Plasma processing apparatus and plasma processing method

Abstract

The present application provides a kind of plasma processing device and plasma processing method, provide a kind of technology capable of inhibiting the attachment of microparticle to substrate.The plasma processing device of one mode of the present disclosure has: processing container, with the cylinder body shape of vertical type, opening is formed in the side wall of processing container, multiple substrates are housed in multiple layers inside the processing container;Plasma partition wall, airtight is arranged on the outer wall of the processing container, covers the opening and defines the plasma generation space;Plasma electrode is arranged along the plasma partition wall;And processing gas supply part, it is arranged outside the plasma generation space, and supplies plasma generation gas.

Description

Technical Field

[0001] This disclosure relates to a plasma processing apparatus and a plasma processing method. Background Technology

[0002] Regarding batch heat treatment apparatus, a technique is known in which a plasma generating section that generates plasma opens into a processing container to connect the container in a connected state (for example, see Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2004-343017 Summary of the Invention

[0006] The problem the invention aims to solve

[0007] This disclosure provides a technique for suppressing the adhesion of microparticles to a substrate.

[0008] Solution for solving the problem

[0009] A plasma processing apparatus according to one aspect of the present disclosure comprises: a processing container having a longitudinal cylindrical shape, an opening formed in the side wall of the processing container, and multiple substrates being housed in multiple layers inside the processing container; a plasma dividing wall being hermetically disposed on the outer wall of the processing container, covering the opening and defining a plasma generation space; a plasma electrode being disposed along the plasma dividing wall; and a processing gas supply unit being disposed outside the plasma generation space for supplying plasma generation gas.

[0010] The effects of the invention

[0011] According to this disclosure, it is possible to suppress the adhesion of microparticles to the substrate. Attached Figure Description

[0012] Figure 1 This is a schematic diagram illustrating an example of a plasma processing apparatus according to an embodiment.

[0013] Figure 2 This is a diagram illustrating the configuration of the gas nozzles.

[0014] Figure 3 This is a diagram illustrating the flow of gas in the plasma processing apparatus of the embodiment.

[0015] Figure 4 This is a diagram illustrating the configuration of the gas nozzles in the first and second examples.

[0016] Figure 5This is a diagram illustrating a first example of the gas supply sequence of the plasma processing method according to an embodiment.

[0017] Figure 6 This is a diagram illustrating a second example of the gas supply sequence of the plasma processing method according to an embodiment.

[0018] Figure 7 This is a diagram used to illustrate the configuration of the gas nozzles in the third and fourth examples.

[0019] Figure 8 This is a diagram illustrating a third example of the gas supply sequence of the plasma processing method according to an embodiment.

[0020] Figure 9 This is a diagram illustrating the fourth example of the gas supply sequence of the plasma processing method according to the embodiment.

[0021] Figure 10 This is a diagram used to illustrate the configuration of the gas nozzle in the reference example.

[0022] Figure 11 This is a diagram illustrating an example of the gas supply sequence in a plasma processing method of the reference example.

[0023] Figure 12 This is a diagram illustrating another example of the gas supply sequence in the plasma processing method of the reference example.

[0024] Figure 13 It is a graph showing the shift in the number of particles.

[0025] Figure 14 It is a diagram used to illustrate the location and type of gas nozzles.

[0026] Figure 15 This is a diagram showing the film thickness and in-plane uniformity of the SiN film.

[0027] Figure 16 This is a diagram showing the film thickness and in-plane uniformity of the SiN film.

[0028] Figure 17 This is a diagram showing the WER of the SiN film.

[0029] Explanation of reference numerals in the attached figures

[0030] 1: Processing container; 20: Gas supply unit; 22: Gas nozzle; 22a: Gas orifice; 23: Gas nozzle; 23a: Gas orifice; 31: Opening; 32: Plasma partition wall; 33: Plasma electrode; 100: Plasma processing device; P: Plasma generation space; W: Wafer. Detailed Implementation

[0031] Hereinafter, non-limiting exemplary embodiments of the present disclosure will be described with reference to the accompanying drawings. In all the drawings, the same or corresponding components or parts are labeled with the same or corresponding reference numerals, and repeated descriptions are omitted.

[0032] [Plasma Processing Device]

[0033] Reference Figures 1 to 3 An example of the plasma processing apparatus of the embodiment will be described. Figure 1 This is a schematic diagram illustrating an example of a plasma processing apparatus according to an embodiment. Figure 2 This is a diagram illustrating the configuration of the gas nozzles. Figure 3 This is a diagram illustrating the flow of gas in the plasma processing apparatus of the embodiment.

[0034] The plasma processing apparatus 100 includes a processing container 1. The processing container 1 is a topped, cylindrical shape with an opening at its lower end. The entire processing container 1 is made of, for example, quartz. A top plate 2 made of quartz is provided near the upper end inside the processing container 1, and the area below the top plate 2 is closed. At the opening at the lower end of the processing container 1, a metal manifold 3, shaped like a cylinder, is connected via a sealing member 4 such as an O-ring.

[0035] The manifold 3 supports the lower end of the processing container 1. A wafer boat 5, in which multiple semiconductor wafers (hereinafter referred to as "wafers W") serving as substrates are arranged in multiple layers, is inserted into the processing container 1 from below the manifold 3. In this way, multiple wafers W are generally horizontally housed within the processing container 1, spaced apart vertically. The wafer boat 5 is, for example, formed of quartz. The wafer boat 5 has three rods 6 (see reference 6). Figure 2 Multiple wafers W are supported by grooves (not shown) formed on rod 6.

[0036] The wafer boat 5 is placed on the worktable 8 via a quartz-formed insulating cylinder 7. The worktable 8 is supported on a rotating shaft 10 through a metal (stainless steel) cover 9, which opens and closes the opening at the lower end of the manifold 3.

[0037] A magnetic fluid seal 11 is provided in the through portion of the rotating shaft 10, which airtightly seals the rotating shaft 10 and supports it in a rotatable manner. A sealing member 12 for maintaining the airtightness of the processing container 1 is provided between the periphery of the cover 9 and the lower end of the manifold 3.

[0038] The rotating shaft 10 is mounted, for example, at the front end of the arm 13 supported by a lifting mechanism (not shown) such as a wafer boat lift. The rotating shaft 10 is raised and lowered integrally with the wafer boat 5 and the cover 9, and is inserted into and detached from the processing container 1. Alternatively, the worktable 8 may be fixedly set on the side of the cover 9, and the wafer W may be processed without rotating the wafer boat 5.

