Cleaning method and film deposition device

Abstract

To clean parts in a film deposition device while restraining damage of the parts.SOLUTION: A film deposition device comprises: a raw material gas supply source for film deposition; a reaction gas supply source for film deposition; a first cleaning gas supply source; a second cleaning gas supply source; a liftable stage which is provided in a treatment container and on which a substrate is mounted; and a cap member provided in the treatment container, and opposed to the stage to form a treatment space. A method for cleaning the film deposition device includes the steps of: forming a film on the substrate by supplying raw material gas for film deposition from the raw material gas supply source for film deposition and reaction gas for film deposition from the reaction gas supply source for film deposition to the treatment space; and cleaning inside of the treatment space by delivering the substrate after the film is formed, and alternately supplying first cleaning gas from the first cleaning gas supply source and second cleaning gas from the second cleaning gas supply source.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a cleaning method and a film forming apparatus. [Background technology]

[0002] For example, Patent Document 1 proposes performing atomic layer etching (ALE) on a substrate to etch a target film at a 1 Å level without damaging the underlying layer on the substrate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2019-519918 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique that can clean parts inside a film forming apparatus while suppressing damage to the parts. [Means for solving the problem]

[0005] According to one aspect of the present disclosure, there is provided a cleaning method for a film formation apparatus including a film formation raw material gas supply source, a film formation reactive gas supply source, a first cleaning gas supply source, a second cleaning gas supply source, a stage provided in a processing vessel, on which a substrate is placed and which can be raised and lowered, and a cap member provided in the processing vessel facing the stage to form a processing space, the cleaning method comprising: forming a film on the substrate by supplying a film formation raw material gas from the film formation raw material gas supply source and a film formation reactive gas from the film formation reactive gas supply source into the processing space; and removing the substrate after the film has been formed, and cleaning the inside of the processing space by alternately supplying a first cleaning gas from the first cleaning gas supply source and a second cleaning gas from the second cleaning gas supply source into the processing space. Effect of the Invention

[0006] According to one aspect, parts inside a film forming apparatus can be cleaned while suppressing damage thereto. [Brief description of the drawings]

[0007] [Figure 1] FIG. 2 is a diagram showing an example of a cycle cleaning method according to an embodiment. [Diagram 2] FIG. 4 is a diagram showing an example of a chemical reaction between first and second cleaning gases according to an embodiment. [Diagram 3] FIG. 4 shows an example of a combination of first and second cleaning gases according to an embodiment. [Figure 4] FIG. 4 shows an example of a combination of first and second cleaning gases according to an embodiment. [Diagram 5] FIG. 4 shows an example of a combination of first and second cleaning gases according to an embodiment. [Figure 6] FIG. 4 shows an example of a combination of first and second cleaning gases according to an embodiment. [Figure 7] FIG. 1 is a diagram showing an example of the configuration of a film forming apparatus according to an embodiment. [Figure 8] 4 is a flowchart showing an example of a processing method in a film forming apparatus according to an embodiment. [Figure 9] 9 is a flowchart showing an example of the film forming process of FIG. 8. [Figure 10] 9 is a flowchart showing an example of the cleaning process in FIG. 8. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, an embodiment of the present disclosure will be described with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals, and duplicated descriptions may be omitted.

[0009] [Cleaning of high-k materials] In a deposition system, after deposition processing, existing cleaning gases such as ClF3 are supplied into the chamber to clean the inside of the chamber in order to remove films and reaction products that have adhered to the inside of the chamber. However, when depositing a high-k film in particular, the film cannot be removed unless the temperature of the inner walls of the chamber and the stage temperature are raised to a high temperature of about 500 to 700°C. This causes a problem that the heat resistance temperature of the chamber and parts inside the chamber may be exceeded during cleaning. It is difficult to dry clean high-k materials with existing cleaning gases such as ClF3, especially in a single-wafer system.

[0010] For this reason, when forming a film of high-k material in a single-wafer equipment, it is possible to install a liner that covers the inside of the chamber in advance and replace the liner when particles are generated. However, the liner must be replaced every time particles adhere, and there is a large time loss when opening the chamber to the atmosphere and replacing the liner. In addition, even if a liner is installed, the film formation gas is likely to circulate in the film formation equipment, so film formation occurs in places where the liner is not installed, so simply installing the liner is insufficient in terms of productivity and cleaning performance. In addition, the more particles adhere to the liner, the shorter the timing for replacing the liner becomes, and productivity decreases.

[0011] In recent years, ALE has been attracting attention. This method alternates between supplying source gas and reactive gas to a logic device on a substrate, and performs etching of about 1 Å in one cycle, for example, etching an extremely thin oxide film or high-k film on the substrate.

[0012] [How to clean] In this embodiment, a cleaning method is provided for cleaning high-k films and the like adhering to the inside of a processing vessel by alternately supplying two types of cleaning gases. A method for ALE-based cleaning of the inside of a processing vessel of a film formation apparatus is provided (hereinafter, referred to as cycle cleaning) by alternately supplying a first cleaning gas and a second cleaning gas after forming a high-k film or a metal film. This makes it possible to clean the inside of the processing vessel while suppressing damage to parts inside the processing vessel.

[0013] High-k materials include alumina (Al2O3), zirconium oxide (ZrO2), hafnium oxide (HfO2), etc. Generally, when these materials adhere to the inside of a processing vessel of a film forming device, they cannot be removed with existing cleaning gases such as ClF3.

[0014] On the other hand, with a desired combination of the first cleaning gas and the second cleaning gas, the inside of the processing vessel can be cleaned by cycle cleaning in which the first cleaning gas and the second cleaning gas are alternately supplied.

[0015] Figure 1 shows an example of cycle cleaning. Figure 1(a) shows an alumina film 101 as an example of a high-k material adhering to a film forming apparatus. When an alumina film is formed in a film forming apparatus, the alumina film and reaction products also adhere to the inner wall of the processing vessel and the parts inside the processing vessel.

[0016] In this state, when HF gas (hydrogen fluoride gas) is supplied as a first cleaning gas into the processing vessel, the surface of the target film 101 is modified to AlF3 to form a modified layer 102, as shown in FIG. 1(b). The chemical reaction at this time is Al2O3+6HF→2AlF3+3H2O. As a result, the surface of the target film 101 becomes a modified layer 102 of AlF3, and H2O volatilizes.

[0017] Next, when TMA (trimethylaluminum: Al(CH3)3) gas shown in FIG. 2(a) is supplied as a second cleaning gas, the modified layer 102 of AlF3 is etched. At this time, as shown in FIG. 2(b), the TMA gas extracts one F from the AlF3 of the modified layer 102, and becomes AlF(CH3)2 as shown in FIG. 2(c). The AlF(CH3)2 volatilizes as shown in FIG. 1(d). Also, as shown in FIG. 2(c), the remaining CH3 of the TMA gas is bonded to the modified layer 102 (AlF2) after the one F has been extracted, and becomes AlF2(CH3). The AlF2(CH3) volatilizes as shown in FIG. 1(d). As a result, the AlF3 of the modified layer 102 is etched (cleaned).

