Method for removing organic metal polymer film, plasma processing method, and plasma processing device

Abstract

To provide a technique capable of efficiently removing an organic metal polymer film from the inside of a processing container.SOLUTION: Disclosed is a method for removing an organic metal polymer film. The method for removing an organic metal polymer film which is deposited in a processing container includes the steps of: supplying a first etching gas into the processing container and generating plasma; and reacting the organic metal polymer film with the plasma, thereby gasifying and removing the organic metal polymer film. The first etching gas includes a hydrogen gas, a carbon-containing gas and a nitrogen-containing gas.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present disclosure relates to a method for removing an organometallic polymer film, a plasma processing method, and a plasma processing apparatus. [Background technology]

[0002] A technique for removing resist material deposited in a processing chamber is disclosed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2022-538554 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique that can efficiently remove organometallic polymer films from inside a processing vessel. [Means for solving the problem]

[0005] A method for removing an organometallic polymer film according to one aspect of the present disclosure is a method for removing an organometallic polymer film deposited in a processing vessel, the method comprising the steps of supplying a first etching gas into the processing vessel to generate plasma, and reacting the organometallic polymer film with the plasma to gasify and remove the organometallic polymer film, wherein the first etching gas includes hydrogen gas, a carbon-containing gas, and a nitrogen-containing gas. [Effects of the Invention]

[0006] According to the present disclosure, organometallic polymer films can be efficiently removed from inside a processing chamber. [Brief explanation of the drawings]

[0007] [Figure 1]1 is a cross-sectional view showing a plasma processing apparatus according to an embodiment. [Figure 2] 1 is a flowchart illustrating a plasma processing method according to an embodiment. [Figure 3] 1A to 1C are cross-sectional views illustrating a plasma processing method according to an embodiment. [Figure 4] 1A to 1C are cross-sectional views illustrating a plasma processing method according to an embodiment. [Figure 5] FIG. 1 is a diagram showing an example of a reaction of an organometallic polymer film. [Figure 6] FIG. 10 is a graph showing the gas species dependence of the etching rate of an organometallic polymer film. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, non-limiting exemplary embodiments of the present disclosure will be described with reference to the accompanying drawings. In all the accompanying drawings, the same or corresponding reference numerals are used to designate the same or corresponding members or components, and redundant descriptions will be omitted.

[0009] [Plasma Processing Apparatus] A plasma processing apparatus 1 according to an embodiment will be described with reference to Fig. 1. Fig. 1 is a cross-sectional view showing the plasma processing apparatus 1 according to an embodiment. The plasma processing apparatus 1 is an example of an apparatus that forms an organometallic polymer film on a substrate W by a chemical vapor deposition (CVD) method using plasma.

[0010] The plasma processing apparatus 1 includes a substantially cylindrical airtight processing chamber 2. An exhaust chamber 21 is provided in the center of the bottom wall of the processing chamber 2.

[0011] The exhaust chamber 21 has, for example, a substantially cylindrical shape that protrudes downward. An exhaust flow path 22 is connected to the exhaust chamber 21, for example, at a side surface of the exhaust chamber 21.

[0012] An exhaust unit 24 is connected to the exhaust flow path 22 via a pressure adjustment unit 23. The pressure adjustment unit 23 includes a pressure adjustment valve such as a butterfly valve. The exhaust unit 24 includes a vacuum pump, for example. The exhaust flow path 22 is configured so that the pressure inside the processing vessel 2 can be reduced by the exhaust unit 24. A transfer port 25 is provided on the side of the processing vessel 2. The transfer port 25 is configured to be freely opened and closed by a gate valve 26. The substrate W is loaded and unloaded between the processing vessel 2 and a transfer chamber (not shown) via the transfer port 25.

[0013] A mounting table 3 for holding the substrate W substantially horizontally is provided within the processing chamber 2. The mounting table 3 is formed in a substantially circular shape in a plan view. The mounting table 3 is supported by a support member 31. A substantially circular recess 32 for mounting the substrate W, for example, having a diameter of 300 mm, is formed in the upper surface 3a of the mounting table 3. The recess 32 has an inner diameter that is slightly larger (for example, about 1 mm to 4 mm) than the diameter of the substrate W. The depth of the recess 32 is configured to be substantially the same as the thickness of the substrate W. The mounting table 3 is made of a ceramic material such as aluminum nitride (AlN). The mounting table 3 may also be made of a metal material such as nickel (Ni). Instead of the recess 32, a guide ring for guiding the substrate W may be provided around the periphery of the upper surface 3a of the mounting table 3.

