Particle suppression method

Abstract

To suppress particles from being formed inside a chamber.SOLUTION: A particle suppression method includes a process (a), a process (b) and a process (c). In the process (a), a first processing gas including halogen elements and metal elements is supplied into a chamber in which a substrate is accommodated, and then made into plasma so as to form a film including the metal elements on the substrate. In the process (b), a second processing gas including a hydrogen gas is supplied into the chamber, and then made into plasma so as to reduce a surface of deposits formed on an inner wall of the chamber. In the process (c), a third processing gas including nitrogen elements is supplied into the chamber to nitride the reduced surface of the deposits.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] Various aspects and embodiments of the present disclosure relate to a particle suppression method.

Background Art

[0002] Patent Document 1 below discloses a technique in which after cleaning the inside of a chamber 11 for performing a CVD film formation process with ClF3 gas, a plasma of a gas containing Ar gas and a reducing gas is formed in the chamber. By this plasma, an adhesion 50 made of an AlF-based substance adhering to the inner wall of the chamber and / or the surface of the chamber internal member is removed. Subsequently, a precoat gas is supplied into the chamber 11, a precoat film 51 is formed on the surface from which the adhesion 50 has been removed, and then a workpiece W is loaded into the chamber 11 and a film formation process is performed.

[0003] Also, Patent Document 2 below describes a method capable of effectively adjusting and passivating a processing chamber used for depositing a plasma enhanced Ti-CVD film after wet cleaning or in-situ chemical cleaning, or each time a deposition process is sequentially performed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present disclosure provides a particle suppression method capable of suppressing the generation of particles in a chamber.

Means for Solving the Problems

[0006] One aspect of the present disclosure is a particle suppression method comprising steps a), b), and c). In step a), a first processing gas containing halogen elements and metallic elements is supplied into a chamber containing a substrate, and the first processing gas is plasma-activated to form a film containing metallic elements on the substrate. In step b), a second processing gas containing hydrogen gas is supplied into the chamber, and the second processing gas is plasma-activated to reduce the surface of deposits formed on the inner wall of the chamber. In step c), a third processing gas containing nitrogen elements is supplied into the chamber to nitride the surface of the reduced deposits. [Effects of the Invention]

[0007] According to various aspects and embodiments of this disclosure, the generation of particles within the chamber can be suppressed. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a schematic cross-sectional view showing an example of a plasma processing apparatus in the first embodiment. [Figure 2] Figure 2 is a flowchart showing an example of a particle suppression method in the first embodiment. [Figure 3A] Figure 3A is a schematic diagram illustrating an example of the coating process of deposits adhering to the inner walls of the chamber and the exhaust chamber. [Figure 3B] Figure 3B is a schematic diagram illustrating an example of the coating process of deposits adhering to the inner walls of the chamber and the exhaust chamber. [Figure 3C] Figure 3C is a schematic diagram illustrating an example of the coating process of deposits adhering to the inner walls of the chamber and the exhaust chamber. [Figure 4] Figure 4 shows an example of the relationship between the change in Gibbs free energy and temperature. [Figure 5A] Figure 5A is a schematic diagram illustrating an example of the coating process of sediments attached to a shower plate. [Figure 5B]Figure 5B is a schematic diagram illustrating an example of the coating process of sediments attached to a shower plate. [Figure 5C] Figure 5C is a schematic diagram illustrating an example of the coating process of sediments attached to a shower plate. [Figure 6] Figure 6 is a flowchart showing an example of a particle suppression method in the second embodiment. [Figure 7] Figure 7 is a flowchart showing an example of a particle suppression method in the third embodiment. [Figure 8] Figure 8 is a flowchart showing an example of a particle suppression method in the fourth embodiment. [Figure 9] Figure 9 shows an example of the measurement results for the number of particles. [Figure 10] Figure 10 shows an example of the relationship between the change in Gibbs free energy and temperature. [Figure 11] Figure 11 is a schematic cross-sectional view showing another example of a plasma processing apparatus. [Modes for carrying out the invention]

[0009] The embodiments of the disclosed particle suppression method will be described in detail below with reference to the drawings. However, the disclosed particle suppression method is not limited to the embodiments described below.

[0010] By the way, in the film formation of a film containing a metal element such as titanium, a raw material gas containing the metal element is supplied into a chamber that houses a substrate, and a film containing the metal element is formed on the substrate. At this time, since the inner wall of the chamber is also exposed to the raw material gas, a film containing the metal element also adheres to the inner wall of the chamber as a reaction by-product (hereinafter referred to as a deposit). Therefore, when the film formation of a film containing a metal element is performed on a plurality of substrates, the deposits adhering to the inner wall of the chamber become thick, and a part of them may scatter into the chamber as particles. Therefore, it is conceivable to perform cleaning in the chamber to remove the deposits before the deposits adhering to the inner wall of the chamber scatter into the chamber as particles.

[0011] When cleaning in the chamber is performed, in order to make the state in the chamber a predetermined state, a process such as precoating of the inner wall of the chamber is performed. Since film formation processing cannot be performed during processes such as cleaning and precoating, it is difficult to improve the throughput of the film formation processing. Although it is also conceivable to reduce the number of cleanings in order to improve the throughput of the film formation processing, if particles are generated during a period when cleaning is not performed, defects may occur in the semiconductor device formed from the substrate due to the generated particles.

[0012] Therefore, the present disclosure provides a technique capable of suppressing the generation of particles in a chamber.

[0013] (First Embodiment) [Configuration of Plasma Processing Apparatus 100] The particle suppression method in the present disclosure is realized by, for example, a plasma processing apparatus 100 shown in FIG. 1. FIG. 1 is a schematic cross-sectional view showing an example of the plasma processing apparatus 100 in the first embodiment. The plasma processing apparatus 100 in the present embodiment is, for example, an apparatus for forming a film containing Ti (titanium) on a substrate W. Ti is an example of a metal element contained in the film formed on the substrate W.

[0014] The plasma processing apparatus 100 has a chamber 1 formed in a substantially cylindrical shape from aluminum or the like, with its inner wall surface treated with anodizing. The chamber 1 is grounded. A susceptor 2 is provided inside the chamber 1. The susceptor 2 is supported by a substantially cylindrical support member 3 provided at the lower center of the chamber 1. The susceptor 2 is a mounting stage for horizontally supporting the substrate W, and is made of a ceramic material such as aluminum nitride (AlN), or a metallic material such as aluminum or nickel alloy. The susceptor 2 is grounded via the support member 3.

