Film forming method and film forming apparatus

Abstract

To provide a technology that can control film properties.SOLUTION: A film formation method includes the steps of: forming a SiCN layer on a substrate using a first silicon material and a first nitriding agent; forming a SiN layer on the SiCN layer using a second silicon material and a second nitriding agent; and repeating the steps of forming the SiCN layer and forming the SiN layer to form a stack film in which the SiCN layer and the SiN layer are stacked, and the first silicon material has a Si-C-Si bond.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] A technique for controlling the film stress of a film formed on a substrate is known (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-145244 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides techniques that allow control of film properties. [Means for solving the problem]

[0005] A film formation method according to one embodiment of the present disclosure includes the steps of forming a SiCN layer on a substrate using a first silicon source and a first nitriding agent, forming a SiN layer on the SiCN layer using a second silicon source and a second nitriding agent, and repeating the steps of forming the SiCN layer and forming the SiN layer to form a laminated film in which the SiCN layer and the SiN layer are stacked, wherein the first silicon source has a Si-C-Si bond. [Effects of the Invention]

[0006] According to the present disclosure, film properties can be controlled. [Brief explanation of the drawings]

[0007] [Figure 1] 2 is a flowchart illustrating a film forming method according to an embodiment. [Figure 2]10 is a flowchart showing an example of a SiCN layer forming step. [Figure 3] 10 is a flowchart showing an example of a SiN layer forming step. [Figure 4] FIG. 2 is a diagram illustrating an example of a first silicon raw material. [Figure 5] 1 is a schematic vertical cross-sectional view showing a film forming apparatus according to an embodiment. [Figure 6] 1 is a schematic horizontal cross-sectional view showing a film forming apparatus according to an embodiment. [Figure 7] FIG. 10 is a diagram illustrating an example of film stress. [Figure 8] FIG. 10 is a diagram showing an example of film density. 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] [Film formation method] A film forming method according to an embodiment will be described with reference to Figures 1 to 4. Figure 1 is a flowchart showing the film forming method according to the embodiment. As shown in Figure 1, the film forming method according to the embodiment includes a preparation step S1, a SiCN layer formation step S2, a SiN layer formation step S3, and a determination step S4.

[0010] (Preparation process S1) The preparation step S1 includes preparing a substrate. The substrate is, for example, a silicon wafer. The substrate may have recesses such as trenches and holes on its surface.

[0011] (SiCN layer formation step S2) The SiCN layer forming step S2 is performed after the preparation step S1. The SiCN layer forming step S2 includes forming a SiCN layer on a substrate using a first silicon source material and a first nitriding agent. The SiCN layer forming step S2 is performed, for example, at a first temperature. The first temperature is, for example, 500°C or higher and 580°C or lower.

[0012] 2 is a flowchart showing an example of the SiCN layer forming step S2. As shown in FIG. 2, the SiCN layer forming step S2 includes steps S21 to S27.

[0013] Step S21 includes supplying an inert gas to the surface of the substrate to purge the surface of the substrate. The inert gas is, for example, nitrogen (N) gas. The inert gas may also be a rare gas such as helium (He) gas or argon (Ar) gas.

[0014] Step S22 is performed after step S21. Step S22 includes supplying a first silicon source material to the surface of the substrate and adsorbing the first silicon source material on the surface of the substrate. FIG. 4 illustrates an example of the first silicon source material. As illustrated in FIG. 4, the first silicon source material is, for example, 1,1,3,3-tetrachloro-1,3-disilacyclobutane (Si2C2Cl4H4). Step S22 may include supplying an inert gas to the surface of the substrate at a flow rate lower than that of step S21. The inert gas is, for example, the same as the inert gas used in step S21.

[0015] Step S23 is performed after step S22. Step S23 includes supplying an inert gas to the surface of the substrate to purge the surface of the substrate. The inert gas is, for example, the same as the inert gas used in step S21.

[0016] Step S24 is performed after step S23. Step S24 includes heat-treating the substrate in an atmosphere containing a first nitriding agent without supplying RF power, thereby thermally nitriding the first silicon precursor adsorbed on the surface of the substrate. This forms a SiCN layer on the surface of the substrate. The first nitriding agent is, for example, ammonia (NH3). Step S24 may include supplying an inert gas to the surface of the substrate at a flow rate lower than that of step S21. The inert gas is, for example, the same inert gas as that used in step S21.