[0039] In addition, the plasma processing apparatus 100 has a gas supply unit 20 for supplying various gases into the processing container 1.

[0040] The gas supply unit 20 has four gas nozzles 21 to 24. However, the gas supply unit 20 may have other gas nozzles besides the four gas nozzles 21 to 24.

[0041] The gas nozzle 21, for example, is formed of quartz and has an L-shape that bends upward and extends vertically after penetrating the inner sidewall of the manifold 3. The vertical portion of the gas nozzle 21 is located outside the plasma generation space P, for example, within the processing container 1, closer to the plasma generation space P than the center C of the processing container 1. However, the vertical portion of the gas nozzle 21 may also be located within the processing container 1, closer to the exhaust port 40 than the center C of the processing container 1. The gas nozzle 21 is connected to a supply source of dichlorosilane (DCS) gas. In the vertical portion of the gas nozzle 21, a plurality of gas holes 21a are formed at intervals along a length corresponding to the wafer support range of the wafer boat 5 in the vertical direction. The gas holes 21a, for example, face the center C of the processing container 1, and eject DCS gas horizontally toward the center C of the processing container 1. However, the gas holes 21a may also face the inner wall side near the processing container 1, for example.

[0042] The gas nozzle 22, for example, is formed of quartz and has an L-shape that bends upward and extends vertically after penetrating the inner sidewall of the manifold 3. The vertical portion of the gas nozzle 22 is located outside the plasma generation space P, for example, within the processing container 1, closer to the plasma generation space P than the center C of the processing container 1. However, the vertical portion of the gas nozzle 22 may also be located within the processing container 1, closer to the exhaust port 40 than the center C of the processing container 1. The gas nozzle 22 is connected to a supply source of ammonia and a supply source of hydrogen. Ammonia and hydrogen are examples of gases used for plasma generation. In the vertical portion of the gas nozzle 22, a plurality of gas holes 22a are formed at intervals along a length corresponding to the wafer support range of the wafer boat 5 in the vertical direction. The gas holes 22a face, for example, the center C of the processing container 1, and eject ammonia and hydrogen horizontally toward the center C of the processing container 1. However, the gas holes 22a may also face the plasma generation space P side, or face the inner wall side near the processing container 1.

[0043] The gas nozzle 23, for example, is formed of quartz and has an L-shape that extends vertically upwards after penetrating the inner sidewall of the manifold 3. The vertical portion of the gas nozzle 23 is disposed in the plasma generation space P. The gas nozzle 23 is connected to a purge gas supply source. In the vertical portion of the gas nozzle 23, a plurality of gas holes 23a are formed at intervals along a length corresponding to the wafer support range of the wafer boat 5 in the vertical direction. The gas holes 23a face, for example, the center C of the processing container 1, and purge gas is ejected horizontally toward the center C of the processing container 1. Examples of purge gases include argon and nitrogen.

[0044] The gas nozzle 24, for example, is formed of quartz and has a straight tube shape that extends horizontally through the sidewall of the manifold 3. The front end of the gas nozzle 24 is located outside the plasma generation space P, for example, inside the processing container 1. The gas nozzle 24 is connected to a purge gas supply source. The gas nozzle 24 has an opening at its front end, through which purge gas is supplied into the processing container 1. Examples of purge gases include argon and nitrogen.

[0045] A plasma generation mechanism 30 is formed on a portion of the sidewall of the processing container 1. The plasma generation mechanism 30 plasma-injects ammonia and hydrogen supplied from the gas nozzle 22 to generate active species.

[0046] The plasma generation mechanism 30 has a plasma dividing wall 32, a pair of plasma electrodes 33, a power supply line 34, an RF power supply 35, and an insulating protective cover 36.

[0047] The plasma partition wall 32 is hermetically welded to the outer wall of the processing container 1. The plasma partition wall 32 is formed, for example, of quartz. The plasma partition wall 32 has a concave cross-section and covers the opening 31 formed on the side wall of the processing container 1. The opening 31 is elongated in the vertical direction to cover all the wafers W supported by the wafer boat 5 in the vertical direction. A gas nozzle 23 for ejecting purge gas is disposed in the inner space defined by the plasma partition wall 32 and communicating with the interior of the processing container 1, i.e., the plasma generation space P. Furthermore, a gas nozzle 21 for ejecting DCS gas and a gas nozzle 22 for ejecting ammonia and hydrogen gas are disposed outside the plasma generation space P, along the inner side wall of the processing container 1, near the wafers W.

[0048] A pair of plasma electrodes 33, each having an elongated shape, are arranged facing each other along the vertical direction on the outer surface of the walls on both sides of the plasma dividing wall 32. A power supply line 34 is connected to the lower end of each plasma electrode 33.

[0049] Power supply line 34 electrically connects each plasma electrode 33 to the RF power supply 35. For example, one end of power supply line 34 is connected to the lower end of the side portion of each plasma electrode 33 that serves as the short side, and the other end is connected to the RF power supply 35.

[0050] RF power supply 35 is connected to the lower end of each plasma electrode 33 via power supply line 34, supplying RF power, for example, 13.56 MHz, to a pair of plasma electrodes 33. This applies RF power to the plasma generation space P defined by the plasma partition wall 32. Ammonia and hydrogen gas (see reference) are ejected from gas nozzle 22 into the processing container 1. Figure 3 A portion of the arrow F1 diffuses in the reverse direction from the processing container 1 through opening 31 into the plasma generation space P (see reference). Figure 3 (Arrows F2 and F3). Then, the counter-diffused ammonia and hydrogen are plasma-generated in the plasma generation space P, and the resulting active species are supplied to the processing container 1 through opening 31 (see reference). Figure 3 Arrows F4 and F5).

[0051] An insulating protective cover 36 is installed on the outside of the plasma partition wall 32, covering it. A refrigerant passage (not shown) is provided on the inner side of the insulating protective cover 36, through which cooled refrigerant such as nitrogen is flowed, thereby cooling the plasma electrode 33. Alternatively, a shield (not shown) may be provided between the plasma electrode 33 and the insulating protective cover 36, covering the plasma electrode 33. The shield is grounded and is formed, for example, by a good conductor such as metal.