[0015] A guide ring 4 is provided on the outer edge of the susceptor 2 to guide the substrate W. A heater 5 made of a high-melting-point metal such as molybdenum is embedded in the susceptor 2. A heater power supply 6 is connected to the heater 5. The heater 5 heats the substrate W supported by the susceptor 2 to a predetermined temperature using the power supplied from the heater power supply 6.

[0016] A shower head 10 is provided on the top wall 1a of the chamber 1 via an insulating member 9. The shower head 10 in this embodiment is a premix type shower head and has a base member 11 and a shower plate 12. The outer circumference of the shower plate 12 is fixed to the base member 11 via a substantially annular intermediate member 13 for preventing sticking.

[0017] The shower plate 12 has a flange shape, and a recess is formed inside the shower plate 12. That is, a gas diffusion space 14 is formed between the base member 11 and the shower plate 12. A flange portion 11a is formed on the outer circumference of the base member 11, and the base member 11 is supported by the insulating member 9 via the flange portion 11a.

[0018] Multiple gas discharge holes 15 are formed in the shower plate 12. A gas inlet hole 16 is formed near the center of the base member 11. The gas inlet hole 16 is connected to the gas supply mechanism 20 via piping 30.

[0019] The gas supply mechanism 20 includes a gas supply source 21a containing halogen elements and metallic elements, a noble gas supply source 21b, a hydrogen (H2) gas supply source 21c, and a gas supply source 21d containing nitrogen elements. In this embodiment, the gas containing halogen elements and metallic elements is, for example, TiCl4 gas. In this embodiment, the noble gas is, for example, Ar gas. In this embodiment, the gas containing nitrogen elements is, for example, ammonia (NH3) gas. TiCl4 gas is an example of a first processing gas, the gas containing Ar gas and H2 gas is an example of a second processing gas, and NH3 gas is an example of a third processing gas.

[0020] The supply source 21a is connected to the piping 30 via valve 22a, mass flow controller (MFC) 23a, and valve 24a. The supply source 21b is connected to the piping 30 via valve 22b, MFC 23b, and valve 24b. The supply source 21c is connected to the piping 30 via valve 22c, MFC 23c, and valve 24c. The supply source 21d is connected to the piping 30 via valve 22d, MFC 23d, and valve 24d. The processed gas supplied through the piping 30 into the gas diffusion space 14 diffuses within the gas diffusion space 14 and is discharged in a shower-like manner into the chamber 1 via the gas discharge hole 15.

[0021] An RF (Radio Frequency) power supply 45 is connected to the base member 11 via a matching unit 44. The RF power supply 45 supplies RF power for plasma generation to the base member 11 via the matching unit 44. The RF power supplied to the base member 11 is radiated into the chamber 1 via the intermediate member 13 and the shower plate 12. The RF power radiated into the chamber 1 causes the processing gas supplied into the chamber 1 to be plasma-generated. Then, due to the active species contained in the plasma, a film containing metal elements is formed on the surface of the substrate W. In this embodiment, a Ti film is formed on the substrate W. When the processing gas is plasma-generated, a film containing metal elements is also deposited and adheres to the inner wall 1c of the chamber 1. In this embodiment, the shower head 10 also functions as the upper electrode of the parallel plate electrode. On the other hand, the susceptor 2 also functions as the lower electrode of the parallel plate electrode.

[0022] A heater 47 is provided on the base member 11 of the shower head 10. A heater power supply 48 is connected to the heater 47. The heater 47 heats the shower head 10 to a predetermined temperature using the power supplied from the heater power supply 48. As a result, the shower plate 12 is heated to, for example, 350°C or higher. An insulating member 49 is provided on the upper surface of the base member 11.

[0023] A roughly circular opening 50 is formed approximately in the center of the bottom wall 1b of the chamber 1. An exhaust chamber 51 is provided in the opening 50 of the bottom wall 1b, projecting downward so as to cover the opening 50. The exhaust chamber 51 is formed of aluminum or the like, with its inner wall 51a surface treated with anodizing. The exhaust chamber 51 is grounded via the chamber 1. An exhaust pipe 52 is connected to the side wall of the exhaust chamber 51. An exhaust device 53, including a vacuum pump, is connected to the exhaust pipe 52. The exhaust device 53 can reduce the pressure inside the chamber 1 to a predetermined vacuum level.

[0024] Furthermore, when the processing gas is turned into plasma in chamber 1, some of the active species contained in the plasma flow into the exhaust chamber 51. As a result, a film containing metallic elements adheres to the inner wall 51a of the exhaust chamber 51 as a deposit.

[0025] The susceptor 2 is provided with multiple (for example, three) lift pins 54 that can be extended and retracted from the surface of the susceptor 2 in order to raise and lower the substrate W. The multiple lift pins 54 are supported by a support plate 55. The support plate 55 is raised and lowered by the drive mechanism 56. As the support plate 55 is raised and lowered, the multiple lift pins 54 are raised and lowered.

[0026] A transport port 57 is provided on the side wall of the chamber 1 for transporting substrates W between the chamber 1 and a substrate transport chamber (not shown) located adjacent to the chamber 1. The transport port 57 is opened and closed by a gate valve 58.

[0027] The plasma processing apparatus 100 includes a control device 60. The control device 60 is, for example, a computer and has a control unit 61 and a storage unit 62. The storage unit 62 stores in advance programs that control various processes performed in the plasma processing apparatus 100. The control unit 61 controls each part of the plasma processing apparatus 100 by reading and executing the programs stored in the storage unit 62.

[0028] The programs pre-stored in the storage unit 62 may be those that were recorded on a computer-readable storage medium and installed from that storage medium to the storage unit 62. Examples of computer-readable storage mediums include hard disks (HDs), flexible disks (FDs), compact disks (CDs), magnetic optical disks (MOs), and memory cards.

[0029] Furthermore, the control device 60 is connected to a user interface 63 which consists of a keyboard for the operator to input commands and perform other operations to manage the plasma processing device 100, and a display that visualizes and displays the operating status of the plasma processing device 100.

[0030] [Methods for suppressing particles] Figure 2 is a flowchart showing an example of a particle suppression method in the first embodiment. Each process illustrated in the flowchart of Figure 2 is realized by the control device 60 controlling each part of the plasma processing device 100.

[0031] First, the control device 60 initializes the variable n1 for counting the number of substrates W to 0 (S100). Then, the substrates W are loaded into the chamber 1 (S101). In step S101, the drive mechanism 56 raises multiple lift pins 54 and opens the gate valve 58. Then, a transport device (not shown) loads the substrates W into the chamber 1 and passes them onto the multiple lift pins 54. Then, the drive mechanism 56 lowers the multiple lift pins 54 and places the substrates W onto the susceptor 2.