[0018] When HF gas (hydrogen fluoride gas) is supplied as a first cleaning gas to a target film 101 made of zirconium oxide, another high-k material, a modified layer 102 is formed in which the surface of the target film 101 is modified to ZrF4.

[0019] When DMAC (dimethylaluminum chloride: AlCl(CH3)2) gas shown in FIG. 2(d) is supplied as the second cleaning gas, the modified layer 102 of ZrF4 is etched. At this time, as shown in FIG. 2(e), the DMAC gas extracts one F from the ZrF4 of the modified layer 102, and becomes AlF(CH3)2 shown in FIG. 2(f), which volatilizes. The remaining Cl in the DMAC gas bonds with the modified layer 102 (ZrF3) after the one F has been extracted, and becomes ZrF3Cl, which volatilizes. As a result, the ZrF4 of the modified layer 102 is etched (cleaned).

[0020] The amount of etching Δ per time of the surface layer of the target film 101 shown in FIG. 1(d) is one layer at the atomic layer level, that is, about 1 Å. In such ALE-like cycle cleaning, etching can be performed by controlling the inside of the processing vessel of the film formation apparatus to about 200°C to 250°C. Therefore, there is an advantage that the inside of the processing vessel can be cleaned not only in a batch-type film formation apparatus but also in a single-wafer type film formation apparatus.

[0021] 1(a)-(d) are repeated a preset number of cycles by alternately supplying HF gas and TMA gas to etch a film attached to a processing vessel or the like to a predetermined thickness. This executes cycle cleaning, etching a film to a thickness corresponding to the number of cycles repeated, and cleaning the inside of the processing vessel. Thus, in the cycle cleaning of this embodiment, the ALE technology is used not for etching on a substrate, but for cleaning a high-k film or a metal film attached to the inside of a processing vessel of a film forming apparatus.

[0022] [Cleaning gas combination] The combination of the first cleaning gas and the second cleaning gas used to clean the film forming apparatus varies depending on the type of film (film to be cleaned) formed on a substrate in the film forming apparatus.

[0023] When forming an oxide film of alumina, hafnium oxide, zirconium oxide, or IGZO as an example of a high-k film on a substrate, the first cleaning gas is a gas containing fluorine.

[0024] For example, when an alumina film is formed on a substrate, the target film for cleaning the film forming apparatus is the alumina film, and an example of a combination of the first cleaning gas and the second cleaning gas is shown in FIG.

[0025] When the first cleaning gas is HF gas, the second cleaning gas may be any one of TMA gas, DMAC gas, Sn(acac)2 gas, a mixed gas of TMA gas and DMAC gas, or a mixed gas of TMA gas, DMAC gas, Sn(acac)2 gas, and SiCl4 gas. When the first cleaning gas is CHF3 gas, the second cleaning gas may be TMA gas. When the first cleaning gas is a mixed gas of HF gas and SF4 gas, the second cleaning gas may be Sn(acac)2 gas.

[0026] FIG. 4 shows an example of a combination of the first cleaning gas and the second cleaning gas when cleaning a film-forming device in forming a hafnium oxide film, a zirconium oxide film, or an IGZO film on a substrate.

[0027] When forming a hafnium oxide film on a substrate, the first cleaning gas may be HF gas, the second cleaning gas may be DMAC gas or a mixture of DMAC gas and TiCl4 gas, and the first cleaning gas may be a mixture of HF gas, XeF2 gas, and SF4 gas, and the second cleaning gas may be a mixture of DMAC gas and TiCl4 gas.

[0028] In the case of forming a zirconium oxide film on a substrate, when the first cleaning gas is HF gas, the second cleaning gas may be DMAC gas, a mixed gas of DMAC gas and TiCl4 gas, or a mixed gas of DMAC gas, TMA gas, Sn(acac)2 gas, and SiCl4 gas. When the first cleaning gas is WF6 gas, the second cleaning gas may be DMAC gas.

[0029] When forming an IGZO film on a substrate, the first cleaning gas may be HF gas and the second cleaning gas may be DMAC gas.

[0030] FIG. 5 shows an example of a combination of the first cleaning gas and the second cleaning gas for cleaning a film forming apparatus when forming a metal film of any of Co, Cu, Fe, Mo, and Ni on a substrate.

[0031] When any of the above metal films is formed, the first cleaning gas is a gas containing oxygen or a gas containing chlorine.

[0032] In the case of forming a Co film on a substrate, when the first cleaning gas is Cl2 gas, the second cleaning gas may be a mixed gas of Hhfac gas and Hacac gas, and when the first cleaning gas is O2 gas, the second cleaning gas may be Hfac gas.

[0033] When forming a Cu film on a substrate, the first cleaning gas may be O3 gas and the second cleaning gas may be Hfac gas.

[0034] When forming an Fe film on a substrate, the first cleaning gas may be Cl2 gas and the second cleaning gas may be Hacac gas.

[0035] When forming a Mo film on a substrate, the first cleaning gas may be O3 gas and the second cleaning gas may be BCl3 gas.

[0036] When forming a Ni film on a substrate, the first cleaning gas may be O2 gas and the second cleaning gas may be Hhfac gas.

[0037] Fig. 6 is a diagram showing an example of a combination of a first cleaning gas and a second cleaning gas according to an embodiment. Fig. 6 shows a representative example of a second cleaning gas and its chemical formula etc. when HF gas or a gas containing oxygen (O2, O3, NO2) is used as the first cleaning gas.

[0038] When HF gas is used as the first cleaning gas, the chemical formula of TMA gas is shown in (a) and the chemical formula of DMAC gas is shown in (b) as an example of the second cleaning gas. When HF gas is used as the first cleaning gas, the chemical formula of TiCl4 gas is shown in (c), the chemical formula of SiCl4 gas is shown in (d), and the chemical formula of Sn(acac)2 gas is shown in (e) as an example of the second cleaning gas.

[0039] When a gas containing oxygen (O2, O3, NO2) is used as the first cleaning gas, the chemical formula of Hfac gas as an example of the second cleaning gas is shown in (f).

[0040] When a gas containing oxygen (O2, O3, NO2) is used as the first cleaning gas, using Hfac gas as the second cleaning gas makes it possible to etch oxides in the processing chamber and clean the piping of the gas line that supplies the precursor of the film formation material.

[0041] Furthermore, Fig. 6 shows the boiling point, vapor pressure, etc. of each gas. When a fill tank for temporarily storing gas is provided in the gas line of a film forming apparatus described later, gas above a certain pressure is stored in the fill tank, and the stored gas can be supplied to the processing vessel at a certain pressure or higher. This allows cleaning gas to be supplied at high speed, and cycle cleaning in which multiple cleaning gases are supplied alternately can be performed at high speed. Therefore, gases with low vapor pressure are not suitable for cycle cleaning.

[0042] For example, TMA has a vapor pressure of 760 Torr at its boiling point of 127°C, and a vapor pressure of 9 Torr at 20°C. Therefore, when TMA is heated to about 40°C to 50°C, TMA with a vapor pressure of about 100 Torr is obtained. Therefore, TMA can be made to have a vapor pressure of 100 Torr to 200 Torr without raising the temperature of TMA to its boiling point of 127°C.