[0014] A grounded lower electrode 33 is embedded in the mounting table 3. A temperature adjustment mechanism 34 is embedded below the lower electrode 33. The temperature adjustment mechanism 34 adjusts the temperature of the mounting table 3 or the substrate W placed thereon to a set temperature based on a control signal from the controller 9. If the mounting table 3 is made entirely of metal, the entire mounting table 3 functions as the lower electrode, and the lower electrode 33 does not need to be embedded in the mounting table 3. The mounting table 3 is provided with a plurality of (e.g., three) lift pins 41 for holding and elevating the substrate W placed on the mounting table 3. The lift pins 41 may be made of, for example, ceramics such as alumina (Al2O3) or quartz. The lower ends of the lift pins 41 are attached to a support plate 42. The support plate 42 is connected to a lift mechanism 44 provided outside the processing chamber 2 via a lift shaft 43.

[0015] The lifting mechanism 44 is installed, for example, at the bottom of the exhaust chamber 21. The bellows 45 is provided between the lifting mechanism 44 and an opening 21a for the lifting shaft 43 formed in the bottom surface of the exhaust chamber 21. The support plate 42 may be shaped so that it can be raised and lowered without interfering with the support member 31 of the mounting table 3. The lifting pins 41 are configured to be able to be raised and lowered between the upper side and the lower side of the upper surface 3a of the mounting table 3 by the lifting mechanism 44. In other words, the lifting pins 41 are configured to be able to protrude from the upper surface 3a of the mounting table 3.

[0016] A gas supply unit 5 is provided on the ceiling wall 27 of the processing vessel 2 via an insulating member 28. The gas supply unit 5 serves as an upper electrode and faces the lower electrode 33. An RF power supply 51 is connected to the gas supply unit 5 via a matching box 52. The frequency band of the RF power supply 51 is, for example, 450 kHz to 2.45 GHz. An RF electric field is generated between the gas supply unit 5 and the lower electrode 33 by supplying RF power from the RF power supply 51 to the gas supply unit 5. The gas supply unit 5 includes a hollow gas diffusion chamber 53. A number of holes 54 are arranged, for example, evenly, on the bottom surface of the gas diffusion chamber 53 for dispersing and supplying the processing gas into the processing vessel 2. A heating mechanism 55 is embedded in the gas supply unit 5, for example, above the gas diffusion chamber 53. The heating mechanism 55 is heated to a set temperature by receiving power from a power supply unit (not shown) based on a control signal from the control unit 9.

[0017] A gas supply path 6 is provided in the gas diffusion chamber 53. The gas supply path 6 is connected to the gas diffusion chamber 53. A gas source 61 is connected to the upstream side of the gas supply path 6 via a gas line 62. The gas source 61 includes, for example, various processing gas supply sources, mass flow controllers, and valves (none of which are shown). The processing gas includes gases used in the plasma processing method described below. The processing gas is introduced from the gas source 61 into the gas diffusion chamber 53 via the gas line 62.

[0018] The plasma processing apparatus 1 includes a control unit 9. The control unit 9 is, for example, a computer and includes a CPU (Central Processing Unit), RAM (Random Access Memory), ROM (Read Only Memory), an auxiliary storage device, etc. The CPU operates based on a program stored in the ROM or the auxiliary storage device, and controls the operation of the plasma processing apparatus 1. The control unit 9 may be provided inside or outside the plasma processing apparatus 1. If the control unit 9 is provided outside the plasma processing apparatus 1, the control unit 9 can control the plasma processing apparatus 1 via communication means such as wired or wireless.

[0019] Although the plasma processing apparatus 1 has been described as a plasma processing apparatus that generates capacitively coupled plasma (CCP), the present invention is not limited to this. It may also be a plasma processing apparatus that generates remote plasma using high frequency (RF, VHF) or microwave (MW). The plasma processing apparatus that generates remote plasma may be a plasma processing apparatus that generates remote plasma in a processing vessel that accommodates a substrate W, or a plasma processing apparatus that supplies the generated remote plasma into the processing vessel that accommodates a substrate W.

[0020] [Plasma Treatment Method] 2 to 5, a plasma processing method performed in the plasma processing apparatus 1 will be described. Fig. 2 is a flowchart showing the plasma processing method according to the embodiment. Figs. 3 and 4 are cross-sectional views showing the plasma processing method according to the embodiment.