[0032] Next, a Ti film is formed on the substrate W (S102). Step S102 is an example of steps a) and a1). In step S102, the substrate W is heated to a predetermined temperature by the heater 5. Then, TiCl4 gas, H2 gas, and Ar gas are supplied into the chamber 1 from the gas supply mechanism 20, and the pressure inside the chamber 1 is controlled to a predetermined pressure by the exhaust device 53. Then, RF power is supplied into the chamber 1 via the matching unit 44 and the shower head 10, causing the gas inside the chamber 1 to become plasma, and the Ti film is formed on the surface of the substrate W by the active species contained in the plasma.

[0033] The main processing conditions in step S102 are as follows, for example: Pressure inside Chamber 1: 50~1333 Pa Temperature of substrate W: 320~700℃ RF power: 10~3000W TiCl4 gas / H2 gas / Ar gas: 5~100 / 1~500 / 10~10000 sccm Processing time: 1-600 seconds

[0034] Then, the RF power supply is cut off, and the TiCl4 gas supply is also cut off. As a result, Chamber 1 is filled with Ar gas and H2 gas.

[0035] Next, the surface of the Ti film formed on the substrate W is nitrided (S103). Step S103 is an example of step a3). In step S103, NH3 gas is supplied into the chamber 1. This nitrides the surface of the Ti film.

[0036] The main processing conditions in step S103 are, for example, as follows: Pressure inside Chamber 1: 50~1333 Pa Temperature of substrate W: 320~700℃ NH3 gas / H2 gas / Ar gas: 10~10000 / 5~10000 / 0~10000 sccm Processing time: 1-180 seconds

[0037] In step S103, RF power may be supplied into chamber 1, and the gas supplied into chamber 1 may be plasma-generated. In this case, the magnitude of the RF power supplied into chamber 1 is, for example, 3000W or less.

[0038] Next, the substrate W is discharged from the chamber 1 (S104). Step S104 is an example of process a4). In step S101, the drive mechanism 56 raises multiple lift pins 54, and the substrate W is lifted. Then, the gate valve 58 is opened, and the substrate W is discharged from the chamber 1 by a transport device (not shown).

[0039] Next, the control device 60 increments the variable n1 by 1 (S105). Then, the control device 60 determines whether or not to terminate the processing of the substrate W (S106). If the processing of the substrate W is terminated (S106: Yes), the control device 60 terminates the process shown in this flowchart.

[0040] On the other hand, if the processing of the substrate W is not completed (S106: No), the control device 60 determines whether the variable n1 is greater than a predetermined constant N1 (S107). In this embodiment, the constant N1 is, for example, an integer greater than or equal to 0. If the variable n1 is less than or equal to the constant N1 (S107: No), the processing shown in step S101 is executed again.

[0041] On the other hand, if the variable n1 is greater than the constant N1 (S107: Yes), the surface of the deposits attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 is reduced (S108). Step S108 is an example of step b). In step S108, H2 gas and Ar gas are supplied into chamber 1 from the gas supply mechanism 20, and the pressure inside chamber 1 is controlled to a predetermined pressure by the exhaust device 53. Then, RF power is supplied into chamber 1 via the matching unit 44 and the shower head 10, causing the gas inside chamber 1 to be plasma-generated. Then, the surface of the deposits attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 is reduced by the active species contained in the plasma.

[0042] The main processing conditions in step S108 are as follows, for example: Pressure inside Chamber 1: 50~1333 Pa RF power: 3000W or less H2 gas / Ar gas: 5-10000 / 0-10000 sccm Processing time: 1-180 seconds

[0043] Next, the surfaces of the deposits adhering to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 are nitrided (S109). Step S109 is an example of step c). In step S109, NH3 gas is supplied into chamber 1 from the gas supply mechanism 20, and the pressure inside chamber 1 is controlled to a predetermined pressure by the exhaust device 53. This nitrides the surfaces of the deposits reduced in step S108.

[0044] The main processing conditions in step S109 are, for example, as follows: Pressure inside Chamber 1: 50~1333 Pa NH3 gas / H2 gas / Ar gas: 10~10000 / 5~10000 / 0~10000 sccm Processing time: 1-180 seconds

[0045] In step S109, RF power may be supplied into chamber 1, and the gas supplied into chamber 1 may be plasma-generated. In this case, the magnitude of the RF power supplied into chamber 1 is, for example, 3000W or less.

[0046] Next, the control device 60 initializes the variable n1 to 0 (S110). Then, the process shown in step S101 is executed again.

[0047] By the way, when the TiCl4 gas is plasma-generated in the chamber 1 in step S102, the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51 will have TiCl4 gas on them, as shown in Figure 3A, for example. x Sediment 70 containing (x is one of 1-3) is attached. x Because the deposit 70 containing [the substance] is brittle, it easily peels off from the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51, and is easily scattered into chamber 1 as particles. Therefore, it is conceivable to make the deposit 70 less likely to peel off by coating the surface of the deposit 70 with a nitride film.

[0048] Here, in step S103, when NH3 gas is supplied into the chamber 1, it appears that the surface of the deposit 70 formed on the surface of the substrate W is also nitrided.

[0049] Figure 4 shows an example of the relationship between the change in Gibbs free energy ΔG and temperature. Trend 1, exemplified in Figure 4, shows the relationship between the change in Gibbs free energy ΔG and temperature in the following reaction equation (1). TiCl3+NH3→TiN+3HCl ···(1)

[0050] Referring to trend 1 illustrated in Figure 4, the reaction of reaction equation (1) proceeds, that is, the change in Gibbs free energy ΔG becomes negative, when the temperature is 320°C or higher. Therefore, if the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 can be maintained at a temperature of 320°C or higher, the surface of the deposit 70 containing TiCl3 attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 will be nitrided by NH3 gas. Then, the surface of the deposit 70 containing TiCl3 will be converted to TiN according to reaction equation (1).

[0051] However, it is difficult to heat both the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 to above 320°C. As a result, deposits 70 whose surfaces are not sufficiently nitrided remain on the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51, becoming a source of particles.

[0052] Therefore, in this embodiment, in step S108, the surface of the deposit 70 is reduced by active species contained in the plasma generated from a gas containing H2 gas, and then the surface of the deposit 70 is nitrided with NH3 gas.

[0053] For example, trend 2 shown in Figure 4 illustrates the relationship between the change in Gibbs free energy ΔG and temperature in the following reaction equation (2). Note that trend 2 in Figure 4 shows the trend when the H2 gas is not plasma-generated. 2TiCl3+H2→2TiCl2+2HCl ···(2)

[0054] Referring to trend 2 in Figure 4, the change in Gibbs free energy ΔG will not be negative unless the temperature is much higher than 600°C, and the reaction shown in reaction equation (2) will not proceed.

