second catalyst gas supply unit 14. The second catalyst gas supply unit 14 is also provided with a carrier gas supply passage 17C for introducing a carrier gas. The carrier gas supplied from the carrier gas supply passage 17C can be flow-controlled by an MFC. Details of the second catalyst gas and carrier gas will be described later.

[0034] A second catalyst gas supply passage 23 is provided between the second catalyst gas supply unit 14 and the processing container 11. This makes it possible to supply the second catalyst gas, which is formed by the vaporization of the liquid second catalyst stored in the second catalyst gas supply unit 14, to the processing container 11. In addition, a needle valve 23a and an on-off valve 23b are sequentially provided in the second catalyst gas supply passage 23 from the upstream side.

[0035] The reaction gas supply unit 15 has the function of supplying reaction gas to the processing vessel 11. Liquid oxidizing agent is stored in the reaction gas supply unit 15. The reaction gas supply unit 15 is also provided with a carrier gas supply channel 17D for introducing carrier gas. The carrier gas supplied from the carrier gas supply channel 17D can be flow-controlled by an MFC. Details of the reaction gas and carrier gas will be described later.

[0036] A reaction gas supply passage 24 is provided between the reaction gas supply unit 15 and the processing container 11. This makes it possible to supply the reaction gas, which is the vaporized reaction gas from the liquid oxidizer stored in the reaction gas supply unit 15, to the processing container 11. In addition, a needle valve 24a and an on-off valve 24b are sequentially provided in the reaction gas supply passage 24 from the upstream side.

[0037] Needle valves 21a, 22a, 23a, and 24a regulate the flow rate of gas through their respective supply lines. Additionally, on-off valves 21b, 22b, 23b, and 24b control the supply or cessation of gas through each supply line by controlling their opening and closing.

[0038] The purge gas supply channel 25 has the function of supplying purge gas into the processing container 11. The purge gas supply channel 25 is connected to the processing container 11 and is equipped with an on-off valve 25a. By controlling the opening and closing of the on-off valve 25a, the supply or cessation of purge gas flowing through the purge gas supply channel 25 is controlled. Details of the purge gas will be described later.

[0039] The discharge passage 26 is connected to the processing container 11 and has the function of exhausting the atmosphere inside the processing container 11. Connected to the discharge passage 26, in order from upstream, are a pressure sensor (not shown) as a pressure detection unit for detecting the pressure inside the processing container 11, an APC (Automatic Pressure Control) valve 27 as a pressure control unit for controlling the pressure inside the processing container 11, and a vacuum pump (not shown) as a vacuum exhaust device. The opening and closing control of the APC valve 27 is performed by PID control based on the measurement of the pressure sensor while the vacuum pump is operating. This makes it possible to arbitrarily adjust the pressure inside the processing container 11.

[0040] Furthermore, the exhaust gas discharged from the discharge passage 26 may contain toxic gases and flammable gases. Therefore, a water scrubber, sulfuric acid scrubber, caustic scrubber, or dry abatement device (none of which are shown) may be installed in the discharge passage 26 to detoxify the exhaust gas and allow it to be released into the atmosphere.

[0041] (Film forming method) Next, a film deposition method relating to one embodiment of this implementation using the film deposition apparatus 1 will be described.

[0042] The film-forming method according to this embodiment enables the formation of a film on an object to be processed. More specifically, as shown in Figure 2, the film-forming method of this embodiment includes at least the following steps: (A)(S1) of placing the substrate W, which is the object to be processed, into the processing container 11; (B)(S2) of supplying a raw material gas into the processing container 11 to adsorb the raw material gas onto the substrate W, and then purging the processing container 11 with a first purge gas; and (C)(S3) of supplying a reaction gas into the processing container 11 after the raw material gas supply step (B) to oxidize the raw material gas adsorbed on the substrate W, and then purging the processing container 11 with a second purge gas. Each step will be described in detail below. Figure 2 is a flowchart illustrating the film-forming method of this embodiment.

[0043] [Step (A) of placing the object to be processed inside the processing container] First, the substrate W to be processed is placed in the processing container 11 in a horizontal position with the processing surface (surface) of the substrate W facing upwards. Here, in this specification, terms such as up, down, and horizontal refer to directions relative to the processing surface (surface) of the substrate W.

[0044] Step (A) may include a step of adjusting the pressure and temperature inside the processing container 11 in which the substrate W is contained. The pressure inside the processing container 11 can be adjusted by vacuuming (reducing pressure exhaust) using a vacuum pump to achieve a desired pressure (vacuum level). At this time, the pressure inside the processing container 11 is measured by a pressure sensor, and the APC valve 27 is PID controlled based on the measurement value of the pressure sensor. Pressure adjustment inside the processing container 11 using a vacuum pump or the like can be continued until the film formation is completed. The temperature inside the processing container 11 can be adjusted by heating using the aforementioned heating mechanism to achieve a desired film formation temperature. Temperature adjustment inside the processing container 11 using the heating mechanism can be continued until the film formation process is completed.

[0045] [Raw material gas supply process (B)] The raw material gas supply step (B) of this embodiment is a step in which a raw material gas is supplied into the processing container 11 to (chemically) adsorb the raw material gas onto the substrate W, and then the inside of the processing container 11 is purged with a first purge gas (S2).

[0046] In the raw material gas supply process (B), the adsorption of the raw material gas onto the substrate W is carried out in one of the following cases, as shown in Figure 2: (b1) when the first catalyst gas is supplied into the processing container 11 together with the raw material gas (S2-1); (b2) when the first catalyst gas is supplied into the processing container 11 before the raw material gas is supplied, and then purged with a third purge gas (S2-2); or (b3) when only the raw material gas is supplied into the processing container 11 (S2-3). These processes (b1), (b2), and (b3), as well as the purging process with the first purge gas, will be explained in order below.

[0047] (1) Step of supplying the first catalyst gas together with the raw material gas (b1) In this process (b1), the raw material gas and the first catalyst gas are supplied to the processing container 11 simultaneously (S2-1).

[0048] When supplying the raw material gas to the processing container 11, the carrier gas is supplied from the carrier gas supply passage 17A to the raw material gas supply unit 12. The carrier gas is not particularly limited and examples include inert gases such as nitrogen gas, argon gas, and helium gas. These inert gases can be used individually or in mixtures. Furthermore, the supply of the carrier gas is controlled by flow rate control using an MFC. In addition, it is preferable to use a carrier gas that contains as little moisture as possible.

[0049] When the carrier gas is supplied to the raw material gas supply unit 12, the carrier gas is discharged from the raw material gas supply passage 21, accompanied by the raw material gas, which is the vaporized raw material stored in liquid form within the raw material gas supply unit 12. In the raw material gas supply passage 21, the on-off valve 21b is in the open state by on-off control, and the flow rate of the mixed gas, consisting of the carrier gas and raw material gas, is regulated by the needle valve 21a, while the mixed gas is supplied into the processing container 11.

[0050] Preferably, the raw material gas is a Group 4 element gas of the periodic table that does not contain halogen ligands and / or silicon gas that does not contain halogen ligands.

[0051] Furthermore, the raw material gas is general formula A m -MB (4-m) (However, A and B are independent of each other, R 1 O group, R 2 R 3 N group, CpR 4 group, C q H 2q It is one of the group consisting of an N group (q=4 or 5) and a hydrogen atom (Note that Cp means cyclopentadienyl ligand). Also, R 1 , R 2 , R 3 and R 4 Each is independent of C r H 2r+1 The base is (r≧0). M is Ti, Zr, Hf, or Si. 0≦m≦4. It can be expressed as follows:

[0052] Furthermore, the raw material gases include those represented by the above general formula, such as Si(OMe)4, Si(NMe2)(OMe)3, Si(NMe2)2(OMe)2, Si(NMe2)3(OMe), Si(NMe2)(OEt)3, Si(NMe2)2(OEt)2, Si(NMe2)3(OEt), Si(NEt2)(OMe)3, and Si(NEt2)(OE tIt is preferable that the raw material gas is at least one gas selected from the group consisting of )3, SiH(NMe2)3, SiH2(NEt2)2, SiH2(NHt-Bu)2, Si(pyrrolidine)(OMe)3, Si(pyrrolidine)2(OMe)2, and Si(pyrrolidine)3(OMe) (wherein Me means a methyl group, Et means an ethyl group, and t-Bu means a tert-butyl group). Furthermore, it is preferable that the raw material gas contains as little moisture as possible. In addition, the example raw material gas can be used in any combination with any of the example carrier gases mentioned above.

[0053] The supply flow rate of the mixed gas, consisting of a raw material gas and a carrier gas (or the supply flow rate of the raw material gas if it consists only of raw material gas), is preferably in the range of 1 sccm or more and 5000 sccm or less, more preferably in the range of 100 sccm or more and 3000 sccm or less, and particularly preferably in the range of 200 sccm or more and 2000 sccm or less. By setting the supply flow rate of the mixed gas (or raw material gas) to 1 sccm or more, the reaction rate (film formation rate) of the raw material gas can be maintained well, and insufficient adsorption of the raw material gas onto the substrate W can be prevented. On the other hand, by setting the supply flow rate of the mixed gas (or raw material gas) to 5000 sccm or less, gas consumption can be reduced. The supply flow rate of the mixed gas (or raw material gas) can be appropriately controlled by adjusting the temperature of the raw material gas, the flow rate of the carrier gas, and the pressure in the raw material gas supply unit 12. The supply flow rate of the carrier gas to be mixed with the raw material gas is not particularly limited and can be appropriately set according to the supply flow rate of the mixed gas as described above.

[0054] Furthermore, when supplying the first catalyst gas to the processing container 11, a carrier gas is supplied to the first catalyst gas supply unit 13 from the carrier gas supply passage 17B. Details of the carrier gas are as described above. The supply of the carrier gas is flow-controlled by the MFC. It is preferable that the carrier gas contains as little moisture as possible.

[0055] When the carrier gas is supplied to the first catalyst gas supply unit 13, the carrier gas is discharged from the first catalyst gas supply passage 22, accompanied by the first catalyst gas, which is the vaporized first catalyst stored in the first catalyst gas supply unit 13. In the first catalyst gas supply passage 22, the on-off valve 22b is in the open state by on-off control, and the flow rate of the mixed gas of the carrier gas and the first catalyst gas is adjusted by the needle valve 22a, while the mixed gas is supplied into the processing container 11.

[0056] A non-aromatic amine gas is preferred as the first catalyst gas. Using a non-aromatic amine gas allows for improved film deposition rates at low temperatures below 200°C. Furthermore, it is preferable that the first catalyst gas contains as little water as possible. Note that using an aromatic gas such as pyridine as the first catalyst gas may significantly reduce the film deposition rate. Also, using NH3 gas as the first catalyst gas may make film formation difficult.

[0057] The non-aromatic amine gas preferably has an acid dissociation constant pKa at 25°C in the range of 9.5 to 14, more preferably in the range of 10 to 14, and particularly preferably in the range of 11 to 14. If the pKa of the non-aromatic amine gas is 9.5 or higher, the film deposition rate can be increased, and the film deposition efficiency can be improved. On the other hand, if the pKa of the non-aromatic amine gas is 14 or lower, damage to the film deposition equipment can be prevented, and hydrolysis of the catalyst itself can be prevented. The pKa can be calculated, for example, by measuring the hydrogen ion concentration using a pH meter and comparing it with the concentration of the substance in question.

[0058] Further specific examples of non-aromatic amine gases include pyrrolidine (acid dissociation constant pKa at 25°C: 11.3) gas, piperidine (acid dissociation constant pKa at 25°C: 11.1) gas, 1,1,3,3-tetramethylguanidine (acid dissociation constant pKa at 25°C: 13.6) gas, 1-methylpiperidine (acid dissociation constant pKa at 25°C: 10.1) gas, and their derivatives. These non-aromatic amine gases can be used individually or in combination of two or more. In addition, the exemplified non-aromatic amine gases can be used in any combination with any of the aforementioned exemplified source gases or carrier gases.

[0059] The supply flow rate of the mixed gas consisting of the first catalyst gas and the carrier gas (or the supply flow rate of the first catalyst gas if it consists only of the first catalyst gas) is preferably in the range of 1 sccm or more and 10,000 sccm or less, more preferably in the range of 100 sccm or more and 5,000 sccm or less, and particularly preferably in the range of 200 sccm or more and 2,000 sccm or less. By setting the supply flow rate of the mixed gas (or first catalyst gas) to 1 sccm or more, the reaction rate (film formation rate) of the raw material gas can be maintained well, and insufficient adsorption of the raw material gas onto the substrate W can be prevented. On the other hand, by setting the supply flow rate of the mixed gas (or first catalyst gas) to 10,000 sccm or less, consumption can be reduced. The supply flow rate of the mixed gas (or first catalyst gas) can be appropriately controlled by adjusting the temperature of the first catalyst gas, the flow rate of the carrier gas, and the pressure in the first catalyst gas supply unit 13. The supply flow rate of the carrier gas to be mixed with the first catalyst gas is not particularly limited and can be appropriately set according to the supply flow rate of the mixed gas as described above.

[0060] When a mixed gas consisting of a raw material gas and a carrier gas, and a mixed gas consisting of a first catalyst gas and a carrier gas are supplied to the processing container 11, the raw material gas is chemically adsorbed onto the substrate W surface. In this embodiment, the adsorption performance of the raw material gas onto the substrate W surface can be improved by supplying the first catalyst gas into the processing container 11 simultaneously with the raw material gas. For example, when the raw material gas is Si(OMe)4 gas and the first catalyst gas is pyrrolidine gas (see Figure 3), when the pyrrolidine gas comes into contact with the surface of the substrate W, the lone pairs of electrons of the N atoms in the pyrrolidine extract H atoms from the OH groups present on the surface of the SiO2 constituting the substrate W. As a result, the charge distribution at the OH groups becomes biased towards negative charge, promoting bonding with Si atoms in the raw material gas Si(OMe)4 that have a charge distribution biased towards positive charge, thereby promoting the chemical adsorption of Si(OMe)4 onto the substrate W surface. Also, at this time, ligand MeO - It is removed. Furthermore, ligand MeO - This combines with the H atom abstracted by pyrrolidine, thereby producing MeOH as a by-product. Figure 3 is a schematic diagram showing how the raw material gas is adsorbed onto the substrate when the raw material gas and the first catalyst gas are supplied simultaneously in this embodiment.

[0061] When supplying the raw material gas (or a mixed gas with a carrier gas) and the first catalyst gas (or a mixed gas with a carrier gas) (hereinafter referred to as "raw material gas, etc."), the temperature inside the processing container 11 is preferably in the range of 200°C or less, more preferably in the range of 50°C or more and 150°C or less, and particularly preferably in the range of 80°C or more and 125°C or less. By keeping the temperature inside the processing container 11 at 200°C or less, for example, even if the substrate W is made of a material with a low heat resistance temperature, it becomes possible to form a film while maintaining the material properties of the substrate W by avoiding thermal effects as much as possible.