[0021] The plasma processing method shown in FIG. 2 is automatically performed by the control unit 9 controlling the operation of each part of the plasma processing apparatus 1. In the following, it is assumed that no film is deposited on the surface inside the processing vessel 2 of the plasma processing apparatus 1 when the plasma processing method is started. The surface inside the processing vessel 2 may include the inner wall surface 2a of the processing vessel 2 and the upper surface 3a of the mounting table 3. In this embodiment, as shown in FIG. 3(a), the upper surface 3a of the mounting table 3 is illustrated as an example of the surface inside the processing vessel 2. However, another surface inside the processing vessel 2, for example, the inner wall surface 2a of the processing vessel 2, may be similar to the upper surface 3a of the mounting table 3.

[0022] The plasma processing method shown in FIG. 2 includes steps S1, S2, S3, S4, S5, S6, and S7.

[0023] (Step S1) 3(b), a first pre-coat film 101 is formed on the upper surface 3a of the mounting table 3 (the inner wall surface 2a of the processing chamber 2). The first pre-coat film 101 reduces the scattering of metal atoms such as aluminum (Al) contained in the mounting table 3 and the processing chamber 2 during the removal process of the organometallic polymer film 103 in step S5. By providing the first pre-coat film 101, metal atoms are less likely to be mixed into the organometallic polymer film 103.

[0024] In this embodiment, the control unit 9 controls the gas source 61 to supply a first film formation gas from the gas supply unit 5 into the processing chamber 2 through the multiple holes 54. The first film formation gas contains a silicon-containing gas and a nitrogen-containing gas. The control unit 9 also controls the RF power supply 51 to supply RF power to the gas supply unit 5. As a result, a plasma P1 is generated from the first film formation gas in the processing chamber 2, and a silicon nitride film is formed on the upper surface 3a of the mounting table 3. The silicon nitride film is an example of a first pre-coat film 101. The first pre-coat film 101 may be a silicon oxide film. In this case, an oxygen-containing gas is used instead of the nitrogen-containing gas. Step S1 is performed, for example, when the substrate W is not placed in the recess 32 of the mounting table 3.

[0025] The silicon-containing gas includes at least one selected from the group consisting of, for example, an aminosilane-based gas, a silicon hydride gas, a halogen-containing silicon gas, and an organic silicon-based gas. Examples of the aminosilane-based gas include DIPAS (diisopropylaminosilane), 3DMAS (trisdimethylaminosilane), and BTBAS (bisterialbutylaminosilane). Examples of the silicon hydride gas include SiH4, Si2H6, Si3H8, and Si4H. 10 Examples of halogen-containing silicon gases that can be used include SiF4, SiHF3, SiH2F2, SiH3F, SiCl4, SiHCl3, SiH2Cl2, SiH3Cl, Si2Cl6, SiBr4, SiHBr3, SiH2Br2, and SiH3Br. Examples of organosilicon gases that can be used include TEOS (tetraethoxysilane), TMOS (tetramethoxysilane), and DMDMOS (dimethyldimethoxysilane).

[0026] The nitrogen-containing gas includes, for example, at least one selected from the group consisting of N2, NH3, N2H2, N2H4, and CH3(NH)NH2.

[0027] The oxygen-containing gas includes, for example, at least one selected from the group consisting of O2, O3, H2O, and N2O.

[0028] (Step S2) 3(c), in step S2, a second pre-coat film 102 is formed on the first pre-coat film 101. The second pre-coat film 102 reduces the diffusion of metal atoms contained in the organometallic polymer film 103 formed in step S3 into the first pre-coat film 101. By providing the second pre-coat film 102, it is less likely that any remaining first pre-coat film 101 will remain when the first pre-coat film 101 is removed in step S7.

[0029] In this embodiment, the control unit 9 controls the gas source 61 to supply a second film formation gas from the gas supply unit 5 into the processing chamber 2 through the multiple holes 54. The second film formation gas contains a carbon-containing gas. The control unit 9 also controls the RF power supply 51 to supply RF power to the gas supply unit 5. As a result, a plasma P2 is generated from the second film formation gas in the processing chamber 2, and a carbon film is formed on the first pre-coat film 101. The carbon film is an example of the second pre-coat film 102. Step S2 is performed, for example, in a state where the substrate W is not placed in the recess 32 of the mounting table 3.