[0017] Step S25 is performed after step S24. Step S25 includes supplying an inert gas to the surface of the substrate to purge the surface of the substrate. The inert gas is, for example, the same as the inert gas used in step S21.

[0018] Step S26 is performed after step S25. Step S26 includes exposing the substrate to hydrogen plasma to modify the thermally nitrided first silicon source material. Step S26 may include generating hydrogen plasma by supplying hydrogen gas to the substrate and RF power. Step S26 may include supplying an inert gas simultaneously with the hydrogen gas. The inert gas is, for example, the same as the inert gas used in step S21. Steps S25 and S26 may not be performed.

[0019] Step S27 is performed after step S26. Step S27 includes determining whether steps S21 to S26 have been performed a first number of times. If the number of times has not reached the first number of times (NO in step S27), steps S21 to S26 are performed again. If the number of times has reached the first number of times (YES in step S27), the SiCN layer forming process S2 is terminated. In this way, in the SiCN layer forming process S2, steps S21 to S26 are repeated until the number of times has reached the first number of times, thereby forming a SiCN layer on the substrate.

[0020] (SiN layer formation step S3) The SiN layer formation step S3 is performed after the SiCN layer formation step S2. The SiN layer formation step S3 includes forming a SiN layer on the substrate using a second silicon source and a second nitriding agent. The SiN layer formation step S3 is performed, for example, at a second temperature. The second temperature is, for example, 500°C or higher. In this case, the SiN layer is easily formed. The second temperature is, for example, the same temperature as the first temperature. In this case, the substrate temperature does not need to be changed when the SiN layer formation step S3 is performed after the SiCN layer formation step S2. This improves productivity. The second temperature may be a temperature different from the first temperature.

[0021] 3 is a flowchart showing an example of the SiN layer forming step S3. As shown in FIG. 3, the SiN layer forming step S3 includes steps S31 to S35.

[0022] Step S31 includes supplying an inert gas to the surface of the substrate to purge the surface of the substrate, the inert gas being, for example, the same as the inert gas used in step S21.

[0023] Step S32 is performed after step S31. Step S32 includes supplying a second silicon source to the surface of the substrate and adsorbing the second silicon source on the surface of the substrate. The second silicon source is different from the first silicon source. The second silicon source is, for example, dichlorosilane (SiH2Cl2). Step S32 may include supplying an inert gas to the surface of the substrate at a flow rate lower than that of step S31. The inert gas is, for example, the same inert gas as that used in step S21.

[0024] Step S33 is performed after step S32. Step S33 includes supplying an inert gas to the surface of the substrate to purge the surface of the substrate. The inert gas is, for example, the same as the inert gas used in step S21.

[0025] Step S34 is performed after step S33. Step S34 includes heat-treating the substrate in an atmosphere containing a second nitriding agent without supplying RF power, thereby thermally nitriding the second silicon precursor adsorbed on the surface of the substrate in step S32. This forms a SiN layer on the surface of the substrate. The second nitriding agent is, for example, the same as the first nitriding agent. The second nitriding agent is, for example, ammonia (NH3). Step S34 may include supplying an inert gas to the surface of the substrate at a flow rate lower than that of step S31. The inert gas is, for example, the same as the inert gas used in step S21.

[0026] Step S35 is performed after step S34. Step S35 includes determining whether steps S31 to S34 have been performed a second number of times. If the number of times has not reached the second number of times (NO in step S35), steps S31 to S34 are performed again. If the number of times has reached the second number of times (YES in step S35), the SiN layer forming process S3 is terminated. In this way, in the SiN layer forming process S3, steps S31 to S34 are repeated until the number of times has reached the second number of times, thereby forming a SiN layer on the SiCN layer.

