Substrate processing method

Abstract

To provide a substrate processing method for forming a carbon-containing film that suppresses film peeling due to heat treatment.SOLUTION: A method for processing a substrate includes the steps of: preparing a substrate having a base film; generating plasma of a processing gas containing a carbon-containing gas to form a carbon-containing film having a film density of 2 g / cm3 or more on the base film; and performing heat treatment on the substrate on which the carbon-containing film is formed. In the step of forming the carbon-containing film, a higher ion energy is supplied to the substrate during a period from a start of forming the carbon-containing film to first time than during a period from the first time to second time.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present disclosure relates to a method for processing a substrate. [Background technology]

[0002] Patent Document 1 discloses a substrate processing method for forming a carbon-based film on a substrate, the substrate processing method including a step of placing the substrate on a mounting table, a first film formation step of forming a first carbon-based film having a first stress, a second film formation step of forming a second carbon-based film having a second stress, and a third film formation step of repeating the first film formation step and the second film formation step to form a stack of the first carbon-based film and the second carbon-based film, wherein the first stress and the second stress are in the same direction and have different strengths.

[0003] Patent Document 2 discloses a method comprising exposing a semiconductor substrate in a chamber to a process gas including a hydrocarbon precursor gas and a helium gas, substantially without other inert gases, and depositing an ashable hardmask film on the substrate by a plasma-enhanced chemical vapor deposition process, the plasma-enhanced chemical vapor deposition process including maintaining a chamber pressure below 500 mTorr and igniting a plasma generated by a dual radio frequency plasma source including a high frequency component and a low frequency component. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2022-128270 [Patent Document 2] Special Publication No. 2022-545720 Summary of the Invention [Problem to be solved by the invention]

[0005] In one aspect, the present disclosure provides a substrate processing method for forming a carbon-containing film that suppresses film peeling due to heat treatment. [Means for solving the problem]

[0006] In order to solve the above problems, according to one embodiment, a method for manufacturing a semiconductor device includes the steps of: preparing a substrate having an undercoat film; generating plasma of a process gas containing a carbon-containing gas; and applying a concentration of 2 g / cm 3 onto the undercoat film. 3 and heat-treating the substrate on which the carbon-containing film has been formed, wherein the carbon-containing film forming step supplies higher ion energy to the substrate during a period from start of formation of the carbon-containing film to a first time than during a period from the first time to a second time. Effect of the Invention

[0007] According to one aspect, it is possible to provide a substrate processing method for forming a carbon-containing film that suppresses film peeling due to heat treatment. [Brief description of the drawings]

[0008] [Figure 1] FIG. 2 is a schematic cross-sectional view showing an example of a processing apparatus according to the present embodiment. [Diagram 2] 4 is a flowchart showing an example of a substrate processing according to the embodiment. [Diagram 3] 5 is an example of a time chart of a carbon-containing film formation process performed by the substrate processing apparatus according to the embodiment. [Figure 4] 1 is a schematic cross-sectional view of a substrate, illustrating an example of a structure of a carbon-containing film formed by the substrate processing apparatus according to the embodiment; [Diagram 5] The results of film peeling when annealing treatment was performed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, an embodiment of the present disclosure will be described with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals, and duplicated descriptions may be omitted.

[0010] [Substrate processing device 1] A substrate processing apparatus 1 according to this embodiment will be described with reference to Fig. 1. Fig. 1 is a schematic cross-sectional view showing an example of the substrate processing apparatus 1 according to this embodiment. The substrate processing apparatus 1 is an apparatus that forms a carbon-containing film 310 (see Fig. 4 described later) on a substrate W such as a wafer by a plasma-enhanced chemical vapor deposition (PECVD) method in a processing chamber 2 under reduced pressure.

[0011] The substrate processing apparatus 1 includes a substantially cylindrical airtight processing vessel 2. An exhaust chamber 21 is provided in the center of the bottom wall of the processing vessel 2.

