Semiconductor device manufacturing method and substrate processing apparatus

Abstract

According to an embodiment, a method for manufacturing a semiconductor device is provided. The method for manufacturing a semiconductor device includes using plasma generated from a process gas containing a hydrogen isotope gas to perform free radical oxidation on a first film.

Description

[Technical Field]

[0001] This embodiment relates to a method for manufacturing a semiconductor device and a substrate processing apparatus. [Related applications can be found here]

[0002] This application enjoys the priority right of Japanese Patent Application No. 2024-105391, filed on June 28, 2024, the entire contents of which are incorporated herein by reference. [Previous Technology]

[0003] In the manufacturing process of semiconductor devices, there are cases where a specific thin film is deposited on or above a substrate, and the deposited specific thin film is subjected to free radical oxidation treatment. In the manufacturing process of semiconductor devices, it is desirable to perform free radical oxidation efficiently. [Summary of the Invention]

[0004] According to this embodiment, a method for manufacturing a semiconductor device is provided. The method for manufacturing a semiconductor device includes using plasma generated from a process gas containing a hydrogen isotope gas to perform free radical oxidation on a first film.

[0005] The method for manufacturing a semiconductor device according to an embodiment will be described in detail below with reference to the drawings. However, the present invention is not limited to this embodiment.

Implementation Method

[0026] (Embodiment Embodiment) The method for manufacturing a semiconductor device according to the embodiment embodiment involves depositing a specific thin film on or above a substrate and subjecting the deposited specific thin film to free radical oxidation, while applying technical measures to efficiently perform free radical oxidation.

[0027] The manufacturing method of the semiconductor device 100 can be performed according to the manner shown in FIG1 and FIG2A to FIG2E. FIG1 is a flowchart of the manufacturing method of the display semiconductor device 100. Hereinafter, the direction perpendicular to the main surface 10a of the substrate 10 is defined as the Z direction, and the two mutually perpendicular directions in the plane perpendicular to the Z direction are defined as the X direction and the Y direction. FIG2A to FIG2E are YZ cross-sectional views of the manufacturing method of the display semiconductor device 100, respectively.

[0028] As shown in FIG2A, a substrate 10 is prepared (S1). The substrate 10 has a slightly disk-shaped form, and in the XY top view, it has a slightly circular shape. The substrate 10 may be formed of a material whose main component is semiconductor (e.g., silicon). The substrate 10 has a main surface 10a on the +Z side.

[0029] Once the substrate 10 is ready, a high aspect ratio structure TR, as shown in FIG2B, is formed on or above the main surface 10a of the substrate 10 (+Z side). FIG2B illustrates the case where a high aspect ratio structure TR is formed on the main surface 10a of the substrate 10.

[0030] A film 11 is deposited on or above the main surface 10a of the substrate 10 by methods such as CVD (chemical vapor deposition) or sputtering. The film 11 may be formed of an insulating material. A photoresist pattern PR having an opening corresponding to a hole 11a1 is formed on the main surface 11a of the film 11. Using a method such as RIE (reactive ion etching), the photoresist pattern PR is used as a mask, and etching is performed under anisotropic processing conditions. As a result, a hole 11a1 with a high aspect ratio is formed on the film 11 in a cross-sectional view including the Z-axis. A high aspect ratio refers to a case where the aspect ratio (i.e., hole depth / hole bottom width) is greater than 1. That is, a high aspect ratio structure TR is obtained by forming a high aspect ratio hole 11a1 on the film 11.

[0031] After the TR with high length and width structure is formed, the treated film 12 (S2) is deposited on the side and bottom surface of the hole 11a1 as shown in FIG2C.

[0032] The film to be treated 12 is deposited on the film 11 by means of CVD, sputtering or the like. In the deposited film to be treated 12, the main surface 11a of the cover film 11 is removed by means of RIE or the like, while the side surface and bottom surface of the cover hole 11a1 are retained.

[0033] When the film to be processed 12 is deposited, the substrate 10 is transported into the substrate processing apparatus 1 shown in FIG3, and the film to be processed 12 is subjected to oxidation treatment (S3). FIG3 shows the configuration of the substrate processing apparatus 1 used in the manufacturing method of semiconductor device 100.

[0034] The oxidation process (S3) can be performed in the substrate processing apparatus 1 by using plasma generated from a processing gas containing hydrogen isotope gas and oxygen to perform free radical oxidation on the film 12 to be processed. The free radical oxidation process using plasma is an isotropic process, which is called PIO (Plasma Isotropic Oxidization) process.

[0035] The substrate processing apparatus 1 includes a vacuum container 2, a platform 3, a gas supply system 4, an electrode 5, a power supply unit 6, an exhaust system 7, and a controller 8.

[0036] The controller 8 is capable of uniformly controlling all parts of the substrate processing device 1.

[0037] The vacuum container 2 forms a processing chamber CH on its inner side. The processing chamber CH is a space in which plasma PL is generated. The vacuum container 2 has an upper wall 2a, a side wall 2b, and a bottom wall 2c. The upper wall 2a is disposed on the +Z side, while the bottom wall 2c is disposed on the -Z side. The upper wall 2a may have cracks 2a1 and 2a2 at an outer position in the XY direction. The bottom wall 2c may have a hole 2i at any position.

[0038] Platform 3 is disposed in processing chamber CH. Platform 3 can be disposed in processing chamber CH near the bottom wall 2c. Platform 3 includes a body 3a, an electrode 3b, and a heater 3c. The body 3a extends in a plate or disc shape in the XY direction. The body 3a can be formed of an insulating material. The +Z side of the body 3a forms a mounting surface 3d. The substrate 10 is mounted in the mounting surface 3d. The electrode 3b and the heater 3c can be embedded in the body 3a respectively. The electrode 3b extends in a plate or disc shape in the XY direction. The electrode 3b can be formed of a conductive material. The electrode 3b can be connected to the ground potential by wiring. The heater 3c can heat the substrate 10 by the body 3a under the control of the controller 8. Even if not shown, platform 3 can still have a mechanism for adsorbing the substrate 10.

[0039] The gas supply system 4 is capable of supplying a processing gas containing hydrogen isotope gas and oxygen to the platform 3 within the processing chamber CH. The hydrogen isotope gas can be either deuterium (D2) or tritium (T2). The following explanation will focus on the case where the hydrogen isotope gas is deuterium, but the following explanation also applies to the case where the hydrogen isotope gas is tritium.

[0040] The gas supply system 4 includes gas cylinders 4a-4c, regulating valves 4d-4f, gas piping 4g-4n, and a cover 4t. Gas cylinders 4a, 4b, and 4c store deuterium (D2), light hydrogen (H2), and oxygen (O2), respectively. Gas cylinder 4c typically stores 16O2 gas. The cover 4t has a gas inlet 4u. Gas cylinders 4a to 4c are each connected to gas piping 4g-4i. The cover 4t covers and maintains a distance from the upper wall 2a in the Z direction, forming a buffer chamber 4v. The buffer chamber 4v is connected to the gas inlet 4u on the +Z side and to slits 2a1 and 2a2 on the -Z side. Regulating valves 4d-4f are respectively disposed between gas piping 4g-4n and can be opened and closed and their degree of opening can be controlled by controller 8.

[0041] Electrode 5 is disposed outside the processing chamber CH at a position separate from platform 3. Electrode 5 may be disposed on the +Z side portion of sidewall 2b. Electrode 5 includes coil 5a. Coil 5a may be wound around the +Z side portion of sidewall 2b.