[0052] An exhaust port 40 for vacuuming the interior of the processing container 1 is provided on the side wall portion facing the opening 31. The exhaust port 40 is elongated in the vertical direction corresponding to the wafer boat 5. An exhaust mask member 41 is installed on the portion of the processing container 1 corresponding to the exhaust port 40, covering the exhaust port 40. The exhaust mask member 41 is shaped with a U-shaped cross section. The exhaust mask member 41 extends upward along the side wall of the processing container 1. At the lower part of the exhaust mask member 41, an exhaust pipe 42 for venting the processing container 1 is connected via the exhaust port 40. A pressure control valve 43 for controlling the pressure inside the processing container 1 and an exhaust device 44 including a vacuum pump are connected to the exhaust pipe 42, and the exhaust device 44 vents the interior of the processing container 1 via the exhaust pipe 42.

[0053] In addition, a cylindrical heating mechanism 50 is provided around the outer periphery of the processing container 1 to heat the processing container 1 and the wafer W inside it.

[0054] In addition, the plasma processing apparatus 100 includes a control unit 60. The control unit 60 controls the operation of various parts of the plasma processing apparatus 100, for example. The control unit 60 may be, for example, a computer. Furthermore, the computer program for performing the operation of each part of the plasma processing apparatus 100 is stored on a storage medium. The storage medium may be, for example, a floppy disk, optical disk, hard disk, flash memory, DVD, etc.

[0055] As explained above, in the plasma processing apparatus 100 according to the embodiment, the gas nozzle 22 for supplying plasma generation gases (ammonia and hydrogen) is located outside the plasma generation space P. This prevents the gas from flowing directly from the plasma generation space P into the wafer W within the processing container 1 during plasma generation. Consequently, it prevents particles (e.g., stripped SiN films, quartz wafers) generated in the plasma generation space P due to plasma sputtering of the inner wall of the plasma partition wall 32 from adhering to the wafer W.

[0056] Furthermore, in the plasma processing apparatus 100 according to the embodiment, since the gas nozzle 22 for supplying plasma generation gas is provided outside the plasma generation space P, the installation area of ​​the gas nozzle 22 can be expanded. This allows for an increase in the nozzle diameter of the gas nozzle 22, or the provision of multiple gas nozzles 22. Therefore, even with an increased gas supply, the flow rate of gas flowing within the gas nozzle 22 can be kept small. As a result, vibrations that may occur in the gas nozzle 22 when a large flow rate of gas passes through it can be reduced, and the generation of particles caused by the vibration of the gas nozzle 22 can be suppressed.

[0057] Furthermore, in the plasma processing apparatus 100 according to the embodiment, since the gas nozzle 22 for supplying plasma generation gas is located outside the plasma generation space P, the deactivation of active species caused by the pressure rise in the plasma generation space P can be suppressed. Therefore, the probability of deactivation of the active gas is reduced, and it is expected that a reaction promotion effect at the wafer center can be achieved.

[0058] Furthermore, in the plasma processing apparatus 100 according to the embodiment, since the gas nozzle 22 for supplying plasma generating gas is located outside the plasma generation space P, the installation area of ​​the gas nozzle 22 can be expanded. Therefore, multiple gas nozzles 22 can be installed. Thus, by simultaneously supplying multiple plasma generating gases into the processing container 1 and causing these multiple plasma generating gases to diffuse in the reverse direction towards the plasma generation space P, multiple plasma generating gases can be used to generate plasma. On the other hand, when the gas nozzle 22 for supplying plasma generating gas is located within the plasma generation space P, the installation area of ​​the gas nozzle 22 is small; therefore, for example, only one gas nozzle 22 can be installed.

[0059] [Plasma processing methods]

[0060] Reference Figure 4 and Figure 5 The first example of the plasma processing method of the embodiment will be described. Figure 4 This is a diagram illustrating the configuration of the gas nozzles in the first and second examples. Figure 5 This diagram illustrates a first example of the gas supply sequence in the plasma processing method of the embodiment, showing an example of the gas supply sequence for one cycle when forming a SiN film using atomic layer deposition (ALD). Below, we will... Figure 5 The gas supply sequence shown is also called "Gas Supply Sequence A".

[0061] In the first and second examples, gas nozzles GN1, GN3, GN5, and GN6 are installed inside the processing container 1 outside the plasma generation space P, and gas nozzle GN2 is installed inside the plasma generation space P.

[0062] Gas nozzles GN1, GN2, GN3, and GN5 are dispersion nozzles extending along the vertical direction of the processing container 1, and they eject gas approximately horizontally toward the wafer W from a plurality of gas holes formed at intervals along the length direction of the dispersion nozzles. Gas nozzle GN6 is a nozzle that ejects gas toward the lower part of the processing container 1.

[0063] Gas nozzle GN1 is connected to the DCS gas supply source, supplying DCS gas into processing container 1. Gas nozzle GN2 is connected to the nitrogen (N2) supply source, supplying nitrogen into the plasma generation space P. Gas nozzle GN3 is connected to the ammonia (NH3) and hydrogen (H2) supply sources, supplying ammonia and hydrogen into processing container 1. Gas nozzle GN5 is connected to the nitrogen (N2) supply source, supplying nitrogen into processing container 1. Gas nozzle GN6 is connected to the nitrogen (N2) supply source, consistently supplying nitrogen to the lower part of processing container 1. Additionally, gas nozzles GN1 and GN3 are also connected to a nitrogen supply source (not shown).

[0064] Figure 5 The plasma processing method shown is a method for forming SiN films by repeatedly performing a cycle including a DCS gas supply step S11, a purging step S12, an ammonia gas supply step S13, and a purging step S14.

[0065] In step S11, where DCS gas is supplied, the DCS gas is adsorbed onto the wafer W. In this embodiment, DCS gas is supplied into the processing container 1 from gas nozzle GN1, nitrogen is supplied into the plasma generation space P from gas nozzle GN2, and nitrogen is supplied into the processing container 1 from gas nozzles GN1, GN3, GN5, and GN6. In step S13, where ammonia is supplied, the DCS gas is temporarily stored in a buffer tank, and in step S11, the DCS gas is supplied into the processing container 1 in a pressurized state. However, it is also possible to supply the DCS gas into the processing container 1 without storing it in a buffer tank. The amount of DCS gas supplied from gas nozzle GN1 is, for example, 300 scc. The flow rates of nitrogen supplied from gas nozzles GN1, GN2, GN3, GN5, and GN6 are, for example, 500 sccm, 500 sccm, 200 sccm, 50 sccm, and 50 sccm, respectively. Furthermore, in the process S11 of supplying DCS gas, no RF power is applied to the plasma generation space P.