[0030] The carbon-containing gas includes at least one selected from the group consisting of a fluorocarbon gas, a hydrofluorocarbon gas, and a hydrocarbon gas. Examples of the fluorocarbon gas include CF4, C2F2, C2F4, C3F8, C4F6, C4F8, and C5F8. Examples of the hydrofluorocarbon gas include CHF3, CH2F2, CH3F, C2HF5, C2H2F4, C2H3F3, C2H4F2, C3HF7, C3H2F2, C3H2F6, C3H2F4, C3H3F5, C4H5F5, C4H2F6, and C5H2F. 10 , c-C5H3F7 or C3H2F4 can be used. Examples of hydrocarbon gases include CH4, C2H2, C2H4, C2H6, C3H6, C3H8 or C4H 10 can be used.

[0031] (Step S3) In step S3, as shown in FIG. 3(d), an organometallic polymer film 103 is formed on the second pre-coat film 102. Step S3 may include forming the organometallic polymer film 103 on the substrate W to be processed. The organometallic polymer film 103 includes metal atoms (M), carbon atoms (C), and hydrogen atoms (H). The metal atoms include, for example, one selected from the group consisting of hafnium (Hf), aluminum (Al), tin (Sn), zirconium (Zr), and titanium (Ti). The organometallic polymer film 103 may further include nitrogen atoms (N). The organometallic polymer film 103 may further include oxygen atoms (O).

[0032] In this embodiment, the control unit 9 controls a transfer device (not shown) to transfer the substrate W to be processed into the processing chamber 2 of the plasma processing apparatus 1 and place it in the recess 32 of the mounting table 3. The control unit 9 also controls the gas source 61 to supply a third film formation gas from the gas supply unit 5 into the processing chamber 2 through the multiple holes 54. The third film formation gas includes an organometallic precursor gas, a hydrocarbon gas, and a carrier gas. The control unit 9 also controls the RF power supply 51 to supply RF power to the gas supply unit 5. As a result, a plasma P3 is generated from the third film formation gas in the processing chamber 2, and a polymerization reaction of the plasma P3 forms an organometallic polymer film 103 on the second pre-coat film 102.

[0033] The organometallic precursor gas may contain a metal atom, a carbon atom, and a hydrogen atom. The metal atom may include, for example, one selected from the group consisting of hafnium, aluminum, tin, zirconium, and titanium. The organometallic precursor gas may further contain a nitrogen atom. The organometallic precursor gas may further contain an oxygen atom. Examples of the organometallic precursor gas that can be used include Hf((NCH3)2)4, Hf(OC4H9)4, Zr((N(CH2)2)4, Sn(CH3)4, Sn(C4H9)2(OC4H9)2, Sn(NCH3)4, and Al(CH3)4. Examples of the hydrocarbon gas include CH4, C2H2, C2H4, C2H6, C3H6, C3H8, and C4H 10 As the carrier gas, for example, argon gas (Ar) or helium gas (He) can be used.

[0034] (Step S4) In step S4, it is determined whether step S3 has been performed a first number of times. If the number of times has reached the first number of times (YES in step S4), the process proceeds to step S5. If the number of times has not reached the first number of times (NO in step S4), step S3 is performed again. When step S3 is repeatedly performed, the thickness of the organometallic polymer film 103 on the second pre-coat film 102 increases, as shown in FIG. 4(a). If the thickness of the organometallic polymer film 103 on the second pre-coat film 102 exceeds a threshold, the organometallic polymer film 103 peels off and particles are generated. For this reason, the first number of times is set so that the thickness of the organometallic polymer film 103 does not exceed the threshold.

[0035] (Step S5) In step S5, as shown in FIG. 4(b), the organometallic polymer film 103 deposited on the upper surface 3a of the mounting table 3 (the inner wall surface 2a of the processing chamber 2) is removed.