[0042] The power supply unit 6 is capable of supplying high-frequency power to the electrode 5. The power supply unit 6 includes a high-frequency power supply 6a, an integrator 6b, and a sensor 6c. The high-frequency power supply 6a supplies high-frequency power to the electrode 5 under the control of the controller 8. The sensor 6c monitors information about the supplied high-frequency progressive or reflected waves and provides the monitoring results to the integrator 6b. The integrator 6b performs impedance integration based on the monitoring results of the sensor 6c to reduce the power of the reflected waves.

[0043] The exhaust system 7 is capable of reducing and adjusting the pressure within the processing chamber CH. The exhaust system 7 includes a vacuum pump 7a, an adjusting valve 7b, and vacuum piping 7c and 7d. The vacuum pump 7a operates under the control of the controller 8. The adjusting valve 7b is located between the vacuum piping 7c and 7d and its opening and closing degree are controlled by the controller 8.

[0044] In the substrate processing apparatus 1, the controller 8 applies a high-frequency voltage between the electrode 3b and the electrode 5, and generates plasma PL (S4) in the processing chamber CH with a processing gas containing hydrogen isotope gas (e.g., D2 gas) and oxygen (O2 gas).

[0045] For example, when the substrate 10 is placed on the mounting surface 3d of the platform 3, the controller 8 will heat up the substrate 10. The controller 8 can control the heater 3c to heat the substrate 10 to a temperature of 300°C or higher and 800°C or lower.

[0046] Furthermore, if the temperature of the substrate 10 is below 300°C, the film formation rate of free radical oxidation may drop below an acceptable level. When the temperature of the substrate 10 exceeds 800°C, in addition to free radical oxidation, thermal oxidation of the treated film 12 is also involved, which may make it difficult to control the film formation rate.

[0047] While the substrate 10 is heated, the controller 8 starts the vacuum pump 7a and controls the opening degree of the regulating valve 7b to keep the pressure of the processing chamber CH between 50Pa and 300Pa, and depressurizes the pressure in the processing chamber CH through the vacuum pipes 7c and 7d.

[0048] Furthermore, if the pressure of CH in the treatment chamber is below 50 Pa, the oxidation rate may be lower than the allowable level and thus decrease. If the pressure of CH in the treatment chamber exceeds 300 Pa, plasma may not be generated inside the CH in the treatment chamber.

[0049] Controller 8 begins supplying a processing gas containing hydrogen isotope gas (e.g., D2 gas) and oxygen (O2 gas) to the processing chamber CH. Controller 8 keeps regulating valve 4e closed while simultaneously opening regulating valves 4d and 4f. Thus, hydrogen isotope gas (e.g., D2 gas) and oxygen (O2 gas) are introduced from gas cylinders 4a and 4c via gas pipes 4g, 4i, 4j, and 4m into gas pipe 4n, where they mix to form a processing gas containing hydrogen isotope gas (e.g., D2 gas) and oxygen (O2 gas). The processing gas system introduces the gas from gas pipe 4n into buffer chamber 4v via gas inlet 4u. The processing gas in buffer chamber 4v is supplied from slits 2a1 and 2a2 to platform 3 within the processing chamber CH.

[0050] At this time, the controller 8 system continues to control the opening degree of the regulating valve 7b so that the pressure of the processing chamber CH is more than 50 Pa and less than 300 Pa. In addition, the controller 8 system controls the opening degree of the regulating valves 4d and 4f respectively so that the flow ratio of hydrogen isotope gas (e.g., D2 gas) to the flow rate of the processing gas is more than 5% and less than 95%.

[0051] In addition, if the gas flow rate of hydrogen isotopes is less than 5%, the step coverage of the oxide film formed by free radical oxidation may be below the permissible level. When the gas flow rate of hydrogen isotopes exceeds 95%, the step coverage of the oxide film formed by free radical oxidation may be below the permissible level.

[0052] When the pressure in the processing chamber CH stabilizes, the controller 8 begins to supply high-frequency power from the power supply unit 6 to the electrode 5. This applies a high-frequency voltage between the electrode 3b and the electrode 5, creating an induced magnetic field within the processing chamber CH. Hydrogen isotopes contained in the processing gas (e.g., D2 gas) and oxygen (O2 gas) are excited by plasma, forming, for example, a ring-shaped plasma PL. This plasma PL can be a plasma with a low electrical potential. The D2 gas and O2 gas systems dissociate via the plasma PL, generating oxidative radicals such as hydroxyl radicals (OH*), deuterium ions, oxygen ions, and other reaction species. Due to the low electrical potential of the plasma PL, deuterium ions and oxygen ions are not accelerated, and oxidative radicals in the processing gas are supplied approximately uniformly to the vicinity of the exposed surface 12a of the processed film 12 on the substrate 10.

[0053] Thus, the treated membrane 12 is oxidized by free radicals (S5). As shown in FIG2D, the free radical oxidation system can be carried out near the exposed surface 12a of the treated membrane 12, and the portion near the exposed surface 12a of the treated membrane 12 can be replaced by an oxide film 13. Alternatively, as shown in FIG2E, the free radical oxidation system can also be carried out on the entire treated membrane 12, and the entire treated membrane 12 can be replaced by an oxide film 13. The dashed arrows in FIG2D and FIG2E indicate that the oxidized free radicals or ions in the treatment gas are supplied approximately uniformly to the vicinity of the exposed surface 12a of the treated membrane 12.

[0054] Then, specific processes are further performed on the substrate 10 shown in FIG2D or FIG2E to manufacture the semiconductor device 100.

[0055] As described above, in the embodiment, the manufacturing method of the semiconductor device 100 uses a plasma generated from a processing gas containing hydrogen isotopes and oxygen, and the film 12 to be processed is oxidized by free radicals. Therefore, compared with the case where the film 12 to be processed is oxidized by free radicals using a plasma generated from a processing gas containing hydrogen and oxygen, free radical oxidation can be performed more effectively.

[0056] For example, when the substrate processing apparatus 1 uses a plasma generated from a processing gas containing hydrogen and oxygen at a flow rate ratio of 30%:70% to perform free radical oxidation on the film 12 to be processed, the thickness of the oxide film 13 corresponding to the processing time varies as shown by the dashed line in FIG4. FIG4 is a graph showing the change in oxide film thickness corresponding to the processing time (at a flow rate ratio of 30%). At processing time t1, an oxide film 13 is formed with a film thickness h1, and at processing time t2 (>t1), an oxide film 13 is formed with a film thickness h2 (>h1).

[0057] On the other hand, when the substrate processing apparatus 1 uses a plasma generated from a processing gas containing D2 and oxygen at a flow rate ratio of 30%:70% to perform free radical oxidation on the film 12 to be processed, the thickness of the oxide film 13 corresponding to the processing time varies as shown by the solid line in FIG4. At processing time t1, the oxide film 13 is formed with a thickness d1, and at processing time t2, the oxide film 13 is formed with a thickness d2 (>d1).

[0058] The film formation amount at each processing time is greater when using a processing gas containing hydrogen isotopes and oxygen than when using a plasma generated from a processing gas containing hydrogen and oxygen. From the perspective of processing time t1, film thickness d1 is greater than film thickness h1. From the perspective of processing time t2, film thickness d2 is greater than film thickness h2.

[0059] The film formation rate is greater when using a plasma generated from a treatment gas containing hydrogen isotopes and oxygen, compared to the case where a plasma generated from a treatment gas containing hydrogen and oxygen is used. When observed during the treatment time t1~t2, the slope of the solid line (d2-d1) / (t2-t1) is greater than the slope of the dashed line (h2-h1) / (t2-t1).