[0055] In contrast, trend 3 shown in Figure 4, for example, illustrates the relationship between the change in Gibbs free energy ΔG in the following reaction equation (3) and temperature. Note that trend 3 in Figure 4 shows the trend when H2 gas is plasma-generated. TiCl3 + H → TiCl2 + HCl ... (3)

[0056] Referring to trend 3 in Figure 4, the change in Gibbs free energy ΔG is negative in almost all temperature ranges. Therefore, the reaction shown in reaction equation (3) proceeds in almost all temperature ranges.

[0057] Furthermore, for example, trend 4 shown in Figure 4 illustrates the relationship between the change in Gibbs free energy ΔG and temperature in the following reaction equation (4). 2TiCl2+2NH3→2TiN+4HCl+H2...(4)

[0058] Referring to trend 4 in Figure 4, in the positive temperature range, the change in Gibbs free energy ΔG is negative, and the reaction shown in reaction equation (4) proceeds even at temperatures lower than 320°C (e.g., room temperature).

[0059] Thus, in the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51, where it is difficult to maintain a temperature of 320°C or higher, even if NH3 gas is supplied to the deposit 70 containing TiCl3, it is difficult to nitride the surface of the deposit 70, as shown in, for example, trend 1 in Figure 4.

[0060] In contrast, in this embodiment, the deposit 70 containing TiCl3 is exposed to a plasma generated from H2 gas, and as shown in trend 3 of Figure 4, the TiCl3 is reduced to TiCl2 at a temperature lower than 320°C. As a result, a layer 71 containing TiCl2 is formed on the surface of the deposit 70, for example, as shown in Figure 3B.

[0061] Then, by exposing the TiCl2-containing layer 71 to NH3 gas, the TiCl2 is nitrided to TiN at a temperature lower than 320°C, as shown in trend 4 in Figure 4 and the aforementioned reaction equation (4). As a result, a TiN-containing nitride layer 72 is formed on the surface of the deposit 70, for example, as shown in Figure 3C. This coats the easily detachable surface of the deposit 70 with the TiN-containing nitride layer 72, suppressing the scattering of the deposit 70. This reduces the number of cleaning steps required to remove the deposit 70, thereby improving the throughput of the film deposition process.

[0062] Furthermore, in step S102, since the H2 gas is plasma-generated in chamber 1, it appears that the surface of the deposit 70 attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 is reduced by the H atoms contained in the plasma. However, the flow rate of the H2 gas in step S102 is about the same as that of the TiCl4 gas. Therefore, the density of H atoms contained in the plasma is more than five orders of magnitude lower than the density of TiCl4 molecules and H2 molecules. Therefore, in step S102, the TiCl4 deposited on the substrate W is reduced. x Even if the deposits can be reduced by H atoms, it is difficult to sufficiently reduce the surface of the deposits 70 attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 with H atoms.

[0063] Furthermore, in step S102, Ar gas is supplied into chamber 1, and the plasma contains Ar ions. Ar ions also contribute to the formation of TiCl xIt is possible to reduce the deposits. However, because Ar ions have a smaller diffusion coefficient than H atoms, although they are abundant between the electrodes where the plasma exists, they have difficulty reaching the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51, which are far from the electrodes. Therefore, it is difficult to sufficiently reduce the surface of the deposits 70 attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 with Ar ions.

[0064] Therefore, in this embodiment, in step S108, when TiCl4 gas is not supplied, H2 gas is plasma-generated in chamber 1. This allows a large number of H atoms to be generated in chamber 1, and H atoms, which have a larger diffusion coefficient than Ar ions, can be diffused into chamber 1. This allows a sufficient amount of H atoms to be supplied to the surface of the deposit 70 attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51. Consequently, the surface of the deposit 70 attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 can be sufficiently reduced by the reaction according to the reaction equation (3) described above.

[0065] Furthermore, if the Ti film deposition process on the substrate W is repeated, deposits 70 are again deposited on top of the nitrided layer 72. In that case, yet another nitrided layer 72 is formed on top of it. In this way, the deposits 70 and nitrided layer 72 are alternately deposited, making it difficult for the deposits 70 to peel off from the inner wall of the chamber 1, etc.

[0066] Furthermore, even for components within Chamber 1, if a component can be heated to 320°C or higher, such as the shower plate 12, TiCl will be applied to the surface of the component. x Instead of deposits 70 containing TiCl, a Ti film 75 is formed, for example, as shown in Figure 5A. The Ti film 75 is TiCl x It is less likely to peel off than the deposit 70 containing the material. However, when the process of depositing a Ti film on multiple substrates W is repeated, the Ti film 75 formed on the surface of the components in the chamber 1 becomes thicker. When the Ti film 75 becomes thicker, the film stress on the Ti film 75 may cause the Ti film 75 to peel off from the inner wall of the chamber 1, etc.

[0067] To prevent the Ti film 75 from peeling off, it is possible to reduce the film stress of the Ti film 75. In this embodiment, in step S109, NH3 gas is supplied into the chamber 1. As a result, the surface of the Ti film 75 is nitrided, as shown in Figure 5B, for example, and a TiN film 76 is formed. Since the TiN film 76 has a film stress opposite to that of the Ti film 75, the film stress of the Ti film 75 can be reduced.

[0068] Subsequently, when the Ti film deposition process on the substrate W is repeated, for example, as shown in Figure 5C, a Ti film 75 is again deposited on top of the TiN film 76. In that case, another TiN film 76 is formed on top of it. By alternately depositing the Ti film 75 and the TiN film 76 in this way, the Ti film 75 can be made less likely to peel off from the inner wall of the chamber 1, etc.

[0069] The first embodiment has been described above. The particle suppression method of this embodiment includes steps a), b), and c). In step a), a first processing gas containing halogen elements and metal elements is supplied into a chamber 1 containing a substrate W, and the first processing gas is plasma-activated to form a film containing metal elements on the substrate W. In step b), a second processing gas containing hydrogen gas is supplied into the chamber 1, and the second processing gas is plasma-activated to reduce the surface of the deposits formed on the inner wall of the chamber 1. In step c), a third processing gas containing nitrogen elements is supplied into the chamber 1 to nitride the surface of the reduced deposits. This makes it possible to suppress the generation of particles in the chamber 1.

[0070] Furthermore, in the particle suppression method of this embodiment, in step c), the surface of the reduced deposit may be nitrided by plasma-forming the third processing gas supplied into the chamber 1.