[0066] The purging step S12 is performed after the DCS gas supply step S11. In the purging step S12, residual DCS gas in the plasma generation space P and the processing container 1 is removed. In this embodiment, nitrogen gas is supplied to the plasma generation space P from gas nozzle GN2, and nitrogen gas is supplied to the processing container 1 from gas nozzles GN1, GN3, GN5, and GN6. This removes the residual DCS gas from the plasma generation space P and the processing container 1, creating a nitrogen atmosphere in both spaces. The flow rates of nitrogen supplied from gas nozzles GN1, GN2, GN3, GN5, and GN6 are, for example, 5000 sccm, 500 sccm, 5000 sccm, 50 sccm, and 50 sccm, respectively. Furthermore, no RF power is applied to the plasma generation space P during the purging step S12.

[0067] The ammonia supply step S13 is performed after the purging step S12. In the ammonia supply step S13, a reaction product is generated between the DCS gas adsorbed on the wafer W and the ammonia. In this embodiment, ammonia is supplied into the processing container 1 from the gas nozzle GN3, nitrogen is supplied into the plasma generation space P from the gas nozzle GN2, and nitrogen is supplied into the processing container 1 from the gas nozzles GN1, GN3, GN5, and GN6. Additionally, RF power is applied to the plasma generation space P by turning on the RF power supply 35. In the ammonia supply step S13, a portion of the ammonia supplied into the processing container 1 from the gas nozzle GN3 diffuses back into the plasma generation space P. Then, the back-diffused ammonia is plasma-generated in the plasma generation space P, and the resulting active species are supplied into the processing container 1, where they react with the DCS gas to generate the reaction product. The flow rate of the ammonia supplied from the gas nozzle GN3 is, for example, 5000 sccm. Preferably, the flow rate of nitrogen supplied from gas nozzle GN2 is smaller than the flow rate of nitrogen supplied from gas nozzle GN2 in step S11 of supplying DCS gas, for example, 50 sccm. In this way, by reducing the flow rate of nitrogen supplied from gas nozzle GN2, the ammonia supplied from gas nozzle GN3 is facilitated to diffuse backward from the processing container 1 into the plasma generation space P. Furthermore, the flow rates of nitrogen supplied from gas nozzles GN1, GN3, GN5, and GN6 are, for example, 1000 sccm, 500 sccm, 50 sccm, and 50 sccm, respectively.

[0068] The purging step S14 is performed after the ammonia supply step S13. In the purging step S14, residual ammonia in the plasma generation space P and the processing container 1 is removed. In this embodiment, nitrogen is supplied to the plasma generation space P from gas nozzle GN2, and nitrogen is supplied to the processing container 1 from gas nozzles GN1, GN3, GN5, and GN6. This removes the residual ammonia in the plasma generation space P and the processing container 1, creating a nitrogen atmosphere in both spaces. The flow rates of nitrogen supplied from gas nozzles GN1, GN2, GN3, GN5, and GN6 are, for example, 500 sccm, 500 sccm, 200 sccm, 50 sccm, and 50 sccm, respectively. Furthermore, no RF power is applied to the plasma generation space P during the purging step S14.

[0069] A SiN film can be formed on a wafer W by repeatedly performing the above steps S11 to S14.

[0070] As explained above, according to the gas supply sequence A, in the ammonia supply step S13, ammonia is supplied from the gas nozzle GN3 located inside the processing container 1 outside the plasma generation space P, and RF power is applied to the plasma generation space P. Consequently, a portion of the ammonia supplied from the gas nozzle GN3 to the processing container 1 diffuses back into the plasma generation space P from the processing container 1. Then, the back-diffused ammonia is plasma-generated in the plasma generation space P, and the resulting active species are supplied to the processing container 1, where they react with the DCS gas to generate reaction products. Therefore, direct gas flow from the plasma generation space P to the wafer W inside the processing container 1 can be suppressed. As a result, the adhesion of particles generated in the plasma generation space P due to plasma sputtering of the inner wall of the plasma partition wall 32 to the wafer W can be suppressed.

[0071] Furthermore, according to the gas supply sequence A, nitrogen gas is supplied from the gas nozzle GN2 located in the plasma generation space P at least in the DCS gas supply step S11, the purging step S12, and the purging step S14. This reduces the amount of film formed on the inner wall of the plasma partition wall 32, suppressing film peeling. Consequently, the amount of particles generated in the plasma generation space P can be reduced.

[0072] Reference Figure 4 and Figure 6 A second example of the plasma processing method of the embodiment will be described. Figure 6 This diagram illustrates a second example of the gas supply sequence in the plasma processing method according to the embodiment, showing an example of the gas supply sequence for one cycle when forming a SiN film using the ALD method. Below, we will... Figure 6 The gas supply sequence shown is also called "Gas Supply Sequence B".

[0073] Figure 6 The plasma processing method shown is a method for forming SiN films by repeatedly performing a cycle including a DCS gas supply step S21, a purging step S22, a hydrogen gas supply step S25, an ammonia gas supply step S23, and a purging step S24.

[0074] The process of supplying DCS gas S21, the process of purging S22, the process of supplying ammonia S23, and the process of purging S24 are the same as the processes S11 to S14 in the first example.

[0075] The hydrogen supply step S25 is performed after the purging step S22 and before the ammonia supply step S23. In the hydrogen supply step S25, hydrogen plasma is generated, and the wafer W housed in the processing container 1 is processed using the hydrogen plasma. In this embodiment, hydrogen is supplied into the processing container 1 from the gas nozzle GN3, nitrogen is supplied into the plasma generation space P from the gas nozzle GN2, and nitrogen is supplied into the processing container 1 from the gas nozzles GN1, GN3, GN5, and GN6. Additionally, RF power is applied to the plasma generation space P by turning on the RF power supply 35. In the hydrogen supply step S25, a portion of the hydrogen supplied into the processing container 1 from the gas nozzle GN3 diffuses back into the plasma generation space P. Then, the back-diffused hydrogen is plasmaified in the plasma generation space P, and the resulting active species are supplied into the processing container 1. The flow rate of hydrogen supplied from the gas nozzle GN3 is, for example, 2000 sccm. Preferably, the flow rate of nitrogen supplied from gas nozzle GN2 is smaller than the flow rate of nitrogen supplied from gas nozzle GN2 in step S11 of supplying DCS gas, for example, 50 sccm. In this way, by reducing the flow rate of nitrogen supplied from gas nozzle GN2, hydrogen supplied from gas nozzle GN3 is more easily allowed to diffuse in the reverse direction from the processing container 1 to the plasma generation space P. Furthermore, the flow rates of nitrogen supplied from gas nozzles GN1, GN3, GN5, and GN6 are, for example, 1000 sccm, 500 sccm, 50 sccm, and 50 sccm, respectively.