[0060] Alternatively, when the substrate processing apparatus 1 uses a plasma generated from a processing gas containing hydrogen and oxygen at a flow rate ratio of 20%:80% to perform free radical oxidation on the film 12 to be processed, the thickness of the oxide film 13 corresponding to the processing time varies as shown by the dashed line in Figure 5. Figure 5 shows the change in oxide film thickness corresponding to the processing time (at a flow rate ratio of 20%). At processing time t11, the oxide film 13 is formed with a film thickness of h11, and at processing time t12 (>t11), the oxide film 13 is formed with a film thickness of h12 (>h11).

[0061] On the other hand, when the substrate processing apparatus 1 uses a plasma generated from a processing gas containing D2 and oxygen at a flow rate ratio of 20%:80% to perform free radical oxidation on the film 12 to be processed, the thickness of the oxide film 13 corresponding to the processing time varies as shown by the solid line in FIG5. At processing time t11, the oxide film 13 is formed with a film thickness d11, and at processing time t12, the oxide film 13 is formed with a film thickness d12 (>d11).

[0062] The film formation amount at each processing time is greater when using a processing gas containing hydrogen isotopes and oxygen than when using a plasma generated from a processing gas containing hydrogen and oxygen. From the perspective of processing time t11, the film thickness d11 is greater than the film thickness h11. From the perspective of processing time t12, the film thickness d12 is greater than the film thickness h12.

[0063] The film formation rate is greater when using a plasma generated from a process gas containing hydrogen isotopes and oxygen, compared to the case where a plasma generated from a process gas containing hydrogen and oxygen is used. Considering the processing time t11~t12, the slope of the solid line (d12-d11) / (t12-t11) is greater than the slope of the dashed line (h12-h11) / (t12-t11).

[0064] Alternatively, when the substrate processing apparatus 1 uses a plasma generated from a processing gas containing hydrogen and oxygen at a flow rate ratio of 5%:95% to perform free radical oxidation on the film 12 to be processed, the thickness of the oxide film 13 corresponding to the processing time varies as shown by the dashed line in Figure 6. Figure 6 shows the change in oxide film thickness corresponding to the processing time (at a flow rate ratio of 5%). At processing time t21, the oxide film 13 is formed with a film thickness of h21, and at processing time t22 (>t21), the oxide film 13 is formed with a film thickness of h22 (>h21).

[0065] On the other hand, when the substrate processing apparatus 1 uses a plasma generated from a processing gas containing D2 and oxygen at a flow rate ratio of 5%:95% to perform free radical oxidation on the film 12 to be processed, the thickness of the oxide film 13 corresponding to the processing time varies as shown by the solid line in FIG6. At processing time t21, the oxide film 13 is formed with a film thickness d21, and at processing time t22, the oxide film 13 is formed with a film thickness d22 (>d21).

[0066] The amount of film formed at each processing time is the same as that generated using a plasma produced by a processing gas containing hydrogen and oxygen, and the same as that generated using a processing gas containing hydrogen isotopes and oxygen. From the perspective of processing time t21, the film thickness d21 is the same as the film thickness h21. From the perspective of processing time t22, the film thickness d22 is the same as the film thickness h22.

[0067] The film formation rate is the same in the case of using a plasma generated from a treatment gas containing hydrogen and oxygen and in the case of using a plasma generated from a treatment gas containing hydrogen isotopes and oxygen. Considering the treatment time t11~t12, the slope of the solid line (d12-d11) / (t12-t11) is the same as the slope of the dashed line (h12-h11) / (t12-t11).

[0068] Alternatively, when the substrate processing apparatus 1 uses plasma generated from a processing gas containing hydrogen at a flow rate of 0% to 100% to perform free radical oxidation on the film 12 being processed, the luminescence intensity of hydroxyl radicals (OH*) is shown by the dashed line in Figure 7. Figure 7 shows the variation of the luminescence intensity of hydroxyl radicals (OH*) according to the flow rate of the corresponding hydrogen or its isotopes. The luminescence intensity of hydroxyl radicals (OH*) is related to the step coverage of the oxide film 13. The luminescence of a specific spectral band (e.g., a spectral band with a wavelength of 306 to 315 nm) is detected at the site in the film 11 that has been oxidized by hydroxyl radicals (OH*). The stronger the luminescence intensity of hydroxyl radicals (OH*), the better the step coverage of the oxide film 13 is estimated. From the variation of the dashed line in Figure 7, the variation of the peak value between 5% and 95% indicates that it is approximately exceeding the threshold value. By keeping the flow rate of hydrogen between 5% and 95%, the luminescence intensity is estimated to be at an acceptable level for the step coverage of the oxide film 13. The critical limit can be experimentally determined in advance as the permissible level corresponding to the step coverage of oxide film 13.

[0069] On the other hand, when the substrate processing apparatus 1 uses plasma generated from a processing gas containing D2 at a flow rate ratio of 0% to 100% to perform free radical oxidation on the film 12 being processed, the luminescence intensity of the hydroxyl radical OH* is shown by the solid line in FIG7. Looking at the changes in the solid line in FIG7, the change in the range of 5% to 95% indicates a peak value that approximately exceeds the threshold. By keeping the hydrogen flow rate ratio at 5% to 95%, the luminescence intensity is estimated to be at an acceptable level for the step coverage of the oxide film 13.

[0070] The luminescence intensity of hydroxyl radicals (OH*) at a flow ratio of 5% to 95% is greater than that of plasma generated using a process gas containing hydrogen and oxygen. With a flow ratio of 5%, the solid line value Id1 is greater than the dashed line value Ih1. With a flow ratio of 95%, the solid line value Id2 is greater than the dashed line value Ih2. Looking at the range of flow ratios from 5% to 95%, the solid line curve is located on the side with a higher luminescence intensity than the dashed line curve. Therefore, compared to plasma generated using a process gas containing hydrogen and oxygen, it is speculated that using plasma generated using a process gas containing a hydrogen isotope and oxygen can improve the step-like coverage of the oxide film 13 caused by radical oxidation.

[0071] Furthermore, the processing gas used in S4 can be hydrogen, a hydrogen isotope gas, and a mixture of oxygen. For example, in S4 shown in FIG1, the controller 8 system begins to supply the processing chamber CH with a processing gas containing hydrogen (H2 gas), a hydrogen isotope gas (e.g., D2 gas), and oxygen (O2 gas). The controller 8 system opens the regulating valves 4d, 4e, and 4f. As a result, hydrogen (e.g., H2 gas), a hydrogen isotope gas (e.g., D2 gas), and oxygen (O2 gas) are introduced from gas cylinders 4a, 4b, and 4c through gas pipes 4g, 4h, 4i, 4j, 4k, and 4m into gas pipe 4n, where they mix to form a processing gas containing a hydrogen (H2 gas) isotope gas (e.g., D2 gas) and oxygen (O2 gas). The processing gas system introduces the gas from gas pipe 4n into the buffer chamber 4v through the gas inlet 4u. The processing gas in buffer chamber 4v is supplied from slits 2a1 and 2a2 to platform 3 within processing chamber CH. At this time, controller 8 controls the opening degree of regulating valves 4d, 4e, and 4f respectively, ensuring that the flow rate ratio of hydrogen isotope gas (e.g., D2 gas) to the processing gas is 5% to 95%. Maintaining this flow rate ratio also improves the step-like coverage of oxide film 13 caused by free radical oxidation.