[0036] In this embodiment, the control unit 9 controls the temperature adjustment mechanism 34 to adjust the temperature of the mounting table 3 to a set temperature. The set temperature may be 80°C or higher and 200°C or lower. The control unit 9 also controls the pressure adjustment unit 23 to adjust the pressure inside the processing chamber 2 to a set pressure. The set pressure may be 0.1 Torr (13.3 Pa) or higher and 10 Torr (1.33 kPa) or lower. The control unit 9 also controls the gas source 61 to supply a first etching gas from the gas supply unit 5 into the processing chamber 2 through the multiple holes 54. The first etching gas contains hydrogen gas, a carbon-containing gas, and a nitrogen-containing gas. The control unit 9 also controls the RF power supply 51 to supply RF power to the gas supply unit 5. This generates plasma P4 from the first etching gas inside the processing chamber 2. The organometallic polymer film 103 reacts with the plasma P4 to be gasified and removed from the upper surface 3a of the mounting table 3 (the inner wall surface 2a of the processing chamber 2). The plasma P4 may contain CH radicals and NH radicals. CH radicals and NH radicals take a long time to disappear. Therefore, the organometallic polymer film 103 deposited at a location far from the plasma P4, for example, on the inner wall surface 2a of the processing chamber 2, can be efficiently removed. Nitrogen atoms (N) and carbon atoms (C) have low ionization energies. This reduces the acceleration of hydrogen ions to high energy. As a result, damage to the surface of the gas supply unit 5 and the occurrence of metal contamination can be reduced. When removing the organometallic polymer film 103, the second pre-coat film 102 may be removed without removing the first pre-coat film 101 formed on the upper surface 3a of the mounting table 3 (the inner wall surface 2a of the processing chamber 2). The first etching gas may further contain an inert gas. Examples of the inert gas include argon gas and helium gas.

[0037] The carbon-containing gas may be at least one of the gases exemplified as the carbon-containing gas in step S2, and the nitrogen-containing gas may be at least one of the gases exemplified as the nitrogen-containing gas in step S1.

[0038] For example, a first etching gas containing hydrogen gas (H), methane gas (CH), and ammonia gas (NH) is used to form a Sn-C xH y Sn-OH bond and Sn-OC bond x H y The case of removing the organometallic polymer film 103 containing bonds will be described. Methane gas is an example of a carbon-containing gas, and ammonia gas is an example of a nitrogen-containing gas. x and y are integers of 1 or more.

[0039] In this case, the reactions represented by the following formulas (1) and (2) occur in the plasma P4, forming a stable amino structure, HN(CH3)2. HN(CH3)2 is a gas.

[0040] NH3+2CH4→CN x ↓+HN(CH3)2+2H2...Formula (1) CN x +H2→HN(CH3)2↑···Formula (2)

[0041] On the surface of the organometallic polymer film 103, the organometallic polymer film 103 is decomposed by the reactions expressed by the following formulas (3), (4), and (5), and metal amino structures such as Sn-N(CH3)2, Sn-N(CH3)2, and Sn-N(CH3)2 are formed. The metal amino structures are stable and do not easily reattach to the reaction surface. This allows the organometallic polymer film 103 to be removed efficiently. In addition, carbon atoms (C) are C x H y+1 , C x H y It is gasified as OH etc. This reduces the adhesion of carbon atoms (C) to the reaction surface.

[0042] Sn-C x H y +HN(CH3)2 → Sn-N(CH3)2+C x H y+1 ↑···Formula (3) Sn-OH+HN(CH3)2→Sn-N(CH3)2+H2O↑···Formula (4) Sn-OC x H y +HN(CH3)2 → Sn-N(CH3)2+C x H yOH↑···Formula (5)

[0043] 5A and 5B illustrate an example of a reaction of the organometallic polymer film 103. As shown in FIG. 5A, the metal atom in the organometallic polymer film 103 is tin (Sn), and the film contains Sn-C2H5 and Sn-O-C2H5 bonds. When plasma P4 is generated from a first etching gas containing hydrogen gas (H2), methane gas (CH4), and ammonia gas (NH3), the organometallic polymer film 103 reacts with HN(CH3)2 contained in the plasma P4. As a result, as shown in FIG. 5B, the Sn-C2H5 and Sn-O-C2H5 bonds in the organometallic polymer film 103 are replaced with Sn-N(CH3)2, and C2H6 and C2H5OH are generated. As the reaction progresses further, as shown in FIG. 5(c), the Sn—O bond is replaced by Sn—N(CH 3 ) 2 , and a portion of the organometallic polymer film 103 is removed as Sn[N(CH 3 ) 2 ] 4 .

[0044] Furthermore, for example, the first etching gas may contain a halogen gas. The halogen gas may be one selected from F2, Cl2, Br2, I2, HF, HCl, HBr, HI, and BCl3. Plasma in which a halogen gas is added to the first etching gas (e.g., NH3 / CH4 / H2) forms a metal halide structure in addition to a metal amino structure, which can increase the decomposition efficiency, particularly in areas with a high oxygen content. This increases the etching efficiency and reduces metal oxide residue.