[0062] The pressure inside the processing container 11 when supplying raw material gas is preferably in the range of 1 Pa or more and 40,000 Pa or less, more preferably in the range of 13 Pa or more and 13,300 Pa or less, and particularly preferably in the range of 133 Pa or more and 6,700 Pa or less. By setting the pressure inside the processing container 11 to 1 Pa or more, the reaction rate (film formation rate) of the raw material gas can be maintained well. On the other hand, by setting the pressure inside the processing container 11 to 40,000 Pa or less, the processing time can be shortened and the purging efficiency can be increased. The pressure inside the processing container 11 can be adjusted by controlling the opening and closing of the APC valve 27 by PID control.

[0063] The supply time (pulse time) of the raw material gas to the processing container 11 is preferably within the range of 0.1 seconds to 600 seconds, more preferably within the range of 1 second to 300 seconds, and particularly preferably within the range of 10 seconds to 180 seconds. By setting the supply time of the raw material gas to 0.1 seconds or more, the reaction rate (film formation rate) of the raw material gas can be maintained well, and insufficient adsorption of the raw material gas onto the substrate W can be prevented. On the other hand, by setting the supply time of the raw material gas to 600 seconds or less, consumption can be reduced and the process time can be shortened. The supply time of the raw material gas can be appropriately controlled by adjusting the temperature of the raw material gas, the flow rate of the carrier gas, the pressure in the raw material gas supply unit 12, and the pressure in the first catalyst gas supply unit 13. Note that the supply time of the raw material gas refers to the time when the on-off valve 21b and the on-off valve 22b are open simultaneously.

[0064] During the supply of raw material gas, etc., in this process (b1), the on-off valve 23b of the second catalyst gas supply passage 23, the on-off valve 24b of the reaction gas supply passage 24, and the on-off valve 25a of the purge gas supply passage 25 are all in a closed state. Furthermore, the end of this process (b1) is achieved by closing the on-off valves 21b and 22b by on-off control, thereby stopping the supply of the mixed gas of raw material gas and carrier gas, and the mixed gas of first catalyst gas and carrier gas, to the processing container 11.

[0065] (2) A process in which the first catalytic gas is supplied, followed by purging, and then the raw material gas is supplied (b2) In this process (b2), first the first catalyst gas is supplied into the processing container 11, then the processing container 11 is purged with a purge gas, and then the raw material gas is supplied into the processing container 11 (S2-2).

[0066] When supplying the first catalyst gas to the processing container 11, the carrier gas is first supplied from the carrier gas supply path 17B to the first catalyst gas supply unit 13. Details of the carrier gas are as described above. Furthermore, the supply of the carrier gas is controlled by the flow rate of the MFC.

[0067] When the carrier gas is supplied to the first catalyst gas supply unit 13, the carrier gas is discharged from the first catalyst gas supply passage 22, accompanied by the first catalyst gas, which is the vaporized first catalyst gas stored in liquid form within the first catalyst gas supply unit 13. In the first catalyst gas supply passage 22, the on-off valve 22b is in the open state by on-off control, and the flow rate of the mixed gas consisting of the carrier gas and the first catalyst gas is adjusted by the needle valve 22a, while the mixed gas is supplied into the processing container 11.

[0068] When a mixed gas consisting of a first catalyst gas and a carrier gas is supplied to the processing container 11, the first catalyst gas is adsorbed onto the surface of the substrate W.

[0069] The supply flow rate of the mixed gas consisting of the first catalyst gas and the carrier gas (or the supply flow rate of the first catalyst gas if it consists only of the first catalyst gas) is preferably in the range of 1 sccm or more and 10,000 sccm or less, more preferably in the range of 100 sccm or more and 5,000 sccm or less, and particularly preferably in the range of 200 sccm or more and 2,000 sccm or less. By setting the supply flow rate of the mixed gas (or first catalyst gas) to 1 sccm or more, the reaction rate (film formation rate) of the raw material gas can be maintained well, and insufficient adsorption of the raw material gas onto the substrate W can be prevented. On the other hand, by setting the supply flow rate of the mixed gas (or first catalyst gas) to 10,000 sccm or less, consumption can be reduced. The supply flow rate of the mixed gas (or first catalyst gas) can be appropriately controlled by adjusting the temperature of the first catalyst gas, the flow rate of the carrier gas, and the pressure in the first catalyst gas supply unit 13. The supply flow rate of the carrier gas to be mixed with the first catalyst gas is not particularly limited and can be appropriately set according to the supply flow rate of the mixed gas as described above.

[0070] The supply time (pulse time; if it consists only of the first catalyst gas, the supply time of the first catalyst gas) of the mixed gas consisting of the first catalyst gas and the carrier gas to the processing container 11 is preferably in the range of 0.1 seconds or more and 600 seconds or less, more preferably in the range of 1 second or more and 300 seconds or less, and particularly preferably in the range of 10 seconds or more and 180 seconds or less. By setting the supply time of the mixed gas (or first catalyst gas) to 0.1 seconds or more, the reaction rate (film formation rate) of the raw material gas can be maintained well, and insufficient adsorption of the raw material gas onto the substrate W can be prevented. On the other hand, by setting the supply time of the mixed gas (or first catalyst gas) to 600 seconds or less, consumption can be reduced and the process time can be shortened. The supply time of the mixed gas (or first catalyst gas) can be appropriately controlled by adjusting the temperature of the first catalyst gas, the flow rate of the carrier gas, and the pressure in the first catalyst gas supply unit 13. Note that the supply time of the first catalyst gas means the time during which the on-off valve 22b is open.

[0071] While the mixed gas consisting of the first catalyst gas and the carrier gas is supplied into the processing container 11, the on-off valve 21b of the raw material gas supply passage 21, the on-off valve 23b of the second catalyst gas supply passage 23, the on-off valve 24b of the reaction gas supply passage 24, and the on-off valve 25a of the purge gas supply passage 25 are all closed by on-off control.

[0072] Next, the processing container 11 is purged to remove the first catalyst gas from within it. Specifically, the on-off valve 25a of the purge gas supply passage 25 is opened by on-off control, and the third purge gas is supplied to the processing container 11 from the purge gas supply passage 25. In addition, the APC valve 27 is opened, and the processing container 11 is evacuated using a vacuum pump or the like (not shown). This removes the atmosphere of the first catalyst gas and carrier gas from within the processing container 11. The third purge gas is not particularly limited and can be an inert gas such as nitrogen gas, helium gas, or argon gas. Furthermore, it is preferable that the third purge gas contains as little moisture as possible.

[0073] The supply flow rate and supply time of the third purge gas are not particularly limited, as long as they are sufficient to remove the first catalyst gas that has not been adsorbed onto the substrate W surface from inside the processing container 11, as well as impurities such as moisture contained in the first catalyst gas.

[0074] Furthermore, while the third purge gas is being supplied into the processing container 11, the on-off valve 21b of the raw material gas supply passage 21, the on-off valve 22b of the first catalyst gas supply passage 22, the on-off valve 23b of the second catalyst gas supply passage 23, and the on-off valve 24b of the reaction gas supply passage 24 are all closed by on-off control.

[0075] When purging with the third purge gas is completed, the on / off valve 25a is closed by the on / off control, thereby stopping the supply of the third purge gas to the processing container 11.

[0076] Next, the raw material gas is supplied into the processing container 11 from which the first catalyst gas has been removed. That is, the carrier gas, whose flow rate is controlled by the MFC, is supplied from the carrier gas supply passage 17A to the raw material gas supply section 12. When the carrier gas is supplied to the raw material gas supply section 12, it is discharged from the raw material gas supply passage 21, accompanied by the raw material gas, which is the vaporized raw material stored in liquid state in the raw material gas supply section 12. In the raw material gas supply passage 21, the on-off valve 21b is in the open state by on-off control, and the flow rate of the mixed gas consisting of the carrier gas and raw material gas is adjusted by the needle valve 21a, while the mixed gas is supplied into the processing container 11. Details of the raw material gas and carrier gas are as described above in step (b1). Therefore, those details are omitted.

[0077] The supply flow rate of the mixed gas, consisting of a raw material gas and a carrier gas (or the supply flow rate of the raw material gas if it consists only of raw material gas), is preferably in the range of 1 sccm or more and 5000 sccm or less, more preferably in the range of 100 sccm or more and 3000 sccm or less, and particularly preferably in the range of 200 sccm or more and 2000 sccm or less. By setting the supply flow rate of the mixed gas (or raw material gas) to 1 sccm or more, the reaction rate (film formation rate) of the raw material gas can be maintained well, and insufficient adsorption of the raw material gas onto the substrate W can be prevented. On the other hand, by setting the supply flow rate of the mixed gas (or raw material gas) to 5000 sccm or less, gas consumption can be reduced. The supply flow rate of the mixed gas (or raw material gas) can be appropriately controlled by adjusting the temperature of the raw material gas, the flow rate of the carrier gas, and the pressure in the raw material gas supply unit 12. The supply flow rate of the carrier gas to be mixed with the raw material gas is not particularly limited and can be appropriately set according to the supply flow rate of the mixed gas as described above.

[0078] The supply time (pulse time; if it consists only of raw material gas, the supply time of the raw material gas) of the mixed gas, consisting of raw material gas and carrier gas, to the processing container 11 is preferably in the range of 0.1 seconds or more and 600 seconds or less, more preferably in the range of 1 second or more and 300 seconds or less, and particularly preferably in the range of 10 seconds or more and 180 seconds or less. By setting the supply time of the mixed gas (or raw material gas) to 0.1 seconds or more, the reaction rate (film formation rate) of the raw material gas can be maintained well, and insufficient adsorption of the raw material gas onto the substrate W can be prevented. On the other hand, by setting the supply time of the mixed gas (or raw material gas) to 600 seconds or less, consumption can be reduced and the process time can be shortened. The supply time of the mixed gas (or raw material gas) can be appropriately controlled by adjusting the temperature of the raw material gas, the flow rate of the carrier gas, and the pressure in the raw material gas supply unit 12. Note that the supply time of the raw material gas means the time during which the on-off valve 21b is open.

[0079] When the raw material gas is supplied into the processing container 11, the raw material gas reacts with the OH groups on the substrate W surface and is adsorbed. At this time, the OH groups have a charge distribution biased towards negative charge due to the action of the first catalyst gas, so the raw material gas can be easily adsorbed onto the substrate W surface.

[0080] This process (b2) enables the formation of highly uniform and high-precision films even when using inexpensive commercially available products as the first catalyst gas. Specifically, commercially available catalysts have a purity of approximately 98% by mass for general products and approximately 99.5% by mass for high-purity products, and even high-purity products contain impurities such as water. Therefore, for example, if the raw material gas and the first catalyst gas are supplied to the processing container 11 simultaneously, as in the aforementioned process (b1), the water contained in the first catalyst gas will react with the raw material gas, forming a thin film similar to that formed by the CVD (Chemical Vapor Deposition) method, which can reduce film uniformity. However, as in this process (b2), the first catalyst gas can be supplied to the substrate W surface alone beforehand to adsorb at the atomic layer level, and then the processing container 11 can be purged to remove the water contained in the first catalyst gas before supplying the raw material gas and adsorbing it onto the substrate W surface. As a result, it becomes possible to form a film with excellent film uniformity.

[0081] When supplying the first catalyst gas (or a mixed gas with a carrier gas) and the raw material gas (or a mixed gas with a carrier gas) (hereinafter sometimes referred to as "first catalyst gas, etc."), the temperature inside the processing container 11 is preferably within the range of 200°C or less, more preferably within the range of 50°C to 150°C, and particularly preferably within the range of 80°C to 125°C. By keeping the temperature inside the processing container 11 below 200°C, for example, even if the substrate W is made of a material with a low heat resistance temperature, it becomes possible to form a film while minimizing the effects of heat and maintaining the material properties of the substrate W.

[0082] When supplying the first catalyst gas, etc., the pressure inside the processing container 11 is preferably within the range of 1 Pa or more and 40,000 Pa or less, more preferably within the range of 13 Pa or more and 13,300 Pa or less, and particularly preferably within the range of 133 Pa or more and 6,700 Pa or less. By setting the pressure inside the processing container 11 to 1 Pa or more, the reaction rate (film formation rate) of the raw material gas can be maintained well. On the other hand, by setting the pressure inside the processing container 11 to 40,000 Pa or less, the processing time can be shortened and the purging efficiency can be increased. The pressure inside the processing container 11 is adjusted by controlling the opening and closing of the APC valve 27 by PID control.

[0083] Furthermore, while the raw material gas is being supplied into the processing container 11, the on-off valve 22b of the first catalyst gas supply passage 22, the on-off valve 23b of the second catalyst gas supply passage 23, the on-off valve 24b of the reaction gas supply passage 24, and the on-off valve 25a of the purge gas supply passage 25 are all kept closed by the on-off control.

[0084] When the supply of raw material gas ends, the on / off valve 21b is closed by on / off control, stopping the supply of the mixed gas of raw material gas and carrier gas.

[0085] (3) Process of supplying only raw material gas (b3) In this process (b3), only the raw material gas is supplied into the processing container 11 (S2-3). We discovered that when a raw material gas containing amino groups is used, it is possible to (chemically) adsorb the raw material onto the substrate W surface without the need for a catalyst. This eliminates the need to supply the first catalyst gas to the processing container 11, resulting in a significant improvement in productivity (throughput).

[0086] For example, if the raw material gas is Si(NMe2)(OMe)3 gas (see Figure 4), when Si(NMe2)(OMe)3 comes into contact with the surface of the substrate W, the N atoms in the Si(NMe2)(OMe)3 react with the H atoms in the OH groups present on the surface of the SiO2 constituting the substrate W. At the same time, because the Si(NMe2)(OMe)3 raw material gas has a positive charge imbalance on the Si atoms, a reaction occurs and (CH3)2NH is produced as a by-product. Figure 4 is a schematic diagram showing how the raw material gas is adsorbed onto the substrate when only the raw material gas is supplied into the processing container 11 in this embodiment.

[0087] When supplying the raw material gas to the processing container 11, the carrier gas, whose flow rate is controlled by the MFC, is supplied to the raw material gas supply unit 12 from the carrier gas supply passage 17A. When the carrier gas is supplied to the raw material gas supply unit 12, it is discharged from the raw material gas supply passage 21, accompanied by the raw material gas, which is the vaporized raw material stored in liquid form in the raw material gas supply unit 12. In the raw material gas supply passage 21, the on-off valve 21b is in the open state by on-off control, and the flow rate of the mixed gas consisting of the carrier gas and raw material gas is adjusted by the needle valve 21a, while the mixed gas is supplied into the processing container 11. Details of the raw material gas and carrier gas are as described in the explanation of process (b1). Therefore, those details are omitted.