[0072] Furthermore, the processing gas system used in S4 may also contain rare gases such as helium or argon. The processing gas system may be a mixture of hydrogen isotope gas, oxygen, and rare gases, or it may be a mixture of hydrogen and hydrogen isotope gas, oxygen, and rare gases. In this case, by making the flow rate ratio of hydrogen isotope gas to processing gas flow rate between 5% and 95%, the step-like coverage of oxide film 13 caused by free radical oxidation can also be improved.

[0073] Alternatively, as a first modification of the embodiment, as shown in FIG8, the oxidation process (S103) may also be performed in the substrate processing apparatus 201 shown in FIG9, using a plasma generated from a processing gas containing a gas containing hydrogen isotopes and a gas containing oxygen isotopes to perform free radical oxidation on the film 12 to be processed. FIG8 is a flowchart showing a method for manufacturing the semiconductor device 100 according to the first modification of the embodiment. FIG9 is a configuration diagram showing the substrate processing apparatus 201 used in the method for manufacturing the semiconductor device 100 according to the first modification of the embodiment.

[0074] The substrate processing apparatus 201 has a gas supply system 204 instead of the gas supply system 4 (see Figure 3). The gas supply system 204 is capable of supplying a processing gas containing hydrogen isotope gas and oxygen isotope gas to the platform 3 in the processing chamber CH. The hydrogen isotope gas can be deuterium (D2) or tritium (T2). The oxygen isotope gas can be oxygen-17 (17O2) gas or oxygen-18 (18O2) gas. Hereinafter, the description will focus on the case where the hydrogen isotope gas is deuterium and the oxygen isotope gas is 17O2, but the following description also applies to cases where the specific examples of hydrogen isotope gas and the specific examples of oxygen isotope gas are other combinations.

[0075] The gas supply system 204 further includes a gas cylinder 4p, a regulating valve 4q, a gas piping 4r, and a gas pipe 4s. The gas cylinder 4p stores 17O2 gas. The gas cylinder 4p is connected to the gas piping 4r. The regulating valve 4q is located between the gas piping 4r and 4s, and its opening and closing degree are controlled by the controller 8.

[0076] In the substrate processing apparatus 201, the controller 8 applies a high-frequency voltage between the electrode 3b and the electrode 5, and generates plasma PL in the processing chamber CH with a processing gas containing hydrogen isotope gas (e.g., D2 gas) and oxygen isotope gas (17O2 gas).

[0077] For example, when the substrate 10 is placed on the mounting surface 3d of the platform 3, the controller 8 will heat up the substrate 10. The controller 8 can control the heater 3c to heat the substrate 10 to a temperature of 300°C or higher and 800°C or lower.

[0078] In parallel with this, the controller 8 starts the vacuum pump 7a and controls the opening degree of the adjusting valve 7b to maintain the pressure of the processing chamber CH between 50Pa and 300Pa, and depressurizes the pressure in the processing chamber CH through the vacuum pipes 7c and 7d.

[0079] Controller 8 begins supplying a processing gas containing hydrogen isotope gas (e.g., D2 gas) and oxygen isotope gas (e.g., 17O2 gas) to the processing chamber CH. Controller 8 keeps regulating valves 4e and 4f closed while simultaneously opening regulating valves 4d and 4q. Thus, hydrogen isotope gas (e.g., D2 gas) and oxygen isotope gas (e.g., 17O2 gas) are introduced from gas cylinders 4a and 4p through gas pipes 4g, 4r, 4j, and 4s into gas pipe 4n, where they mix to form a processing gas containing hydrogen isotope gas (e.g., D2 gas) and oxygen isotope gas (e.g., 17O2 gas). The processing gas system introduces the gas from gas pipe 4n into buffer chamber 4v via gas inlet 4u. The processing gas in buffer chamber 4v is supplied from slits 2a1 and 2a2 to platform 3 within the processing chamber CH.

[0080] At this time, the controller 8 system continues to control the opening degree of the regulating valve 7b so that the pressure of the processing chamber CH is more than 50 Pa and less than 300 Pa. In addition, the controller 8 system controls the opening degree of the regulating valves 4d and 4q respectively so that the flow rate ratio of hydrogen isotope gas (e.g., D2 gas) to the flow rate of the processing gas is more than 5% and less than 95%.

[0081] When the pressure in the processing chamber CH stabilizes, the controller 8 begins to supply high-frequency power from the power supply unit 6 to the electrode 5. This applies a high-frequency voltage between the electrode 3b and the electrode 5, creating an induced magnetic field within the processing chamber CH. The hydrogen isotope gas (e.g., D2 gas) and the oxygen isotope gas (e.g., 17O2 gas) contained in the processing gas are excited by plasma, forming, for example, a ring-shaped plasma PL. This plasma PL can be a plasma with a low electrical potential. The D2 gas and 17O2 gas systems dissociate via the plasma PL, generating oxidative radicals such as hydroxyl radicals (OH*), deuterium ions, oxygen ions, and other reaction species. Due to the low electrical potential of the plasma PL, deuterium ions and oxygen ions are not accelerated, and oxidative radicals in the processing gas are supplied approximately uniformly to the vicinity of the exposed surface 12a of the processed film 12 on the substrate 10.

[0082] Thus, the treated membrane 12 is oxidized by free radicals (S105). As shown in FIG2D, the free radical oxidation system can be carried out near the exposed surface 12a of the treated membrane 12, and the portion near the exposed surface 12a of the treated membrane 12 can be replaced by an oxide film 13. Alternatively, as shown in FIG2E, the free radical oxidation system can also be carried out on the entire treated membrane 12, and the entire treated membrane 12 can be replaced by an oxide film 13. The dashed arrows in FIG2D and FIG2E indicate that the oxidized free radicals or ions in the treatment gas are supplied approximately uniformly to the vicinity of the exposed surface 12a of the treated membrane 12.

[0083] Thus, in the method for manufacturing the semiconductor device 100, a plasma generated from a processing gas containing hydrogen isotopes and oxygen isotopes is used to oxidize the film 12 by free radicals. As a result, free radical oxidation can be performed more effectively than when the film 12 is oxidized by a plasma generated from a processing gas containing hydrogen and oxygen.

[0084] For example, the film formation rate is greater when using a process gas containing a gas containing a hydrogen isotope and an oxygen isotope than when using a plasma generated from a process gas containing a hydrogen isotope and an oxygen isotope.

[0085] or the stepped coating of oxide film 13 is greater than the case of plasma generated by a processing gas containing hydrogen isotopes and oxygen isotopes compared to the case of plasma generated by a processing gas containing hydrogen isotopes and oxygen isotopes.

[0086] However, in the semiconductor device 100 manufacturing method, the processing gas used in S4 can be a mixture of hydrogen, a hydrogen isotope gas, and an oxygen isotope gas, or a mixture of hydrogen, a hydrogen isotope gas, oxygen, and an oxygen isotope gas. For example, in S4 shown in FIG10, the controller 8 system starts supplying the processing chamber CH with a processing gas containing hydrogen (H2 gas), a hydrogen isotope gas (e.g., D2 gas), oxygen (O2 gas), and an oxygen isotope gas (e.g., 17O2 gas). The controller 8 system opens the regulating valves 4d, 4e, 4f, and 4q. Therefore, hydrogen (H2 gas), hydrogen isotope gas (e.g., D2 gas), oxygen (O2 gas), and oxygen isotope gas (e.g., ¹⁷O2 gas) are introduced from gas cylinders 4a, 4b, 4c, and 4p through gas pipes 4g, 4h, 4i, 4r, 4j, 4k, 4m, and 4s into gas pipe 4n. In gas pipe 4n, hydrogen (H2 gas), hydrogen isotope gas (e.g., D2 gas), oxygen (e.g., O2 gas), and oxygen isotope gas (e.g., ¹⁷O2 gas) are mixed to form a processing gas. The processing gas system introduces the gas from gas pipe 4n into buffer chamber 4v via gas inlet 4u. The processing gas in buffer chamber 4v is supplied from slits 2a1 and 2a2 to platform 3 within processing chamber CH. The controller 8 controls the opening degree of the regulating valves 4d, 4e, 4f, and 4q respectively, so that the flow rate ratio of hydrogen isotope gas (e.g., D2 gas) to the flow rate of the processed gas is 5% to 95%. At this time, by keeping the flow rate ratio of hydrogen isotope gas to the flow rate of the processed gas at 5% to 95%, the step coverage of the oxide film 13 caused by free radical oxidation can also be improved.