[0027] (Judgment step S4) The determination step S4 is performed after the SiN layer forming step S3. The determination step S4 includes determining whether the SiCN layer forming step S2 and the SiN layer forming step S3 have been performed a set number of times. If the number of times has not reached the set number (NO in the determination step S4), the SiCN layer forming step S2 and the SiN layer forming step S3 are performed again. If the number of times has reached the set number of times (YES in the determination step S4), the process ends. In this way, in the film forming method according to the embodiment, the SiCN layer forming step S2 and the SiN layer forming step S3 are repeated until the number of times has reached the set number, thereby forming a stacked film in which a SiCN layer and a SiN layer are stacked.

[0028] As described above, the film forming method according to the embodiment includes a SiCN layer forming step S2, a SiN layer forming step S3, and a determination step S4. In the SiCN layer forming step S2, a SiCN layer is formed on a substrate using 1,1,3,3-tetrachloro-1,3-disilacyclobutane, an example of a first silicon source, and ammonia, an example of a first nitriding agent. In the SiN layer forming step S3, a SiN layer is formed on the SiCN layer using dichlorosilane, an example of a second silicon source, and ammonia, an example of a second nitriding agent. In the determination step S4, the SiCN layer forming step S2 and the SiN layer forming step S3 are repeated. In this case, by controlling the first number of times in the SiCN layer forming step S2 and the second number of times in the SiN layer forming step S3, the ratio of SiCN layers to SiN layers in the stacked film can be adjusted, thereby controlling the film properties of the stacked film.

[0029] [Film forming equipment] A film formation apparatus 100 according to an embodiment will be described with reference to Fig. 5 and Fig. 6. Fig. 5 is a schematic vertical cross-sectional view showing the film formation apparatus 100 according to the embodiment. Fig. 6 is a schematic horizontal cross-sectional view showing the film formation apparatus 100 according to the embodiment. As shown in Figs. 5 and 6, the film formation apparatus 100 includes a processing chamber 1, a gas supply unit 20, a plasma generation unit 30, an exhaust unit 40, a heating unit 50, and a control unit 90.

[0030] The processing vessel 1 has a vertical cylindrical shape with a ceiling and an open bottom end. The processing vessel 1 is made of, for example, quartz. A ceiling plate 2 is provided near the upper end of the processing vessel 1, and the area below the ceiling plate 2 is sealed. The ceiling plate 2 is made of, for example, quartz. A cylindrical metal manifold 3 is connected to the opening at the lower end of the processing vessel 1 via a sealing member 4. The sealing member 4 is, for example, an O-ring.

[0031] The manifold 3 supports the lower end of the processing vessel 1. The boat 5 is inserted into the processing vessel 1 from below the manifold 3. The boat 5 holds multiple (e.g., 25 to 150) substrates W approximately horizontally with spacing between them in the vertical direction. The boat 5 is made of, for example, quartz. The boat 5 has, for example, three support columns 6, and the multiple substrates W are supported by grooves formed in the support columns 6.

[0032] The boat 5 is placed on a rotating table 8 via a heat-insulating tube 7. The heat-insulating tube 7 is made of, for example, quartz. The heat-insulating tube 7 suppresses heat radiation from the opening at the lower end of the manifold 3. The rotating table 8 is supported on a rotating shaft 10. The opening at the lower end of the manifold 3 is opened and closed by a lid 9. The lid 9 is made of, for example, a metal material such as stainless steel. The rotating shaft 10 passes through the lid 9.

[0033] A magnetic fluid seal 11 is provided at the penetration portion of the rotating shaft 10. The magnetic fluid seal 11 airtightly seals the rotating shaft 10 and rotatably supports it. A seal member 12 is provided between the periphery of the lid 9 and the lower end of the manifold 3 to maintain airtightness inside the processing vessel 1. The seal member 12 is, for example, an O-ring.

[0034] The rotating shaft 10 is attached to the tip of an arm 13 supported by an elevator mechanism such as a boat elevator. When the arm 13 moves up and down, the boat 5, the heat-retaining cylinder 7, the turntable 8, and the lid 9 move up and down together with the rotating shaft, and are inserted into and removed from the processing vessel 1.

[0035] The gas supply unit 20 supplies various gases into the processing vessel 1. The gas supply unit 20 includes, for example, a gas nozzle 21, a gas nozzle 22, and a gas nozzle 23. The gas nozzle 21, the gas nozzle 22, and the gas nozzle 23 are made of, for example, quartz. The gas supply unit 20 may further include another gas nozzle.