[0088] The supply flow rate of the mixed gas, consisting of a raw material gas and a carrier gas (or the supply flow rate of the raw material gas if it consists only of raw material gas), is preferably in the range of 1 sccm or more and 5000 sccm or less, more preferably in the range of 100 sccm or more and 3000 sccm or less, and particularly preferably in the range of 200 sccm or more and 2000 sccm or less. By setting the supply flow rate of the mixed gas (or raw material gas) to 1 sccm or more, the reaction rate (film formation rate) of the raw material gas can be maintained well, and insufficient adsorption of the raw material gas onto the substrate W can be prevented. On the other hand, by setting the supply flow rate of the mixed gas (or raw material gas) to 5000 sccm or less, gas consumption can be reduced. The supply flow rate of the mixed gas (or raw material gas) can be appropriately controlled by adjusting the temperature of the raw material gas, the flow rate of the carrier gas, and the pressure in the raw material gas supply unit 12. The supply flow rate of the carrier gas to be mixed with the raw material gas is not particularly limited and can be appropriately set according to the supply flow rate of the mixed gas as described above.

[0089] The supply time (pulse time; if it consists only of raw material gas, the supply time of the raw material gas) of the mixed gas, consisting of raw material gas and carrier gas, to the processing container 11 is preferably in the range of 0.1 seconds or more and 300 seconds or less, more preferably in the range of 1 second or more and 120 seconds or less, and particularly preferably in the range of 10 seconds or more and 60 seconds or less. By setting the supply time of the mixed gas (or raw material gas) to 0.1 seconds or more, the reaction rate (film formation rate) of the raw material gas can be maintained well, and insufficient adsorption of the raw material gas onto the substrate W can be prevented. On the other hand, by setting the supply time of the mixed gas (or raw material gas) to 300 seconds or less, consumption can be reduced and the process time can be shortened. The supply time of the mixed gas (or raw material gas) can be appropriately controlled by adjusting the temperature of the raw material gas, the flow rate of the carrier gas, and the pressure in the raw material gas supply unit 12.

[0090] Furthermore, the temperature inside the processing container 11 when supplying the raw material gas (or a mixed gas with a carrier gas) is preferably in the range of 200°C or less, more preferably in the range of 50°C or more and 150°C or less, and particularly preferably in the range of 80°C or more and 125°C or less. By keeping the temperature inside the processing container 11 at 200°C or less, it becomes possible to form a film while maintaining the material properties of the substrate W, for example, even if the substrate W is made of a material with a low heat resistance temperature, by minimizing the effects of heat.

[0091] Furthermore, the pressure inside the processing container 11 when supplying the raw material gas (or a mixed gas with the carrier gas) is preferably in the range of 1 Pa or more and 13,300 Pa or less, more preferably in the range of 7 Pa or more and 2,660 Pa or less, and particularly preferably in the range of 67 Pa or more and 1,330 Pa or less. By setting the pressure inside the processing container 11 to 1 Pa or more, the reaction rate (film formation rate) of the raw material gas can be maintained well. On the other hand, by setting the pressure inside the processing container 11 to 13,000 Pa or less, the processing time can be shortened and the purging efficiency can be increased. The pressure inside the processing container 11 is adjusted by controlling the opening and closing of the APC valve 27 using PID control.

[0092] Furthermore, while the raw material gas is being supplied into the processing container 11, the on-off valve 22b of the first catalyst gas supply passage 22, the on-off valve 23b of the second catalyst gas supply passage 23, the on-off valve 24b of the reaction gas supply passage 24, and the on-off valve 25a of the purge gas supply passage 25 are all kept closed by the on-off control.

[0093] When the supply of raw material gas ends, the on / off valve 21b is closed by on / off control, stopping the supply of the mixed gas of raw material gas and carrier gas.

[0094] (4) Purge process The purging process (S2-4) aims to remove the atmosphere inside the processing container 11 during the raw material gas supply process (B). Specifically, if the raw material gas supply process (B) is a process (b1) in which the first catalyst gas is supplied together with the raw material gas, the purging process (S2-4) aims to remove unreacted raw material gas, by-product gas, and the first catalyst gas from inside the processing container 11. Furthermore, if the raw material gas supply process (B) is a process (b2) in which the first catalyst gas is supplied, followed by purging and then the raw material gas is supplied, or if it is a process (b3) in which only the raw material gas is supplied, the purging process (S2-4) aims to remove unreacted raw material gas and by-product gas.

[0095] The purging process specifically involves opening the on / off valve 25a by on / off control and supplying the first purge gas to the processing container 11 from the purge gas supply passage 25. Additionally, the APC valve 27 is opened, and the processing container 11 is evacuated using a vacuum pump or the like (not shown). This removes unreacted raw material gases from the processing container 11. The first purge gas is not particularly limited and can be an inert gas such as nitrogen, helium, or argon. Furthermore, it is preferable that the first purge gas contains as little moisture as possible.

[0096] The supply flow rate and supply time of the first purge gas are not particularly limited, as long as they are sufficient to remove unreacted raw material gas, by-product gas, and first catalyst gas from inside the processing container 11. While the first purge gas is supplied into the processing container 11, the on-off valve 21b of the raw material gas supply passage 21, the on-off valve 22b of the first catalyst gas supply passage 22, the on-off valve 23b of the second catalyst gas supply passage 23, and the on-off valve 24b of the reaction gas supply passage 24 are each closed by on-off control.

[0097] When purging with the first purge gas is completed, the on / off valve 25a is closed by the on / off control, thereby stopping the supply of the first purge gas to the processing container 11.

[0098] [Reaction gas supply process (C)] The reaction gas supply step (C) of this embodiment is a step in which a reaction gas is supplied into the processing container 11 after the raw material gas supply step (B) to oxidize the raw material gas adsorbed on the substrate W, and then the processing container 11 is purged with a second purge gas (S3).

[0099] In the reaction gas supply step (C), the (chemical) adsorption of the raw material gas onto the substrate W is carried out in one of the following cases, as shown in Figure 2: (c1) when the second catalyst gas is supplied into the processing vessel 11 together with the reaction gas (S3-1); (c2) when the second catalyst gas is supplied into the processing vessel 11 before the reaction gas is supplied, and then purged with a second purge gas (S3-2); or (c3) when only the reaction gas is supplied into the processing vessel 11 (S3-3). Below, these steps (c1), (c2), and (c3), as well as the purging step with the second purge gas, will be explained in order.

[0100] (1) Step (c1) Supplying the second catalyst gas together with the reaction gas. In step (c1), the reaction gas and the second catalyst gas are supplied to the processing vessel 11 simultaneously (S3-1).

[0101] When supplying the reaction gas to the processing vessel 11, the carrier gas is supplied from the carrier gas supply passage 17D to the reaction gas supply unit 15. The carrier gas is not particularly limited and examples include inert gases such as nitrogen gas, argon gas, and helium gas. These inert gases can be used individually or in mixtures. The supply of the carrier gas is controlled by flow rate control using an MFC.

[0102] When the carrier gas is supplied to the reaction gas supply unit 15, the carrier gas is discharged from the reaction gas supply passage 24, accompanied by the reaction gas, which is the vaporized oxidizer stored in liquid form within the reaction gas supply unit 15. In the reaction gas supply passage 24, the on-off valve 24b is in the open state by on-off control, and the flow rate of the mixed gas, consisting of the carrier gas and the reaction gas, is regulated by the needle valve 24a, while the mixed gas is supplied into the processing container 11.

[0103] As the reaction gas, an oxidizing agent gas containing oxygen atoms is preferred. As the oxidizing agent gas, for example, at least one gas selected from the group consisting of water, hydrogen peroxide, formic acid, and aldehydes is preferred.

[0104] The supply flow rate of the mixed gas, which consists of a reaction gas and a carrier gas (or the supply flow rate of the reaction gas if it consists only of a reaction gas), is preferably in the range of 1 sccm or more and 20,000 sccm or less, more preferably in the range of 100 sccm or more and 10,000 sccm or less, and particularly preferably in the range of 200 sccm or more and 5,000 sccm or less. By setting the supply flow rate of the mixed gas (or reaction gas) to 1 sccm or more, it is possible to prevent insufficient introduction of OH groups to the adsorbed molecules of the raw material gas adsorbed on the substrate W surface. On the other hand, by setting the supply flow rate of the mixed gas (or reaction gas) to 20,000 sccm or less, it is possible to reduce the amount of raw material consumed and increase the purging efficiency. The supply flow rate of the mixed gas (or reaction gas) can be appropriately controlled by adjusting the temperature of the reaction gas, the flow rate of the carrier gas, and the pressure inside the reaction gas supply unit 15. The supply flow rate of the carrier gas to be mixed with the reaction gas is not particularly limited and can be appropriately set according to the supply flow rate of the mixed gas as described above.

[0105] Furthermore, when supplying the second catalyst gas to the processing container 11, the carrier gas is supplied from the carrier gas supply path 17C to the second catalyst gas supply unit 14. Details of the carrier gas are as described above. The supply of the carrier gas is also controlled by the MFC flow rate. In addition, it is preferable to use a carrier gas that contains as little moisture as possible.

[0106] When the carrier gas is supplied to the second catalyst gas supply unit 14, the carrier gas is discharged from the second catalyst gas supply passage 23, accompanied by the second catalyst gas, which is the vaporized second catalyst stored in the second catalyst gas supply unit 14. In the second catalyst gas supply passage 23, the on-off valve 23b is in the open state by on-off control, and the flow rate of the mixed gas of the carrier gas and the second catalyst gas is adjusted by the needle valve 23a, while the mixed gas is supplied into the processing container 11.

[0107] Examples of the second catalyst gas include those exemplified in the first catalyst gas section above. The second catalyst gas can be the same type or a different type from those exemplified in the first catalyst gas section. The second catalyst gas can be used in any combination with the aforementioned exemplified raw material gas and first catalyst gas. Furthermore, it is preferable that the second catalyst gas contains as little moisture as possible.

[0108] The supply flow rate of the mixed gas consisting of the second catalyst gas and the carrier gas (or the supply flow rate of the second catalyst gas if it consists only of the second catalyst gas) is preferably in the range of 1 sccm or more and 10,000 sccm or less, more preferably in the range of 100 sccm or more and 5,000 sccm or less, and particularly preferably in the range of 200 sccm or more and 2,000 sccm or less. By setting the supply flow rate of the mixed gas (or second catalyst gas) to 1 sccm or more, it is possible to prevent insufficient introduction of OH groups to the adsorbed molecules of the raw material gas adsorbed on the substrate W surface. On the other hand, by setting the supply flow rate of the mixed gas (or second catalyst gas) to 10,000 sccm or less, consumption can be reduced. The supply flow rate of the mixed gas (or second catalyst gas) can be appropriately controlled by adjusting the temperature of the second catalyst gas, the flow rate of the carrier gas, and the pressure in the second catalyst gas supply unit 14. The supply flow rate of the carrier gas to be mixed with the second catalyst gas is not particularly limited and can be appropriately set according to the supply flow rate of the mixed gas as described above.

[0109] When a mixed gas consisting of a reaction gas and a carrier gas, and a mixed gas consisting of a second catalyst gas and a carrier gas are supplied to the processing container 11, the reaction gas introduces OH groups to the adsorbed molecules of the raw material gas adsorbed on the substrate W surface. In this embodiment, the introduction of OH groups to the adsorbed molecules is improved by supplying the second catalyst gas into the processing container 11 simultaneously with the reaction gas. For example, if -Si(OMe)3 groups are bonded to the substrate W surface by siloxane bonds, the reaction gas is H2O, and the second catalyst gas is pyrrolidine gas (see Figure 5), when pyrrolidine gas comes into contact with H2O, the lone pairs of electrons of the N atoms in pyrrolidine extract H atoms from H2O. As a result, the charge distribution at the O atom of the OH group becomes biased towards negative charge, and the OH group bonds with the Si atom, which has a charge distribution biased towards positive charge, through an oxidation reaction in order to replace the ligand (-OMe group) in the -Si(OMe)3 group bonded to the substrate W surface. Also, at this time, the ligand MeO was removed from the -Si(OMe)3 group. - This combines with the H atom abstracted by pyrrolidine, thereby producing MeOH as a by-product. Figure 5 is a schematic diagram showing how OH groups are introduced to adsorbed molecules adsorbed on the substrate W surface when the reaction gas and the second catalyst gas are supplied simultaneously in this embodiment.

[0110] The temperature inside the processing container 11 when supplying the reaction gas (or a mixed gas with a carrier gas) and the second catalyst gas (or a mixed gas with a carrier gas) is preferably in the range of 200°C or less, more preferably in the range of 50°C or more and 150°C or less, and particularly preferably in the range of 80°C or more and 125°C or less. By keeping the temperature inside the processing container 11 at 200°C or less, for example, even if the substrate W is made of a material with a low heat resistance temperature, it becomes possible to form a film while maintaining the material properties of the substrate W by avoiding thermal effects as much as possible.

[0111] The pressure inside the processing vessel 11 when supplying the reaction gas (or a mixed gas with a carrier gas) and the second catalyst gas (or a mixed gas with a carrier gas) is preferably in the range of 1 Pa or more and 40,000 Pa or less, more preferably in the range of 13 Pa or more and 13,300 Pa or less, and particularly preferably in the range of 133 Pa or more and 6,700 Pa or less. By setting the pressure inside the processing vessel 11 to 1 Pa or more, the reaction rate (film formation rate) of the reaction gas can be maintained well. On the other hand, by setting the pressure inside the processing vessel 11 to 40,000 Pa or less, the processing time can be shortened and the purging efficiency can be increased. The pressure inside the processing vessel 11 is adjusted by controlling the opening and closing of the APC valve 27 by PID control.

[0112] The supply time (pulse time) of the reaction gas (or mixed gas with carrier gas) and the second catalyst gas (or mixed gas with carrier gas) to the processing container 11 is preferably within the range of 0.1 seconds to 600 seconds, more preferably within the range of 1 second to 300 seconds, and particularly preferably within the range of 10 seconds to 180 seconds. By setting the supply time of the reaction gas to 0.1 seconds or more, it is possible to prevent insufficient introduction of OH groups to the adsorbed molecules of the raw material gas adsorbed on the substrate W surface. On the other hand, by setting the supply time of the reaction gas to 600 seconds or less, consumption can be reduced and the process time can be shortened. The supply time of the reaction gas can be appropriately controlled by adjusting the temperature of the reaction gas and the second catalyst gas, the flow rate of the carrier gas, the pressure in the reaction gas supply unit 15, and the pressure in the second catalyst gas supply unit 14. Furthermore, the supply time of the reaction gas and the second catalyst gas refers to the time when the on-off valve 24b and the on-off valve 23b are open simultaneously.

[0113] During this process (c1), while the reaction gas (or a mixed gas with carrier gas) and the second catalyst gas (or a mixed gas with carrier gas) are being supplied, the on-off valve 21b of the raw material gas supply passage 21, the on-off valve 22b of the first catalyst gas supply passage 22, and the on-off valve 25a of the purge gas supply passage 25 are all in a closed state. Furthermore, this process (c1) is terminated by closing the on-off valves 23b and 24b by on-off control, thereby stopping the supply of the mixed gas of the reaction gas and carrier gas, and the mixed gas of the second catalyst gas and carrier gas, to the processing container 11.