[0087] Furthermore, the processing gas system used in S4 may also contain rare gases such as helium or argon. The processing gas system may be a mixture of hydrogen isotope gas, oxygen isotope gas, and rare gases; it may also be a mixture of hydrogen and hydrogen isotope gas, oxygen isotope gas, and rare gases; or it may be a mixture of hydrogen and hydrogen isotope gas, oxygen and oxygen isotope gas, and rare gases. In this case, by making the flow rate ratio of hydrogen isotope gas to processing gas between 5% and 95%, the step-like coverage of the oxide film 13 caused by free radical oxidation can also be improved.

[0088] Alternatively, as a second modification of the embodiment, the idea of ​​the embodiment can also be applied to the formation of a bulk insulating film in the manufacturing method of a semiconductor device 300, such as a 3D memory. For example, the manufacturing method of the semiconductor device 300 can also be performed as shown in Figures 10 to 13. Figure 10 is a flowchart showing the manufacturing method of the semiconductor device 300 according to the second modification of the embodiment. Figures 11A, 11B, 12A, 12B, and 13 are YZ cross-sectional views showing the manufacturing method of the semiconductor device 300.

[0089] When preparing the substrate 10 (S1), a laminate SST as shown in FIG11A is formed on or above (+Z side) the main surface 10a of the substrate 10 (S206). FIG11A illustrates the case where the laminate SST is formed on the main surface 10a of the substrate 10.

[0090] An insulating layer 111 and a sacrificial layer 151 are alternately and repeatedly deposited on the main surface 10a of the substrate 10. In FIG11A, the case of 6 repetitions is illustrated, but the number of repetitions is not limited to 6 and may be more. The insulating layer 111 may be formed of a material whose main component is a semiconductor oxide (e.g., silicon oxide). The sacrificial layer 151 is formed of a material that can ensure the etch selectivity of the insulating layer 111. The sacrificial layer 151 may be formed of a material whose main component is a semiconductor nitride (e.g., silicon nitride). An insulating layer 113 is deposited on the sacrificial layer 151 on the Z-side. The insulating layer 113 may be formed of a material whose main component is a semiconductor oxide (e.g., silicon oxide). Thus, the insulating layer 111 and the sacrificial layer 151 are alternately and repeatedly deposited to obtain a laminate SST in which the insulating layer 113 is further deposited.

[0091] When the laminate SST is obtained, a memory via 120 is formed on the laminate SST (S207).

[0092] On the main surface 113a of the insulating layer 113 on the +Z side of the laminate SST, a photoresist pattern RP1 with an opening RP1a corresponding to the memory via 120 is formed. Using the photoresist pattern RP1 as a mask, etching is performed under anisotropic processing conditions using methods such as RIE until the substrate 10 is reached. Thus, as shown in FIG11B, a memory via 120 is formed on the laminate SST, extending the laminate SST along the Z direction and reaching the substrate 10.

[0093] However, the memory via 120 can also be formed by alternating and repeating the process shown in FIG11A and FIG11B multiple times. Thus, a memory via 120 with a high aspect ratio can be easily formed.

[0094] When the memory via 120 is formed, as shown in FIG12A, a semiconductor nitride film 312 is deposited on the side and bottom surfaces of the memory via 120 by means of CVD (S202). The semiconductor nitride film 312 can be formed from a material with silicon nitride as the main component.

[0095] When the semiconductor nitride film 312 is deposited, the substrate 10 is moved into the substrate processing apparatus 1 (see Figure 3) and the semiconductor nitride film 312 is subjected to oxidation treatment (S203).

[0096] The oxidation treatment (S203) can be performed in the substrate processing apparatus 1 by using plasma generated by a processing gas containing hydrogen isotope gas and oxygen to perform free radical oxidation PIO treatment on the semiconductor nitride film 312.

[0097] In the substrate processing apparatus 1, the controller 8 applies a high-frequency voltage between the electrode 3b and the electrode 5, and generates a plasma PL (S4) in the processing chamber CH using a processing gas containing hydrogen isotope gas (e.g., D2 gas) and oxygen (O2 gas). By applying a high-frequency voltage between the electrode 3b and the electrode 5, an induced magnetic field is formed in the processing chamber CH. The hydrogen isotope gas (e.g., D2 gas) and oxygen (O2 gas) contained in the processing gas are excited by the plasma to form, for example, a ring-shaped plasma PL. This plasma PL can be a plasma with a low electrical potential. The D2 gas and O2 gas systems are dissociated by the plasma PL to generate oxidative radicals such as hydroxyl radicals OH*, deuterium ions, oxygen ions, and other reaction species. Since the plasma PL has a low electrical potential, deuterium ions and oxygen ions are not accelerated, and oxidative radicals in the processing gas are supplied approximately uniformly to the vicinity of the exposed surface 312a of the semiconductor nitride film 312 through the memory via 120.

[0098] Thus, the semiconductor nitride film 312 is oxidized by free radicals (S205). The free radical oxidation can be carried out near the exposed surface 312a of the semiconductor nitride film 312, and the portion near the exposed surface 312a of the semiconductor nitride film 312 can be replaced by an oxide film 313. Alternatively, as shown in FIG12B, the free radical oxidation can also be carried out on the entire semiconductor nitride film 312, replacing the entire semiconductor nitride film 312 with an oxide film 313. The dashed arrows in FIG12B indicate that oxidized free radicals or ions in the process gas are supplied approximately uniformly to the vicinity of the exposed surface 312a of the semiconductor nitride film 312. Thus, a bulk insulating film containing an oxide film 313 is formed on the side and bottom surfaces of the memory via 120.

[0099] In the memory via 120, a charge storage film and a tunnel insulating film are sequentially deposited. The charge storage film can be formed of an insulating material such as silicon nitride. The tunnel insulating film can be formed of an insulating material such as silicon oxide. The bottom surface portion of the memory via 120 in the block insulating film, the charge storage film, and the tunnel insulating film is selectively removed.

[0100] A semiconductor film is deposited on the side and bottom surfaces of the memory via 120. The semiconductor film system can be formed from a material whose main component is a semiconductor (e.g., polycrystalline silicon) that is substantially free of impurities. The semiconductor film is heat-treated at a specific temperature to improve its crystallinity. Then, a core component is embedded in the memory via 120. The core component system can be formed from an insulating material such as silicon oxide. Thus, a columnar structure penetrating the laminate SST in the Z direction is formed.

[0101] The sacrificial layer 151 of the laminate SST is removed. An insulating film is formed on the exposed surface formed by removing the voids. The insulating film can be formed of an insulating material such as aluminum oxide. A conductive layer 112 is further embedded in the voids. The conductive layer 112 can be formed of a material whose main component is a conductive material (such as a metal such as tungsten). Thus, a laminate SST is formed by repeatedly and alternately laminating conductive layers 112 and insulating layers 111, and further laminating insulating layers 113.