[0045] (Step S6) In step S6, it is determined whether steps S2 to S5 have been performed a second number of times. If the number of times has reached the second number of times (YES in step S6), the process proceeds to step S7. If the number of times has not reached the second number of times (NO in step S6), the process returns to step S2, and steps S2 to S5 are performed again. The second number of times is set according to at least one of the conditions for forming the second pre-coat film 102, the conditions for forming the organometallic polymer film 103, and the conditions for removing the organometallic polymer film 103, for example.

[0046] (Step S7) In step S7, as shown in FIG. 4(c), the first pre-coat film 101 formed on the upper surface 3a of the mounting table 3 (the inner wall surface 2a of the processing chamber 2) is removed.

[0047] In this embodiment, the control unit 9 controls the gas source 61 to supply a second etching gas from the gas supply unit 5 into the processing chamber 2 through the multiple holes 54. The second etching gas contains a fluorine-containing gas. This removes the first pre-coat film 101 from the upper surface 3a of the mounting table 3 (the inner wall surface 2a of the processing chamber 2). The second etching gas may further contain an inert gas. Examples of the inert gas include argon gas and helium gas. The fluorine-containing gas is, for example, nitrogen trifluoride gas (NF3).

[0048] As described above, according to the embodiment, the first etching gas is supplied into the processing chamber 2 to generate plasma P4, and the organometallic polymer film 103 is reacted with the plasma P4 to gasify and remove the organometallic polymer film 103. The first etching gas contains hydrogen gas, a carbon-containing gas, and a nitrogen-containing gas. In this case, the organometallic polymer film 103 can be efficiently removed from the processing chamber 2.

[0049] Note that, after step S5, a purging step may be performed by supplying an inert gas into the processing vessel 2 without supplying the first etching gas into the processing vessel 2. Also, after step S5, a purging step may be performed without supplying any gas into the processing vessel 2. Also, step S5 and the purging step may be alternately repeated, or step S5 and the evacuating step may be alternately repeated, or step S5, the purging step, and the evacuating step may be repeated in this order. This allows the gasified organometallic polymer film 103 to be removed more efficiently.

[0050] Furthermore, the pressure in the processing vessel 2 may be changed during step S5. For example, step S5 may include a step of maintaining the pressure in the processing vessel 2 at a first pressure and a step of maintaining the pressure in the processing vessel 2 at a second pressure higher than the first pressure. In this case, the organometallic polymer film 103 deposited at various positions on the surface in the processing vessel 2 can be efficiently removed.

[0051] [Experimental results] FIG. 6 is a graph showing the gas type dependence of the etching rate of organometallic polymer film 103. In FIG. 6, the horizontal axis represents etching time (seconds), and the vertical axis represents the residual thickness of organometallic polymer film 103. The residual thickness is expressed as a relative value, with the thickness of organometallic polymer film 103 at an etching time of 0 seconds set to 1. The solid line in FIG. 6 represents the etching rate of organometallic polymer film 103 when exposed to plasma generated from an etching gas containing hydrogen gas, methane gas, and ammonia gas (hereinafter referred to as "first plasma"). The dashed line in FIG. 6 represents the etching rate of organometallic polymer film 103 when exposed to plasma generated from an etching gas containing hydrogen gas and methane gas but not containing ammonia gas (hereinafter referred to as "second plasma").

[0052] As shown in FIG. 6, when the organometallic polymer film 103 is exposed to the first plasma, the residual film thickness is less than 0.1 μm after 120 seconds, and the residual film thickness does not increase over time. In contrast, when the organometallic polymer film 103 is exposed to the second plasma, the residual film thickness is still about 0.3 μm even after 180 seconds, and the residual film thickness increases after 180 seconds. This result suggests that exposing the organometallic polymer film 103 to plasma generated from an etching gas containing hydrogen gas, a carbon-containing gas, and a nitrogen-containing gas can reduce the redeposition of reaction products generated by the reaction between the plasma and the organometallic polymer film 103 onto the reaction surface. As a result, the organometallic polymer film 103 can be efficiently removed.