[0043] Similarly, DMAC has a vapor pressure of 760 Torr at its boiling point of 183°C, and 79 Torr at 60°C. Therefore, when DMAC is heated to about 65°C to 70°C, DMAC with a vapor pressure of about 100 Torr is obtained. Therefore, DMAC can be made to have a vapor pressure of 100 Torr to 200 Torr without raising the temperature of DMAC to its boiling point of 183°C.

[0044] A high vapor pressure is required to supply the gas stored in the fill tank installed in the gas line of the film formation device to the processing vessel at high speed. In the case of TMA gas with a boiling point of 127°C and DMAC gas with a boiling point of 183°C, if the liquid TMA or DMAC is heated to about 100°C to become gaseous, the vapor pressure is expected to be about 100 Torr. In this way, TMA or DMAC is made gaseous and temporarily stored in the fill tank at a relatively high vapor pressure, and a relatively large amount of gas is supplied at high speed (called fill flow). This enables high-speed gas replacement.

[0045] TiCl4, SiCl4, Sn(acac)2, and Hfac shown in Figure 6 can also be made into a gaseous state and temporarily stored in a fill tank at a relatively high vapor pressure, achieving a fill flow that supplies a relatively large amount of gas at high speed.

[0046] This allows high-speed cycle cleaning by switching the first cleaning gas and the second cleaning gas at high speed and supplying them alternately. By using fill-flow, the time per cycle when the first cleaning gas and the second cleaning gas are alternately and repeatedly supplied can be reduced to 2 seconds or less. For example, in cycle cleaning using fill-flow, one cycle is 0.5 to 1 second. In other words, 1 Å of etching (cleaning) can be performed in 0.5 to 1 second. Up to 2 Å of etching can be performed in 1 second. If 2 Å of etching is performed in 1 second, 7200 Å of film can be removed by etching in 1 hour, and 1.4 μm of film can be removed in 2 hours.

[0047] [Film forming equipment] Next, a configuration example of a film formation apparatus for performing a cleaning method according to an embodiment will be described with reference to Fig. 7. Fig. 7 is a diagram showing a configuration example of a film formation apparatus according to an embodiment.

[0048] The film formation apparatus 100 supplies Zyald ((C5H5)Zr[N(CH3)2]3) gas, which is an example of a film formation source gas, and O3 gas, which is an example of a film formation reactive gas, to a substrate W such as a wafer, to form a zirconium oxide film, which is an example of a high-k film, on the substrate W. Zirconium oxide may include ZrO and ZrO2. The film formation apparatus 100 is, for example, configured with an ALD (Atomic Layer Deposition) apparatus or the like.

[0049] The film forming apparatus 100 includes a processing vessel 1, a stage 2, a shower head 3, an exhaust unit 4, a gas supply unit 5, and a control device 6. The processing vessel 1 is made of a metal such as aluminum and has a substantially cylindrical shape. A loading / unloading port 11 is formed in a side wall of the processing vessel 1 for loading or unloading a substrate W, and the loading / unloading port 11 can be opened and closed by a gate valve 12. An annular exhaust duct 13 having a rectangular cross section is provided on the main body of the processing vessel 1. A slit 13a is formed along the inner peripheral surface of the exhaust duct 13. An exhaust port 13b is formed in the outer wall of the exhaust duct 13. A ceiling wall 14 is provided on the upper surface of the exhaust duct 13 so as to close the upper opening of the processing vessel 1. The space between the ceiling wall 14 and the exhaust duct 13 is airtightly sealed by a seal ring 15. A partition member 16 partitions the inside of the processing vessel 1 into upper and lower sections when the stage 2 and the cover member 22 are raised to the film forming processing position. The stage 2 and the cover member 22 in FIG. 7 are in the film forming processing position.

[0050] The stage 2 horizontally supports the substrate W in the processing chamber 1 and is provided so as to be movable up and down. The stage 2 is disk-shaped and has a size corresponding to the substrate W, and is supported by a support member 23. The stage 2 is made of a ceramic material such as aluminum nitride (AlN) or a metal material such as aluminum or a nickel-based alloy, and has a heater 21 embedded therein for heating the substrate W. The heater 21 generates heat when powered by a heater power supply (not shown). The substrate W is controlled to a predetermined temperature by controlling the output of the heater 21 using a temperature signal from a thermocouple (not shown) provided near the upper surface (substrate placement surface) of the stage 2.

[0051] The stage 2 is provided with a cover member 22 made of ceramics such as alumina so as to cover the outer peripheral region of the substrate placement surface and the side surface of the stage 2. The support member 23 extends from the center of the bottom surface of the stage 2 through a hole formed in the bottom wall of the processing vessel 1 to below the processing vessel 1, and its lower end is connected to a lifting mechanism 24. The lifting mechanism 24 allows the stage 2 to be raised and lowered via the support member 23 between a transfer position where the substrate W can be transferred, as shown by a two-dot chain line in FIG. 7, a film forming position, as shown by a solid line in FIG. 7, and a cleaning processing position (not shown) that is slightly higher than the film forming processing position. In addition, a flange 25 is attached to the support member 23 below the processing vessel 1, and a bellows 26 is provided between the bottom surface of the processing vessel 1 and the flange 25 to separate the atmosphere inside the processing vessel 1 from the outside air and expand and contract with the raising and lowering operation of the stage 2.

[0052] Three substrate support pins 27 (only two shown) are provided near the bottom surface of the processing vessel 1 so as to protrude upward from a lift plate 27a. The substrate support pins 27 can be raised and lowered via the lift plate 27a by a lift mechanism 28 provided below the processing vessel 1, and are inserted into through holes 2a provided in the stage 2 so as to be protruding and retracting from the upper surface of the stage 2. By raising and lowering the substrate support pins 27 in this manner, the substrate W is transferred between a substrate transport mechanism (not shown) and the stage 2.

[0053] The shower head 3 supplies a processing gas into the processing vessel 1 in a shower-like manner. The shower head 3 is made of metal, is provided to face the stage 2, and has approximately the same diameter as the stage 2. The shower head 3 has a main body 31 fixed to the ceiling wall 14 of the processing vessel 1, and a cap member 32 connected below the main body 31. A gas diffusion space 33 is formed between the main body 31 and the cap member 32, and a gas introduction hole 36 is provided in the gas diffusion space 33 so as to penetrate the center of the main body 31 and the ceiling wall 14 of the processing vessel 1. A circular protrusion 34 protruding downward is formed on the periphery of the cap member 32, and a gas hole 35 is formed on the inner flat surface of the circular protrusion 34 of the cap member 32. The cap member 32 faces the stage 2 to form a processing space 37, and the gas introduction hole 36 supplies a film-forming source gas and a film-forming reactive gas to the processing space 37.