[0036] The gas nozzle 21 has an L-shape that penetrates the sidewall of the manifold 3 inward, bends upward, and extends vertically. The vertical portion of the gas nozzle 21 is provided inside the processing vessel 1. The vertical portion of the gas nozzle 21 has multiple gas holes 21a. The multiple gas holes 21a are provided at predetermined intervals along the extension direction of the gas nozzle 21. Each gas hole 21a is oriented toward the center CT of the processing vessel 1, for example.

[0037] A supply path L1 is connected to the gas nozzle 21. The supply path L1 is provided with a 1,1,3,3-tetrachloro-1,3-disilacyclobutane supply source G1, a mass flow controller F1, and an on-off valve V1, in this order from upstream to downstream in the gas flow direction. 1,1,3,3-tetrachloro-1,3-disilacyclobutane is an example of a first silicon source. The supply timing of 1,1,3,3-tetrachloro-1,3-disilacyclobutane from the supply source G1 is controlled by the on-off valve V1, and the flow rate is adjusted to a predetermined value by the mass flow controller F1. 1,1,3,3-tetrachloro-1,3-disilacyclobutane flows from the supply path L1 into the gas nozzle 21 and is ejected horizontally toward the center CT of the processing vessel 1 through multiple gas holes 21a.

[0038] A supply path L2 is connected to the gas nozzle 21. The supply path L2 may be connected to the supply path L1 downstream of the on-off valve V1. A dichlorosilane supply source G2, a mass flow controller F2, and an on-off valve V2 are provided on the supply path L2, in this order from upstream to downstream in the gas flow direction. Dichlorosilane is an example of a second silicon raw material. The supply timing of dichlorosilane from the supply source G2 is controlled by the on-off valve V2, and the flow rate is adjusted to a predetermined value by the mass flow controller F2. Dichlorosilane flows from the supply path L2 into the gas nozzle 21 and is ejected horizontally from multiple gas holes 21a toward the center CT of the processing chamber 1.

[0039] Gas nozzle 22 has an L-shape that penetrates the sidewall of manifold 3 inward, bends upward, and extends vertically. The vertical portion of gas nozzle 22 is provided in plasma generation space P, which will be described later. The vertical portion of gas nozzle 22 is provided with multiple gas holes 22a. The multiple gas holes 22a are provided at predetermined intervals along the extension direction of gas nozzle 22. Each gas hole 22a is oriented toward the center CT of processing vessel 1, for example.

[0040] A supply path L3 is connected to the gas nozzle 22. An ammonia supply source G3, a mass flow controller F3, and an on-off valve V3 are provided on the supply path L3, in this order from upstream to downstream in the gas flow direction. Ammonia is an example of a first nitriding agent and a second nitriding agent. The on-off valve V3 controls the supply timing of the ammonia from the supply source G3, and the mass flow controller F3 adjusts the flow rate to a predetermined value. The ammonia flows from the supply path L3 into the gas nozzle 22 and is discharged horizontally toward the center CT of the processing vessel 1 through multiple gas holes 22a.

[0041] A supply path L4 is connected to the gas nozzle 22. The supply path L4 may be connected to the supply path L3 downstream of the on-off valve V3. A hydrogen gas supply source G4, a mass flow controller F4, and an on-off valve V4 are provided on the supply path L4, in this order from upstream to downstream in the gas flow direction. The supply timing of the hydrogen gas from the supply source G4 is controlled by the on-off valve V4, and the flow rate is adjusted to a predetermined value by the mass flow controller F4. The hydrogen gas flows from the supply path L4 into the gas nozzle 22 and is discharged horizontally from multiple gas holes 22a toward the center CT of the processing chamber 1.

[0042] The gas nozzle 23 has a straight pipe shape that extends horizontally and penetrates the sidewall of the manifold 3. The gas nozzle 23 is connected to an inert gas supply source G5. The tip of the gas nozzle 23 is installed inside the processing vessel 1. The tip of the gas nozzle 23 is open, and the inert gas is supplied into the processing vessel 1 from the opening.