[0012] 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. An exhaust unit 24 is connected to the exhaust flow path 22 via a pressure adjustment unit 23. The pressure adjustment unit 23 includes, for example, a pressure adjustment valve such as a butterfly valve. The exhaust flow path 22 is configured so that the inside of the processing vessel 2 can be decompressed by the exhaust unit 24. A transfer port 25 is provided at a side surface of the processing vessel 2. The transfer port 25 is configured so as to be freely opened and closed by a gate valve 26. The substrate W is loaded and unloaded between the inside of 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 in the processing vessel 2. The mounting table 3 is formed in a substantially circular shape in a plan view, and is supported by a support member 31. A substantially circular recess 32 for mounting the substrate W having a diameter of, for example, 300 mm is formed on the surface 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 formed of a ceramic material such as aluminum nitride (AlN). The mounting table 3 may be formed of a metal material such as nickel (Ni). Instead of the recess 32, a guide ring for guiding the substrate W may be provided on the periphery of the surface of the mounting table 3.

[0014] A 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 substrate W placed on the mounting table 3 to a set temperature based on a control signal from the control unit 9. When the mounting table 3 is entirely made of metal, the entire mounting table 3 functions as the lower electrode, so that the lower electrode 33 does not need to be embedded in the mounting table 3.

[0015] A power supply that applies a bias voltage for attracting ions to the substrate W during plasma processing is connected to the lower electrode 33. In other words, the power supply increases the energy of the ions attracted to the substrate W. That is, the power supply increases the ion energy supplied to the substrate W.

[0016] In the example shown in FIG. 1, a DC pulse power supply 35 is connected to the lower electrode 33. The DC pulse power supply 35 applies a DC pulse bias voltage to the lower electrode 33 in order to supply ion energy to the substrate W during plasma processing. The power supply that supplies ion energy to the substrate W is not limited to this configuration. It may be a DC power supply that applies a DC bias voltage to the lower electrode 33. It may also be an RF power supply that applies low-frequency bias power. For example, an RF power supply (not shown) is connected to the lower electrode 33 via a matching box (not shown). The RF power supply applies low-frequency power (LF; Low Frequency) to the lower electrode 33, the frequency of which is lower than the frequency of an RF power supply 51 described later. The high-frequency power generated by the RF power supply is used as a high-frequency power for biasing to attract ions to the substrate W. The frequency of the RF power supply is, for example, 13.56 MHz.

[0017] The mounting table 3 is provided with a plurality of (e.g., three) lift pins 41 for holding and lifting the substrate W mounted on the mounting table 3. The material of the lift pins 41 may be, 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 via a lift shaft 43 to a lift mechanism 44 provided outside the processing chamber 2.

[0018] 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 211 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 freely raised and lowered between the upper side and the lower side of the surface 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 top surface of the mounting table 3.

[0019] Furthermore, the lower end of the support member 31 penetrates the opening 212 of the exhaust chamber 21, and is supported by a lifting mechanism 46 via a lifting plate 47 disposed below the processing vessel 2. A bellows 48 is provided between the bottom of the exhaust chamber 21 and the lifting plate 47, so that the airtightness inside the processing vessel 2 is maintained even when the lifting plate 47 moves up and down.

[0020] The lifting mechanism 46 lifts and lowers the lifting plate 47, thereby lifting and lowering the mounting table 3. In this way, the gap between the mounting table 3 and the gas supply unit 5 can be adjusted.

[0021] 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 constitutes 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 unit 511. The RF power supply 51 applies high frequency power to the upper electrode (gas supply unit 5). The high frequency power generated by the RF power supply 51 is used as high frequency power for generating plasma required for film formation on the substrate W. The frequency of the RF power supply 51 is, for example, 40 MHz to 300 MHz. An RF electric field is generated between the upper electrode (gas supply unit 5) and the lower electrode 33 by supplying RF power from the RF power supply 51 to the upper electrode (gas supply unit 5). The gas supply unit 5 includes a hollow gas diffusion chamber 52. A number of holes 53 for dispersing and supplying the processing gas into the processing vessel 2 are arranged, for example, evenly, on the lower surface of the gas diffusion chamber 52. A heating mechanism 54 is embedded in the gas supply unit 5, for example, above the gas diffusion chamber 52. The heating mechanism 54 is heated to a set temperature by being supplied with power from a power supply unit (not shown) based on a control signal from the control unit 9.