[0114] (2) A step in which the second catalytic gas is supplied, followed by purging, and then the reaction gas is supplied (c2) In step (c2), first the second catalyst gas is supplied into the processing container 11, then the processing container 11 is purged with a purge gas, and then the raw material gas is supplied into the processing container 11 (S3-2).

[0115] Here, when supplying the second catalyst gas to the processing container 11, the carrier gas is first supplied from the carrier gas supply path 17C to the second catalyst gas supply unit 14. Details of the carrier gas are as described above. Furthermore, the supply of the carrier gas is controlled by the MFC (Moisture Flow Control) via flow rate control.

[0116] When the carrier gas is supplied to the second catalyst gas supply unit 14, the carrier gas is discharged from the second catalyst gas supply passage 23, accompanied by the second catalyst gas, which is the vaporized second catalyst stored in liquid form within the second catalyst gas supply unit 14. In the second catalyst gas supply passage 23, the on-off valve 23b is in the open state by on-off control, and the flow rate of the mixed gas consisting of the carrier gas and the second catalyst gas is adjusted by the needle valve 23a, while the mixed gas is supplied into the processing container 11.

[0117] The supply flow rate of the mixed gas consisting of the second catalyst gas and the carrier gas (or the supply flow rate of the second catalyst gas if it consists only of the second catalyst gas) is preferably in the range of 1 sccm or more and 10,000 sccm or less, more preferably in the range of 100 sccm or more and 5,000 sccm or less, and particularly preferably in the range of 200 sccm or more and 2,000 sccm or less. By setting the supply flow rate of the mixed gas (or second catalyst gas) to 1 sccm or more, it is possible to prevent insufficient introduction of OH groups to the adsorbed molecules of the raw material gas adsorbed on the substrate W surface. On the other hand, by setting the supply flow rate of the mixed gas (or second catalyst gas) to 10,000 sccm or less, consumption can be reduced. The supply flow rate of the mixed gas (or second catalyst gas) can be appropriately controlled by adjusting the temperature of the second catalyst gas, the flow rate of the carrier gas, and the pressure in the second catalyst gas supply unit 14. The supply flow rate of the carrier gas to be mixed with the second catalyst gas is not particularly limited and can be appropriately set according to the supply flow rate of the mixed gas as described above.

[0118] The supply time (pulse time; if it consists only of the second catalyst gas, the supply time of the second catalyst gas) of the mixed gas consisting of the second catalyst gas and the carrier gas to the processing container 11 is preferably in the range of 0.1 seconds or more and 600 seconds or less, more preferably in the range of 1 second or more and 300 seconds or less, and particularly preferably in the range of 10 seconds or more and 180 seconds or less. By setting the supply time of the mixed gas (or second catalyst gas) to 0.1 seconds or more, the reaction between the second catalyst gas and the adsorbed molecules of the raw material gas adsorbed on the substrate W surface can be maintained well. On the other hand, by setting the supply time of the mixed gas (or second catalyst gas) to 600 seconds or less, consumption can be reduced and the process time can be shortened. The supply time of the mixed gas (or second catalyst gas) can be appropriately controlled by adjusting the temperature of the second catalyst gas, the flow rate of the carrier gas, and the pressure in the second catalyst gas supply unit 14. Note that the supply time of the second catalyst gas means the time during which the on-off valve 23b is open.

[0119] While the mixed gas consisting of the second catalyst gas and the carrier gas is supplied into the processing container 11, the on-off valve 21b of the raw material gas supply passage 21, the on-off valve 22b of the first catalyst gas supply passage 22, the on-off valve 24b of the reaction gas supply passage 24, and the on-off valve 25a of the purge gas supply passage 25 are all closed by on-off control.

[0120] Next, the processing container 11 is purged to remove the second catalyst gas from within it. Specifically, the on-off valve 25a of the purge gas supply passage 25 is opened by on-off control, and the fourth purge gas is supplied to the processing container 11 from the purge gas supply passage 25. In addition, the APC valve 27 is opened, and the processing container 11 is evacuated using a vacuum pump or the like (not shown). This removes the second catalyst gas from within the processing container 11. The fourth purge gas is not particularly limited and can be an inert gas such as nitrogen gas, helium gas, or argon gas. Furthermore, it is preferable that the fourth purge gas contains as little moisture as possible.

[0121] The supply flow rate and supply time of the fourth purge gas are not particularly limited, as long as they are sufficient to remove the second catalyst gas from inside the processing container 11.

[0122] Furthermore, while the third purge gas is being supplied into the processing container 11, the on-off valve 21b of the raw material gas supply passage 21, the on-off valve 22b of the first catalyst gas supply passage 22, the on-off valve 23b of the second catalyst gas supply passage 23, and the on-off valve 24b of the reaction gas supply passage 24 are all closed by on-off control.

[0123] When purging with the fourth purge gas is completed, the on / off valve 25a is closed by the on / off control, thereby stopping the supply of the fourth purge gas to the processing container 11.

[0124] Next, the reaction gas is supplied to the processing vessel 11 from which the second catalyst gas has been removed. That is, the carrier gas, whose flow rate is controlled by the MFC, is supplied from the carrier gas supply passage 17D to the reaction gas supply unit 15. When the carrier gas is supplied to the reaction gas supply unit 15, it is discharged from the reaction gas supply passage 24, accompanied by the reaction gas, which is the vaporized oxidizer stored in liquid state in the reaction gas supply unit 15. In the reaction gas supply passage 24, the on-off valve 24b is in the open state by on-off control, and the flow rate of the mixed gas consisting of the carrier gas and the reaction gas is adjusted by the needle valve 24a, while the mixed gas is supplied to the processing vessel 11. Details of the reaction gas and carrier gas are as described above in step (c1). Therefore, those details are omitted.

[0125] The supply flow rate of the mixed gas, which consists of a reaction gas and a carrier gas (or the supply flow rate of the reaction gas if it consists only of a reaction gas), is preferably in the range of 1 sccm or more and 20,000 sccm or less, more preferably in the range of 100 sccm or more and 10,000 sccm or less, and particularly preferably in the range of 200 sccm or more and 5,000 sccm or less. By setting the supply flow rate of the mixed gas (or reaction gas) to 1 sccm or more, it is possible to prevent insufficient introduction of OH groups to the adsorbed molecules of the raw material gas adsorbed on the substrate W surface. On the other hand, by setting the supply flow rate of the mixed gas (or reaction gas) to 20,000 sccm or less, it is possible to reduce the amount of raw material consumed and increase the purging efficiency. The supply flow rate of the mixed gas (or reaction gas) can be appropriately controlled by adjusting the temperature of the reaction gas, the flow rate of the carrier gas, and the pressure inside the reaction gas supply unit 15. The supply flow rate of the carrier gas to be mixed with the reaction gas is not particularly limited and can be appropriately set according to the supply flow rate of the mixed gas as described above.

[0126] The supply time (pulse time; if it consists only of reaction gas, the supply time of the reaction gas) of the mixed gas, which consists of reaction gas and carrier gas, to the processing container 11 is preferably in the range of 0.1 seconds or more and 600 seconds or less, more preferably in the range of 1 second or more and 300 seconds or less, and particularly preferably in the range of 10 seconds or more and 180 seconds or less. By setting the supply time of the mixed gas (or reaction gas) to 0.1 seconds or more, the introduction of OH groups to the adsorbed molecules of the raw material gas adsorbed on the substrate W surface by the reaction gas can be well maintained. On the other hand, by setting the supply time of the mixed gas (or reaction gas) to 600 seconds or less, the amount of gas consumed can be reduced and the process time can be shortened. The supply time of the mixed gas (or reaction gas) can be appropriately controlled by adjusting the temperature of the reaction gas, the flow rate of the carrier gas, and the pressure in the reaction gas supply unit 15. Note that the supply time of the reaction gas means the time during which the on-off valve 24b is open.

[0127] When the reaction gas is supplied into the processing container 11, the reaction gas introduces OH groups to the adsorbed molecules of the raw material gas adsorbed on the substrate W surface. Then, the pre-supplied second catalyst gas acts to promote the oxidation reaction between the adsorbed molecules of the raw material gas adsorbed on the substrate W surface and the reaction gas (see Figure 5).

[0128] When supplying the second catalyst gas (or a mixed gas with a carrier gas) and the reaction gas (or a mixed gas with a carrier gas), the temperature inside the processing container 11 is preferably in the range of 200°C or less, more preferably in the range of 50°C or more and 150°C or less, and particularly preferably in the range of 80°C or more and 125°C or less. By keeping the temperature inside the processing container 11 below 200°C, for example, even if the substrate W is made of a material with a low heat resistance temperature, it becomes possible to form a film while minimizing the effects of heat and maintaining the material properties of the substrate W.

[0129] The pressure inside the processing container 11 when supplying the second catalyst gas (or a mixed gas with a carrier gas) and the reaction gas (or a mixed gas with a carrier gas) is preferably in the range of 1 Pa or more and 40,000 Pa or less, more preferably in the range of 13 Pa or more and 13,300 Pa or less, and particularly preferably in the range of 133 Pa or more and 6,700 Pa or less. By setting the pressure inside the processing container 11 to 13 Pa or more, the reaction rate (film formation rate) of the reaction gas can be maintained well. On the other hand, by setting the pressure inside the processing container 11 to 40,000 Pa or less, the processing time can be shortened and the purging efficiency can be increased. The pressure inside the processing container 11 is adjusted by controlling the opening and closing of the APC valve 27 by PID control.

[0130] Furthermore, while the reaction gas is being supplied into the processing container 11, the on-off valve 21b of the raw material gas supply passage 21, the on-off valve 22b of the first catalyst gas supply passage 22, the on-off valve 23b of the second catalyst gas supply passage 23, and the on-off valve 25a of the purge gas supply passage 25 are all kept closed by the on-off control.

[0131] When the supply of reaction gas ends, the on / off valve 24b is closed by the on / off control, stopping the supply of the mixed gas of reaction gas and carrier gas.

[0132] (3) Step of supplying only reaction gas (c3) In this step (c3), only the reaction gas is supplied into the processing container 11 (S3-3). In this step (c3), OH groups are introduced to the adsorbed molecules of the raw material gas adsorbed on the substrate W surface without supplying the second catalyst gas to the processing container 11. Therefore, a significant improvement in productivity (throughput) can be achieved. However, this step (c3) is not performed when the raw material gas supply step (B) is the same as step (b3) in which only the raw material gas is supplied to the processing container 11.

[0133] For example, if -Si(OMe)3 groups are bonded to the substrate W surface via siloxane bonds, and the reaction gas is H2O, when H2O comes into contact with the -Si(OMe)3 groups, the OH group will bond to the Si atom, which has a charge distribution biased towards positive charge, through an oxidation reaction in order to replace the ligand (-OMe group) in the -Si(OMe)3 groups bonded to the substrate W surface (Figure 6(a)). Also, at this time, the ligand MeO is detached from the -Si(OMe)3 groups. - H is the H of H2O + It combines with, thereby producing MeOH as a by-product (Figure 6(b)). Figure 6 is a schematic diagram showing how OH groups are introduced to adsorbed molecules adsorbed on the substrate W surface when only the reaction gas is supplied in this embodiment.

[0134] When supplying the reaction gas to the processing vessel 11, the carrier gas, whose flow rate is controlled by the MFC, is supplied to the reaction gas supply unit 15 from the carrier gas supply passage 17D. When the carrier gas is supplied to the reaction gas supply unit 15, it is discharged from the reaction gas supply passage 24, accompanied by the reaction gas, which is the vaporized oxidizer stored in liquid form in the reaction gas supply unit 15. In the reaction gas supply passage 24, the on-off valve 24b is in the open state by the on-off control, and the flow rate of the mixed gas consisting of the carrier gas and reaction gas is regulated by the needle valve 24a, while the mixed gas is supplied to the processing vessel 11. Details of the reaction gas and carrier gas are as described above in step (c1). Therefore, those details are omitted.

[0135] The supply flow rate of the mixed gas, which consists of a reaction gas and a carrier gas (or the supply flow rate of the reaction gas if it consists only of a reaction gas), is preferably in the range of 1 sccm or more and 20,000 sccm or less, more preferably in the range of 100 sccm or more and 10,000 sccm or less, and particularly preferably in the range of 200 sccm or more and 5,000 sccm or less. By setting the supply flow rate of the mixed gas (or reaction gas) to 1 sccm or more, it is possible to prevent insufficient introduction of OH groups to the adsorbed molecules of the raw material gas adsorbed on the substrate W surface. On the other hand, by setting the supply flow rate of the mixed gas (or reaction gas) to 20,000 sccm or less, it is possible to reduce the amount of raw material consumed and increase the purging efficiency. The supply flow rate of the mixed gas (or reaction gas) can be appropriately controlled by adjusting the temperature of the reaction gas, the flow rate of the carrier gas, and the pressure inside the reaction gas supply unit 15. The supply flow rate of the carrier gas to be mixed with the reaction gas is not particularly limited and can be appropriately set according to the supply flow rate of the mixed gas as described above.

[0136] The supply time (pulse time; if it consists only of reaction gas, the supply time of the reaction gas) of the mixed gas, which consists of reaction gas and carrier gas, to the processing container 11 is preferably in the range of 0.1 seconds or more and 600 seconds or less, more preferably in the range of 1 second or more and 300 seconds or less, and particularly preferably in the range of 10 seconds or more and 180 seconds or less. By setting the supply time of the mixed gas (or reaction gas) to 0.1 seconds or more, the introduction of OH groups to the adsorbed molecules of the raw material gas adsorbed on the substrate W surface by the reaction gas can be well maintained. On the other hand, by setting the supply time of the mixed gas (or reaction gas) to 600 seconds or less, consumption can be reduced and the process time can be shortened. The supply time of the mixed gas (or reaction gas) can be appropriately controlled by adjusting the temperature of the reaction gas, the flow rate of the carrier gas, and the pressure in the reaction gas supply unit 15. The supply time of the mixed gas (or reaction gas) refers to the time that the on-off valve 24b is open.

[0137] Furthermore, the temperature inside the processing container 11 when supplying the reaction gas (or a mixed gas with a carrier gas) is preferably 200°C or lower, more preferably in the range of 50°C to 150°C, and particularly preferably in the range of 80°C to 125°C. By keeping the temperature inside the processing container 11 at 200°C or lower, it becomes possible to form a film while maintaining the material properties of the substrate W, for example, even if the substrate W is made of a material with a low heat resistance temperature, by minimizing the effects of heat.

[0138] Furthermore, the pressure inside the processing container 11 when supplying the reaction gas (or a mixed gas with a carrier gas) is preferably in the range of 13 Pa or more and 40,000 Pa or less, more preferably in the range of 133 Pa or more and 13,300 Pa or less, and particularly preferably in the range of 1,330 Pa or more and 6,700 Pa or less. By setting the pressure inside the processing container 11 to 13 Pa or more, the reaction rate (film formation rate) of the reaction gas can be maintained well. On the other hand, by setting the pressure inside the processing container 11 to 40,000 Pa or less, the processing time can be shortened and the purging efficiency can be increased. The pressure inside the processing container 11 is adjusted by controlling the opening and closing of the APC valve 27 using PID control.