[0043] The plasma generating unit 30 is provided in a part of the sidewall of the processing vessel 1. The plasma generating unit 30 generates plasma from hydrogen gas supplied from the gas nozzle 22. The plasma generating unit 30 includes a plasma partition wall 32, a pair of plasma electrodes 33, a power supply line 34, an RF power supply 35, and an insulating protective cover 36.

[0044] The plasma compartment wall 32 is airtightly welded to the outer wall of the processing vessel 1. The plasma compartment wall 32 is made of, for example, quartz. The plasma compartment wall 32 has a concave cross section and covers an opening 31 formed in the side wall of the processing vessel 1. The opening 31 is elongated in the vertical direction so that it can cover all of the substrates W supported by the boat 5 in the vertical direction. A gas nozzle 22 is disposed in a plasma generation space P, which is an inner space defined by the plasma compartment wall 32 and communicates with the inside of the processing vessel 1. The gas nozzle 21 is provided outside the plasma generation space P at a position close to the substrates W along the inner wall of the processing vessel 1.

[0045] The pair of plasma electrodes 33 each have an elongated shape and are arranged facing each other in the vertical direction on the outer surfaces of both sides of the plasma compartment wall 32. A power supply line 34 is connected to the lower end of each plasma electrode 33.

[0046] The power supply line 34 electrically connects each plasma electrode 33 to the RF power supply 35. For example, one end of the power supply line 34 is connected to the lower end, which is the side of the short side of each plasma electrode 33, and the other end is connected to the RF power supply 35.

[0047] The RF power supply 35 is electrically connected to the lower end of each plasma electrode 33 via a power supply line 34. The RF power supply 35 supplies RF power of, for example, 13.56 MHz to the pair of plasma electrodes 33. This applies the RF power to the plasma generation space P defined by the plasma partition wall 32.

[0048] The insulating protective cover 36 is attached to the outside of the plasma compartment wall 32 so as to cover the plasma compartment wall 32. A coolant passage (not shown) is provided inside the insulating protective cover 36. The plasma electrode 33 is cooled by flowing a coolant such as cooled nitrogen gas through the coolant passage. A shield (not shown) may be provided between the plasma electrode 33 and the insulating protective cover 36 so as to cover the plasma electrode 33. The shield is made of a good conductor such as metal and is electrically grounded.

[0049] The exhaust unit 40 has an exhaust port 41. The exhaust port 41 is provided in a portion of the sidewall of the processing vessel 1 opposite the opening 31. The exhaust port 41 is elongated in the vertical direction to correspond to the boat 5. A cover member 42 having a U-shaped cross section is attached to the portion of the processing vessel 1 corresponding to the exhaust port 41 so as to cover the exhaust port 41. The cover member 42 extends upward along the sidewall of the processing vessel 1. An exhaust pipe 43 is connected to the lower part of the cover member 42. A pressure adjustment valve 44 and a vacuum pump 45 are provided in the exhaust pipe 43, in this order from upstream to downstream in the gas flow direction. The exhaust unit 40 operates the pressure adjustment valve 44 and the vacuum pump 45 under the control of the control unit 90 to suck gas from the processing vessel 1 into the vacuum pump 45, while adjusting the pressure in the processing vessel 1 using the pressure adjustment valve 44.

[0050] The heating unit 50 includes a heater 51. The heater 51 has a cylindrical shape that surrounds the processing vessel 1 on the radially outer side of the processing vessel 1. The heater 51 heats the entire periphery of the processing vessel 1, thereby heating each substrate W accommodated in the processing vessel 1.

[0051] The control unit 90 is an electronic circuit such as a CPU (Central Processing Unit), FPGA (Field Programmable Gate Array), ASIC (Application Specific Integrated Circuit), etc. The control unit 90 executes various control operations described in this specification by executing instruction codes stored in a memory or by being a circuit designed for a specific application.

[0052] [Operation of the Film Forming Apparatus] The operation of the film forming apparatus 100 when the film forming method according to the embodiment is performed in the film forming apparatus 100 will be described.

[0053] First, the control unit 90 raises the arm 13 to load the boat 5 holding the substrates W into the processing vessel 1, and then airtightly closes the opening at the bottom of the processing vessel 1 with the lid 9. Next, the control unit 90 controls the exhaust unit 40 so that the pressure inside the processing vessel 1 is set to a set pressure, and controls the heating unit 50 so that the substrates W are heated to a first temperature.