[0071] Furthermore, the particle suppression method in this embodiment further includes step a4), which is performed after step a), in which the substrate W on which a film containing a metal element is formed is removed from the chamber 1, and steps b) and c) are performed after step a4). This makes it possible to reduce the influence that the processing to suppress particle generation in the chamber 1 has on the film quality of the substrate W.

[0072] Furthermore, in this embodiment, step b) is performed based on the number of substrates W on which step a) has been performed. This allows the surface of the deposits 70 to be nitrided before the deposits 70 adhering to the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51 are peeled off.

[0073] Furthermore, in this embodiment, the halogen element contained in the first processing gas is Cl, and the metallic element contained in the first processing gas is Ti. Also, the first processing gas is TiCl4 gas. The second processing gas is a mixture of H2 gas and a noble gas. The third processing gas is NH3 gas. This makes it possible to suppress the generation of particles in the chamber 1 when forming a film containing a metallic element on the substrate W in the chamber 1.

[0074] (Second embodiment) In this embodiment, each time a Ti film is deposited on a predetermined number of substrates W, cleaning of the chamber 1 and pre-coating of the inner wall of the chamber 1 are performed. During the pre-coating of the inner wall of the chamber 1, TiClx is deposited, the surface of the deposited material is reduced, and the surface of the reduced deposited material is nitrided. This suppresses the generation of particles from the pre-coat film after cleaning.

[0075] Figure 6 is a flowchart showing an example of a particle suppression method in the second embodiment. Each process illustrated in the flowchart of Figure 6 is realized by the control device 60 controlling each part of the plasma processing device 100. In Figure 6, processes that are denoted by the same reference numerals as in Figure 2 are the same as the processes described in Figure 2, so a detailed explanation is omitted.

[0076] First, the control device 60 initializes the variables n1 and n2, which are used to count the number of substrates W, to 0 (S120). Then, the process shown in step S101 is executed.

[0077] Furthermore, after the process shown in step S104 is executed, the control device 60 increments variables n1 and n2 by 1 each (S121). Then, the process shown in step S106 is executed.

[0078] Furthermore, if variable n1 is greater than the constant N1 (S107: Yes), the control device 60 determines whether variable n2 is greater than a predetermined constant N2 (S122). In this embodiment, the constant N2 is, for example, 1499. If variable n2 is less than or equal to the constant N2 (S122: No), the process shown in step S108 is executed.

[0079] On the other hand, if the variable n2 is greater than the constant N2 (S122: Yes), the control device 60 performs cleaning in the chamber 1 (S123). Step S123 is an example of process d). In step S123, a cleaning gas containing fluorine is supplied into the chamber 1 from a cleaning gas supply source (not shown), and the pressure inside the chamber 1 is controlled to a predetermined pressure by the exhaust device 53. This removes deposits adhering to the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51. Examples of cleaning gases containing fluorine include ClF3 gas. The cleaning gas containing fluorine is an example of a fourth gas.

[0080] Next, the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 are pre-coated (S124). Step S124 is an example of step e). In step S124, TiCl4 gas, H2 gas, and Ar gas are supplied into chamber 1 from the gas supply mechanism 20, and the pressure inside chamber 1 is controlled to a predetermined pressure by the exhaust device 53. Then, RF power is supplied into chamber 1 via the matching unit 44 and showerhead 10, causing the gas inside chamber 1 to be plasma-generated, and deposits are formed on the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 by the active species contained in the plasma.

[0081] The main processing conditions in step S124 are as follows, for example: Pressure inside Chamber 1: 50~1333 Pa RF power: 10~3000W TiCl4 gas / H2 gas / Ar gas: 5~100 / 1~500 / 10~10000 sccm Processing time: 1-600 seconds

[0082] Next, the surfaces of the deposits formed on the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 are reduced (S125). Step S125 is an example of step f). In step S125, H2 gas and Ar gas are supplied into chamber 1 from the gas supply mechanism 20, and the pressure inside chamber 1 is controlled to a predetermined pressure by the exhaust device 53. Then, RF power is supplied into chamber 1 via the matching unit 44 and showerhead 10, causing the gas inside chamber 1 to be plasma-generated. The active species contained in the plasma then reduce the surfaces of the deposits attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51.

[0083] The main processing conditions in step S125 are as follows, for example: Pressure inside Chamber 1: 50~1333 Pa RF power: 10~3000W H2 gas / Ar gas: 5-10000 / 0-10000 sccm Processing time: 1-180 seconds

[0084] Next, the surfaces of the deposits formed on the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 are nitrided (S126). Step S126 is an example of step g). In step S126, NH3 gas is supplied into chamber 1 from the gas supply mechanism 20, and the pressure inside chamber 1 is controlled to a predetermined pressure by the exhaust device 53. This causes the surface of the reduced deposits to be nitrided.

[0085] The main processing conditions in step S126 are, for example, as follows: Pressure inside Chamber 1: 50~1333 Pa NH3 gas / H2 gas / Ar gas: 10~10000 / 5~10000 / 0~10000 sccm Processing time: 1-180 seconds

[0086] In step S126, RF power may be supplied into chamber 1, and the gas supplied into chamber 1 may be plasma-generated. In this case, the magnitude of the RF power supplied into chamber 1 is, for example, 3000W or less.

[0087] Next, the control device 60 initializes the variable n2 to 0 (S127). Then, the process shown in step S101 is executed again.

[0088] In the example shown in Figure 6, steps S124, S125, and S126 are each executed once after step S123, but the disclosed technology is not limited to this. As another example, after step S123 is executed, steps S124, S125, and S126 may be repeated multiple times in this order.

[0089] The second embodiment has been described above. The particle suppression method of this embodiment further includes steps d), e), f), and g). Step d) removes deposits adhering to the inner wall of chamber 1 by supplying a fourth processing gas containing fluorine into chamber 1. Step e) forms deposits on the inner wall of chamber 1 by supplying a first processing gas into chamber 1 and plasma-generating the first processing gas. Step f) reduces the surface of the deposits formed on the inner wall of chamber 1 by supplying a second processing gas into chamber 1 and plasma-generating the second processing gas. Step g) nitrides the surface of the reduced deposits by supplying a third processing gas into chamber 1. This makes it possible to suppress the generation of particles from the pre-coat film after cleaning.

[0090] Furthermore, in the particle suppression method of this embodiment, in step g), the surface of the reduced deposit may be nitrided by plasma-forming the third processing gas supplied into the chamber 1.

[0091] (Third embodiment) In this embodiment, the pre-coating of the inner wall of the chamber 1, which is performed before the deposition of the Ti film on the substrate W, involves the deposition of TiClx, reduction of the surface of the deposited material, and nitriding of the surface of the reduced deposited material. This suppresses the generation of particles from the pre-coat film.