[0054] A gas path 31a is formed inside the main body 31. The gas path 31a extends outside the outer periphery of the annular protrusion 34 and communicates with a plurality of gas holes 31a1 that open downward. The gas path 31a may be formed radially or circularly. The gas path 31a does not communicate with the gas inlet hole 36, and serves as a path for supplying the cleaning gas to a region (region outside the processing space) 39 outside the processing space 37. The region outside the processing space 39 includes an annular space inside the exhaust duct 13.

[0055] When the stage 2 is in the film formation processing position, a processing space 37 is formed between the cap member 32 and the stage 2, and the lower surface of the annular protrusion 34 and the upper surface of the cover member 22 of the stage 2 are close to each other to form an annular gap 38. Furthermore, when the stage 2 is in the film formation processing position, the upper surface of the cover member 22 is located at the same position as or higher than the upper surface of the partition member 16. When the stage 2 is in the cleaning processing position, the upper surface of the cover member 22 is located further above the film formation processing position. Therefore, the annular gap 38 (gap width G) when the stage 2 is in the cleaning processing position is narrower than the gap width G when the stage 2 is in the film formation processing position.

[0056] When a film is formed on the substrate W, the stage 2 may be fixed at a predetermined height. When the processing space 37 is cleaned, the stage 2 is raised. This makes the gap width G when the processing space 37 is cleaned narrower than the gap width G during film formation.

[0057] The exhaust unit 4 exhausts the inside of the processing vessel 1. The exhaust unit 4 has an exhaust pipe 41 connected to the exhaust port 13b of the exhaust duct 13, an APC (Auto Pressure Controller) valve 42, an opening / closing valve 43, and a vacuum pump 44. One end of the exhaust pipe 41 is connected to the exhaust port 13b of the exhaust duct 13, and the other end is connected to the suction port of the vacuum pump 44. Between the exhaust duct 13 and the vacuum pump 44, the APC valve 42 and the opening / closing valve 43 are provided in this order from the upstream side. The APC valve 42 adjusts the conductance of the exhaust path to adjust the pressure of the processing space 37. The opening / closing valve 43 switches the exhaust pipe 41 between opening and closing. During processing, the partition member 16 and the stage 2 (cover member 22) partition the inside of the processing vessel 1 into an upper space including the processing space 37 and a lower space on the back side of the stage 2. As a result, the gas in the processing space 37 reaches the annular space inside the exhaust duct 13 through the annular gap 38 and the slit 13a, and is exhausted from the exhaust port 13b of the exhaust duct 13 through the exhaust piping 41 by the vacuum pump 44 of the exhaust unit 4. The lower space is kept in a purged atmosphere by a purge gas supply mechanism (not shown). Therefore, the gas in the processing space 37 does not flow into the lower space.

[0058] The gas supply unit 5 includes a film-forming raw gas supply line L1, a film-forming reactive gas supply line L2, a first continuous N2 gas supply line L3, and a first flush purge line L4. The gas supply unit 5 further includes a first cleaning gas line L5, a second cleaning gas line L6, a second continuous N2 gas supply line L7, and a second flush purge line L8.

[0059] The film-forming source gas supply line L1 extends from a film-forming source gas supply source GS1, which is a supply source of a film-forming source gas, for example, Zyald ((C5H5)Zr[N(CH3)2]3) gas, and is connected to a junction pipe L9. The junction pipe L9 is connected to a gas inlet 36. The film-forming source gas supply line L1 is provided with a mass flow controller M1, a buffer tank T1, and an on-off valve V1 in this order from the source gas supply source GS1 side. The mass flow controller M1 controls the flow rate of the Zyald ((C5H5)Zr[N(CH3)2]3) gas flowing through the film-forming source gas supply line L1. The buffer tank T1 temporarily stores the Zyald gas and supplies the required Zyald gas in a short time. The on-off valve V1 switches the supply and stop of the Zyald gas during the ALD process.

[0060] The film-forming reactive gas supply line L2 extends from a film-forming reactive gas supply source GS2, which is a supply source of a reactive gas, for example, O3 gas, and is connected to a junction pipe L9. The film-forming reactive gas supply line L2 is provided with a mass flow controller M2, a buffer tank T2, and an on-off valve V2, in this order from the film-forming reactive gas supply source GS2 side. The mass flow controller M2 controls the flow rate of O3 gas flowing through the film-forming reactive gas supply line L2. The buffer tank T2 temporarily stores O3 gas and supplies the required O3 gas in a short time. The on-off valve V2 switches the supply and stop of O3 gas during the ALD process.

[0061] The first continuous N2 gas supply line L3 extends from an N2 gas supply source GS3, which is a supply source of N2 gas, and is connected to a junction pipe L9. As a result, N2 gas is supplied to the junction pipe L9 side through the first continuous N2 gas supply line L3. The first continuous N2 gas supply line L3 constantly supplies N2 gas during film formation by the ALD method, and functions as a carrier gas for Zyald gas and O3 gas, and also functions as a purge gas. The first continuous N2 gas supply line L3 is provided with a mass flow controller M3, an on-off valve V3, and an orifice F3 in this order from the N2 gas supply source GS3 side. The mass flow controller M3 controls the flow rate of N2 gas flowing through the first continuous N2 gas supply line L3. The orifice F3 suppresses the gas supplied by the buffer tanks T1, T2, and T4 at a relatively large flow rate from flowing back into the first continuous N2 gas supply line L3.

[0062] The first flush purge line L4 extends from an N2 gas supply source GS4, which is a supply source of N2 gas, and is connected to a junction pipe L9. As a result, N2 gas is supplied to the junction pipe L9 side through the first flush purge line L4. The first flush purge line L4 supplies N2 gas only during a purge step during film formation by the ALD method. The first flush purge line L4 is provided with a mass flow controller M4, a buffer tank T4, and an on-off valve V4 in this order from the N2 gas supply source GS4 side. The mass flow controller M4 controls the flow rate of N2 gas flowing through the first flush purge line L4. The buffer tank T4 temporarily stores N2 gas and supplies the required N2 gas in a short time. The on-off valve V4 switches between supplying and stopping N2 gas during purging in the ALD process.

[0063] The first cleaning gas line L5 extends from a first cleaning gas supply source GS5, which is a supply source of a first cleaning gas, for example, HF gas, and is connected to a junction pipe L10 and a branch pipe L11 branched from the junction pipe L10. The junction pipe L10 is connected to a gas inlet 36. The branch pipe L11 branches from the junction pipe L10 and is connected to a gas path 31a in the main body 31. The first cleaning gas line L5 is provided with a mass flow controller M5, a buffer tank T5, and an on-off valve V5 in this order from the first cleaning gas supply source GS5 side. The mass flow controller M5 controls the flow rate of the HF gas flowing through the first cleaning gas line L5. The buffer tank T5 temporarily stores the HF gas and supplies the required HF gas in a short time. The on-off valve V5 switches between supply and stop of the HF gas, which is one of the cleaning gases in a cycle cleaning process in which two types of cleaning gas are alternately supplied.