[0022] The gas diffusion chamber 52 is provided with a gas supply path 6. The gas supply path 6 is connected to the gas diffusion chamber 52. 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, a mass flow controller, and a valve (none of which are shown). The various processing gases include a film formation gas containing carbon atoms (for example, at least one selected from CxHy (x and y are any integers) such as CH4, C2H2, C3H6, and C2H4) used in the above-mentioned carbon-based film formation method. In addition, the various processing gases may include a carrier gas (for example, at least one selected from H2, Ar, He, O2, and N2). The various processing gases are introduced from the gas source 61 to the gas diffusion chamber 52 via the gas line 62.

[0023] The substrate processing apparatus 1 includes a control unit 9. The control unit 9 is, for example, a computer, and includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a 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 substrate processing apparatus 1. The control unit 9 may be provided inside or outside the substrate processing apparatus 1. When the control unit 9 is provided outside the substrate processing apparatus 1, the control unit 9 can control the substrate processing apparatus 1 by a communication means such as a wired or wireless communication means.

[0024] [Substrate processing] Next, an example of the substrate processing according to this embodiment will be described with reference to Fig. 2. Fig. 2 is a flow chart showing the example of the substrate processing according to this embodiment.

[0025] In step S101, a substrate W is prepared. An undercoat film 300 (see FIG. 4) is formed on the substrate W. The undercoat film 300 is, for example, a silicon-containing film containing silicon (Si). The undercoat film 300 is any one of Si, SiO2, SiN, SiC, SiON, SiCON, etc. The undercoat film 300 may also be a metal-containing film containing metal atoms. The metal atoms of the metal-containing film may be any one of Ti, Ta, Zr, Hf, etc. The undercoat film 300 is any one of TiN, TaN, ZrN, HfN, etc.

[0026] In step S102, the substrate W having the base film 300 is subjected to DHF treatment. Here, DHF (diluted HF) is supplied to the surface of the substrate W having the base film 300 (see FIG. 4), and a wet etching treatment is performed on the surface of the base film 300. This cleans the surface of the base film 300. In addition, a natural oxide film (not shown) formed on the surface of the base film 300 and the like are removed. Note that the treatment shown in step S102 is not essential and may be omitted.

[0027] In step S103, a carbon-containing film 310 (see FIG. 4) is formed on the substrate W having the undercoat film 300. The carbon-containing film 310 is, for example, an amorphous carbon film. The carbon-containing film 310 is, for example, a diamond-like carbon (DLC) film. The carbon-containing film 310 has a film density of 2 g / cm3. 3 The carbon-containing film has the above-mentioned high density. The high density carbon-containing film 310 has high etching resistance. Therefore, the carbon-containing film 310 can be used as a hard mask when etching the base film 300, for example. The carbon-containing film 310 has a film thickness of 3 nm or more. Therefore, by having a high density and a film thickness of 3 nm or more, the carbon-containing film 310 has high film stress. The film stress of the carbon-containing film 310 is 1 GPa or more.

[0028] 1 is used to form a carbon-containing film 310 on an undercoat film 300 on a substrate W. A method for forming the carbon-containing film 310 according to this embodiment will be described later with reference to FIGS.

[0029] In step S104, the substrate W on which the carbon-containing film 310 has been formed is subjected to an annealing treatment (heat treatment). For example, the substrate W is heated at an annealing temperature in the range of 400°C to 800°C in an N2 atmosphere at atmospheric pressure or a pressure lower than atmospheric pressure, and the substrate W is subjected to the annealing treatment. By subjecting the substrate W to the annealing treatment, hydrogen (H) in the carbon-containing film 310 is reduced, thereby reducing the film stress. The pressure lower than atmospheric pressure is, for example, a pressure in the range of 1 Torr to 700 Torr.

[0030] 2, the substrate processing method according to this embodiment is described as performing an annealing process (step S104) on the substrate W after the process of forming the carbon-containing film 310 on the substrate W (step S103), but this is not limited thereto. After step S103 and before step S104, another process may be added. Also, after step S104, another process may be added.