[0092] Figure 7 is a flowchart showing an example of a particle suppression method in the third embodiment. Each process illustrated in the flowchart of Figure 7 is realized by the control device 60 controlling each part of the plasma processing device 100. In Figure 7, processes that are denoted by the same reference numerals as in Figure 2 are the same as the processes described in Figure 2, so a detailed explanation is omitted.

[0093] After the initialization of the variable n1, the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 are pre-coated (S130). Step S130 is an example of step h). In step S130, TiCl4 gas, H2 gas, and Ar gas are supplied into chamber 1 from the gas supply mechanism 20, and the pressure inside chamber 1 is controlled to a predetermined pressure by the exhaust device 53. Then, RF power is supplied into chamber 1 via the matching unit 44 and showerhead 10, causing the gas inside chamber 1 to be plasma-generated, and deposits are formed on the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 by the active species contained in the plasma.

[0094] The main processing conditions in step S130 are as follows, for example: Pressure inside Chamber 1: 50~1333 Pa RF power: 10~3000W TiCl4 gas / H2 gas / Ar gas: 5~100 / 1~500 / 10~10000 sccm Processing time: 1-600 seconds

[0095] Next, the surfaces of deposits attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 are reduced (S131). Step S131 is an example of process i). In step S131, H2 gas and Ar gas are supplied into chamber 1 from the gas supply mechanism 20, and the pressure inside chamber 1 is controlled to a predetermined pressure by the exhaust device 53. Then, RF power is supplied into chamber 1 via the matching unit 44 and showerhead 10, causing the gas inside chamber 1 to be plasma-generated. The active species contained in the plasma then reduce the surfaces of deposits attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51.

[0096] The main processing conditions in step S131 are as follows, for example: Pressure inside Chamber 1: 50~1333 Pa RF power: 10~3000W H2 gas / Ar gas: 5-10000 / 0-10000 sccm Processing time: 1-180 seconds

[0097] Next, the surfaces of the deposits adhering to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 are nitrided (S132). Step S132 is an example of process j). In step S132, NH3 gas is supplied into chamber 1 from the gas supply mechanism 20, and the pressure inside chamber 1 is controlled to a predetermined pressure by the exhaust device 53. This nitrides the surface of the deposits reduced in step S131. Then, the process shown in step S101 is performed.

[0098] The main processing conditions in step S132 are, for example, as follows: Pressure inside Chamber 1: 50~1333 Pa NH3 gas / H2 gas / Ar gas: 10~10000 / 5~10000 / 0~10000 sccm Processing time: 1-180 seconds

[0099] In step S132, RF power may be supplied into chamber 1, and the gas supplied into chamber 1 may be plasma-generated. In this case, the magnitude of the RF power supplied into chamber 1 is, for example, 3000W or less.

[0100] The third embodiment has been described above. The particle suppression method of this embodiment further includes steps h), i), and j). Step h) is performed before step a), in which a first processing gas is supplied into the chamber 1 and the first processing gas is plasma-activated to form a deposit on the inner wall of the chamber 1. Step i) is performed before step a) and after step h), in which a second processing gas is supplied into the chamber 1 and the second processing gas is plasma-activated to reduce the surface of the deposit formed on the inner wall of the chamber 1. Step j) is performed before step a) and after step i), in which a third processing gas is supplied into the chamber 1 to nitride the surface of the reduced deposit. This makes it possible to suppress the generation of particles from the precoat film formed on the inner wall of the chamber 1, etc., before the formation of the Ti film on the substrate W.

[0101] Furthermore, in the particle suppression method of this embodiment, in step j), the surface of the reduced deposit may be nitrided by plasma-forming the third processing gas supplied into the chamber 1.

[0102] (Fourth embodiment) In this embodiment, after a Ti film is formed on the substrate W, and before nitriding the surface of the Ti film formed on the substrate W, the surface of the Ti film formed on the substrate W is reduced using plasma generated from H2 gas. This reduces the time required for nitriding the surface of the Ti film formed on the substrate W. In addition, the plasma generated from H2 gas can be used to reduce the surface of deposits attached to the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51. This reduces the time required to reduce the surface of deposits attached to the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51 after the substrate W has been removed.

[0103] Figure 8 is a flowchart showing an example of a particle suppression method in the fourth embodiment. Each process illustrated in the flowchart of Figure 8 is realized by the control device 60 controlling each part of the plasma processing device 100. In Figure 8, processes that are denoted by the same reference numerals as in Figure 2 are the same as the processes described in Figure 2, so a detailed explanation is omitted.

[0104] In step S102, a Ti film is formed on the surface of the substrate W, and then the surface of the Ti film is reduced (S140). Step S140 is an example of step a2). In step S140, H2 gas is supplied into the chamber 1 from the gas supply mechanism 20, and the pressure inside the chamber 1 is controlled to a predetermined pressure by the exhaust device 53. Then, RF power is supplied into the chamber 1 via the matching unit 44 and the shower head 10, causing the gas inside the chamber 1 to be plasma-generated, and the surface of the Ti film formed on the substrate W is reduced by the active species contained in the plasma. Then, the process shown in step S103 is executed.

[0105] The main processing conditions in step S140 are, for example, as follows: Pressure inside Chamber 1: 0~1333 Pa RF power: 10~3000W H2 gas / Ar gas: 5-10000 / 0-10000 sccm Processing time: 1-180 seconds

[0106] Figure 9 shows an example of the measurement results for the number of particles. Comparative Example 1 shown in Figure 9 is an example in which the process in step S108 is not performed in the process illustrated in Figure 8. Comparative Example 2 is an example in which the processes in steps S140 and S108 are not performed in the process illustrated in Figure 8.

[0107] As shown in Figure 9, in Comparative Examples 1 and 2, approximately 50 particles were detected on the 1500th substrate W, indicating that cleaning of the chamber 1 and exhaust chamber 51 with the fourth processing gas and initialization of the inner walls 1c and 51a by pre-coating were necessary. In contrast, when the processing according to this embodiment was performed on the 1501st substrate W, the number of particles detected on the substrate W was suppressed to about 10. Therefore, the method of this embodiment can reduce the number of particles generated in the chamber 1.

[0108] The fourth embodiment has been described above. In this embodiment, step a) includes steps a1), a2), and a3). Step a1) involves supplying a first processing gas into the chamber 1 and plasma-generating the first processing gas to form a film containing a metal element on the substrate W. Step a2) involves supplying a second processing gas into the chamber 1 and plasma-generating the second processing gas to reduce the surface of the film containing the metal element formed on the substrate W. Step a3) involves supplying a third processing gas into the chamber 1 and exposing the surface of the film containing the metal element to the third processing gas to nitride the surface of the reduced film containing the metal element. This reduces the time required for nitriding the surface of the Ti film formed on the substrate W. Furthermore, the plasma generated from H2 gas can reduce the surface of deposits adhering to the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51. This makes it possible to reduce the time required to reduce the surface of deposits adhering to the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51 after the substrate W has been removed.