[0076] A SiN film can be formed on a wafer W by repeatedly performing the above steps S21 to S25.

[0077] As explained above, according to the gas supply sequence B, in the ammonia supply step S23, ammonia is supplied from the gas nozzle GN3 located inside the processing container 1 outside the plasma generation space P, and RF power is applied to the plasma generation space P. Consequently, a portion of the ammonia supplied from the gas nozzle GN3 to the processing container 1 diffuses back into the plasma generation space P from the processing container 1. Then, the back-diffused ammonia is plasma-generated in the plasma generation space P, and the resulting active species are supplied to the processing container 1, where they react with the DCS gas to generate reaction products. Therefore, direct gas flow from the plasma generation space P to the wafer W inside the processing container 1 can be suppressed. As a result, it is possible to suppress the adhesion of particles generated in the plasma generation space P due to plasma sputtering of the inner wall of the plasma partition wall 32 to the wafer W.

[0078] Furthermore, according to the gas supply sequence B, nitrogen gas is supplied from the gas nozzle GN2 located in the plasma generation space P at least in the DCS gas supply step S21, the purging step S22, and the purging step S24. This reduces the amount of film formed on the inner wall of the plasma partition wall 32, suppressing film peeling. Consequently, the amount of particles generated in the plasma generation space P can be reduced.

[0079] Furthermore, according to the gas supply sequence B, in the hydrogen supply step S25, hydrogen is supplied from the gas nozzle GN3 installed inside the processing container 1 outside the plasma generation space P, and RF power is applied to the plasma generation space P. As a result, a portion of the hydrogen supplied from the gas nozzle GN3 to the processing container 1 diffuses back into the plasma generation space P from inside the processing container 1. Then, the back-diffused hydrogen is plasma-plated in the plasma generation space P, and the resulting active species are supplied into the processing container 1. Therefore, it is possible to suppress the direct flow of gas from the plasma generation space P to the wafer W inside the processing container 1. Consequently, it is possible to suppress the adhesion of particles generated in the plasma generation space P due to plasma sputtering of the inner wall of the plasma partition wall 32 to the wafer W.

[0080] Reference Figure 7 and Figure 8 A third example of the plasma processing method according to the embodiments will be described. Figure 7 This is a diagram used to illustrate the configuration of the gas nozzles in the third and fourth examples. Figure 8 This diagram illustrates a third example of the gas supply sequence in the plasma processing method according to the embodiment, showing an example of the gas supply sequence for one cycle when forming a SiN film using the ALD method. Below, we will... Figure 8 The gas supply sequence shown is also called "Gas Supply Sequence C".

[0081] In the third and fourth examples, gas nozzles GN1, GN3, GN5, and GN6 are installed inside the processing container 1 outside the plasma generation space P, but gas nozzle GN2 is not installed inside the plasma generation space P.

[0082] Gas nozzles GN1, GN3, and GN5 are dispersion nozzles extending vertically along the processing container 1, ejecting gas approximately horizontally toward the wafer W from multiple gas holes spaced apart along the length of the dispersion nozzle. Gas nozzle GN6 is a nozzle that ejects gas toward the lower part of the processing container 1. Gas nozzles GN1, GN3, GN5, and GN6 are... Figure 4 same.

[0083] Figure 8 The plasma processing method shown is a method for forming SiN films by repeatedly performing a cycle including a DCS gas supply step S31, a purging step S32, an ammonia gas supply step S33, and a purging step S34.

[0084] The difference between gas supply sequence C and gas supply sequence A is that nitrogen is not supplied to the plasma generation space P in processes S31 to S34. Otherwise, it is the same as gas supply sequence A.

[0085] According to the gas supply sequence C, in the ammonia supply step S33, ammonia is supplied from a gas nozzle GN3 located inside the processing container 1 outside the plasma generation space P, and RF power is applied to the plasma generation space P. As a result, a portion of the ammonia supplied from the gas nozzle GN3 to the processing container 1 diffuses back into the plasma generation space P from the processing container 1. Then, the back-diffused ammonia is plasma-plated in the plasma generation space P, and the resulting active species are supplied to the processing container 1, where they react with the DCS gas to generate reaction products. Therefore, direct gas flow from the plasma generation space P to the wafer W inside the processing container 1 can be suppressed. Consequently, the adhesion of particles generated in the plasma generation space P due to plasma sputtering of the inner wall of the plasma partition wall 32 to the wafer W can be suppressed.

[0086] Reference Figure 7 and Figure 9 A fourth example of the plasma processing method according to the embodiments will be described. Figure 9 This diagram illustrates a fourth example of the gas supply sequence in the plasma processing method according to the embodiment, showing an example of the gas supply sequence for one cycle when forming a SiN film using the ALD method. Below, we will... Figure 9 The gas supply sequence shown is also called "Gas Supply Sequence D".

[0087] Figure 9 The plasma processing method shown is a method for forming SiN films by repeatedly performing a cycle including a DCS gas supply step S41, a purging step S42, a hydrogen gas supply step S45, an ammonia gas supply step S43, and a purging step S44.

[0088] The difference between gas supply sequence D and gas supply sequence B is that nitrogen is not supplied to the plasma generation space P in processes S41 to S45. Otherwise, it is the same as gas supply sequence B.

[0089] According to the gas supply sequence D, in the ammonia supply step S43, ammonia is supplied from a gas nozzle GN3 located inside the processing container 1 outside the plasma generation space P, and RF power is applied to the plasma generation space P. As a result, a portion of the ammonia supplied from the gas nozzle GN3 to the processing container 1 diffuses back into the plasma generation space P from the processing container 1. Then, the back-diffused ammonia is plasma-generated in the plasma generation space P, and the resulting active species are supplied to the processing container 1, where they react with the DCS gas to generate reaction products. Therefore, direct gas flow from the plasma generation space P to the wafer W inside the processing container 1 can be suppressed. Consequently, the adhesion of particles generated in the plasma generation space P due to plasma sputtering of the inner wall of the plasma partition wall 32 to the wafer W can be suppressed.