[0053] The embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive, and the above-described embodiments may be omitted, substituted, or modified in various ways without departing from the scope and spirit of the appended claims. [Explanation of symbols]

[0054] 1. Plasma processing equipment 2. Processing vessel 2a Inner wall surface 3. Mounting table 3a Top side 5 Gas supply section 6 Gas supply line 9 Control Unit 21 Exhaust chamber 21a opening 22 Exhaust flow path 23 Pressure adjustment section 24 Exhaust section 25 Transport entrance 26 Gate valve 27 Ceiling wall 28 Insulating material 31 Support member 32 recess 33 Lower electrode 34 Temperature control mechanism 41 Lifting pin 42 Support plate 43 Elevating axis 44 Lifting mechanism 45 Bellows 51 RF power supply 52 Matching box 53 Gas diffusion chamber 54 holes 55 Heating mechanism 61 Gas Source 62 Gas Line 101 First pre-coated film 102 Second pre-coated film 103 Organometallic polymer film W substrate

Claims

1. 1. A method for removing an organometallic polymer film deposited in a processing vessel, comprising: supplying a first etching gas into the processing chamber to generate plasma; reacting the organometallic polymer film with the plasma to gasify and remove the organometallic polymer film; and the first etching gas includes hydrogen gas, a carbon-containing gas, and a nitrogen-containing gas; A method for removing organometallic polymer films.

2. the generating the plasma includes generating an amino structure from the first etching gas; the step of gasifying and removing the organometallic polymer film includes generating metal amino structures containing metal atoms contained in the organometallic polymer film; 10. A method for removing the organometallic polymer film of claim 1.

3. The plasma contains CH radicals and NH radicals.

10. A method for removing the organometallic polymer film of claim 1.

4. The organometallic polymer film contains metal atoms, carbon atoms, and hydrogen atoms. A method for removing the organometallic polymer film according to any one of claims 1 to 3.

5. The metal atom comprises one selected from the group consisting of hafnium, aluminum, tin, zirconium, and titanium; The method for removing the organometallic polymer film of claim 4.

6. the organometallic polymer film contains at least one of nitrogen atoms and oxygen atoms; A method for removing the organometallic polymer film according to any one of claims 1 to 3.

7. The carbon-containing gas is a hydrocarbon gas. A method for removing the organometallic polymer film according to any one of claims 1 to 3.

8. The nitrogen-containing gas is nitrogen gas or ammonia gas. A method for removing the organometallic polymer film according to any one of claims 1 to 3.

9. The first etching gas further includes an inert gas. A method for removing the organometallic polymer film according to any one of claims 1 to 3.

10. the first etching gas further contains a halogen gas; A method for removing the organometallic polymer film according to any one of claims 1 to 3.

11. The halogen gas is F ２ , Cl ２ ,Br ２ , I ２ , HF, HCl, HBr, HI, BCl ３ is one selected from The method for removing the organometallic polymer film of claim 10.

12. forming a first pre-coat film including at least one of a silicon nitride film and a silicon oxide film in a processing chamber of the plasma processing apparatus; forming a second pre-coat film including a carbon film on the first pre-coat film in the processing chamber; forming an organometallic polymer film on the second pre-coat film in the processing chamber; After the step of forming the organometallic polymer film, supplying a first etching gas into the processing chamber to generate plasma; after the step of generating the plasma, a step of gasifying and removing the organometallic polymer film by reacting the organometallic polymer film with the plasma; and the first etching gas includes hydrogen gas, a carbon-containing gas, and a nitrogen-containing gas; Plasma treatment method.

13. the removing step includes removing the second pre-coat film. The plasma processing method according to claim 12.

14. The method includes repeating the steps of forming the second pre-coat film, forming the organometallic polymer film, generating the plasma, and removing the second pre-coat film in this order. The plasma processing method according to claim 12 or 13.

15. a step of removing the first pre-coat film by supplying a second etching gas into the processing chamber after the repeating step; the second etching gas includes a fluorine-containing gas; The plasma processing method according to claim 14.

16. A plasma processing apparatus for forming an organometallic polymer film, comprising: A processing vessel; a gas supply unit; A control unit; Equipped with the gas supply unit is configured to supply a first etching gas containing a hydrogen gas, a carbon-containing gas, and a nitrogen-containing gas into the processing chamber; The control unit supplying a first etching gas into the processing chamber having the organometallic polymer film formed therein to generate plasma; reacting the organometallic polymer film with the plasma to gasify and remove the organometallic polymer film; configured to control the gas supply unit to perform Plasma processing equipment.

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