[0102] Thus, as shown in Figure 13, a memory cell array structure MCA with a complex number of memory cells MC arranged in three dimensions is formed. In the memory cell array structure MCA, a complex number of memory cells MC and their Z-direction selection gates SGS and SGD are formed at a complex number of positions where the complex conductive layers 112 in the laminate SSTA intersect with the semiconductor films SF of the complex columnar structures PL. However, the conductive region (not shown) disposed on the -Z side of the laminate SSTA functions as the source region in the memory cell array structure MCA. The conductive layer 112 closest to the -Z side among the complex conductive layers 112 functions as the source-side selection gate line. The conductive layer 112 closest to the +Z side among the complex conductive layers 112 functions as the drain-side selection gate line. The remaining conductive layers 112 in the complex conductive layers 112 each function as word lines.

[0103] That is, to manufacture a semiconductor device 300 that functions as a 3D memory.

[0104] Thus, in the method for manufacturing the semiconductor device 300, a plasma generated from a processing gas containing hydrogen isotopes and oxygen is used to oxidize the semiconductor nitride film 312 by free radicals. Therefore, compared with the case where the semiconductor nitride film 312 is oxidized by free radicals using a plasma generated from a processing gas containing hydrogen and oxygen, free radical oxidation can be performed more effectively.

[0105] Furthermore, in the manufacturing method of the semiconductor device 300, by using free radical oxidation in the formation of the bulk insulating film, the step coverage of the oxide film 313 can be easily improved, thereby improving the insulation performance of the formed bulk insulating film. This suppresses the back tunneling phenomenon, where charge tunnels through the conductive layer 112 (which serves as a word line) through the bulk insulating film and accumulates in the charge accumulation film. Therefore, in the semiconductor device 300, the operational reliability of the memory cell MC can be improved.

[0106] Alternatively, as a third variation of the embodiment, the idea of ​​the embodiment can also be applied to the oxidation of the exposed surface of the semiconductor film in the manufacturing method of a semiconductor device 400 such as a 3D memory. For example, the manufacturing method of the semiconductor device 400 can also be performed as shown in Figures 14 to 16. Figure 14 is a flowchart showing the manufacturing method of the semiconductor device 400 according to the third variation of the embodiment. Figures 15 and 16 are YZ cross-sectional views showing the manufacturing method of the semiconductor device 400. Figures 17A and 17B are YZ cross-sectional views showing the bending of the substrate 10.

[0107] After performing S1 to S207 in the same manner as in the second variation of embodiment, as shown in FIG15, an insulating film 414 is deposited on the side and bottom surfaces of the memory via 120 by means of CVD or the like (S308). The insulating film 414 may be a multilayer film consisting of a block insulating film 414a, a charge storage film 414b, and a tunnel insulating film 414c.

[0108] A block insulating film 414a, a charge storage film 414b, and a tunnel insulating film 414c are sequentially deposited on the side and bottom surfaces of the memory via 120. The block insulating film 414a may be formed of an insulating material such as silicon oxide. The charge storage film 414b may be formed of an insulating material such as silicon nitride. The tunnel insulating film 414c may be formed of an insulating material such as silicon oxide. The bottom surface portion of the memory via in the block insulating film 414a, the charge storage film 414b, and the tunnel insulating film 414c is selectively removed.

[0109] A semiconductor film 412 is deposited on the side and bottom surfaces of the memory via (S302). The semiconductor film 412 may be formed from a material whose main component is a semiconductor (e.g., polycrystalline silicon) that is substantially free of impurities.

[0110] The semiconductor film 412 is subjected to heat treatment at a specific temperature (S309) to improve the crystallinity of the semiconductor film 412.

[0111] At this time, due to the different directions and amounts of thermal deformation of the films formed on the +Z side of the substrate 10, as shown in FIG17A, the substrate 10 tends to warp towards the -Z side in a convex shape. The substrate 10 that warps convexly on the -Z side is difficult to vacuum adsorb onto the platform ST of the device in subsequent processes, and is difficult to handle.

[0112] In contrast, the substrate 10 is moved into the substrate processing apparatus 1 (see Figure 3) and the semiconductor film 412 is subjected to oxidation treatment (S303).

[0113] The oxidation treatment (S303) can be performed in the substrate processing apparatus 1 by using plasma generated by a processing gas containing hydrogen isotope gas and oxygen to perform free radical oxidation PIO treatment on the semiconductor film 412.

[0114] In the substrate processing apparatus 1, the controller 8 applies a high-frequency voltage between the electrode 3b and the electrode 5, and generates a plasma PL (S4) in the processing chamber CH using a processing gas containing a hydrogen isotope gas (e.g., D2 gas) and oxygen (O2 gas). By applying a high-frequency voltage between the electrode 3b and the electrode 5, an induced magnetic field is formed in the processing chamber CH. The hydrogen isotope gas (e.g., D2 gas) and oxygen (O2 gas) contained in the processing gas are excited by the plasma to form, for example, a ring-shaped plasma PL. This plasma PL can be a plasma with a low electrical potential. The D2 gas and O2 gas systems are dissociated by the plasma PL to generate oxidative radicals such as hydroxyl radicals OH*, deuterium ions, oxygen ions, and other reaction species. Since the plasma PL has a low electrical potential, deuterium ions and oxygen ions are not accelerated, and oxidative radicals in the processing gas are supplied approximately uniformly to the vicinity of the exposed surface 412a of the semiconductor film 412 through the memory via 120.

[0115] Thus, the semiconductor film 412 is oxidized by free radicals (S305). As shown in FIG16, the free radical oxidation can be carried out near the exposed surface 412a of the semiconductor film 412 (see FIG15), and the portion near the exposed surface 412a of the semiconductor film 412 can be replaced by an oxide film 413. The dashed arrows in FIG16 indicate that oxidized free radicals or ions in the process gas are supplied approximately uniformly to the vicinity of the exposed surface 412a of the semiconductor film 412.

[0116] At this time, in addition to the different directions and amounts of thermal deformation of each film formed on the +Z side of the substrate 10, the direction and amount of thermal deformation of the oxide film 413 are also added, as shown in FIG17B, so the substrate 10 as a whole can be convexly warped towards the +Z side. The substrate 10 convexly warped on the +Z side is easy to vacuum adsorb onto the platform ST of the device in subsequent processes, and is easy to handle.

[0117] Subsequently, a core component is embedded in the memory via 120. The core component can be formed of an insulating material such as silicon oxide. Thus, a columnar body is formed that penetrates the laminate SST in the Z direction.

[0118] The sacrificial layer 151 of the laminate SST is removed. An insulating film is formed on the exposed surface formed by removing the voids. The insulating film can be formed of an insulating material such as aluminum oxide. A conductive layer 112 is further embedded in the voids. The conductive layer 112 can be formed of a material whose main component is a conductive material (such as a metal such as tungsten). Thus, a laminate SST, in which the conductive layer 112 and the insulating layer 111 are repeatedly laminated alternately, is formed.