[0090] Furthermore, according to the gas supply sequence D, in the hydrogen supply step S45, hydrogen is supplied from the gas nozzle GN3 installed inside the processing container 1 outside the plasma generation space P, and RF power is applied to the plasma generation space P. As a result, a portion of the hydrogen supplied from the gas nozzle GN3 to the processing container 1 diffuses back into the plasma generation space P from inside the processing container 1. Then, the back-diffused hydrogen is plasma-plated in the plasma generation space P, and the resulting active species are supplied into the processing container 1. Therefore, it is possible to suppress the direct flow of gas from the plasma generation space P to the wafer W inside the processing container 1. Consequently, it is possible to suppress the adhesion of particles generated in the plasma generation space P due to plasma sputtering of the inner wall of the plasma partition wall 32 to the wafer W.

[0091] Reference Figure 10 and Figure 11 An example of the plasma processing method of the reference example will be described. Figure 10 This is a diagram used to illustrate the configuration of the gas nozzle in the reference example. Figure 11 This diagram illustrates an example of a plasma processing method for a reference example, showing an example of the gas supply sequence for one cycle when forming a SiN film using the ALD method. Below, we will... Figure 11The gas supply sequence shown is also called "gas supply sequence Y".

[0092] In the reference example, gas nozzles GN1, GN4, GN5, and GN6 are provided inside the processing container 1 outside the plasma generation space P, and gas nozzle GN2 is provided inside the plasma generation space P.

[0093] Gas nozzles GN1, GN2, GN4, and GN5 are dispersion nozzles extending along the vertical direction of the processing container 1, and they eject gas approximately horizontally toward the wafer W from a plurality of gas holes formed at intervals along the length direction of the dispersion nozzles. Gas nozzle GN6 is a nozzle that ejects gas toward the lower part of the processing container 1.

[0094] Gas nozzle GN1 is connected to the DCS gas supply source, supplying DCS gas into the processing container 1. Gas nozzle GN2 is connected to the hydrogen (H2), ammonia (NH3), and nitrogen (N2) supply sources, supplying hydrogen, ammonia, and nitrogen into the plasma generation space P. Gas nozzle GN4 is connected to the nitrogen (N2) supply source, supplying nitrogen into the processing container 1. Gas nozzle GN5 is connected to the nitrogen (N2) supply source, supplying nitrogen into the processing container 1. Gas nozzle GN6 is connected to the nitrogen (N2) supply source, consistently supplying nitrogen to the lower part of the processing container 1. Additionally, gas nozzle GN1 is also connected to a nitrogen supply source (not shown).

[0095] Figure 11 The plasma processing method shown is a method for forming SiN films by repeatedly performing a cycle including a DCS gas supply step S81, a purging step S82, an ammonia gas supply step S83, and a purging step S84.

[0096] The difference between gas supply sequence Y and gas supply sequence A is that in the ammonia supply step S83, ammonia is supplied to the plasma generation space P from the gas nozzle GN2 located in the plasma generation space P. Otherwise, it is the same as gas supply sequence A.

[0097] In the gas supply sequence Y, ammonia gas flows out from the plasma generation space P to excite the gas. Therefore, particles generated by plasma sputtering are transported to the wafer W along with the gas flow from the plasma generation space P into the processing container 1. As a result, the particles readily adhere to the wafer W.

[0098] Reference Figure 10 and Figure 12 Another example of the plasma processing method of the reference example will be described. Figure 12This is a diagram illustrating another example of the plasma processing method of the reference example, showing an example of the gas supply sequence for one cycle when forming a SiN film by the ALD method. Below, we will... Figure 12 The gas supply sequence shown is also called "gas supply sequence Z".

[0099] Figure 12 The plasma processing method shown is a method for forming SiN films by repeatedly performing a cycle including a DCS gas supply step S91, a purging step S92, a hydrogen gas supply step S95, an ammonia gas supply step S93, and a purging step S94.

[0100] The difference between gas supply sequence Z and gas supply sequence B is that in the ammonia supply step S93, ammonia is supplied to the plasma generation space P from the gas nozzle GN2 located in the plasma generation space P. Another difference between gas supply sequence Z and gas supply sequence B is that in the hydrogen supply step S95, hydrogen is supplied to the plasma generation space P from the gas nozzle GN2 located in the plasma generation space P. Otherwise, all other aspects are the same as in gas supply sequence B.

[0101] In the gas supply sequence Z, ammonia and hydrogen flow from the plasma generation space P to excite the gas. Therefore, the particles generated by plasma sputtering are transported to the wafer W along with the gas flow from the plasma generation space P into the processing container 1. As a result, the particles readily adhere to the wafer W.

[0102] [Evaluation of Particles]

[0103] To confirm the effectiveness of the plasma processing apparatus 100 of the embodiment, the effect of the difference in the supply position of ammonia gas on the number of particles attached to the wafer W when forming a SiN film on the wafer W using the ALD method with DCS gas and ammonia gas was evaluated.

[0104] In the evaluation of the microparticles, a series of actions were repeatedly performed, including: transferring wafer W into processing container 1; performing a SiN film deposition process on the transferred wafer W; removing the processed wafer W; and measuring the number of microparticles attached to the processed wafer W. Gas supply sequence A and gas supply sequence Y were used in the film deposition process.

[0105] Figure 13 It is a graph showing the shift in the number of particles. Figure 13 of (a), Figure 13 (b) and Figure 13(c) shows the results for the upper (TOP), central (CTR), and lower (BTM) regions of the wafer W mounted on the wafer boat 5 in the vertical direction. Figure 13 (a)~ Figure 13 In (c), the horizontal axis represents the thickness [μm] of the deposit deposited on the inner wall of the processing container 1, and the vertical axis represents the number of particles with a diameter of 1 μm or larger attached to the wafer W [pcs]. Additionally, in Figure 13 (a)~ Figure 13 In (c), the solid line represents the result obtained when using gas supply sequence A, that is, when ammonia is supplied from a gas nozzle located outside the plasma generation space P. The dashed line represents the result obtained when using gas supply sequence Y, that is, when ammonia is supplied from a gas nozzle located in the plasma generation space P.

[0106] like Figure 13 As shown in (a), when ammonia is supplied from a gas nozzle located in the plasma generation space P, the number of particles attached to the wafer W in the TOP region increases when the thickness of the deposit deposited on the inner wall of the processing container 1 exceeds 1.5 μm. In contrast, when ammonia is supplied from a gas nozzle located outside the plasma generation space P, no increase in the number of particles attached to the wafer W is observed even when the thickness of the deposit deposited on the inner wall of the processing container 1 reaches 2.5 μm.