[0064] The second cleaning gas line L6 extends from a second cleaning gas supply source GS6, which is a supply source of a second cleaning gas, for example, TMA gas, and is connected to a junction pipe L10 and a branch pipe L11. The second cleaning gas line L6 is provided with a mass flow controller M6, a buffer tank T6, and an on-off valve V6, in this order from the second cleaning gas supply source GS6 side. The mass flow controller M6 controls the flow rate of the TMA gas flowing through the second cleaning gas line L6. The buffer tank T6 temporarily stores the TMA gas and supplies the required TMA gas in a short period of time. The on-off valve V6 switches between supply and stop of the TMA gas, which is the other cleaning gas in a cycle cleaning process in which two types of cleaning gas are supplied alternately.

[0065] The second continuous N2 gas supply line L7 extends from an N2 gas supply source GS7, which is a supply source of N2 gas, and is connected to a junction pipe L10 and a branch pipe L11. As a result, N2 gas is supplied to the junction pipe L10 and the branch pipe L11 side through the second continuous N2 gas supply line L7. The second continuous N2 gas supply line L7 constantly supplies N2 gas during cycle cleaning, and functions as a carrier gas for the first cleaning gas and the second cleaning gas, and also functions as a purge gas. The second continuous N2 gas supply line L7 is provided with a mass flow controller M7, an on-off valve V7, and an orifice F4 in this order from the N2 gas supply source GS7 side. The mass flow controller M7 controls the flow rate of the N2 gas flowing through the second continuous N2 gas supply line L7. The orifice F4 suppresses the gas supplied by the buffer tanks T5, T6, and T8 at a relatively large flow rate from flowing back into the second continuous N2 gas supply line L7.

[0066] The second flush purge line L8 extends from an N2 gas supply source GS8, which is a supply source of N2 gas, and is connected to a junction pipe L10 and a branch pipe L11. As a result, N2 gas is supplied to the junction pipe L10 and the branch pipe L11 side through the second flush purge line L8. The second flush purge line L8 supplies N2 gas only during the purge step during cycle cleaning. The second flush purge line L8 is provided with a mass flow controller M8, a buffer tank T8, and an on-off valve V8 in this order from the N2 gas supply source GS8 side. The mass flow controller M8 controls the flow rate of N2 gas flowing through the second flush purge line L8. The buffer tank T8 temporarily stores N2 gas and supplies the required N2 gas in a short time. The on-off valve V8 switches the supply and stop of N2 gas during purging of the cycle cleaning process.

[0067] The control device 6 controls the operation of each part of the film forming apparatus 100. The control device 6 has a CPU (Central Processing Unit), a ROM (Read Only Memory), and a RAM (Random Access Memory). The CPU executes a desired process according to a recipe stored in a storage area such as the RAM. The recipe sets control information for the apparatus with respect to process conditions. The control information may be, for example, gas flow rate, pressure, temperature, and process time. The recipe and the program used by the control device 6 may be stored in, for example, a hard disk or a semiconductor memory. The recipe and the like may be set at a predetermined position in a state where it is stored in a portable computer-readable storage medium such as a CD-ROM or DVD, and may be read out.

[0068] [Processing method] Next, a processing method using the film forming apparatus 100 according to this embodiment will be described with reference to Fig. 8. Fig. 8 is a flow chart showing an example of a processing method using the film forming apparatus 100 according to this embodiment.

[0069] In step S101, the substrate W is loaded into the processing chamber 1 of the film forming apparatus 100. Specifically, the stage 2 heated to a predetermined temperature (e.g., 200° C. to 250° C.) by the heater 21 is lowered to the transfer position (indicated by a two-dot chain line in FIG. 7), and the gate valve 12 is opened. Next, the substrate W is loaded into the processing chamber 1 via the load / unload port 11 by a transfer arm (not shown), and is supported by the substrate support pins 27. When the transfer arm is retracted from the load / unload port 11, the gate valve 12 is closed. Furthermore, the substrate support pins 27 are lowered, and the substrate W is placed on the stage 2.

[0070] In step S102, the controller 6 controls the lifting mechanism 24 to lift the stage 2 to a film forming processing position (indicated by a solid line in FIG. 7). As a result, the inside of the processing vessel 1 is divided into an upper space on the front surface (substrate mounting surface) side of the stage 2 including the processing space 37, and a lower space on the back surface side of the stage 2.

[0071] In step S103, the temperature of the substrate W on the stage 2 is increased, and the aperture of the APC valve 42 is adjusted. That is, the temperature of the substrate W on the stage 2 is increased to a predetermined temperature by the heater 21. The controller 6 also controls the exhaust unit 4 to adjust the inside of the processing chamber 1 to a predetermined vacuum level. Thereafter, the controller 6 opens the on-off valve V3 and closes the on-off valves V1, V2, V4 to V8. As a result, N2 gas is supplied from the N2 gas supply source GS3 through the first continuous N2 gas supply line L3 into the processing space 37 to increase the pressure. The controller 6 also adjusts the aperture of the APC valve 42 so that the pressure in the processing space 37 becomes a desired pressure, based on a pressure sensor (not shown) that detects the pressure in the processing space 37. As a result, the controller 6 stores the pressure in the processing space 37 and the aperture of the APC valve 42 in association with each other. At this time, Zyald gas is supplied from the film forming source gas supply source GS1 into the buffer tank T1, and the pressure in the buffer tank T1 is maintained at a substantially constant level. O3 gas is supplied from the film forming reactive gas supply source GS2 into the buffer tank T2, and the pressure in the buffer tank T2 is maintained at a substantially constant level. N2 gas is supplied from the N2 gas supply source GS4 into the buffer tank T4, and the pressure in the buffer tank T4 is maintained at a substantially constant level. HF gas is supplied from the first cleaning gas supply source GS5 into the buffer tank T5, and the pressure in the buffer tank T5 is maintained at a substantially constant level. TMA gas is supplied from the second cleaning gas supply source GS6 into the buffer tank T6, and the pressure in the buffer tank T6 is maintained at a substantially constant level. N2 gas is supplied from the N2 gas supply source GS8 into the buffer tank T8, and the pressure in the buffer tank T8 is maintained at a substantially constant level.

[0072] In step S104, a film forming process is performed. In this film forming process, a zirconium oxide film is formed on the substrate W, which will be described later with reference to Fig. 9. When the film forming process is completed, the process proceeds to step S105.

[0073] In step S105, the control device 6 controls the lifting mechanism 24 to lower the stage 2 to the transfer position.

[0074] In step S106, the substrate W is unloaded from the processing chamber 1 of the film formation apparatus 100. Specifically, the substrate support pins 27 are raised to lift the substrate W placed on the stage 2 and support it on the substrate support pins 27. The gate valve 12 is also opened. Next, the substrate W is unloaded from the processing chamber 1 via the load / unload port 11 by a transfer arm (not shown). When the transfer arm retreats from the load / unload port 11, the gate valve 12 is closed. This completes the process of forming a zirconium oxide film on the substrate W in the film formation apparatus 100.