[0139] Furthermore, while the reaction gas is being supplied into the processing container 11, the raw material gas supply... road The on-off valve 21b of valve 21, the on-off valve 22b of the first catalytic gas supply passage 22, the on-off valve 23b of the second catalytic gas supply passage 23, and the on-off valve 25a of the purge gas supply passage 25 are all in a closed state due to on-off control.

[0140] When the supply of reaction gas ends, the on / off valve 24b is closed by the on / off control, stopping the supply of the mixed gas of reaction gas and carrier gas.

[0141] (4) Purge process The purging process (S3-4) aims to remove the atmosphere inside the processing vessel 11 during the reaction gas supply process (C). Specifically, if the reaction gas supply process (C) is a process (c1) in which the second catalyst gas is supplied together with the reaction gas, the purging process (S3-4) aims to remove unreacted reaction gas, by-product gas, and the second catalyst gas from inside the processing vessel 11. Furthermore, if the reaction gas supply process (C) is a process (c2) in which the second catalyst gas is supplied, followed by purging and then the reaction gas is supplied, or if it is a process (c3) in which only the reaction gas is supplied, the purging process (S3-4) aims to remove unreacted reaction gas and by-product gas.

[0142] The purging process specifically involves opening the on / off valve 25a by on / off control and supplying the second purge gas to the processing container 11 from the purge gas supply passage 25. Additionally, the APC valve 27 is opened, and the processing container 11 is evacuated using a vacuum pump or the like (not shown). This removes unreacted reaction gases from the processing container 11. The second purge gas is not particularly limited and can be an inert gas such as nitrogen, helium, or argon. Furthermore, it is preferable that the second purge gas contains as little moisture as possible.

[0143] The supply flow rate and supply time of the second purge gas are not particularly limited, as long as they are sufficient to remove unreacted reaction gas, by-product gas, and second catalyst gas from inside the processing container 11. While the second purge gas is being supplied into the processing container 11, the on-off valve 21b of the raw material gas supply passage 21, the on-off valve 22b of the first catalyst gas supply passage 22, the on-off valve 23b of the second catalyst gas supply passage 23, and the on-off valve 24b of the reaction gas supply passage 24 are all kept closed by on-off control.

[0144] When purging with the second purge gas is completed, the on / off valve 25a is closed by the on / off control, thereby stopping the supply of the second purge gas to the processing container 11.

[0145] [Other matters] In the film formation method of this embodiment, for example, the two steps of raw material gas supply step (B) and reaction gas supply step (C) can be considered as one cycle. By repeating the cycle of raw material gas supply step (B) and reaction gas supply step (C) multiple times, a film of a desired thickness can be formed on the surface of the substrate W (S4). Furthermore, the thickness of the formed film can be controlled at the atomic layer level. When repeating the cycle of raw material gas supply step (B) and reaction gas supply step (C) multiple times, steps (b1), (b2), and (b3) in the raw material gas supply step (B) and steps (c1), (c2), and (c3) in the reaction gas supply step (C) can be arbitrarily combined. However, in this invention, the combination in which the raw material gas supply step (B) is step (b3) and the reaction gas supply step (C) is step (c3) is excluded. [Examples]

[0146] (Example 1) In this embodiment, an SiO2 film was deposited on the substrate surface using the film deposition apparatus 1 shown in Figure 1, based on the SiO2 film deposition sequence shown in Figure 7. However, in the film deposition apparatus 1, a raw material gas supply container with an internal volume of 200 ml was used as the raw material gas supply unit 12, a catalyst gas supply container with an internal volume of 200 ml was used as the first catalyst gas supply unit 13 and the second catalyst gas supply unit, and a reaction gas supply container with an internal volume of 200 ml was used as the reaction gas supply unit 15. In addition, the film deposition apparatus 1 was equipped with a dry-type vacuum pump with an ultimate vacuum of 0.1 torr as a vacuum evacuation device to adjust the pressure inside the processing container 11. Furthermore, a sulfuric acid scrubber and a caustic scrubber were provided in the discharge passage 26 to remove harmful substances contained in the exhaust gas. Figure 7 is a diagram showing the SiO2 film deposition sequence in this embodiment 1. Each step in this embodiment will be described in detail below.

[0147] (1) Raw material gas supply process (B) TMOS (tetrakismethoxysilane) gas (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) was used as the raw material gas, and N2 gas (purity 99.999%) was supplied as a carrier gas to the raw material gas supply container, thereby supplying a mixed gas containing TMOS gas to the processing container 11. The temperature inside the raw material gas supply container when supplying TMOS gas was 30°C and the pressure was 300 torr. The flow rate of N2 gas supplied to the raw material gas supply container was 100 sccm. Furthermore, the flow rate of the mixed gas consisting of TMOS gas and N2 gas supplied to the processing container 11 was 110 sccm.

[0148] In addition to supplying TMOS gas to the processing container 11, a first catalyst gas was also supplied to the processing container 11. Pyrrolidine gas (manufactured by Sigma-Aldrich, purity 99.5%) was used as the first catalyst gas. By supplying N2 gas as a carrier gas to the catalyst gas supply container, pyrrolidine gas was entrained with the N2 gas, and a mixed gas consisting of N2 gas and pyrrolidine gas was supplied to the processing container 11. The temperature inside the catalyst gas supply container when supplying pyrrolidine gas was 30°C and the pressure was 250 torr. The flow rate of N2 gas supplied to the catalyst gas supply container was 50 sccm. The flow rate of the mixed gas consisting of pyrrolidine gas and N2 gas supplied to the processing container 11 was 80 sccm.

[0149] When supplying a mixed gas consisting of TMOS gas and N2 gas, and a mixed gas consisting of pyrrolidine gas and N2 gas, to the processing container 11 simultaneously, the temperature inside the processing container 11 was maintained at 80°C, and the pressure inside the processing container 11 was set to 23.3 torr (3.1 kPa). Furthermore, the supply pressure (film formation pressure) when supplying these mixed gases to the processing container 11 was set within the range of 25 to 90 torr, and the supply time was set to 60 seconds.

[0150] Next, the processing container 11 was purged. N2 gas was used as the first purge gas and supplied into the processing container 11 at a flow rate of 500 sccm. The N2 gas supply time was set to 60 seconds. Furthermore, the pressure inside the processing container 11 was set to 2-3 torr.

[0151] (2) Reaction gas supply process (C) As the reaction gas, H2O gas, obtained by vaporizing pure water (electrical resistivity 17.5 MΩ·cm), was used. N2 gas was supplied as a carrier gas to the reaction gas supply container, and a mixed gas containing H2O gas was supplied to the processing container 11. The temperature inside the reaction gas supply container when supplying H2O gas was 75°C and the pressure was 460 torr. The flow rate of N2 gas supplied to the reaction gas supply container was 200 sccm. Furthermore, the flow rate of the mixed gas consisting of H2O gas and N2 gas supplied to the processing container 11 was 460 sccm.

[0152] In addition to supplying H2O gas to the processing container 11, a second catalyst gas was also supplied to the processing container 11. Pyrrolidine gas was used as the second catalyst gas, and, similar to the supply of the first catalyst gas in the raw material gas supply process (B), N2 gas was supplied to the catalyst gas supply container, thereby entraining the N2 gas with pyrrolidine gas, and a mixed gas consisting of N2 gas and pyrrolidine gas was supplied to the processing container 11. The temperature inside the catalyst gas supply container when supplying pyrrolidine gas was 30°C and the pressure was 250 torr. The flow rate of N2 gas supplied to the first catalyst gas supply container was 50 sccm. The flow rate of the mixed gas consisting of pyrrolidine gas and N2 gas supplied to the processing container 11 was 80 sccm.

[0153] When supplying a mixed gas consisting of H2O gas and N2 gas, and a mixed gas consisting of pyrrolidine gas and N2 gas, to the processing container 11 simultaneously, the temperature inside the processing container 11 was maintained at 80°C, and the pressure inside the processing container 11 was set to 43.5 torr (5.8 kPa). Furthermore, the supply pressure (film formation pressure) when supplying these mixed gases to the processing container 11 was set within the range of 25 to 90 torr, and the supply time was set to 60 seconds.

[0154] Next, the processing container 11 was purged. N2 gas was used as the second purge gas and supplied into the processing container 11 at a flow rate of 500 sccm. The N2 gas supply time was set to 90 seconds. Furthermore, the pressure inside the processing container 11 was set to 2-3 torr.

[0155] (3) Results The process consisted of two steps: the raw material gas supply process (B) and the reaction gas supply process (C). A total of 400 cycles were performed to deposit an SiO2 film on the substrate surface. The film density of the deposited SiO2 film was 2.1 g / cm³. 3 The film thickness was 52.9 nm and the surface roughness was 0.2 nm. The deposition rate of the SiO2 film was 0.13 nm / cycle.

[0156] (Example 2) In this embodiment, a SiO2 film was deposited on the substrate surface using the film deposition apparatus 1 used in Example 1, based on the SiO2 film deposition sequence shown in Figure 8. Figure 8 is a diagram showing the SiO2 film deposition sequence in this embodiment 2. Each step in this embodiment will be described in detail below.

[0157] (1) Raw material gas supply process (B) First, pyrrolidine gas was supplied to the processing container 11 as the first catalyst gas. The temperature inside the first catalyst gas supply container was 30°C and the pressure was 250 torr when supplying the pyrrolidine gas. The flow rate of N2 gas supplied to the first catalyst gas supply container was 50 sccm. In addition, the flow rate of the mixed gas consisting of pyrrolidine gas and N2 gas supplied to the processing container 11 was 80 sccm.

[0158] Furthermore, when supplying the mixed gas consisting of pyrrolidine gas and N2 gas to the processing container 11, the temperature inside the processing container 11 was maintained at 80°C, and the pressure inside the processing container 11 was set to 26.3 torr (3.5 kPa). In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 11 was set within the range of 25 to 90 torr, and the supply time was set to 60 seconds.

[0159] Next, the processing container 11 was purged. N2 gas was used as the third purge gas and supplied into the processing container 11 at a flow rate of 500 sccm. The N2 gas supply time was set to 90 seconds. Furthermore, the pressure inside the processing container 11 was set to 2-3 torr.

[0160] Next, TMOS gas was supplied to the processing container 11 as a raw material gas. The temperature inside the raw material gas supply container when supplying the TMOS gas was set to 30°C and the pressure to 300 torr. The flow rate of N2 gas supplied to the raw material gas supply container was set to 100 sccm. Furthermore, the flow rate of the mixed gas consisting of TMOS gas and N2 gas supplied to the processing container 11 was set to 110 sccm.

[0161] Furthermore, when supplying the mixed gas consisting of TMOS gas and N2 gas to the processing container 11, the temperature inside the processing container 11 was maintained at 80°C, and the pressure inside the processing container 11 was set to 30 torr (4.00 kPa). In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 11 was set within the range of 25 to 90 torr, and the supply time was set to 60 seconds.

[0162] Next, the processing container 11 was purged. N2 gas was used as the first purge gas and supplied into the processing container 11 at a flow rate of 500 sccm. The N2 gas supply time was set to 60 seconds. Furthermore, the pressure inside the processing container 11 was set to 2-3 torr.

[0163] (2) Reaction gas supply process (C) For the reaction gas supply step (C), the pressure inside the processing vessel was changed from 43.5 torr (5.8 kPa) to 83.3 torr (11.1 kPa). Otherwise, the reaction gas supply step (C) was carried out in the same manner as in Example 1.

[0164] (3) Results The process consisted of two steps: the raw material gas supply step (B) and the reaction gas supply step (C). A total of 400 cycles were performed to deposit an SiO2 film on the substrate surface. The film density of the deposited SiO2 film was 2.2 g / cm³. 3 The film thickness was 32.6 nm and the surface roughness was 0.2 nm. The deposition rate of the SiO2 film was 0.08 nm / cycle.

[0165] (Example 3) In this embodiment, a SiO2 film was deposited on the substrate surface using the film deposition apparatus 1 used in Example 1, based on the SiO2 film deposition sequence shown in Figure 9. Figure 9 is a diagram showing the SiO2 film deposition sequence in this embodiment 3. Each step in this embodiment will be described in detail below.

[0166] (1) Raw material gas supply process (B) 3DMAS (tris(dimethylamino)silane) gas (manufactured by Tri-Chemical Laboratories Co., Ltd., purity 99.9%) was used as the raw material gas. N2 gas was supplied as a carrier gas to the raw material gas supply container, and a mixed gas containing 3DMAS gas was supplied to the processing container 11. The temperature inside the raw material gas supply container when supplying the 3DMAS gas was 27°C and the pressure was 680 torr. The flow rate of N2 gas supplied to the raw material gas supply container was 100 sccm. Furthermore, the flow rate of the mixed gas consisting of 3DMAS gas and N2 gas supplied to the processing container 11 was 101 sccm.

[0167] Furthermore, when supplying the mixed gas consisting of 3DMAS gas and N2 gas to the processing container 11, the temperature inside the processing container 11 was maintained at 80°C, and the pressure inside the processing container 11 was set to 14.3 torr (1.9 kPa). In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 11 was within the range of 1 torr, and the supply time was set to 12 seconds.

[0168] Next, the processing container 11 was purged. N2 gas was used as the first purge gas and supplied into the processing container 11 at a flow rate of 500 sccm. The N2 gas supply time was set to 60 seconds. Furthermore, the pressure inside the processing container 11 was set to 2-3 torr.

[0169] (2) Reaction gas supply process (C) For the reaction gas supply step (C), the pressure inside the processing vessel was changed from 43.5 torr (5.8 kPa) to 42.0 torr (5.6 kPa). Otherwise, the procedure was the same as in Example 1.

[0170] (3) Results The process consisted of two steps: the raw material gas supply step (B) and the reaction gas supply step (C). A total of 400 cycles were performed to deposit an SiO2 film on the substrate surface. The film density of the deposited SiO2 film was 2.2 g / cm³. 3 The film thickness was 35.2 nm and the surface roughness was 0.2 nm. The deposition rate of the SiO2 film was 0.088 nm / cycle.

[0171] (Example 4) In this embodiment, a SiO2 film was deposited on the substrate surface using the film deposition apparatus 1 used in Example 1, based on the SiO2 film deposition sequence shown in Figure 10. Figure 10 is a diagram showing the SiO2 film deposition sequence in this embodiment 4. Each step in this embodiment will be described in detail below.

[0172] (1) Raw material gas supply process (B) Dimethylaminotrimethoxysilane was used as the raw material gas. N2 gas was supplied as a carrier gas to the raw material gas supply container, and a mixed gas containing dimethylaminotrimethoxysilane was supplied to the processing container 11. The temperature inside the raw material gas supply container when supplying dimethylaminotrimethoxysilane was 27°C and the pressure was 385 torr. The flow rate of N2 gas supplied to the raw material gas supply container was 100 sccm. Furthermore, the flow rate of the mixed gas consisting of dimethylaminotrimethoxysilane gas and N2 gas supplied to the processing container 11 was 102 sccm.