[0107] like Figure 13 As shown in (b), when ammonia is supplied from a gas nozzle located in the plasma generation space P, the number of particles attached to the wafer W in the CTR region increases when the thickness of the deposit deposited on the inner wall of the processing container 1 exceeds 0.25 μm. In contrast, when ammonia is supplied from a gas nozzle located outside the plasma generation space P, no increase in the number of particles attached to the wafer W is observed even when the thickness of the deposit deposited on the inner wall of the processing container 1 reaches 2.5 μm.

[0108] like Figure 13 As shown in (c), no difference was observed in the number of particles in the BTM region when ammonia was supplied from a gas nozzle located outside the plasma generation space P and when ammonia was supplied from a gas nozzle located within the plasma generation space P.

[0109] Based on these results, it can be said that supplying ammonia from a gas nozzle located outside the plasma generation space P can suppress the adhesion of particles to the wafer W, compared to supplying ammonia from a gas nozzle located in the plasma generation space P.

[0110] [Evaluation of film thickness]

[0111] To confirm the effect on the film properties of the SiN film formed by the plasma processing apparatus 100 of the embodiment, the effect of the difference in the supply position of ammonia gas on the film thickness when forming a SiN film on a wafer W using the ALD method with DCS gas and ammonia gas was evaluated.

[0112] In the evaluation of film thickness, wafer W is placed into processing container 1, and a SiN film deposition process is performed on the wafer W after placement. The processed wafer W is then removed, and the SiN film thickness is measured at multiple locations within the surface of the processed wafer W. Gas supply sequence A and gas supply sequence Y are used in the film deposition process.

[0113] Specifically, silicon-containing gas was supplied from a gas nozzle located outside the plasma generation space P. Figure 14 (a)~ Figure 14 The gas nozzle shown in (c) was supplied with ammonia. Figure 14 The gas nozzle GN-a shown in (a) is a dispersion nozzle that extends along the vertical direction of the processing container 1 inside the plasma generation space P, and ejects gas approximately horizontally toward the wafer W from a plurality of gas holes that are spaced apart along the length of the dispersion nozzle. Figure 14 The gas nozzle GN-b shown in (b) is a dispersion nozzle that extends along the vertical direction of the processing container 1 outside the plasma generation space P, and ejects gas approximately horizontally toward the wafer W from a plurality of gas holes that are spaced apart along the length of the dispersion nozzle. Figure 14 The gas nozzle GN-c shown in (c) is an L-shaped nozzle located outside the plasma generation space P, which ejects gas from below the processing container 1 upwards. Furthermore, Figure 14 It is a diagram used to illustrate the location and type of gas nozzles.

[0114] Figure 15 This is a diagram showing the film thickness and in-plane uniformity of the SiN film, illustrating the film thickness and in-plane uniformity of the SiN film in the TOP region, CTR region, and BTM region. Figure 15 The left axis represents the film thickness. The right axis represents in-plane uniformity (WinW Uniformity) [±%]. Figure 15 In the diagram, the solid-lined black triangles, solid-lined black circles, and solid-lined black diamonds indicate the SiN film thicknesses when using gas nozzles GN-a, GN-b, and GN-c, respectively. Additionally, in... Figure 15In the diagram, the blackened triangles without solid lines, the blackened circles without solid lines, and the blackened rhombuses without solid lines respectively indicate the in-plane uniformity of the SiN film thickness when using gas nozzles GN-a, GN-b, and GN-c.

[0115] like Figure 15 As shown, regarding the in-plane uniformity of the SiN film thickness, even when using gas nozzles GN-b and GN-c located outside the plasma generation space P, approximately the same result can be obtained as when using gas nozzle GN-a located inside the plasma generation space P. Furthermore, regarding the SiN film thickness, even when using a dispersion nozzle GN-b located outside the plasma generation space P, approximately the same result can be obtained as when using a dispersion nozzle GN-a located inside the plasma generation space P. Additionally, regarding the SiN film thickness, when using an L-shaped nozzle GN-c located outside the plasma generation space P, the SiN film thickness in the CTR and TOP regions becomes slightly thinner. Based on these results, it can be said that, from the viewpoint of minimizing the impact on the SiN film thickness and its in-plane uniformity when a gas nozzle supplying ammonia is located outside the plasma generation space P, the dispersion nozzle GN-b is preferable.

[0116] Next, the cases where gas supply sequence B and gas supply sequence Z are used in the film formation process will be explained.

[0117] Specifically, silicon-containing gas was supplied from a gas nozzle located outside the plasma generation space P. Figure 14 The gas nozzle GN-a shown in (a) and Figure 14 The gas nozzle GN-b shown in (b) was supplied with ammonia and hydrogen.

[0118] Figure 16 This is a diagram showing the film thickness and in-plane uniformity of the SiN film, illustrating the film thickness and in-plane uniformity of the SiN film in the TOP region, CTR region, and BTM region. Figure 16 The left axis of represents film thickness The right axis represents in-plane uniformity [±%]. Figure 16 In the diagram, the hollow triangles with solid lines and the hollow circles with solid lines indicate the SiN film thicknesses when using gas nozzles GN-a and GN-b, respectively. Additionally, in... Figure 16 In the diagram, the hollow triangle without a solid line and the hollow circle without a solid line indicate the in-plane uniformity of the SiN film thickness when using gas nozzle GN-a and gas nozzle GN-b, respectively.

[0119] like Figure 16 As shown, regarding the SiN film thickness and its in-plane uniformity, even when using a gas nozzle GN-b located outside the plasma generation space P, approximately the same results can be obtained as when using a gas nozzle GN-a located inside the plasma generation space P. Based on this result, it can be considered that even when gas nozzles supplying hydrogen and ammonia are located outside the plasma generation space P, the impact on the SiN film thickness and its in-plane uniformity is small.

[0120] [Evaluation of membrane material]

[0121] To confirm the effect on the film properties of the SiN film formed by the plasma processing apparatus 100 of the embodiment, the effect of the difference in the supply position of ammonia gas on the film quality was evaluated when the SiN film was formed on the wafer W by the ALD method using DCS gas and ammonia gas.