[0031] Here, the carbon-containing film 310 formed by the PECVD method in step S103 has high film stress. Therefore, by performing an annealing treatment in step S104, the film stress of the carbon-containing film 310 is reduced. Furthermore, the higher the annealing temperature, the more the film stress of the carbon-containing film 310 decreases.

[0032] On the other hand, 2 g / cm 3 In the above-described high-density carbon-containing film 310, when the substrate W is subjected to an annealing treatment at a high temperature of 400° C. or more, there is a risk that the carbon-containing film 310 may peel off from the base film 300 of the substrate W during the annealing treatment.

[0033] Next, the process of forming the carbon-containing film 310 in step S103 performed by the substrate processing apparatus 1 according to this embodiment will be described with reference to FIGS.

[0034] Fig. 3 is an example of a time chart of a process for forming a carbon-containing film 310 performed by the substrate processing apparatus 1 according to this embodiment. Fig. 4 is an example of a schematic cross-sectional view of a substrate W showing an example of a structure of a carbon-containing film 310 formed by the substrate processing apparatus 1 according to this embodiment.

[0035] The control unit 9 controls a transfer device (not shown) to place the substrate W on the mounting table 3 of the substrate processing apparatus 1. The substrate processing apparatus 1 forms a carbon-containing film 310 on an undercoat film 300 of the substrate W. The carbon-containing film 310 is used, for example, as a hard mask. The undercoat film 300 is a film in which structures such as trenches, channels, and holes are formed by dry etching through a pattern formed in the carbon-containing film 310. When the transfer device retreats from the transfer port 25, the control unit 9 closes the gate valve 26.

[0036] The control unit 9 also controls the temperature adjustment mechanism 34 to set the temperature of the substrate W to a predetermined temperature. The temperature adjustment mechanism 34 also controls the pressure adjustment unit 23 and the exhaust unit 24 to set the inside of the processing chamber 2 to a predetermined pressure.

[0037] Next, the control unit 9 forms a carbon-containing film 310 on the substrate W. First, the control unit 9 controls the gas source 61 to supply a processing gas into the processing vessel 2. Here, as the processing gas, a carbon-containing gas (e.g., C2H2 gas), an inert gas (e.g., Ar gas), or the like is supplied into the processing vessel 2. In addition, an additive gas (e.g., H2 gas) may be supplied as the processing gas.

[0038] In step S201 of FIG. 3, the control unit 9 controls the RF power supply 51 to apply high frequency power for plasma generation to the upper electrode (gas supply unit 5). At the same time, the control unit 9 controls the DC pulse power supply 35 to apply a DC pulse bias voltage (bias voltage) to the lower electrode 33. In other words, the ion energy supplied to the substrate W is made higher than that in step S202 described later. Note that the processing gas is continuously supplied into the processing vessel 2. As a result, as shown in FIG. 4, in step S201, an initial layer 311 of the carbon-containing film 310 is formed on the base film 300. That is, the initial layer 311 of the carbon-containing film 310 is a portion of the carbon-containing film 310 that is formed in the process of step S201.

[0039] An example of a recipe in step S201 is shown below. Pressure inside processing vessel: 5mTorr~1Torr Carbon-containing gas supply: 10sccm to 1500sccm Inert gas supply: 100sccm~2000sccm RF power: 100W~2000W DC pulse: 0.1kV~2kV, duty ratio 10%~90%

[0040] The period during which the process of step S201 is performed is the period from the start of formation T0 of the carbon-containing film 310 until the first time T1 has elapsed. The start of formation T0 is, for example, the timing at which RF is applied. Here, the processing time of step S201 (the time from the start of formation T0 until the first time T1 has elapsed) is preferably within a range of 1 second to 10 seconds. Also, the film thickness of the initial layer 311 is preferably within a range of 1 nm to 10 nm.

[0041] When the first time T1 has elapsed, the process of the control unit 9 proceeds to step S202.