[0173] Furthermore, when supplying dimethylaminotrimethoxysilane to the processing container 11, the temperature inside the processing container 11 was maintained at 80°C, and the pressure inside the processing container 11 was set to 1 torr (0.17 kPa). In addition, when supplying these mixed gases to the processing container 11, the supply pressure (film formation pressure) was set to within the range of 2 to 3 torr, and the supply time was set to 20 seconds.

[0174] Next, the processing container 11 was purged. N2 gas was used as the first purge gas and supplied into the processing container 11 at a flow rate of 500 sccm. The N2 gas supply time was set to 60 seconds. Furthermore, the pressure inside the processing container 11 was set to 2-3 torr.

[0175] (2) Reaction gas supply process (C) For the reaction gas supply step (C), the supply time for the mixed gas consisting of H2O gas and N2 gas and the mixed gas consisting of pyrrolidine gas and N2 gas was changed to 30 seconds, and the pressure inside the processing vessel was changed from 43.5 torr (5.8 kPa) to 48.8 torr (6.5 kPa). Otherwise, the reaction gas supply step (C) was carried out in the same manner as in Example 1.

[0176] (3) Results The process consisted of two steps: the raw material gas supply step (B) and the reaction gas supply step (C). A total of 400 cycles were performed to deposit an SiO2 film on the substrate surface. The film density of the deposited SiO2 film was 2.2 g / cm³. 3 The film thickness was 46.6 nm and the surface roughness was 0.2 nm. The deposition rate of the SiO2 film was 0.12 nm / cycle.

[0177] (Examples 5-8) In Examples 5 to 8, the number of cycles in the raw material gas supply process (B) and the reaction gas supply process (C) were changed to 40, 80, 160, and 220 cycles, respectively. Otherwise, the SiO2 film was deposited on the substrate in the same manner as in Example 2. The physical properties of the SiO2 films obtained in each example are shown in Table 1.

[0178] (Result 1) As can be seen from Examples 1 to 4, even when the raw material gas supply process (B) and the reaction gas supply process (C) were carried out at a low temperature of 80°C, it was possible to deposit a SiO2 film with high film density and good film quality on the substrate.

[0179] Furthermore, in Examples 1 and 5-8, the relationship between the number of cycles and the film thickness was investigated, and as shown in Figure 11, it was confirmed that there was a proportional relationship between the number of cycles and the film thickness of the SiO2 film, indicating that an ideal film could be formed. Figure 11 is a graph showing the correlation between the number of cycles and the film thickness of the SiO2 film when TMOS gas is used as the raw material gas.

[0180] [Table 1]

[0181] (Example 9) In this example, a SiO2 film was deposited on the substrate surface using the film deposition apparatus 1 used in Example 1. More specifically, the procedure was as follows.

[0182] (1) Raw material gas supply process (B) First, pyrrolidine gas was supplied to the processing container 11 as the first catalyst gas. The temperature inside the first catalyst gas supply container was 30°C and the pressure was 250 torr when supplying the pyrrolidine gas. The flow rate of N2 gas supplied to the first catalyst gas supply container was 50 sccm. In addition, the flow rate of the mixed gas consisting of pyrrolidine gas and N2 gas supplied to the processing container 11 was 80 sccm.

[0183] Furthermore, when supplying the mixed gas consisting of pyrrolidine gas and N2 gas to the processing container 11, the temperature inside the processing container 11 was maintained at 50°C, and the pressure inside the processing container 11 was set to 26.3 torr (3.5 kPa). In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 11 was set within the range of 25 to 90 torr, and the supply time was set to 60 seconds.

[0184] Next, the processing container 11 was purged. N2 gas was used as the third purge gas and supplied into the processing container 11 at a flow rate of 500 sccm. The N2 gas supply time was set to 90 seconds. Furthermore, the pressure inside the processing container 11 was set to 2-3 torr.

[0185] Next, TMOS gas was supplied to the processing container 11 as a raw material gas. The temperature inside the raw material gas supply container when supplying the TMOS gas was 30°C and the pressure was 272 torr. The flow rate of N2 gas supplied to the raw material gas supply container was 100 sccm. Furthermore, the flow rate of the mixed gas consisting of TMOS gas and N2 gas supplied to the processing container 11 was 110 sccm.

[0186] Furthermore, when supplying the mixed gas consisting of TMOS gas and N2 gas to the processing container 11, the temperature inside the processing container 11 was maintained at 50°C, and the pressure inside the processing container 11 was set to 30.0 torr (4.0 kPa). In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 11 was set within the range of 25 to 90 torr, and the supply time was set to 60 seconds.

[0187] Next, the processing container 11 was purged. N2 gas was used as the first purge gas and supplied into the processing container 11 at a flow rate of 500 sccm. The N2 gas supply time was set to 60 seconds. Furthermore, the pressure inside the processing container 11 was set to 2-3 torr.

[0188] (2) Reaction gas supply process (C) For the reaction gas supply step (C), the temperature (film formation temperature) inside the processing vessel 11 was changed from 80°C to 50°C, and the pressure inside the processing vessel 11 was changed from 43.5 torr (5.8 kPa) to 82.5 torr (11.0 kPa). Other than these changes, the reaction gas supply step (C) was carried out in the same manner as in Example 1.

[0189] (3) Results The process consisted of two steps: the raw material gas supply process (B) and the reaction gas supply process (C). A total of 80 cycles were performed to deposit an SiO2 film on the substrate surface. The physical properties of the deposited SiO2 film are shown in Table 2.

[0190] (Examples 10 and 11) In Example 10, the pressure inside the processing vessel 11 in the reaction gas supply step (C) was changed from 83.3 torr (11.1 kPa) to 82.5 torr (11.0 kPa). In Example 11, the temperature (film deposition temperature) inside the processing vessel 11 in the raw material gas supply step (B) and the reaction gas supply step (C) was changed from 50°C to 175°C. Except for these changes, the SiO2 film was deposited on the substrate in the same manner as in Example 9. The physical properties of the deposited SiO2 film are shown in Table 2.

[0191] (Comparative Example 1) In this comparative example, an SiO2 film was deposited on the substrate surface using the film deposition apparatus 100 shown in Figure 20. The film deposition apparatus 100 shown in Figure 20 includes a raw material gas supply container 102 (internal volume 200 ml) for supplying raw material gas to the processing container 101, reaction For supplying gas to the processing container 101 reaction The apparatus 100 includes a gas supply container 103 (internal volume 200 ml), a purge gas supply passage 104 for supplying purge gas to the processing container 101, and a discharge passage 105 for discharging the atmosphere inside the processing container 101. The film deposition apparatus 100 is also equipped with a dry-type vacuum pump with an ultimate vacuum of 0.1 torr as a vacuum evacuation device for adjusting the pressure inside the processing container 101. Furthermore, the discharge passage 105 is equipped with a sulfuric acid scrubber and a caustic scrubber to remove harmful substances contained in the exhaust gas. Each step in this comparative example is described in detail below.

[0192] (1) Raw material gas supply process TMOS gas was supplied to the processing container 101 as a raw material gas. The temperature inside the raw material gas supply container 102 when supplying the TMOS gas was 30°C and the pressure was 272 torr. The flow rate of N2 gas supplied to the raw material gas supply container 102 was 100 sccm. Furthermore, the flow rate of the mixed gas consisting of TMOS gas and N2 gas supplied to the processing container 101 was 110 sccm.

[0193] Furthermore, when supplying the mixed gas consisting of TMOS gas and N2 gas to the processing container 101, the temperature inside the processing container 101 was maintained at 50°C, and the pressure inside the processing container 101 was set to 1 torr (1.3 kPa). In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 101 was set within the range of 25 to 90 torr, and the supply time was set to 60 seconds.

[0194] Next, purging was performed inside the processing container 101. N2 gas was used as the purging gas and supplied into the processing container 101 at a flow rate of 500 sccm. The N2 gas supply time was set to 60 seconds. Furthermore, the pressure inside the processing container 101 was set to 2-3 torr.

[0195] (2) Reaction gas supply process Ozone gas was used as the reaction gas. O2 gas was supplied to the reaction gas supply container 103, and a portion of it was converted into ozone gas within the container. This resulted in a mixed gas consisting of ozone gas and O2 gas being supplied to the processing container 101. The temperature inside the reaction gas supply container 103 was 27°C and the pressure was 0.4 torr when supplying this mixed gas. Furthermore, the flow rate of the mixed gas consisting of ozone gas and O2 gas supplied to the processing container 101 was 200 sccm.

[0196] Furthermore, when supplying the mixed gas consisting of ozone gas and O2 gas to the processing container 101, the temperature inside the processing container 101 was maintained at 50°C, and the pressure inside the processing container 101 was set to 1.3 kPa. In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 101 was set within the range of 25 to 90 torr, and the supply time was set to 20 seconds.

[0197] Next, purging was performed inside the processing container 101. N2 gas was used as the purging gas and supplied into the processing container 101 at a flow rate of 200 sccm. The N2 gas supply time was set to 12 seconds. Furthermore, the pressure inside the processing container 101 was set to 0.5 torr.

[0198] (3) Results The process consisted of two steps: raw material gas supply and reaction gas supply. This was repeated for a total of 80 cycles to deposit an SiO2 film on the substrate surface. Table 2 shows the physical properties of the deposited SiO2 film.

[0199] (Comparative Examples 2 and 3) In Comparative Examples 2 and 3, the temperature inside the processing vessel 101 (film formation temperature) in the raw material gas supply process and the reaction gas supply process was changed from 50°C to 100°C and 200°C, respectively. Otherwise, the SiO2 film was formed on the substrate in the same manner as in Comparative Example 1. The physical properties of the formed SiO2 films are shown in Table 2.

[0200] (Comparative Example 4) In this comparative example, a SiO2 film was deposited on the substrate surface using the film deposition apparatus 100 used in Comparative Example 1. More specifically, the procedure was as follows.

[0201] (1) Raw material gas supply process In the raw material gas supply process, the temperature (film formation temperature) inside the processing container 101 was changed from 50°C to 80°C, and the pressure inside the processing container 101 was changed from 43.5 torr (1.3 kPa) to 56.3 torr (7.5 kPa). Except for these changes, a mixed gas consisting of TMOS gas and N2 gas was supplied to the processing container 101 in the same manner as in Comparative Example 1.

[0202] (2) Reaction gas supply process H2O gas was used as the reaction gas. N2 gas was supplied as a carrier gas to the reaction gas supply container 103, and a mixed gas of N2 gas and H2O gas was supplied to the processing container 101. The temperature inside the reaction gas supply container 103 when supplying H2O gas was 30°C and the pressure was 460 torr. The flow rate of N2 gas supplied to the reaction gas supply container 103 was 200 sccm. Furthermore, the flow rate of the mixed gas consisting of H2O gas and N2 gas supplied to the processing container 101 was 236 sccm.

[0203] Furthermore, when supplying the mixed gas consisting of H2O gas and N2 gas to the processing container 101, the temperature inside the processing container 101 was maintained at 80°C, and the pressure inside the processing container 101 was set to 4 kPa. In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 101 was set within the range of 25 to 90 torr, and the supply time was set to 60 seconds.

[0204] Next, purging was performed inside the processing container 101. N2 gas was used as the purging gas and supplied into the processing container 101 at a flow rate of 500 sccm. The N2 gas supply time was set to 60 seconds. Furthermore, the pressure inside the processing container 101 was set to 2-3 torr.

[0205] (3) Results The process consisted of two steps: raw material gas supply and reaction gas supply. This was repeated for a total of 80 cycles to deposit an SiO2 film on the substrate surface. Table 2 shows the physical properties of the deposited SiO2 film.

[0206] (Comparative Example 5) In Comparative Example 5, the temperature inside the processing vessel 101 (film formation temperature) in the raw material gas supply process and the reaction gas supply process was changed from 80°C to 300°C. Otherwise, the SiO2 film was formed on the substrate in the same manner as in Comparative Example 4. The physical properties of the formed SiO2 film are shown in Table 2.

[0207] (Comparative Example 6) In this comparative example, a SiO2 film was deposited on the substrate surface using the film deposition apparatus 100 used in Comparative Example 1. More specifically, the procedure was as follows.

[0208] (1) Raw material gas supply process TMOS gas was used as the raw material gas. N2 gas was supplied as a carrier gas to the raw material gas supply container 102, and the mixed gas, which consisted of N2 gas and TMOS gas, was supplied to the processing container 101. The temperature inside the raw material gas supply container 102 when supplying TMOS gas was 30 °C and the pressure was 272 torr. The flow rate of N2 gas supplied to the raw material gas supply container 102 was 100 sccm. Furthermore, the flow rate of the mixed gas consisting of TMOS gas and N2 gas supplied to the processing container 101 was 110 sccm.

[0209] In addition to supplying TMOS gas to the processing container 101, a catalyst gas was also supplied to the processing container 101. NH3 (ammonia) gas was used as the catalyst gas. The temperature of the NH3 gas was set to 23°C, and the flow rate of the NH3 gas supplied to the processing container 101 was set to 400 sccm.

[0210] Furthermore, when supplying a mixed gas consisting of TMOS gas and N2 gas, along with NH3 gas, to the processing container 101 simultaneously, the temperature inside the processing container 101 was maintained at 25°C, and the pressure inside the processing container 101 was set to 42 torr (5.6 kPa). In addition, the supply pressure (film formation pressure) when supplying these mixed gases to the processing container 101 was set within the range of 25 to 90 torr, and the supply time was set to 42 seconds.

[0211] Next, purging was performed inside the processing container 101. N2 gas was used as the purging gas and supplied into the processing container 101 at a flow rate of 200 sccm. The N2 gas supply time was set to 12 seconds. Furthermore, the pressure inside the processing container 101 was set to 2-3 torr.

[0212] (2) Reaction gas supply process H2O gas was used as the reaction gas. N2 gas was supplied as a carrier gas to the reaction gas supply container 103, and a mixed gas of N2 gas and H2O gas was supplied to the processing container 101. The temperature inside the reaction gas supply container 103 when supplying H2O gas was 30°C and the pressure was 42 torr. The flow rate of N2 gas supplied to the reaction gas supply container 103 was 100 sccm. Furthermore, the flow rate of the mixed gas consisting of H2O gas and N2 gas supplied to the processing container 101 was 114 sccm.

[0213] In addition to supplying H2O gas to the processing container 101, a catalyst gas was also supplied to the processing container 101. NH3 (ammonia) gas was used as the catalyst gas. The temperature of the NH3 gas was set to 27°C, and the flow rate of the NH3 gas supplied to the processing container 101 was set to 400 sccm.

[0214] Furthermore, when supplying a mixed gas consisting of H2O gas and N2 gas and NH3 gas to the processing container 101 simultaneously, the temperature inside the processing container 101 was maintained at 30°C, and the pressure inside the processing container 101 was set to 42 torr (5.6 kPa). In addition, the supply pressure (film formation pressure) when supplying these mixed gases to the processing container 101 was set within the range of 25 to 90 torr, and the supply time was set to 42 seconds.