[0109] [others] This disclosure is not limited to the embodiments described above, and numerous modifications are possible within the scope of its essence.

[0110] For example, in the embodiment described above, Ti was used as an example of a metallic element contained in the film formed on the substrate W, but the disclosed technology is not limited to this. In addition to Ti, other metallic elements such as Ta (tantalum) and W (tungsten) can also be considered as metallic elements contained in the film formed on the substrate W. When forming a film containing Ta on the substrate W, for example, TaCl5 gas can be used as the first processing gas instead of TiCl4 gas.

[0111] Figure 10 shows an example of the relationship between the change in Gibbs free energy ΔG and temperature. Trend 5, exemplified in Figure 10, shows the relationship between the change in Gibbs free energy ΔG and temperature in the following reaction equation (5). 2TaCl4+2NH3→2TaN+6HCl+Cl2...(5)

[0112] Referring to trend 5 illustrated in Figure 10, the reaction of reaction equation (5) proceeds, that is, the change in Gibbs free energy ΔG becomes negative, when the temperature is approximately 400°C or higher. Therefore, if the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 can be maintained at a temperature of 400°C or higher, the surface of the deposits containing TaCl4 etc. attached to the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51 will be nitrided by NH3 gas. Then, the surface of the deposits containing TaCl4 etc. will be converted to TaN according to reaction equation (5).

[0113] Furthermore, for example, trend 6 shown in Figure 10 illustrates the relationship between the change in Gibbs free energy ΔG in the following reaction equation (6) and temperature. Note that trend 6 in Figure 10 shows the trend when the H2 gas is not plasma-generated. TaCl4+H2→TaCl2+2HCl ···(6)

[0114] Furthermore, for example, trend 7 shown in Figure 10 illustrates the relationship between the change in Gibbs free energy ΔG in the following reaction equation (7) and temperature. Note that trend 7 in Figure 10 shows the trend when the H2 gas is not plasma-generated. 2TaCl4+H2→2TaCl3+2HCl ···(7)

[0115] Referring to trends 6 and 7 in Figure 10, the change in Gibbs free energy ΔG is not negative unless the temperature is much higher than 400°C. Therefore, the reactions shown in reaction equations (6) and (7) will not proceed unless the temperature is much higher than 400°C.

[0116] Furthermore, for example, trend 8 shown in Figure 10 illustrates the relationship between the change in Gibbs free energy ΔG and temperature in the following reaction equation (8). Note that trend 8 in Figure 10 shows the trend when H2 gas is plasma-generated. TaCl3 + H → TaCl2 + HCl ... (8)

[0117] Furthermore, for example, trend 9 shown in Figure 10 illustrates the relationship between the change in Gibbs free energy ΔG in the following reaction equation (9) and temperature. Note that trend 9 in Figure 10 shows the trend when H2 gas is plasma-generated. TaCl4 + H → TaCl3 + HCl ... (9)

[0118] Referring to trends 8 and 9 in Figure 10, the change in Gibbs free energy ΔG is negative in almost all temperature ranges. Therefore, the reactions shown in reaction equations (8) and (9) proceed in almost all temperature ranges.

[0119] Furthermore, for example, the trend 10 shown in Figure 10 illustrates the relationship between the change in Gibbs free energy ΔG and temperature in the following reaction equation (10). TaCl3+NH3→TaN+3HCl ···(10)

[0120] Furthermore, for example, trend 11 shown in Figure 10 illustrates the relationship between the change in Gibbs free energy ΔG and temperature in the following reaction equation (11). Note that trend 11 in Figure 10 shows the trend when NH3 gas is plasma-generated. 2TaCl2+2NH3→2TaN+4HCl+H2...(11)

[0121] Referring to trends 10 and 11 in Figure 10, the change in Gibbs free energy ΔG is negative in the positive temperature range. Therefore, even at temperatures below 400°C (e.g., room temperature), the nitriding reaction with NH3 gas shown in reaction equations (10) and (11) proceeds.

[0122] Thus, in the inner wall 1c of chamber 1 and the inner wall 51a of exhaust chamber 51, where it is difficult to maintain a temperature of 400°C or higher, even if NH3 gas is supplied to the deposits containing TaCl4, it is difficult to nitride the surface of the deposits, as shown in trend 5 of Figure 10.

[0123] In contrast, by exposing deposits containing TaCl4 to a plasma generated from a gas containing H2, the TaCl4 is reduced to TaCl2 or TaCl3 at temperatures below 400°C, as shown in trends 8 and 9 in Figure 10.

[0124] Next, the sediment containing TaCl2 or TaCl3 is exposed to NH3 gas. As a result, TaCl2 or TaCl3 is nitrided to TaN at a temperature lower than 400°C, as shown in trends 10 and 11 in Figure 10 and in the reaction equations (10) and (11) above. This coats the surface of the easily detachable sediment with a nitrided layer containing TaN, thereby suppressing the scattering of the sediment.

[0125] Furthermore, in each of the embodiments described above, since the processing gas and RF power are supplied into the chamber 1 from the showerhead 10, many active species contained in the plasma are present near the substrate W. However, depending on the processing conditions, the active species contained in the plasma may not sufficiently reach the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51. Therefore, in addition to the showerhead 10, the matching unit 44, and the RF power supply 45, a remote plasma generation unit 80 may be provided separately, for example as shown in Figure 11, to supply active species near the deposit to be coated.

[0126] In the example shown in Figure 11, the remote plasma generation unit 80 is connected to the exhaust chamber 51 via piping 81. The remote plasma generation unit 80 supplies active species contained in the plasma generated from a gas containing H2 gas to the deposits formed on the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51. Then, NH3 gas is supplied into the chamber 1 from the gas supply mechanism 20. This allows for more efficient nitriding of the surfaces of the deposits formed on the inner wall 1c and the inner wall 51a of the exhaust chamber 51.

[0127] Furthermore, in each of the embodiments described above, the reduction and nitriding treatment of deposits formed on the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51 is performed according to the number of substrates W on which the film deposition treatment is carried out, but the disclosed technology is not limited thereto. If the reduction and nitriding treatment of deposits is performed before the deposits formed on the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51 peel off, the reduction and nitriding treatment of deposits may be carried out based on other information. For example, the reduction and nitriding treatment of deposits formed on the inner wall 1c of the chamber 1 and the inner wall 51a of the exhaust chamber 51 may be carried out based on the cumulative thickness of the Ti film formed on the multiple substrates W, or the cumulative time of plasma treatment when forming the Ti film on the substrates W, etc.