[0042] In step S202 of FIG. 3, the control unit 9 controls the DC pulse power supply 35 to stop the DC pulse bias voltage (bias voltage) to the lower electrode 33. In other words, the ion energy supplied to the substrate W is made lower compared to that in step S201. Note that, continuing from step S201, the processing gas is supplied into the processing vessel 2, and high frequency power for plasma generation is applied to the upper electrode (gas supply unit 5). Thereby, as shown in FIG. 4, in step S202, the main layer 312 of the carbon-containing film 310 is formed following the initial layer 311. That is, the main layer 312 of the carbon-containing film 310 is a portion of the carbon-containing film 310 that is formed in the process of step S202.

[0043] An example of the recipe in step S202 is shown below. Pressure inside processing vessel: 5mTorr~1Torr Carbon-containing gas supply: 10sccm to 1500sccm Inert gas supply: 100sccm~2000sccm RF power: 100W~2000W

[0044] In this manner, the process of step S201 and the process of step S202 are different in that a bias voltage is applied to the lower electrode 33, but the other conditions are the same. That is, in the process of step S201 and the process of step S202, the process pressure (pressure inside the process vessel) is the same, the flow rates of the process gases (supply rate of carbon-containing gas, supply rate of inert gas) are the same, and the power (RF power) for generating plasma is the same.

[0045] The period during which the process of step S202 is performed is the period from the first time T1 to the second time T2.

[0046] Moreover, the period from the formation start T0 to the first time T1 is shorter than the period from the first time T1 to the second time T2. Moreover, the thickness of the carbon-containing film 310 formed during the period from the formation start T0 to the first time T1 is thinner than the thickness of the carbon-containing film 310 formed during the period from the first time T1 to the second time T2. That is, the thickness of the initial layer 311 is formed thinner than the thickness of the main body layer 312.

[0047] Here, the initial layer 311 formed in the process of step S201 is formed by supplying high ion energy to the substrate W. Here, in the process of step S201, the ion energy supplied to the substrate W is preferably within a range of 100 eV to 2000 eV.

[0048] When the initial layer 311 is formed, high ion energy is supplied to the substrate W, which strengthens the bond between carbon (C) provided from the carbon-containing gas (e.g., C2H2 gas) and silicon (Si) of the underlayer 300. This strengthens the bond at the interface between the carbon-containing film 310 and the underlayer 300, which is considered to suppress peeling of the carbon-containing film 310 during annealing.

[0049] In addition, when forming the initial layer 311, it is only necessary to supply high ion energy to the substrate W, and the bias voltage supplied to the lower electrode 33 is not limited to a DC pulse bias voltage. It may be a DC bias voltage or a low-frequency bias power.

[0050] When the bias voltage supplied to the lower electrode 33 is a DC pulse bias voltage, 0.1kV~2.0kV 100kHz~250kHz Duty ratio 10%~30% It is preferable that the range is within the range of .

[0051] When the bias voltage supplied to the lower electrode 33 is a DC bias voltage, 0.1kV~2.0kV It is preferable that the range is within the range of .

[0052] When the bias voltage supplied to the lower electrode 33 is a low-frequency bias power, 400kHz~13.56MHz 100W~4000W It is preferable that the range is within the range of .

[0053] Then, the ion energy supplied to the substrate W is reduced when the main body layer 312 is formed. This makes it possible to increase the film density of the carbon-containing film 310 (main body layer 312).

[0054] Next, an example of the experimental results will be described with reference to Fig. 5. Fig. 5 shows an example of the deposition results of various carbon-containing films. Here, the conditions (ion energy, film stress, deposition time (film thickness)) for depositing the initial layer 311 in step S201 and the results of film peeling after annealing are shown.