[0119] Thus, a memory cell array structure MCA (see Figure 13) with a complex number of memory cells MC arranged in three dimensions is formed. In the memory cell array structure MCA, a complex number of memory cells MC are formed at a complex number of positions where a complex number of conductive layers 112 in the laminate SSTA intersect with a complex number of semiconductor films SF of columnar structures PL. However, the conductive region (not shown) disposed on the +Z side of the laminate SSTA functions as the source region in the memory cell array structure MCA. The conductive layer 112 closest to the +Z side among the complex conductive layers 112 functions as the source-side gate selection line. The conductive layer 112 closest to the -Z side among the complex conductive layers 112 functions as the drain-side gate selection line. The remaining conductive layers 112 in the complex conductive layers 112 each function as word lines.

[0120] That is, manufacturing a semiconductor device 400 that functions as a 3D memory.

[0121] Thus, in the method for manufacturing the semiconductor device 400, a plasma generated from a process gas containing hydrogen isotopes and oxygen is used to oxidize the exposed surface 412a of the semiconductor film 412 with free radicals. Therefore, compared to the case where free radical oxidation is performed on the exposed surface 412a of the semiconductor film 412 using a plasma generated from a process gas containing hydrogen and oxygen, free radical oxidation can be performed more effectively.

[0122] Furthermore, in the manufacturing method of the semiconductor device 400, by effectively free radical oxidizing the exposed surface 412a of the semiconductor film 412, the warping direction of the substrate 10 can be easily changed from the convex direction to the -Z side to the +Z side to the convex direction.

[0123] Alternatively, as a fourth variation of the embodiment, the idea of ​​the embodiment can also be applied to the formation of the tunnel insulating film in the manufacturing method of a semiconductor device 500 such as a 3D memory. For example, the manufacturing method of the semiconductor device 500 can also be performed as shown in Figures 18 to 20. Figure 18 is a flowchart showing the manufacturing method of the semiconductor device 500 according to the fourth variation of the embodiment. Figures 19 and 20 are YZ cross-sectional views showing the manufacturing method of the semiconductor device 300.

[0124] After performing S1 to S207 in the same manner as in the second modified embodiment, as shown in FIG19, an insulating film is deposited on the side and bottom surfaces of the memory via 120 by means of CVD or the like (S408).

[0125] On the side and bottom surfaces of the memory via 120, a block insulating film 514 and a charge storage film 515 are sequentially deposited as insulating films. The block insulating film 514 may be formed of an insulating material such as silicon oxide. The charge storage film 515 may be formed of an insulating material such as silicon nitride.

[0126] Furthermore, as shown in FIG19, a semiconductor nitride film 512 (S402) is deposited on the side and bottom surfaces of the memory via 120 by means of CVD or the like. The semiconductor nitride film 512 can be formed of a material with silicon nitride as the main component.

[0127] When the semiconductor nitride film 512 is deposited, the substrate 10 is moved into the substrate processing apparatus 1 (see Figure 3) and the semiconductor nitride film 512 is subjected to oxidation treatment (S403).

[0128] The oxidation treatment (S403) can be performed in the substrate processing apparatus 1 by using plasma generated by a processing gas containing hydrogen isotope gas and oxygen to perform free radical oxidation PIO treatment on the semiconductor nitride film 512.

[0129] In the substrate processing apparatus 1, the controller 8 applies a high-frequency voltage between the electrode 3b and the electrode 5, and generates a plasma PL (S4) in the processing chamber CH using a processing gas containing a hydrogen isotope gas (e.g., D2 gas) and oxygen (O2 gas). By applying a high-frequency voltage between the electrode 3b and the electrode 5, an induced magnetic field is formed in the processing chamber CH. The hydrogen isotope gas (e.g., D2 gas) and oxygen (O2 gas) contained in the processing gas are excited by the plasma to form, for example, a ring-shaped plasma PL. This plasma PL can be a plasma with a low electrical potential. The D2 gas and O2 gas systems are dissociated by the plasma PL to generate oxidative radicals such as hydroxyl radicals OH*, deuterium ions, oxygen ions, and other reaction species. Since the plasma PL has a low electrical potential, deuterium ions and oxygen ions are not accelerated, and oxidative radicals in the processing gas are supplied approximately uniformly to the vicinity of the exposed surface 512a of the semiconductor nitride film 512 through the memory via 120.

[0130] Thus, the semiconductor nitride film 512 is oxidized by free radicals (S405). Alternatively, as shown in FIG20, the free radical oxidation system can also be carried out on the entire semiconductor nitride film 512, replacing the entire semiconductor nitride film 512 with an oxide film 513. The dashed arrows in FIG20 indicate that oxidized free radicals or ions in the process gas are supplied approximately uniformly to the vicinity of the exposed surface 512a of the semiconductor nitride film 512. Thus, a tunnel insulating film containing an oxide film 513 is formed on the side and bottom surfaces of the memory via 120.

[0131] In the memory via 120, a portion of the bottom surface of the memory via 120 in the block insulating film 514, charge storage film 515, and tunnel insulating film 513 is selectively removed.

[0132] A semiconductor film is deposited on the side and bottom surfaces of the memory via 120. The semiconductor film system can be formed from a material whose main component is a semiconductor (e.g., polycrystalline silicon) that is substantially free of impurities. The semiconductor film is heat-treated at a specific temperature to improve its crystallinity. Then, a core component is embedded in the memory via 120. The core component system can be formed from an insulating material such as silicon oxide. Thus, a columnar structure penetrating the laminate SST in the Z direction is formed.

[0133] The sacrificial layer 151 of the laminate SST is removed. An insulating film is formed on the exposed surface formed by removing the voids. The insulating film can be formed of an insulating material such as aluminum oxide. A conductive layer 112 is further embedded in the voids. The conductive layer 112 can be formed of a material whose main component is a conductive material (such as a metal such as tungsten). Thus, a laminate SST is formed by repeatedly and alternately laminating conductive layers 112 and insulating layers 111, and further laminating insulating layers 113.

[0134] Thus, a memory cell array structure MCA (see Figure 13) with a complex number of memory cells MC arranged in three dimensions is formed. In the memory cell array structure MCA, a complex number of memory cells MC and their Z-direction selection gates SGS and SGD are formed at a complex number of positions where the complex conductive layers 112 in the laminate SSTA intersect with the semiconductor film SF of the complex columnar bodies PL. However, the conductive region (not shown) disposed on the -Z side of the laminate SSTA functions as the source region in the memory cell array structure MCA. The conductive layer 112 closest to the -Z side among the complex conductive layers 112 functions as the source-side selection gate line. The conductive layer 112 closest to the +Z side among the complex conductive layers 112 functions as the drain-side selection gate line. The remaining conductive layers 112 in the complex conductive layers 112 each function as word lines.

[0135] That is, to manufacture a semiconductor device 500 that functions as a 3D memory.

[0136] Thus, in the method for manufacturing the semiconductor device 500, a plasma generated from a process gas containing hydrogen isotopes and oxygen is used to oxidize the semiconductor nitride film 512 by free radicals. Therefore, compared with the case where the semiconductor nitride film 512 is oxidized by free radicals using a plasma generated from a process gas containing hydrogen and oxygen, free radical oxidation can be performed more effectively.

[0137] Furthermore, in the manufacturing method of the semiconductor device 500, by using free radical oxidation in a processing gas containing a hydrogen isotope during the formation of the tunnel insulating film, the step coverage of the oxide film 513 can be easily improved, and a structure with hydrogen isotope (e.g., deuterium) terminations at the interface between the charge accumulation film and the tunnel insulating film can be formed. This suppresses bonding defects caused by electrical stress at the interface between the charge accumulation film and the tunnel insulating film during writing operating data to the memory cell MC and during erase operations, thus suppressing malfunctions caused by bonding defects. Therefore, the operational reliability of the memory cell MC can be improved in the semiconductor device 500.