[0054] Next, the control unit 90 controls each unit of the film forming apparatus 100 to perform the SiCN layer forming step S2, the SiN layer forming step S3, and the determination step S4. As a result, a stacked film in which a SiCN layer and a SiN layer are stacked is formed on each substrate W. The control unit 90 adjusts the ratio of the SiCN layer to the SiN layer contained in the stacked film by controlling the first number of times in the SiCN layer forming step S2 and the second number of times in the SiN layer forming step S3. This allows the film properties of the stacked film to be controlled.

[0055] Next, the control unit 90 increases the pressure inside the processing vessel 1 to atmospheric pressure, and decreases the temperature inside the processing vessel 1 to the unloading temperature, and then lowers the arm 13 to unload the boat 5 from the processing vessel 1. This completes the processing of the multiple substrates W.

[0056] [Experimental results] In the experiment, a stacked film was formed on a substrate by performing the preparation step S1, the SiCN layer formation step S2, the SiN layer formation step S3, and the evaluation step S4 in this order in the film formation apparatus 100, and the film stress and film density of the formed stacked film were measured. In the experiment, stacked films were formed under multiple conditions (SiCN:SiN = 1:0, 1:1, 1:3, 0:1) with different ratios of the first number of times in the SiCN layer formation step S2 to the second number of times in the SiN layer formation step S3 (hereinafter referred to as "SiCN:SiN"). SiCN:SiN = 1:0 refers to a condition in which the SiCN layer formation step S2 was performed but the SiN layer formation step S3 was not performed. SiCN:SiN = 0:1 refers to a condition in which the SiCN layer formation step S2 was not performed but the SiN layer formation step S3 was performed. The conditions for the SiCN layer formation step S2 and the SiN layer formation step S3 were as follows.

[0057] (SiCN layer formation step S2) Substrate temperature: 550℃ First silicon source: 1,1,3,3-tetrachloro-1,3-disilacyclobutane First nitriding agent: Ammonia

[0058] (SiN layer formation step S3) Substrate temperature: 550℃ Second silicon source: dichlorosilane Second nitriding agent: Ammonia

[0059] Fig. 7 is a graph showing an example of film stress, which shows the film stress [MPa] of the laminated film when SiCN:SiN is 1:0, 1:1, 1:3, and 0:1, from the left.

[0060] 7, it can be seen that the film stress of the laminated film changes by changing the SiCN:SiN ratio. From this result, it can be said that the film stress of the laminated film can be controlled by controlling the ratio between the first number of times in the SiCN layer formation step S2 and the second number of times in the SiN layer formation step S3.

[0061] 7, when the SiCN:SiN ratio was 1:3, the film stress of the laminated film was 1158 MPa. From this result, it can be said that by laminating the SiCN layer formed in the SiCN layer formation step S2 and the SiN layer formed in the SiN layer formation step S3, a laminated film having high film stress (for example, film stress higher than 1 GPa) can be formed at a low temperature of 550°C or less.

[0062] Fig. 8 is a diagram showing an example of film density. The graph in Fig. 8 shows the film density [g / cm 3 ] of the laminated film when the SiCN:SiN ratio is 1:0, 1:1, 1:3, and 0:1, in that order from the left. 3 ] is shown.

[0063] 8, it can be seen that the film density of the laminated film changes by changing the SiCN:SiN ratio. From this result, it can be said that the film density of the laminated film can be controlled by controlling the ratio between the first number of times in the SiCN layer formation step S2 and the second number of times in the SiN layer formation step S3.

[0064] As shown in FIG. 8, when the ratio of SiCN to SiN is 1:3, the film density of the laminated film is 2.83 g / cm 3 From this result, it can be said that by stacking the SiCN layer formed in the SiCN layer forming step S2 and the SiN layer formed in the SiN layer forming step S3, a laminated film having high film density can be formed at a low temperature of 550°C or less.

[0065] 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.