[0055] In No. 1, the initial layer 311 of the carbon-containing film 310 was formed on the substrate W subjected to the DHF treatment shown in step S102 of FIG. 2 under conditions where the film stress of the initial layer 311 of the carbon-containing film 310 was low and the ion energy was low (no DC application). That is, the initial layer 311 of the carbon-containing film 310 was formed with a film thickness of 10 nm under the conditions of RF power being a first power (e.g., 100 W), DC application being a first voltage (e.g., 0 V), and pressure being a first pressure (e.g., 100 mTorr), for a processing time of 5 seconds (sec) in step S201. Note that the film stress when only the initial layer 311 was formed to a thickness of 50 nm under these conditions was -280 MPa. Thereafter, following the initial layer 311, the main layer 312 of the carbon-containing film 310 was formed to a thickness of 40 nm. The main body layer 312 of the carbon-containing film 310 was formed as a high stress film under the following conditions: RF power was set to a second power (e.g., 300 W) higher than the first power, DC was applied to a first voltage (e.g., 0 V), and the pressure was set to a second pressure (e.g., 20 mTorr) lower than the first pressure.

[0056] In No. 2, the initial layer 311 of the carbon-containing film 310 was formed on the substrate W subjected to the DHF treatment shown in step S102 of FIG. 2 under conditions where the film stress of the initial layer 311 of the carbon-containing film 310 was low and the ion energy was high (with DC application). That is, the initial layer 311 of the carbon-containing film 310 was formed with a film thickness of 1 nm under conditions where the RF power was a first power (e.g., 300 W), the DC application was a first voltage (e.g., 2 kV) that gives high ion energy, and the pressure was a first pressure (e.g., 20 mTorr), for a processing time of 1 second (sec) in step S201. Note that the film stress when only the initial layer 311 was formed to a thickness of 50 nm under these conditions was -0.5 GPa. Note that the film stress when the initial layer 311 of No. 2 was formed to a thickness of 50 nm was higher than the film stress when the initial layer 311 of No. 1 was formed to a thickness of 50 nm. In the initial layer 311 of No. 2, the film thickness is reduced to form a low stress film. Then, following the initial layer 311, a main layer 312 of the carbon-containing film 310 was formed to a thickness of 40 nm. The main layer 312 of the carbon-containing film 310 was formed as a high stress film by applying a DC voltage of a second voltage (e.g., 0 V) ​​lower than the first voltage that provides low ion energy, and by using the same RF power and pressure conditions as those for the initial layer 311.

[0057] In No. 3, the initial layer 311 of the carbon-containing film 310 was formed on the substrate W subjected to the DHF treatment shown in step S102 of FIG. 2 under conditions in which the film stress of the initial layer 311 of the carbon-containing film 310 was high and the ion energy was high (with DC application). That is, the initial layer 311 of the carbon-containing film 310 was formed with a film thickness of 10 nm under the conditions of RF power being a first power (e.g., 300 W), DC application being a first voltage (e.g., 1 kV) that gives high ion energy, and pressure being a first pressure (e.g., 20 mTorr), for a processing time of 5 seconds (sec) in step S201. Note that the film stress when only the initial layer 311 was formed to a thickness of 50 nm under these conditions was -1 GPa. Thereafter, following the initial layer 311, the main layer 312 of the carbon-containing film 310 was formed to a thickness of 40 nm. The main layer 312 of the carbon-containing film 310 was formed as a high stress film by applying a DC voltage of a second voltage (e.g., 0 V) ​​lower than the first voltage that provides low ion energy, and by using the same RF power and pressure conditions as those for the initial layer 311.

[0058] In No. 4, the initial layer 311 of the carbon-containing film 310 was formed under the same conditions as in No. 3, except that the DHF treatment shown in step S102 in Fig. 2 was omitted. Then, following the initial layer 311, the main layer 312 of the carbon-containing film 310 was formed to a thickness of 40 nm.

[0059] Fig. 5 shows the results of film peeling when annealing was performed at 600° C. As shown in Fig. 5, in No. 1, film peeling occurred in the carbon-containing film 310.

[0060] On the other hand, in No. 2, although the film stress of the initial layer 311 was increased compared to No. 1, peeling of the carbon-containing film 310 did not occur.

[0061] Further, in No. 3, the initial layer 311 was thicker than in No. 2, in other words, the film stress of the initial layer 311 was higher than in No. 2, but peeling of the carbon-containing film 310 did not occur.

[0062] In addition, in No. 4, even when the DHF treatment was omitted, the carbon-containing film 310 did not peel off.