[0075] In step S107, the control device 6 determines whether or not a predetermined number of substrates W have been formed. If the control device 6 determines that the predetermined number of substrates W have not been formed, the processing method ends without cleaning the inside of the processing vessel 1. If the control device 6 determines that the predetermined number of substrates W have been formed, the process proceeds to step S108, where a cleaning process (cycle cleaning) is performed to clean the inside of the processing vessel 1, and the processing method ends.

[0076] [Film formation process] Next, the film formation process in step S104 in Fig. 8 will be further described with reference to Fig. 9. Fig. 9 is a flow chart showing an example of the film formation process in the film formation apparatus 100 according to the present embodiment. The cleaning process (cycle cleaning) in step S108 in Fig. 8 will be described later with reference to Fig. 10.

[0077] In step S201, the control device 6 controls the lifting mechanism 24 to start an upward movement to move (raise) the stage 2 to the film forming processing position (see FIG. 1), and adjusts the aperture of the APC valve 42. The adjustment of the aperture of the APC valve is determined based on the pressure described in the recipe and the relationship between the pressure and the aperture stored in step S103. The control device 6 also sets the flow rate of the mass flow controller M3 to a predetermined flow rate set in the recipe. The carrier N2 gas is supplied into the processing space 37 from the N2 gas supply source GS3 through the first continuous N2 gas supply line L3.

[0078] In step S202, the control device 6 opens the on-off valve V1 to supply Zyald gas, which is a source gas, into the processing space 37. Here, the gap width G of the annular gap 38 is narrow (e.g., 0.5 mm). Therefore, the Zyald gas supplied into the processing space 37 is confined within the processing space 37, and the pressure within the processing space 37 increases. This prevents the supplied Zyald gas from being exhausted immediately, and makes it possible to increase the frequency of contact between the source gas molecules and the substrate W. This allows the source gas molecules to be adsorbed onto the surface of the substrate W.

[0079] In step S203, the control device 6 closes the on-off valve V1. The control device 6 also controls the lift mechanism 24 to start a lowering operation to move (lower) the stage 2. This can improve the efficiency of replacement with the purge gas in the next step. However, the stage 2 may be controlled to be fixed during the film formation process.

[0080] In step S204, the controller 6 opens the on-off valve V4 to supply N2 gas into the processing space 37. At this time, since the N2 gas is temporarily stored in the buffer tank T4 before being supplied into the processing vessel 1, a relatively large flow rate can be supplied. In addition, the gap width G is wider than the gap width G during the supply of the source gas. This allows the excess Zyald gas and the like in the processing space 37 to be flush purged.

[0081] In step S205, the controller 6 closes the on-off valve V4. The controller 6 also controls the lifting mechanism 24 to move (raise) the stage 2 to the film forming processing position.

[0082] In step S206, the control device 6 increases the flow rate (flow rate of carrier N2 gas) of the mass flow controller M3 to a value greater than that in step S205. For example, the flow rate is returned to that in steps S201 to S204. The control device 6 opens the on-off valve V2 to supply O3 gas, which is a reactive gas, into the processing space 37. Here, the gap width G is narrow (for example, 0.5 mm). Therefore, the O3 gas supplied into the processing space 37 is confined within the processing space 37, and the pressure in the processing space 37 increases. This makes it possible to increase the frequency of contact between the reactive gas molecules and the substrate W without the supplied O3 gas being exhausted immediately. This allows the O3 gas to react with the source gas molecules adsorbed on the surface of the substrate W.

[0083] In step S207, the control device 6 closes the on-off valve V2. Also, the control device 6 controls the lift mechanism 24 to lower the stage 2 to the purge processing position. This can improve the efficiency of replacement with the purge gas in the next step. However, the stage 2 may be controlled to be fixed during the film formation process.

[0084] In step S208, the controller 6 opens the on-off valve V4 to supply N2 gas into the processing space 37. At this time, the N2 gas is temporarily stored in the buffer tank T4 before being supplied into the processing vessel 1, so that a relatively large flow rate can be supplied. In addition, the gap width G is wider than the gap width G during the supply of the reaction gas. This allows the processing space 37 to be flush-purged of excess O3 gas and the like.

[0085] After that, the control device 6 closes the on-off valve V4. The control device 6 also sets the flow rate (flow rate of carrier N2 gas) of the mass flow controller M3 to be smaller than that during the reaction gas supply and the flash purge (steps S206 to S208). The gap width G is also wider (for example, 6 mm) than that during film formation. This makes it easier to discharge reaction products, excess O3 gas, N2 gas, and the like.

[0086] Through the processes of steps S201 to S208, one cycle of the ALD process is completed.

[0087] In step S209, the control device 6 determines whether or not a predetermined number of film formation cycles have been completed. If the predetermined number of film formation cycles has not been completed, the processes of steps S201 to S208 are repeated until the predetermined number of film formation cycles have been completed. If the predetermined number of film formation cycles has been completed, the film formation process is terminated.

[0088] [Cleaning process (cycle cleaning)] Next, the cleaning process (cycle cleaning) in step S108 in Fig. 8 will be further described with reference to Fig. 10. Fig. 10 is a flow chart showing an example of the cleaning process (cycle cleaning) in the film forming apparatus 100 according to this embodiment.

[0089] In step S301, the control device 6 controls the lifting mechanism 24 to start an upward movement to move (raise) the stage 2 to the cleaning processing position, and adjusts the aperture of the APC valve 42. Here, the cleaning processing position is slightly higher than the film formation processing position, and the gap width G of the annular gap 38 is narrower (for example, less than 0.5 mm) than during film formation.

[0090] The control device 6 sets the flow rate of the mass flow controller M7 to a predetermined flow rate set in the recipe. The carrier N2 gas is supplied from the N2 gas supply source GS7 to the processing space 37 through the second continuous N2 gas supply line L7.

[0091] In step S302, the control device 6 opens the on-off valve V5 to supply HF gas, which is an example of a first cleaning gas, into the processing space 37 through the junction pipe L10 and the gas introduction hole 36. Here, the gap width G is narrow (for example, less than 0.5 mm). Therefore, the HF gas supplied into the processing space 37 is confined within the processing space 37, and the pressure within the processing space 37 increases. This makes it possible to increase the frequency of contact between the HF gas and parts such as the inner wall within the processing space 37 without the supplied HF gas being immediately exhausted. This makes it possible to promote the modification of the surfaces of the parts within the processing space 37.

[0092] The control device 6 also supplies HF gas, which is a first cleaning gas, from the gas hole 31a1 through the junction pipe L10, the branch pipe L11, and the gas path 31a to a processing space outer region 39 outside the processing space 37 (annular protrusion 34). This makes it possible to modify the zirconium oxide film attached to the surface of the part in the processing space outer region 39.

[0093] In step S303, the controller 6 closes the on-off valve V5. The controller 6 also controls the lift mechanism 24 to start a lowering operation to move (lower) the stage 2. This can improve the efficiency of replacement with the purge gas in the next step. However, during the cleaning process, the stage 2 may be controlled to be fixed at the cleaning process position.