[0122] In the evaluation of film quality, wafer W was placed into processing container 1, and a SiN film was formed on the wafer W after placement. The processed wafer W was then removed, and the etch resistance of the SiN film formed on the processed wafer W was evaluated. For the etch resistance evaluation, the SiN film was wet-etched using 0.25% DHF (diluted hydrofluoric acid), and the amount of etching was measured to calculate the etch rate (WER). A lower WER indicates higher etch resistance and signifies a good film quality.

[0123] Specifically, silicon-containing gas was supplied from a gas nozzle located outside the plasma generation space P. Figure 14 The gas nozzle GN-a shown in (a) and Figure 14 The gas nozzle GN-b shown in (b) was supplied with ammonia and hydrogen.

[0124] Figure 17 This is a diagram showing the WER of the SiN film, illustrating the WER of the SiN film in the TOP region, CTR region, and BTM region. Figure 17 The vertical axis represents WER exist Figure 17In the diagram, the solid-lined black triangles indicate the WER of SiN films formed using gas nozzle GN-a with gas supply sequence Y, and the solid-lined black circles indicate the WER of SiN films formed using gas nozzle GN-b with gas supply sequence A. Additionally, the solid-lined hollow triangles indicate the WER of SiN films formed using gas nozzle GN-a with gas supply sequence Z, and the solid-lined hollow circles indicate the WER of SiN films formed using gas nozzle GN-b with gas supply sequence B.

[0125] like Figure 17 As shown, almost no difference in WER was observed between the SiN film formed via gas supply sequence A and the SiN film formed via gas supply sequence Y. Furthermore, in the CTR and BTM regions, the WER of the SiN film formed via gas supply sequence B was slightly larger than that of the SiN film formed via gas supply sequence Z.

[0126] Furthermore, in the above embodiments, gas nozzle 22 is an example of a processing gas supply unit, and gas nozzle 23 is an example of a purging gas supply unit. Additionally, DCS gas is an example of a raw material gas, ammonia is an example of a reactant gas, and hydrogen is an example of a modifying gas.

[0127] It should be considered that the embodiments disclosed herein are illustrative in all respects and not restrictive. The above embodiments may be omitted, substituted, or modified in various ways without departing from the appended claims and their spirit.

[0128] In the above embodiments, the case in which the plasma processing apparatus 100 has a pair of plasma electrodes 31 arranged in opposite directions, i.e., the case in which the plasma processing apparatus 100 has capacitively coupled plasma electrodes 31, has been described as an example, but this disclosure is not limited thereto. For example, the plasma processing apparatus 100 may also have inductively coupled plasma electrodes provided along the length direction of the plasma dividing wall 32.

[0129] In the above embodiments, the case where the processing container 1 has a single-tube structure has been described as an example, but this disclosure is not limited thereto. For example, the processing container 1 may also have a double-tube structure including an inner tube (inner layer tube) and an outer tube (outer layer tube).

[0130] In the above embodiments, the case of film formation and deposition via ALD was used as an example for illustration, but this disclosure is not limited thereto. For example, it can also be applied to the case of film formation and deposition via chemical vapor deposition (CVD).

[0131] In the above embodiments, ammonia and hydrogen were used as examples of plasma generating gases, but this disclosure is not limited thereto. For example, the plasma generating gas may also be nitrogen, argon, helium, or oxygen.

Claims

1. A plasma processing apparatus, comprising: The processing container has a longitudinal cylindrical shape and an opening is formed on the side wall of the processing container. Multiple substrates are housed in multiple layers inside the processing container. A plasma partition wall is hermetically disposed on the outer wall of the processing container, covering the opening and defining the plasma generation space; Plasma electrodes, which are disposed along the plasma partition wall; and A processing gas supply unit, located outside the plasma generation space and inside the processing container, supplies plasma generation gas. The plasma generating gas supplied by the processing gas supply unit diffuses in the reverse direction from the processing container to the plasma generating space and plasmaizes within the plasma generating space to generate plasma.

2. The plasma processing apparatus according to claim 1, wherein, The opening is elongated in the height direction of the processing container.

3. The plasma processing apparatus according to claim 1 or 2, wherein, The opening has a length that can cover the entire length of the plurality of substrates in the height direction.

4. The plasma processing apparatus according to claim 1 or 2, wherein, The processing gas supply unit includes a dispersing nozzle that extends along the height direction of the processing container and has a plurality of gas holes spaced apart along its length direction.

5. The plasma processing apparatus according to claim 1 or 2, wherein, It includes a purge gas supply unit, which is located in the plasma generation space and supplies purge gas.

6. The plasma processing apparatus according to claim 5, wherein, The purging gas supply unit includes a dispersing nozzle that extends along the height direction of the processing container and has a plurality of gas holes spaced apart along its length direction.

7. The plasma processing apparatus according to claim 1 or 2, wherein, The plasma electrode includes a pair of electrodes arranged facing each other on the outer surfaces of the plasma partition wall.

8. The plasma processing apparatus according to claim 1 or 2, wherein, The plasma electrode includes an inductively coupled electrode disposed along the length of the plasma dividing wall.

9. A plasma treatment method, comprising the following steps: Multiple substrates are housed in multiple layers inside the processing container, which has a longitudinal cylindrical shape and openings formed in its side walls; and Plasma generating gas is supplied to the processing container, which is outside the plasma generation space defined by the plasma dividing wall. The plasma generating gas supplied to the processing container diffuses in the reverse direction toward the plasma generation space. Furthermore, the plasma generating gas is plasmaified by supplying radio frequency power to plasma electrodes arranged along the plasma dividing wall, which is hermetically disposed on the side wall of the processing container and covers the opening.

10. The plasma processing method according to claim 9 further includes the following steps: Purge gas is supplied to the plasma generation space.

11. The plasma processing method according to claim 10 further comprises the following steps: Supply raw material gas into the processing container. in, The plasma generating gas is a reaction gas that reacts with the raw material gas to generate reaction products. In the plasma processing method, a cycle is repeatedly performed including the steps of supplying the raw material gas, plasmaizing the plasma generating gas, and supplying the purging gas.

12. The plasma processing method according to claim 11 further includes the following steps: The modified gas is plasmaified by supplying a modified gas into the processing container, which serves as the exterior of the plasma generation space, and by supplying radio frequency power to the plasma electrodes. In the plasma processing method, a cycle is repeatedly performed including the steps of supplying the raw material gas, plasmaizing the plasma generating gas, supplying the purging gas, and plasmaizing the modified gas.

13. The plasma processing method according to claim 12, wherein, The raw material gas is dichlorosilane gas, the reaction gas is ammonia gas, and the modifying gas is hydrogen gas.

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