[0215] Next, purging was performed inside the processing container 101. N2 gas was used as the purging gas and supplied into the processing container 101 at a flow rate of 200 sccm. The N2 gas supply time was set to 12 seconds. Furthermore, the pressure inside the processing container 101 was set to 2-3 torr. (3) Results The process consisted of two steps: raw material gas supply and reaction gas supply. This was repeated for a total of 80 cycles to deposit an SiO2 film on the substrate surface. Table 2 shows the physical properties of the deposited SiO2 film.

[0216] (Result 2) As shown in Figure 12, in the film deposition methods of Examples 9 to 11, even when the raw material gas supply step (B) and reaction gas supply step (C) were performed at low temperatures of 175°C or below, it was possible to deposit SiO2 films with high film density and good film quality on the substrate. In particular, in Examples 9 and 10, which were performed at temperatures below 100°C, high film deposition rates of 0.08 nm / cycle or higher were obtained. On the other hand, in the film deposition methods of Comparative Examples 1 to 6, the film deposition rate was 0.01 nm / cycle or lower at all temperatures. Figure 12 is a graph showing the relationship between the temperature inside the processing vessel and the film deposition rate of the SiO2 film in various film deposition methods.

[0217] [Table 2]

[0218] (Examples 12-14) In Examples 12 to 14, the pressure inside the processing container 11 in the raw material gas supply process (B) was changed from 14.3 torr (1.9 kPa) to 15.0 torr (2.0 kPa). The number of cycles was also changed to 80, 160, and 220 cycles, respectively. Other than these changes, the SiO2 film was deposited on the substrate in the same manner as in Example 3. Table 3 shows the physical properties of the SiO2 films obtained in each example.

[0219] (Result 3) In Examples 12-14, the relationship between the number of cycles and the film thickness was investigated. The results showed that even when 3DMAS gas was used as the raw material gas, the number of cycles and the film thickness of the SiO2 film were proportional, as shown in Figure 13, confirming that an ideal film could be formed. Figure 13 is a graph showing the correlation between the number of cycles and the film thickness of the SiO2 film when 3DMAS gas is used as the raw material gas.

[0220] [Table 3]

[0221] (Example 15) In this example, an SiO2 film was deposited on the substrate surface using the film deposition apparatus 1 shown in Figure 1. More specifically, the procedure was as follows.

[0222] (1) Raw material gas supply process (B) 3DMAS gas was supplied to the processing container 11 as a raw material gas. The temperature inside the raw material gas supply container when supplying the 3DMAS gas was 27°C and the pressure was 685 torr. The flow rate of N2 gas supplied to the raw material gas supply container was 100 sccm. Furthermore, the flow rate of the mixed gas consisting of 3DMAS gas and N2 gas supplied to the processing container 11 was 101 sccm.

[0223] Furthermore, when supplying the mixed gas consisting of 3DMAS gas and N2 gas to the processing container 11, the temperature inside the processing container 11 was maintained at 80°C, and the pressure inside the processing container 11 was set to 1 torr (0.17 kPa). In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 11 was within the range of 10 to 90 torr, and the supply time was set to 12 seconds.

[0224] Furthermore, the processing container 11 was purged. N2 gas was used as the purge gas and supplied into the processing container 11 at a flow rate of 500 sccm. The N2 gas supply time was set to 60 seconds. In addition, the pressure inside the processing container 11 was set to 2-3 torr.

[0225] (2) Reaction gas supply process (C) The reaction gas supply step (C) was carried out in the same manner as in Example 1. Therefore, a detailed explanation thereof is omitted.

[0226] (3) Results The process consisted of two steps: the raw material gas supply process (B) and the reaction gas supply process (C). A total of 160 cycles were performed to deposit an SiO2 film on the substrate surface. Table 4 shows the physical properties of the deposited SiO2 film.

[0227] (Examples 16 and 17) In Examples 16 and 17, the temperature inside the processing vessel 11 (film formation temperature) in the raw material gas supply process (B) and the reaction gas supply process (C) was changed from 80°C to 125°C and 175°C, respectively. Otherwise, the SiO2 film was formed on the substrate in the same manner as in Example 15. The physical properties of the SiO2 films obtained in each example are shown in Table 4.

[0228] (Comparative Example 7) In this comparative example, an SiO2 film was deposited on the substrate surface using the film deposition apparatus 100 used in Comparative Example 1. More specifically, the procedure was as follows.

[0229] (1) Raw material gas supply process 3DMAS gas was supplied to the processing container 101 as a raw material gas. The temperature inside the raw material gas supply container 102 when supplying the 3DMAS gas was 27°C and the pressure was 760 torr. The flow rate of N2 gas supplied to the raw material gas supply container 102 was 100 sccm. Furthermore, the flow rate of the mixed gas consisting of 3DMAS gas and N2 gas supplied to the processing container 101 was 500 sccm.

[0230] Furthermore, when supplying the mixed gas consisting of 3DMAS gas and N2 gas to the processing container 101, the temperature inside the processing container 101 was maintained at 50°C, and the pressure inside the processing container 101 was set to 3.8 torr (0.5 kPa). In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 101 was set within the range of 25 to 90 torr, and the supply time was set to 12 seconds.

[0231] Furthermore, purging was performed inside the processing container 101. N2 gas was used as the purging gas and supplied into the processing container 101 at a supply flow rate of 500 sccm. The N2 gas supply time was set to 12 seconds. In addition, the pressure inside the processing container 101 was set to 3.4 torr.

[0232] (2) Reaction gas supply process Ozone gas was used as the reaction gas and supplied to the processing vessel 101. The temperature inside the reaction gas supply vessel 103 when supplying ozone gas was set to 27°C. Also, the supply flow rate of O2 gas to the reaction gas supply vessel 103 was set to 200 sccm. Furthermore, the supply flow rate of the mixed gas composed of ozone gas and N2 gas to the processing vessel 101 was set to 200 sccm.

[0233] Also, when supplying the mixed gas composed of ozone gas and O2 gas to the processing vessel 101, the temperature inside the processing vessel 101 was maintained at 50°C, and the pressure inside the processing vessel 101 was set to 3.8 torr (0.5 kPa). Furthermore, the supply pressure (film formation pressure) when supplying the mixed gas to the processing vessel 101 was within the range of 25 - 90 torr, and the supply time was set to 12 seconds.

[0234] Subsequently, purging was performed inside the processing vessel 101. N2 gas was used as the purge gas and supplied into the processing vessel 101 at a supply flow rate of 500 sccm. Also, the supply time of N2 gas was set to 12 seconds. Furthermore, the pressure inside the processing vessel 101 was set to 2 - 3 torr.

[0235] (3) Results Two steps, namely the raw material gas supply and the reaction gas supply steps, were defined as one cycle, and a total of 160 cycles were performed to form a SiO2 film on the substrate surface. The physical property values of the formed SiO2 film are shown in Table 4.

[0236] (Comparative Examples 8 - 14) In Comparative Examples 8 - 14, the temperature (film formation temperature) and pressure inside the processing vessel 101 in the raw material gas supply step and the reaction gas supply step were changed to the values shown in Table 4, respectively. Also, the number of cycles was changed to the value shown in Table 4. Otherwise, a SiO2 film was formed on the substrate in the same manner as in Comparative Example 7. The physical property values of the SiO2 films obtained in each comparative example are shown in Table 4.

[0237] (Comparative Example 15) In this comparative example, a SiO2 film was formed on the substrate surface using the film formation apparatus 100 used in Comparative Example 1. More specifically, it was performed as follows.

[0238] (1) Raw material gas supply process The temperature (film formation temperature) inside the processing container 101 was changed from 50°C to 80°C, and the pressure was changed from 3.8 torr (0.5 kPa) to 15 torr (2.0 kPa). Otherwise, the mixed gas consisting of 3DMAS gas and N2 gas was supplied to the processing container 101 in the same manner as in Comparative Example 7.

[0239] (2) Reaction gas supply process H2O gas was used as the reaction gas. N2 gas was supplied as a carrier gas to the reaction gas supply container 103, and a mixed gas of N2 gas and H2O gas was supplied to the processing container 101. The temperature inside the reaction gas supply container 103 when supplying H2O gas was 75°C and the pressure was 460 torr. The flow rate of N2 gas supplied to the reaction gas supply container was 200 sccm. Furthermore, the flow rate of the mixed gas consisting of H2O gas and N2 gas supplied to the processing container 101 was 460 sccm.

[0240] Furthermore, when supplying the mixed gas consisting of H2O gas and N2 gas to the processing container 101, the temperature inside the processing container 101 was maintained at 80°C, and the pressure inside the processing container 101 was set to 36 torr (4.8 kPa). In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 101 was set within the range of 25 to 90 torr, and the supply time was set to 12 seconds.

[0241] Next, the processing container 101 was purged. N2 gas was used as the purge gas and supplied to the processing container 101 at a flow rate of 500 sccm. The N2 gas supply time was set to 12 seconds. Furthermore, the pressure inside the processing container 101 was set to 2-3 torr. (3) Results The process consisted of two steps: raw material gas supply and reaction gas supply. This was repeated for a total of 160 cycles to deposit an SiO2 film on the substrate surface. Table 4 shows the physical properties of the deposited SiO2 film.

[0242] (Comparative Example 16) In Comparative Example 16, the temperature inside the processing vessel 101 (film formation temperature) in the raw material gas supply process and the reaction gas supply process was changed from 80°C to 300°C. Otherwise, the SiO2 film was formed on the substrate in the same manner as in Comparative Example 15. The physical properties of the formed SiO2 film are shown in Table 4.

[0243] (Comparative Example 17) In this comparative example, an SiO2 film was deposited on the substrate surface using the film deposition apparatus 100 used in Comparative Example 1. More specifically, the procedure was as follows.

[0244] (1) Raw material gas supply process The temperature (film formation temperature) inside the processing container 101 was changed from 50°C to 30°C, and the pressure was changed from 3.8 torr (0.5 kPa) to 40.5 torr (5.4 kPa). Otherwise, the same procedure as in Comparative Example 7 was followed, and a mixed gas consisting of 3DMAS gas and N2 gas was supplied to the processing container 101.

[0245] (2) Reaction gas supply process H2O gas was used as the reaction gas. A reaction gas supply container with an internal volume of 200 ml was used as the reaction gas supply unit for supplying H2O gas. N2 gas was supplied to the reaction gas supply container as a carrier gas, thereby supplying a mixed gas containing H2O gas to the processing container 101. The temperature inside the reaction gas supply container when supplying H2O gas was 27°C and the pressure was 760 torr. The flow rate of N2 gas supplied to the reaction gas supply container was 100 sccm. Furthermore, the flow rate of the mixed gas consisting of H2O gas and N2 gas supplied to the processing container 101 was 500 sccm.

[0246] In addition to supplying H2O gas to the processing container 101, a catalyst gas was also supplied to the processing container 101. NH3 (ammonia) gas was used as the catalyst gas. The temperature of the NH3 gas was set to 27°C, and the flow rate of the NH3 gas supplied to the processing container 101 was set to 400 sccm.

[0247] When supplying a mixed gas consisting of H2O gas and N2 gas, and a mixed gas consisting of NH3 gas and N2 gas, to the processing container 101 simultaneously, the temperature inside the processing container 101 was maintained at 30°C, and the pressure inside the processing container 101 was set to 40.5 torr (5.4 kPa). Furthermore, the supply pressure (film formation pressure) when supplying these mixed gases to the processing container 101 was set within the range of 25 to 90 torr, and the supply time was set to 42 seconds.

[0248] Furthermore, purging was performed inside the processing container 101. NH3 gas was used as the purging gas and supplied to the processing container 101 at a flow rate of 400 sccm. The NH3 gas supply time was 12 seconds. Additionally, the pressure inside the processing container 101 was set to 30.5 torr (4.1 kPa).

[0249] (3) Results The process consisted of two steps: raw material gas supply and reaction gas supply. This was repeated for a total of 200 cycles to deposit an SiO2 film on the substrate surface. The physical properties of the deposited SiO2 film are shown in Table 4.

[0250] (Comparative Example 18) In Comparative Example 18, the pressure inside the processing vessel 101 during the raw material gas supply process and the reaction gas supply process was changed from 15 torr (2.0 kPa) to 40.5 torr (5.4 kPa). The number of cycles was also changed from 160 to 40. Other than these changes, the SiO2 film was deposited on the substrate in the same manner as in Comparative Example 15. The physical properties of the deposited SiO2 film are shown in Table 4.

[0251] (Result 4) As shown in Fig. 14, it was confirmed that in the film formation methods of Examples 15 to 17, even when the raw material gas supply step (B) and the reaction gas supply step (C) were carried out at a low temperature of 175°C or lower, a SiO2 film with good film quality could be formed on the substrate. In particular, in Example 15 where the temperature was 100°C or lower, a high film formation rate of 0.10 nm / cycle or more was obtained. On the other hand, in the film formation methods of Comparative Examples 7 to 18, the film formation rate at a low temperature of 200°C or lower was 0.03 nm / cycle or less, and it was confirmed that they were not suitable for film formation in the low temperature region. Note that Fig. 14 is a graph showing the relationship between the temperature in the processing vessel and the film formation rate of the SiO2 film in various film formation methods.

[0252]

Table 4

[0253] (Example 18) In this example, a SiO2 film was formed on the surface of the substrate using the film formation apparatus 1 used in Example 1. More specifically, it was carried out as follows.

[0254] (1) Raw material gas supply step (B) In the raw material gas supply step (B), 1,1,3,3-tetramethylguanidine (TMG) gas was used instead of pyrrolidine gas as the first catalyst gas. Also, when simultaneously supplying a mixed gas composed of TMOS gas and N2 gas and a mixed gas composed of TMG gas and N2 gas into the processing vessel 11, the temperature in the processing vessel 11 was 60°C, the pressure in the processing vessel 11 was changed to 90 torr (12 kPa), and the supply time was changed to 30 minutes. Other than that, the raw material gas supply step (B) was carried out in the same manner as in Example 1.

[0255] (2) Reaction gas supply step (C) In reaction gas supply step (C), TMG gas was used as the second catalyst gas instead of pyrrolidine gas. Furthermore, when simultaneously supplying a mixed gas consisting of H2O gas and N2 gas, and a mixed gas consisting of TMG gas and N2 gas, to the processing vessel 11, the temperature inside the processing vessel 11 was changed to 60°C, the pressure inside the processing vessel 11 to 90 torr (12 kPa), and the supply time to 30 minutes. Other than these changes, reaction gas supply step (C) was performed in the same manner as in Example 1.

[0256] (3) Results The raw material gas supply process (B) and the reaction gas supply process (C) were carried out to deposit an SiO2 film on the substrate surface. The film density of the deposited SiO2 film was 1.7 g / cm³. 3 The film thickness was 6.9 nm and the surface roughness was 0.8 nm. The deposition rate of the SiO2 film was 0.23 nm / cycle.