[0128] Furthermore, in each of the embodiments described above, the first processing gas supplied from the supply source 21a is, for example, TiCl4 gas, but the disclosed technology is not limited thereto. In other embodiments, the first processing gas supplied from the supply source 21a may be TaCl5 gas, WCl4 gas, WCl5 gas, or WCl6 gas, etc.

[0129] Furthermore, in each of the embodiments described above, the second processing gas is a mixture of H2 gas and Ar gas, but the disclosed technology is not limited thereto. In other embodiments, the second processing gas may be a mixture of H2 gas and other noble gases. Alternatively, the second processing gas may be H2 gas.

[0130] Furthermore, in each of the embodiments described above, the third processing gas supplied from the supply source 21d is NH3 gas, but the disclosed technology is not limited to this. In other embodiments, the third processing gas may be N2 gas, or a mixture of H2 gas and N2 gas.

[0131] Furthermore, in the embodiments described above, a plasma processing apparatus 100 using capacitively coupled plasma (CCP) was described as an example of a plasma source, but the plasma source is not limited to this. Examples of plasma sources other than capacitively coupled plasma include inductively coupled plasma (ICP), microwave-excited surface wave plasma (SWP), electron cycloton resonance plasma (ECP), and helicon wave-excited plasma (HWP).

[0132] It should be noted that the embodiments disclosed herein are illustrative and not restrictive in all respects. Indeed, the embodiments described above can be embodied in a variety of forms. Furthermore, the embodiments described above may be omitted, replaced, or modified in various ways without departing from the scope and spirit of the appended claims. [Explanation of symbols]

[0133] W board 100 Plasma Processing Equipment 1 Chamber 1a Ceiling wall 1b Bottom wall 1c inner wall 2 Susceptors 3. Support member 4 Guide Rings 5 Heater 6 Heater power supply 9. Insulating material 10 shower heads 11 Base member 11a Flange section 12 shower plates 13 Intermediate member 14 Gas diffusion space 15 Gas discharge holes 16 Gas inlet 20 Gas supply mechanism 21 Source 22 valves 23 MFC 24 valves 30 Piping 44 Matching box 45 RF power supply 47 Heater 48 Heater power supply 49. Insulation material 50 openings 51 Exhaust chamber 51a Inner wall 52 Exhaust pipe 53 Exhaust system 54 Lift Pins 55 Support plate 56 Drive mechanism 57 Conveyor Port 58 Gate valve 60 Control device 61 Control Unit 62 Storage section 63 User Interface 70 Sediment 71 layers 72 Nitride layer 75Ti film 76 TiN film 80 Remote Plasma Generation Unit 81 Piping

Claims

1. a) A step of supplying a first processing gas containing halogen elements and metal elements into a chamber containing a substrate, and forming a film containing the metal elements on the substrate by plasma-generating the first processing gas; a4) A step performed after step a) in which the substrate on which the film containing the metal element is formed is removed from the chamber, b) H 2 gas, or H 2 A second processing gas, which is a mixture of gas and noble gas, is supplied into the chamber, and the second processing gas is plasma-generated to reduce the surface of deposits formed on the inner wall of the chamber. c) A step performed after step b) in which a third treatment gas containing nitrogen is supplied into the chamber to nitride the surface of the reduced deposit. Includes, Steps b) and c) are particle suppression methods performed after step a4).

2. The particle suppression method according to claim 1, wherein in step c), the surface of the reduced deposit is nitrided by plasma-forming the third processing gas supplied into the chamber.

3. The aforementioned step a) is, a1) A step of supplying the first processing gas into the chamber and plasma-forming the first processing gas to form a film containing the metal element on the substrate, a2) A step of supplying the second processing gas into the chamber and plasma-generating the second processing gas to reduce the surface of the film containing the metal element formed on the substrate, a3) A step of supplying the third processing gas into the chamber and exposing the surface of the film containing the metal element to the third processing gas, thereby nitriding the surface of the film containing the reduced metal element. A particle suppression method according to claim 1 or 2, including the following:

4. The aforementioned step b) is, A particle suppression method according to any one of claims 1 to 3, which is carried out based on at least one of the number of substrates on which step a) is performed, the cumulative thickness of the film containing the metal element formed on the substrates by performing step a) on a plurality of substrates, and the cumulative time of the plasma treatment in step a).

5. d) A step of removing the deposits adhering to the inner wall of the chamber by supplying a fourth processing gas containing fluorine into the chamber, e) A step of supplying the first processing gas into the chamber and plasma-generating the first processing gas to form the deposit on the inner wall of the chamber, f) A step of supplying the second processing gas into the chamber and plasma-generating the second processing gas to reduce the surface of the deposit formed on the inner wall of the chamber, g) A step of nitriding the surface of the reduced deposit by supplying the third processing gas into the chamber. A particle suppression method according to any one of claims 1 to 4, further comprising:

6. The particle suppression method according to claim 5, wherein in step g), the surface of the reduced deposit is nitrided by plasma-forming the third processing gas supplied into the chamber.

7. h) A step performed before step a), comprising supplying the first processing gas into the chamber and plasma-ifying the first processing gas to form the deposit on the inner wall of the chamber, i) A step performed before step a) and after step h), comprising supplying the second processing gas into the chamber and plasma-ifying the second processing gas to reduce the surface of the deposit formed on the inner wall of the chamber, j) A step performed before step a) and after step i), wherein the surface of the reduced deposit is nitrided by supplying the third processing gas into the chamber. A particle suppression method according to any one of claims 1 to 4, further comprising:

8. The particle suppression method according to claim 7, wherein in step j), the third processing gas supplied into the chamber is plasma-activated to nitride the surface of the reduced deposit.

9. The halogen element contained in the first processing gas is Cl. The particle suppression method according to any one of claims 1 to 8, wherein the metal element contained in the first processing gas is Ti, Ta, or W.

10. The first processing gas is TiCl 4 Gas, TaCl 5 Gas, WCl 4 Gas, WCl 5 gas, or WCl 6 A particle suppression method according to any one of claims 1 to 9, wherein the substance is a gas.

11. The third processing gas is NH 3 gas, N 2 gas, or a mixed gas of H 2 gas and N 2 gas, according to any one of claims 1 to 10, is a particle suppression method.

12. The particle suppression method according to any one of claims 1 to 11, wherein steps b) and c) are performed while the temperature of the inner wall of the chamber is controlled to a temperature lower than 320°C.

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