[0066] In the above embodiment, the first silicon source material is 1,1,3,3-tetrachloro-1,3-disilacyclobutane. However, the present disclosure is not limited to this. The first silicon source material may be any material as long as it has a Si-C-Si bond. For example, 1,1,3,3-tetrachloro-1,3-disilacyclopentane (C3H6Cl4Si2) may be used as the first silicon source material. That is, the shape of the cyclic structure composed of silicon (Si) and carbon (C) contained in the first silicon source material is not limited to a quadrangle. Furthermore, the cyclic structure is not limited to a structure in which silicon (Si) and carbon (C) are alternately bonded. Furthermore, 1,1,3,3-tetrafluoro-1,3-disilacyclobutane (C2H4F4Si2) may be used as the first silicon source material. That is, the first silicon source material may contain another halogen, such as fluorine (F), bromine (Br), or iodine (I), instead of chlorine (Cl).

[0067] In the above embodiment, the second silicon source is dichlorosilane (SiH2Cl2), but the present disclosure is not limited to this. The second silicon source may be any halogen-containing silicon. Examples of halogen-containing silicon include fluorine-containing silicon gases such as SiF4, SiHF3, SiH2F2, and SiH3F; chlorine-containing silicon gases such as SiCl4, SiHCl3, SiH2Cl2, SiH3Cl, and Si2Cl6; bromine-containing silicon gases such as SiBr4, SiHBr3, SiH2Br2, and SiH3Br; and combinations thereof.

[0068] In the above embodiment, the first and second nitriding agents are ammonia (NH), but the present disclosure is not limited thereto. The first and second nitriding agents may be ammonia (NH), diazene (NH), hydrazine (NH), monomethylhydrazine (CH(NH)NH), or a combination thereof. The first and second nitriding agents may be the same or different.

[0069] In the above embodiment, the film forming apparatus is a batch type apparatus that processes multiple substrates at once, but the present disclosure is not limited to this. For example, the film forming apparatus may be a single-wafer type apparatus that processes substrates one by one. [Explanation of symbols]

[0070] S2 SiCN layer formation process S3 SiN layer formation process S4 Judgment process

Claims

1. forming a SiCN layer on a substrate using a first silicon source and a first nitriding agent; forming a SiN layer on the SiCN layer using a second silicon source and a second nitriding agent; a step of repeating the step of forming the SiCN layer and the step of forming the SiN layer to form a laminated film in which the SiCN layer and the SiN layer are laminated; and The first silicon source has a Si—C—Si bond. Film formation method.

2. The step of forming the SiCN layer includes: providing the first silicon source material to the substrate; supplying the first nitriding agent to the substrate; performing the step of supplying the first silicon source and the step of supplying the first nitriding agent a first number of times; and The step of forming the SiN layer includes: supplying the second silicon source material to the substrate; supplying the second nitriding agent to the substrate; performing the step of supplying the second silicon source and the step of supplying the second nitriding agent a second number of times; and the step of forming the stacked film includes controlling the first number of times and the second number of times to control the film stress of the stacked film. The film forming method according to claim 1 .

3. The step of forming the SiCN layer is performed at a temperature of 500° C. or higher and 580° C. or lower. The film forming method according to claim 1 .

4. forming the SiCN layer includes exposing the substrate to a plasma generated from hydrogen gas; The film forming method according to claim 1 .

5. the first silicon source is 1,1,3,3-tetrachloro-1,3-disilacyclobutane; The film forming method according to claim 1 .

6. the second silicon source is dichlorosilane; The film forming method according to claim 1 .

7. the first nitriding agent and the second nitriding agent are ammonia; The film forming method according to claim 1 .

8. a processing vessel for accommodating a substrate; a gas supply unit that supplies a first silicon source material, a second silicon source material, a first nitriding agent, and a second nitriding agent into the processing chamber; A control unit; Equipped with the first silicon source has a Si—C—Si bond; The control unit forming a SiCN layer on the substrate using the first silicon source material and the first nitriding agent; forming a SiN layer on the SiCN layer using the second silicon source material and the second nitriding agent; a step of repeating the step of forming the SiCN layer and the step of forming the SiN layer to form a laminated film in which the SiCN layer and the SiN layer are laminated; and controlling the gas supply unit to perform the steps of: Film deposition equipment.

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