[0063] As described above, according to the substrate processing method of this embodiment, by supplying ion energy to the substrate W in the early stage of formation of the carbon-containing film 310, peeling of the carbon-containing film 310 during annealing can be suppressed.

[0064] The substrate processing method for forming the carbon-containing film 310 has been described above. However, the present disclosure is not limited to the above-described embodiments, and various modifications and improvements are possible within the scope of the gist of the present disclosure described in the claims. [Explanation of symbols]

[0065] W substrate 1. Substrate Processing Equipment 2. Treatment vessel 3. Placement table 5 Gas supply section (upper electrode) 6 Gas supply line 9. Control Unit 33 Lower electrode 35 DC Pulse Power Supply 51 RF power supply

Claims

1. Providing a substrate having an undercoat film; A plasma of a processing gas containing a carbon-containing gas is generated, and 2 g / cm is deposited on the undercoat film. ３ forming a carbon-containing film having a film density of at least and heat-treating the substrate on which the carbon-containing film is formed, The step of forming a carbon-containing film includes: supplying a higher ion energy to the substrate during a period from the start of formation of the carbon-containing film to a first time than during a period from the first time to a second time; A method for processing a substrate.

2. A bias voltage is applied to a lower electrode provided on a mounting table supporting the substrate during a period from the start of the formation of the carbon-containing film to the first time period. The method for processing a substrate according to claim 1 .

3. The bias voltage is Either a DC pulse bias voltage, a DC bias voltage, or a low-frequency bias power; The substrate processing method according to claim 2 .

4. The bias voltage is A DC pulse bias voltage, 0.1 kV to 2.0 kV, 100 kHz to 250 kHz, and duty ratio within the range of 10% to 30%. The substrate processing method according to claim 2 .

5. The bias voltage is A DC bias voltage, Within the range of 0.1 kV to 2.0 kV; The substrate processing method according to claim 2 .

6. The bias voltage is A low frequency bias power, 400kHz to 13.56MHz, 100W to 4000W; The substrate processing method according to claim 2 .

7. The ion energy is in the range of 100 eV to 2000 eV; The method for processing a substrate according to claim 1 .

8. a period from the start of formation of the carbon-containing film to the first time is shorter than a period from the first time to the second time; The method for processing a substrate according to claim 1 .

9. a period from the start of the formation of the carbon-containing film to the first time is within a range of 1 second to 10 seconds; The substrate processing method according to claim 8 .

10. a thickness of the carbon-containing film formed during a period from the start of the formation to the first time is smaller than a thickness of the carbon-containing film formed during a period from the first time to the second time; The method for processing a substrate according to claim 1 .

11. The thickness of the carbon-containing film formed during the period from the start of the formation to the first time is within a range of 1 nm to 10 nm. The method of claim 10.

12. a processing pressure during a period from the start of the formation to the first time and a processing pressure during a period from the first time to the second time are the same pressure; The method for processing a substrate according to claim 1 .

13. a flow rate of the processing gas during a period from the start of the formation to the first time and a flow rate of the processing gas during a period from the first time to the second time are equal to each other; The method for processing a substrate according to claim 1 .

14. A power for generating plasma during a period from the start of the formation to the first time is equal to a power for generating plasma during a period from the first time to the second time. The method of claim 12.

15. The carbon-containing gas is CH ４ , C ２ H ２ , C ３ H ６ , C ２ H ４ At least one selected from The method for processing a substrate according to claim 1 .

16. The process gas is Further comprising an inert gas. The method for processing a substrate according to claim 1 .

17. The inert gas is H ２ , Ar, He, O ２ , N ２ At least one selected from The method of claim 16.

18. The heat treatment is in the range of 400°C to 800°C. The method for processing a substrate according to claim 1 .

19. The heat treatment is carried out at atmospheric pressure and in N ２ Processed under atmosphere, The method of claim 18.

20. The heat treatment is performed at a pressure in the range of 1 Torr to 700 Torr, and N ２ Processed under atmosphere, The method of claim 18.

21. The undercoat film is a silicon-containing film or a metal-containing film. The method for processing a substrate according to claim 1 .

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