[0094] In step S304, the controller 6 opens the on-off valve V8 to supply N2 gas into the processing space 37. At this time, since the N2 gas is temporarily stored in the buffer tank T8 and then supplied into the processing vessel 1, a relatively large flow rate can be supplied. In addition, the gap width G is wider than the gap width G when HF gas is supplied. This allows excess HF gas, etc. in the processing space 37 to be flash purged.

[0095] In step S305, the controller 6 closes the on-off valve V8. The controller 6 also controls the lifting mechanism 24 to move (raise) the stage 2 to the cleaning processing position.

[0096] In step S306, the control device 6 increases the flow rate (flow rate of the carrier N2 gas) of the mass flow controller M7 to a value larger than that in step S305. For example, the flow rate is returned to that in steps S301 to S304. The control device 6 opens the on-off valve V6 to supply TMA gas, which is an example of a second cleaning gas, into the processing space 37. Here, the gap width G is narrow (for example, less than 0.5 mm). Therefore, the TMA gas supplied into the processing space 37 is confined within the processing space 37, and the pressure in the processing space 37 increases. This makes it possible to increase the frequency of contact between the TMA gas and parts such as the inner wall in the processing space 37 without immediately exhausting the supplied TMA gas. This makes it possible to remove the modified layer of the zirconium oxide film attached to the surface of the parts in the processing space 37 by etching, and clean the processing space 37.

[0097] In addition, the control device 6 supplies the TMA gas from the gas hole 31a1 through the junction pipe L10, the branch pipe L11, and the gas path 31a to the outside processing space region 39. This makes it possible to remove the modified layer of the zirconium oxide film adhering to the surface of the parts in the outside processing space region 39 by etching, and to clean the outside processing space region 39.

[0098] In step S307, the control device 6 closes the on-off valve V6. Also, the control device 6 controls the lift mechanism 24 to lower the stage 2 to the purge processing position. This can improve the efficiency of replacement with the purge gas in the next step. However, during the cleaning process, the stage 2 may be controlled to be fixed at the cleaning processing position.

[0099] The control device 6 opens the on-off valve V8 to supply N2 gas into the processing space 37. At this time, the N2 gas is temporarily stored in the buffer tank T8 before being supplied into the processing vessel 1, so that a relatively large flow rate can be supplied. In addition, the gap width G is wider than the gap width G during the supply of the reaction gas. This allows the processing space 37 to be flush purged of excess TMA and the like.

[0100] Thereafter, the control device 6 closes the on-off valve V8. The control device 6 also sets the flow rate (flow rate of the carrier N2 gas) of the mass flow controller M7 to be smaller than that during the first cleaning gas supply and the flash purge (steps S306 to S308). The gap width G is also set to be wider (for example, 6 mm) than that during film formation. This makes it possible to easily exhaust reaction products, excess TMA gas, N2 gas, and the like.

[0101] By carrying out steps S301 to S308, one cycle of the cyclic cleaning process in which two types of cleaning gas are alternately supplied to the substrate in the same manner as ALE is completed.

[0102] In step S309, the control device 6 determines whether or not a predetermined number of cleaning cycles have been completed. If the predetermined number of cleaning cycles has not been completed, the processes of steps S301 to S308 are repeated until the predetermined number of cleaning cycles have been completed. If the predetermined number of cleaning cycles has been completed, cycle cleaning is terminated.

[0103] As described above, in the processing method performed by the film formation apparatus 100, during film formation, a film formation source gas from the film formation source gas supply source GS1 and a film formation reactive gas from the film formation reactive gas supply source GS2 are alternately supplied to the processing space 37. In this way, a film is formed on the substrate W by the ALD method. However, the film formation source gas and the film formation reactive gas may be supplied to the processing space 37 at the same time.

[0104] Examples of source gases for film formation include TiCl4, Zyald ((C5H5)Zr[N(CH3)2]3), and Hydride (C 11 H 23 Examples of the types of films that can be formed include TiAlN, TiAlC, HfSiO, ZrHfSiO.HfSiON, ZrO, HfO, and AlO.

[0105] After a predetermined number of films are formed, the substrate W is unloaded, and then the first cleaning gas from the first cleaning gas supply source GS5 and the second cleaning gas from the second cleaning gas supply source GS6 are alternately supplied to the processing space 37. This allows the inside of the processing space 37 to be cyclically cleaned in an ALE manner.

[0106] The film forming apparatus 100 may include a buffer tank T5 (first buffer tank) installed in a first cleaning gas line L5 connecting the processing vessel 1 and a first cleaning gas supply source GS5, and a buffer tank T6 (second buffer tank) installed in a second cleaning gas line L6 connecting the processing vessel 1 and a second cleaning gas supply source GS6. In this case, the first cleaning gas temporarily stored in the buffer tank T5 and the second cleaning gas temporarily stored in the buffer tank T6 are alternately supplied to the processing space 37. However, the film forming apparatus 100 may supply the cleaning gas without using a buffer tank.

[0107] When cleaning the inside of the processing space 37, the first cleaning gas and the second cleaning gas may be alternately supplied to the inside of the processing space 37 and the area 39 outside the processing space through the gas hole 35 formed in the cap member 32 and the gas hole 31a1 formed in the main body 31. This makes it possible to clean the inside of the processing space 37 and the area 39 outside the processing space 37.

[0108] The pressure in the processing space 37 when cleaning the inside of the processing space 37 is about several hundred Torr, and the pressure in the processing space 37 when forming a film on the substrate W is about 10 Torr. Therefore, the pressure in the processing space 37 when cleaning the inside of the processing space 37 is higher than the pressure in the processing space 37 when forming a film on the substrate W.

[0109] [effect] According to the cleaning method (cycle cleaning) of this embodiment, when a fill tank is provided, gas above a certain pressure is stored in the fill tank, and the stored gas can be supplied into the processing vessel 1 at a certain pressure or higher. This allows the first cleaning gas and the second cleaning gas to be switched at high speed. As a result, the time per cycle when the first cleaning gas and the second cleaning gas are alternately and repeatedly supplied can be reduced to 2 seconds or less, enabling high-speed cycle cleaning. This allows the time per cycle to be reduced to 0.5 seconds or less when high-speed cycle cleaning is used, so that etching can be performed at 120 Å in 1 minute and 7200 Å in 1 hour. Similarly, film formation can be performed using high-speed ALD in which the film formation source gas and the film formation reactive gas are switched at high speed. The processing space 37 during film formation is the range surrounded by the cap member 32 and the stage 2, but high-k films such as zirconium oxide films attached to the processing space 37 can be etched (cleaned). This allows the interval until the liner parts are replaced to be extended. This allows productivity to be improved.

[0110] The cleaning method and the film forming apparatus 100 according to the presently disclosed embodiment should be considered as illustrative and not restrictive in all respects. The embodiments can be modified and improved in various forms without departing from the scope and spirit of the appended claims. The matters described in the above embodiments can be configured in other ways without any contradiction, and can be combined without any contradiction.