[0257] (Examples 19-22) In Examples 19 to 22, the temperature inside the processing vessel 11 during the raw material gas supply process (B) and the reaction gas supply process (C) was changed to 80°C in Example 19, 100°C in Example 20, 140°C in Example 21, and 175°C in Example 22, respectively. Otherwise, the SiO2 film was deposited on the substrate in the same manner as in Example 18. The physical properties of the deposited SiO2 film are shown in Table 5.

[0258] (Examples 23-28) In Examples 23 to 28, pyrrolidine gas was used instead of TMG gas as the first and second catalyst gases. The pressure inside the processing vessel 11 during the raw material gas supply process (B) and the reaction gas supply process (C) was changed to 60 torr (8 kPa). The temperature inside the processing vessel 11 during the raw material gas supply process (B) and the reaction gas supply process (C) was changed to 80°C in Example 24, 100°C in Example 25, 120°C in Example 26, 200°C in Example 27, and 250°C in Example 28, respectively. Except for these changes, the SiO2 film was deposited on the substrate in the same manner as in Example 18. The physical properties of the deposited SiO2 film are shown in Table 5.

[0259] (Comparative Examples 19-22) In Comparative Examples 19 to 22, pyridine gas was used instead of TMG gas as the first and second catalyst gases. Furthermore, the temperature inside the processing vessel 101 during the raw material gas supply process (B) and the reaction gas supply process (C) was changed to 80°C for Comparative Example 19, 100°C for Comparative Example 20, 120°C for Comparative Example 21, and 150°C for Comparative Example 22, respectively. Except for these changes, the SiO2 film was deposited on the substrate in the same manner as in Example 18. The physical properties of the deposited SiO2 films are shown in Table 5.

[0260] (Result 5) As shown in Figure 15, in Examples 18-21 and 23-26, where non-aromatic TMG gas and pyrrolidine gas were used as the first and second catalyst gases, it was confirmed that the deposition rate of the SiO2 film could be increased even in the low-temperature range of approximately 140°C or below, and that sufficient film deposition was possible. Furthermore, in Examples 22, 27, and 28, SiO2 films with good film quality were obtained. On the other hand, when aromatic pyridine gas was used, it was confirmed that the deposition rate of the SiO2 film was significantly low even in the low-temperature range, and the deposition efficiency was not good. Figure 15 is a graph showing the relationship between the temperature inside the processing vessel and the deposition rate of the SiO2 film in various film deposition methods.

[0261] [Table 5]

[0262] (Examples 29-32) In Examples 29 to 32, the pressure inside the processing vessel 11 during the raw material gas supply process (B) and the reaction gas supply process (C) was changed to 30 torr (4 kPa) in Examples 29 and 30, and to 202.5 torr (27 kPa) in Example 32, respectively. The temperature inside the processing vessel 11 during the raw material gas supply process (B) and the reaction gas supply process (C) was also changed to 80°C. Furthermore, the supply time for simultaneously supplying the mixed gas consisting of TMOS gas and N2 gas, the mixed gas consisting of reaction gas H2O and N2 gas, and the mixed gas consisting of TMG gas and N2 gas to the processing vessel 11 was changed to 30 minutes in Examples 29 and 31, 60 minutes in Example 30, and 15 minutes in Example 32. Except for these changes, the SiO2 film was deposited on the substrate in the same manner as in Example 18. The physical properties of the deposited SiO2 film are shown in Table 6.

[0263] (Examples 33-36) In Examples 33 to 36, pyrrolidine gas was used instead of TMG gas as the first and second catalyst gases. Furthermore, the pressure inside the processing vessel 11 during the raw material gas supply process (B) and the reaction gas supply process (C) was changed to 0.1 kPa in Example 33, 8 kPa in Example 35, and 16 kPa in Example 36, respectively. Except for these changes, the SiO2 film was deposited on the substrate in the same manner as in Example 29. The physical properties of the deposited SiO2 film are shown in Table 6.

[0264] (Comparative Examples 23-27) In Comparative Examples 23 to 27, pyridine gas was used instead of TMG gas as the first and second catalyst gases. Furthermore, the pressure inside the processing vessel 101 during the raw material gas supply process (B) and the reaction gas supply process (C) was changed to 1.3 kPa in Comparative Example 23, 4.0 kPa in Comparative Example 24, 8.0 kPa in Comparative Example 25, 12.0 kPa in Comparative Example 26, and 26.7 kPa in Comparative Example 27, respectively. Except for these changes, the SiO2 film was deposited on the substrate in the same manner as in Example 29. The physical properties of the deposited SiO2 films are shown in Table 6.

[0265] (Comparative Example 28) In Comparative Example 28, NH3 gas was used instead of TMG gas as the first and second catalyst gases. Furthermore, the pressure inside the processing vessel 101 during the raw material gas supply process (B) and the reaction gas supply process (C) was changed to 4.0 kPa. Except for these changes, the SiO2 film was deposited on the substrate in the same manner as in Example 29. The physical properties of the deposited SiO2 film are shown in Table 6.

[0266] (Result 6) As shown in Figure 16, in Examples 29-32 and 34-36, where non-aromatic TMG gas (acid dissociation constant pKa at 25°C: 13.6) and pyrrolidine gas (acid dissociation constant pKa at 25°C: 11.3) were used as the first and second catalyst gases, a good SiO2 film deposition rate was observed at pressures of 4.0 kPa or higher. In particular, TMG gas, with its larger pKa value, showed a higher deposition rate than pyrrolidine gas, confirming that using a catalyst gas with a large pKa value as a non-aromatic amine gas can improve film deposition efficiency. On the other hand, pyridine gas, which is aromatic (acid dissociation constant pKa at 25°C: 5.25), showed a significantly lower deposition rate, and NH3 gas could not deposit an SiO2 film. Figure 16 is a graph showing the relationship between the pressure inside the processing vessel and the SiO2 film deposition rate in various film deposition methods.

[0267] [Table 6]

[0268] (Example 37) In this embodiment, a SiO2 film was deposited on the substrate surface using the film deposition apparatus 1 shown in Figure 1, based on the SiO2 film deposition sequence shown in Figure 17. Figure 17 is a diagram showing the SiO2 film deposition sequence in this embodiment 18. Each step in this embodiment will be described in detail below.

[0269] (1) Raw material gas supply process (B) Si(NMe2)(OMe)3 gas was used as the raw material gas. N2 gas was supplied as a carrier gas to the raw material gas supply container, and a mixed gas containing Si(NMe2)(OMe)3 gas was supplied to the processing container 11. The temperature inside the raw material gas supply container when supplying Si(NMe2)(OMe)3 gas was 27°C and the pressure was 385 torr. The flow rate of N2 gas supplied to the raw material gas supply container was 100 sccm. Furthermore, the flow rate of the mixed gas consisting of Si(NMe2)(OMe)3 gas and N2 gas supplied to the processing container 11 was 102 sccm.

[0270] Furthermore, when supplying the mixed gas consisting of Si(NMe2)(OMe)3 gas and N2 gas to the processing container 11, the temperature inside the processing container 11 was maintained at 80°C, and the pressure inside the processing container 11 was set to 1-2 torr (0.13kPa-0.27kPa). In addition, the supply pressure (film formation pressure) when supplying the mixed gas to the processing container 11 was set to within the range of 45-50 torr, and the supply time was set to 60 seconds.

[0271] Next, the processing container 11 was purged. N2 gas was used as the first purge gas and supplied into the processing container 11 at a flow rate of 500 sccm. The N2 gas supply time was set to 60 seconds. Furthermore, the pressure inside the processing container 11 was set to 2-3 torr.

[0272] (2) Reaction gas supply process (C) In the reaction gas supply step (C), the pressure inside the processing container 11 was set to 40-50 torr (5.33 kPa-6.67 kPa), and the supply pressure (film deposition pressure) when simultaneously supplying a mixed gas consisting of H2O gas and N2 gas and a mixed gas consisting of pyrrolidine gas and N2 gas to the processing container 11 was set to within the range of 45-50 torr, with a supply time (pulse time) of 12 seconds. Furthermore, when purging the processing container 11 using N2 gas, which is the second purge gas, the supply flow rate of N2 gas was set to 500 sccm. Except for these, the SiO2 film was deposited on the substrate in the same manner as in the reaction gas supply step (C) of Example 1.

[0273] (3) Results The process consisted of two steps: the raw material gas supply process (B) and the reaction gas supply process (C). A total of 80 cycles were performed to deposit an SiO2 film on the substrate surface. Table 7 shows the physical properties of the deposited SiO2 film.

[0274] (Examples 38 and 39) In Examples 38 and 39, during the reaction gas supply step (C), the supply time (pulse time) for simultaneously supplying a mixed gas consisting of H2O gas and N2 gas, and a mixed gas consisting of pyrrolidine gas and N2 gas, to the processing container 11 was set to 30 seconds and 60 seconds, respectively. Otherwise, the SiO2 film was formed on the substrate in the same manner as in Example 37.

[0275] Furthermore, the raw material gas supply process (B) and the reaction gas supply process (C) were considered as one cycle, and a total of 80 cycles were performed to deposit SiO2 films on the substrate surface. The physical properties of the SiO2 films obtained in each example are shown in Table 7.

[0276] (Examples 40-42) In Examples 40 to 42, 1-methylpiperidine gas (manufactured by Sigma-Aldrich, 99% purity) was used as the second catalyst gas in the reaction gas supply step (C). Furthermore, the supply time (pulse time) for simultaneously supplying the mixed gas consisting of H2O and N2, and the mixed gas consisting of 1-methylpiperidine and N2 to the processing container 11 was set to 30 seconds, 60 seconds, and 90 seconds, respectively. Except for these differences, the SiO2 film was deposited on the substrate in the same manner as in Example 37. The physical properties of the SiO2 films obtained in each example are shown in Table 7.

[0277] (Examples 43-45) In Examples 43 to 45, tetramethylguanidine gas (manufactured by Sigma-Aldrich, 99% purity) was used as the second catalyst gas in the reaction gas supply step (C). Furthermore, the supply times (pulse times) for simultaneously supplying the mixed gas consisting of H2O and N2, and the mixed gas consisting of tetramethylguanidine and N2, to the processing container 11 were set to 6 seconds, 12 seconds, and 30 seconds, respectively. Except for these differences, the SiO2 film was deposited on the substrate in the same manner as in Example 37. The physical properties of the SiO2 films obtained in each example are shown in Table 7.

[0278] (Result 7) As shown in Figure 18, in Examples 37-39, where pyrrolidine gas with a pKa of 11.3 was used as the second catalyst gas supplied along with the reaction gas, the deposition rate of the SiO2 film increased to 0.13 nm / cycle. Similarly, in Examples 43-45, where 1,1,3,3-tetramethylguanidine gas with a pKa of 13.7 was used as the second catalyst gas, the deposition rate of the SiO2 film was 0.13-0.14 nm / cycle. On the other hand, in Examples 40-42, where 1-methylpiperidine gas with a pKa of 10.1 was used as the second catalyst gas, the deposition rate of the SiO2 film was 0.04-0.08 nm / cycle. These results confirm that using a catalyst with a larger pKa value as the second catalyst gas makes it possible to increase the deposition rate and improve the deposition efficiency. Figure 18 is a graph showing the relationship between the reaction gas supply time (pulse time) and the deposition rate of the SiO2 film.

[0279] [Table 7] [Explanation of Symbols]

[0280] 1…Film deposition apparatus, 11…Processing container, 12…Raw material gas supply unit, 13…First catalyst gas supply unit, 14…Second catalyst gas supply unit, 15…Reaction gas supply unit, 17A~17D…Carrier gas supply path, 21…Raw material gas supply path, 22…First catalyst gas supply path, 23…Second catalyst gas supply path, 24…Reaction gas supply path, 25…Purge gas supply path, 26…Discharge path, 27…APC valve

Claims

1. A method for forming a film on an object to be processed, Step (A) involves placing the object to be processed inside the processing container, A raw material gas supply step (B) involves supplying a raw material gas into the processing container, adsorbing the raw material gas onto the object to be processed, and then purging the inside of the processing container with a first purge gas. The process includes a reaction gas supply step (C) in which a reaction gas is supplied into the processing container after the raw material gas supply step (B) to oxidize the raw material gas adsorbed on the object to be processed, and then the processing container is purged with a second purge gas. The supply of the raw material gas in the raw material gas supply process (B) is as follows: Step (b1): Supplying the first catalyst gas into the processing container together with the raw material gas; (b2) A step in which the first catalyst gas is supplied into the processing container, then purged with a third purge gas, and then the raw material gas is supplied; or, The process is one of the steps (b3) in which only the aforementioned raw material gas is supplied into the processing container. The supply of the reaction gas in the reaction gas supply step (C) is as follows: Step (c1): Supplying a second catalyst gas into the processing vessel together with the reaction gas; Step (c2): Before supplying the reaction gas, supply a second catalyst gas into the processing vessel and then purge it with a fourth purge gas; or, The process is one of the steps (c3) in which only the reaction gas is supplied into the processing container. When the raw material gas supply step (B) is step (b3), this does not include the case where the reaction gas supply step (C) is step (c3). The source gas is Si(OMe) 4 , Si(NMe 2 )(OMe) 3 , Si(NMe 2 ) 2 (OMe) 2 , Si(NMe 2 ) 3 (OMe), Si(NMe 2 )(OEt) 3 , Si(NMe 2 ) 2 (OEt) 2 , Si(NMe 2 ) 3 (OEt), Si(NEt 2 )(OMe) 3 , Si(NEt 2 )(OE t ) 3 , SiH(NMe 2 ) 3 , SiH 2 (NEt 2 ) 2 , SiH 2 (NHt-Bu) 2 , Si(pyrrolidine) (OMe) 3 , Si(pyrrolidine) It is at least one gas selected from the group consisting of 2 (OMe)2 and Si(pyrrolidine)3 (OMe), The first catalyst gas and the second catalyst gas are the same or different non-aromatic amine gases. The non-aromatic amine gas is at least one selected from the group consisting of pyrrolidine gas, piperidine gas, 1,1,3,3-tetramethylguanidine gas, 1-methylpiperidine gas, and derivatives thereof. A film formation method in which the reaction gas is an oxidizing agent gas consisting of at least one gas selected from the group consisting of water, hydrogen peroxide solution, formic acid, and aldehydes.

2. The method for forming a film according to claim 1, wherein the acid dissociation constant pKa of the non-aromatic amine gas at 25°C is in the range of 9.5 or more and 14 or less.

3. The supply of the raw material gas and / or the first catalyst gas in the raw material gas supply process is carried out so that the pressure inside the processing container is within the range of 13 Pa or more and 40,000 Pa or less. The film-forming method according to claim 1 or 2, wherein the supply of the reaction gas and / or second catalyst gas in the reaction gas supply step is carried out such that the pressure in the processing vessel is within the range of 13 Pa or more and 40,000 Pa or less.

4. The film-forming method according to any one of claims 1 to 3, wherein the temperature inside the processing vessel in the raw material gas supply step and / or the reaction gas supply step is 200°C or less.

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