[0111] In the above embodiment, the film forming apparatus 100 is a single-wafer type apparatus that processes wafers one by one, but the present disclosure is not limited to this. For example, the film forming apparatus 100 may be a batch type apparatus that processes a large number of wafers at once, or a semi-batch type apparatus that processes a plurality of wafers. [Explanation of symbols]

[0112] W substrate 1 Processing vessel 2 Stage 3. Shower head 4 Exhaust section 5 Gas supply section 6. Control device 22 Cover member 24 Lifting mechanism 32 Cap member 34 Annular protrusion 37 Processing Space 38 Annular gap L1 Film deposition source gas supply line L2 Reactive gas supply line for film formation L3 First continuous N2 gas supply line L4 1st flash purge line L5 First cleaning gas line L6 Second cleaning gas line L7 Second continuous N2 gas supply line L8 Second flash purge line

Claims

1. A source of a film forming gas; A film forming reactive gas supply source; a first cleaning gas source; a second cleaning gas source; a stage provided within the processing chamber, on which a substrate is placed and which can be raised and lowered; a cap member provided in the processing chamber and facing the stage to define a processing space; A method for cleaning a film forming apparatus comprising: supplying a film-forming source gas from the film-forming source gas supply source and a film-forming reactive gas from the film-forming reactive gas supply source into the processing space to form a film on the substrate; unloading the substrate after the film is formed, and alternately supplying a first cleaning gas from the first cleaning gas supply source and a second cleaning gas from the second cleaning gas supply source into the processing space, thereby cleaning the inside of the processing space; The cleaning method according to claim 1,

2. a film is formed on the substrate by alternately supplying a film-forming raw material gas from the film-forming raw material gas supply source and a film-forming reactive gas from the film-forming reactive gas supply source into the processing space; The cleaning method according to claim 1 .

3. the film forming apparatus includes a first buffer tank installed in a first cleaning gas line connecting the processing vessel and the first cleaning gas supply source, and a second buffer tank installed in a second cleaning gas line connecting the processing vessel and the second cleaning gas supply source; The first cleaning gas temporarily stored in the first buffer tank and the second cleaning gas temporarily stored in the second buffer tank are alternately supplied to the processing space. The cleaning method according to claim 1 .

4. When cleaning the inside of the processing space, the stage is raised to make a distance between the stage and the cap member when cleaning the inside of the processing space narrower than a distance between the stage and the cap member when forming the film on the substrate. The cleaning method according to any one of claims 1 to 3.

5. the film forming apparatus includes a shower head having a main body and the cap member; the first cleaning gas and the second cleaning gas are alternately supplied from a gas hole formed in the cap member and a gas hole formed in the main body portion to the inside of the processing space and to a region outside the processing space outside the processing space, thereby cleaning the inside of the processing space and the region outside the processing space. The cleaning method according to any one of claims 1 to 3.

6. the film formed on the substrate is a high-k film, and when the high-k film is an oxide film, the first cleaning gas is a gas containing fluorine; The cleaning method according to any one of claims 1 to 3.

7. When the film formed on the substrate is made of alumina, the combination of the first cleaning gas and the second cleaning gas is When the first cleaning gas is HF gas, the second cleaning gas is TMA gas, DMAC gas, Sn(acac) ２ gas, a mixture of TMA gas and DMAC gas, or a mixture of TMA gas, DMAC gas, and Sn(acac) ２ Gas and SiCl ４ It is either a gas mixture with The first cleaning gas is CHF ３ When the second cleaning gas is a gas, the second cleaning gas is TMA gas; The first cleaning gas is a mixture of HF gas and SF ４ When mixed with gas, the second cleaning gas is Sn(acac) ２ It is a gas, The cleaning method according to claim 6.

8. When the film formed on the substrate is hafnium oxide, the combination of the first cleaning gas and the second cleaning gas is When the first cleaning gas is HF gas, the second cleaning gas is DMAC gas, or DMAC gas and TiCl ４ It is either a gas mixture with The first cleaning gas is HF gas and XeF ２ Gas and SF ４ When the second cleaning gas is a mixed gas of DMAC gas and TiCl ４ It is a mixture of gas and The cleaning method according to claim 6.

9. In the case where the film formed on the substrate is zirconium oxide, the combination of the first cleaning gas and the second cleaning gas is When the first cleaning gas is HF gas, the second cleaning gas is DMAC gas, or DMAC gas and TiCl ４ Mixture of DMAC gas, TMA gas and Sn(acac) ２ Gas and SiCl ４ It is either a gas mixture with The first cleaning gas is WF ６ When the second cleaning gas is a gas, the second cleaning gas is a DMAC gas. The cleaning method according to claim 6.

10. In the case where the film to be formed on the substrate is IGZO, the combination of the first cleaning gas and the second cleaning gas is as follows: The first cleaning gas is HF gas, and the second cleaning gas is DMAC gas. The cleaning method according to claim 6.

11. the film formed on the substrate is a metal film, and the first cleaning gas is a gas containing oxygen or a gas containing chlorine; The cleaning method according to any one of claims 1 to 3.

12. When the film formed on the substrate is Co, The first cleaning gas is Cl ２ When the second cleaning gas is a gas, the second cleaning gas is a mixture of Hhfac gas and Hacac gas; The first cleaning gas is O ２ When the second cleaning gas is a gas, the second cleaning gas is Hfac gas. The cleaning method according to claim 11.

13. When the film formed on the substrate is Cu, The first cleaning gas is O ３ gas, and the second cleaning gas is Hfac gas; The cleaning method according to claim 11.

14. When the film formed on the substrate is Fe, The first cleaning gas is Cl ２ gas, and the second cleaning gas is Hacac gas; The cleaning method according to claim 11.

15. When the film formed on the substrate is Mo, The first cleaning gas is O ３ gas, and the second cleaning gas is BCl ３ It is a gas, The cleaning method according to claim 11.

16. When the film formed on the substrate is Ni, The first cleaning gas is O ２ gas, and the second cleaning gas is Hhfac gas; The cleaning method according to claim 11.

17. The time per cycle when the first cleaning gas and the second cleaning gas are alternately and repeatedly supplied is 2 seconds or less. The cleaning method according to any one of claims 1 to 3.

18. a pressure in the processing space when cleaning the processing space is higher than a pressure in the processing space when forming the film on the substrate; The cleaning method according to any one of claims 1 to 3.

19. A source of a film forming gas; A film forming reactive gas supply source; a first cleaning gas source; a second cleaning gas source; a stage provided within the processing chamber, on which a substrate is placed and which can be raised and lowered; a cap member provided in the processing chamber and facing the stage to define a processing space; a first cleaning gas line connecting the processing vessel and the first cleaning gas supply source; a second cleaning gas line connecting the processing vessel and the second cleaning gas supply source; A control device, The control device includes: supplying a film-forming raw material gas from the film-forming raw material gas supply source and a film-forming reactive gas from the film-forming reactive gas supply source into the processing space to form a film on the substrate; unloading the substrate after the film is formed, and supplying a first cleaning gas from the first cleaning gas supply source and a second cleaning gas from the second cleaning gas supply source alternately into the processing space via the second cleaning gas line, thereby cleaning the inside of the processing space; The deposition apparatus performs control including:

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