[0138] Although several embodiments of the present invention have been described, these embodiments are provided as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, substitutions, or modifications can be made without departing from the spirit and scope of the invention. These embodiments or modifications are included in the scope or spirit of the invention, as well as the invention described in the patent claim and its equivalents. [Simplified Explanation of the Diagram]

[0006] [Figure 1] is a flowchart showing a semiconductor device manufacturing method according to an embodiment.

[0007] [Figure 2A]~[Figure 2E] are cross-sectional views showing the manufacturing method of the semiconductor device in the embodiment.

[0008] [Figure 3] is a configuration diagram showing the substrate processing apparatus used in the manufacturing method of a semiconductor device according to an embodiment.

[0009] [Figure 4] shows the change in oxide film thickness corresponding to the processing time (when the flow rate is 30%).

[0010] [Figure 5] shows the change in oxide film thickness corresponding to the processing time (when the flow rate is 20%).

[0011] [Figure 6] shows the change in oxide film thickness corresponding to the processing time (when the flow rate is 5%).

[0012] [Figure 7] shows the variation in the luminescence intensity of the hydroxyl radical OH* according to the flow ratio of the corresponding hydrogen or its isotope.

[0013] [Figure 8] is a flowchart showing a method for manufacturing a semiconductor device according to the first modified embodiment.

[0014] [Figure 9] is a configuration diagram showing the substrate processing apparatus used in the manufacturing method of the semiconductor device according to the first modified example of the embodiment.

[0015] [Figure 10] is a flowchart showing a method for manufacturing a semiconductor device according to the second modification of the embodiment.

[0016] [Figure 11A] and [Figure 11B] are cross-sectional views showing a method for manufacturing a semiconductor device according to the second modification of the embodiment.

[0017] [Figure 12A] and [Figure 12B] are cross-sectional views showing a method for manufacturing a semiconductor device according to the second modification of the embodiment.

[0018] [Fig. 13] is a cross-sectional view showing a method for manufacturing a semiconductor device according to the second modified embodiment.

[0019] [Figure 14] is a flowchart showing a method for manufacturing a semiconductor device according to the third modification of the embodiment.

[0020] [Fig. 15] is a cross-sectional view showing a method for manufacturing a semiconductor device according to the third modified embodiment.

[0021] [Fig. 16] is a cross-sectional view showing a method for manufacturing a semiconductor device according to the third modified embodiment.

[0022] [Fig. 17A] and [Fig. 17B] are cross-sectional views showing the bending of the substrate in the third modified example of the embodiment.

[0023] [Figure 18] is a flowchart showing a method for manufacturing a semiconductor device according to the fourth modification of the embodiment.

[0024] [Fig. 19] is a cross-sectional view showing a method for manufacturing a semiconductor device according to the fourth modification of the embodiment.

[0025] [Fig. 20] is a cross-sectional view showing a method for manufacturing a semiconductor device according to the fourth modified embodiment.

Claims

1. A method for manufacturing a semiconductor device, characterized in that it includes using a plasma generated from a processing gas containing a hydrogen isotope gas to perform free radical oxidation on a first film, wherein the flow rate ratio is the ratio of the flow rate of the hydrogen isotope gas to the flow rate of the processing gas, and the hydrogen isotope gas system is contained in the processing gas at a flow rate ratio of 5% to 95%.

2. The method for manufacturing a semiconductor device as described in claim 1, wherein, The aforementioned free radical oxidation system uses plasma generated from the aforementioned treatment gas containing the aforementioned hydrogen isotope gas and oxygen to oxidize the aforementioned first membrane free radicals.

3. The method for manufacturing a semiconductor device as described in claim 1, wherein, The aforementioned free radical oxidation system uses plasma generated from the aforementioned treatment gas containing hydrogen and the aforementioned hydrogen isotope gas and oxygen to oxidize the aforementioned first membrane free radicals.

4. A method for manufacturing a semiconductor device, characterized by comprising using a plasma generated from a process gas containing a hydrogen isotope gas to perform free radical oxidation on a first film, wherein... The aforementioned free radical oxidation system uses plasma generated from the aforementioned treatment gas containing the aforementioned hydrogen isotope gas and oxygen isotope gas to oxidize the aforementioned first membrane free radicals.

5. A method for manufacturing a semiconductor device as described in claim 1, wherein, The aforementioned free radical oxidation system uses plasma generated from the aforementioned treatment gas containing the aforementioned hydrogen isotope gas, oxygen, and rare gases to oxidize the aforementioned first membrane free radicals.

6. A method for manufacturing a semiconductor device as described in claim 1, wherein, The aforementioned free radical oxidation system uses a plasma generated from the aforementioned treatment gas containing hydrogen, the aforementioned hydrogen isotope gas, oxygen, and rare gases to oxidize the aforementioned first membrane free radicals.

7. A method for manufacturing a semiconductor device as described in claim 1, wherein, The aforementioned free radical oxidation system uses a plasma generated from the aforementioned treatment gas containing the aforementioned hydrogen isotope gas, oxygen isotope gas, and rare gas to oxidize the aforementioned first membrane free radicals.

8. A method for manufacturing a semiconductor device as described in claim 1, wherein, The aforementioned free radical oxidation system uses plasma generated from the aforementioned processing gas containing the aforementioned hydrogen isotope gas to oxidize the aforementioned first membrane free radicals at a temperature of 300°C to 800°C.

9. A method for manufacturing a semiconductor device as described in claim 1, wherein, The aforementioned free radical oxidation system uses a plasma generated from the aforementioned processing gas containing the aforementioned hydrogen isotope gas to oxidize the aforementioned first membrane free radicals at a pressure of 50 Pa to 300 Pa.

10. A method for manufacturing a semiconductor device as described in claim 1, wherein, The aforementioned free radical oxidation system uses plasma generated from the aforementioned processing gas containing the aforementioned hydrogen isotope gas to perform free radical oxidation near the exposed surface of the aforementioned first membrane.

11. A method for manufacturing a semiconductor device as described in claim 1, wherein, The aforementioned free radical oxidation system uses a plasma generated from the aforementioned processing gas containing the aforementioned hydrogen isotope gas to perform free radical oxidation on the entire membrane of the aforementioned first membrane.

12. A method for manufacturing a semiconductor device as described in claim 1, wherein, It further includes: forming a laminate in which a first insulating film and a second insulating film are alternately laminated multiple times; forming a hole extending the laminate in the lamination direction; and depositing a semiconductor nitride film as the first film on the inner side and bottom surface of the hole; and performing the aforementioned free radical oxidation system to generate the aforementioned processing gas plasma, thereby causing the exposed surface of the aforementioned semiconductor nitride film to be oxidized by free radicals.

13. A method for manufacturing a semiconductor device as described in claim 1, wherein, Furthermore, it comprises: forming a laminate in which a first insulating film and a second insulating film are alternately laminated multiple times; forming a hole extending the laminate in the lamination direction; depositing a third insulating film on the inner side and bottom surface of the hole; and depositing a semiconductor film as the first film on the inner side and bottom surface of the third insulating film in the hole; and performing the aforementioned free radical oxidation system to generate the aforementioned processing gas plasma, thereby causing the exposed surface of the aforementioned semiconductor film to be oxidized by free radicals.

14. A method for manufacturing a semiconductor device as described in claim 1, wherein, Furthermore, it comprises: forming a laminate in which a first insulating film and a second insulating film are alternately laminated multiple times; forming a hole extending the laminate in the lamination direction; depositing a third insulating film on the inner side and bottom surface of the hole; and depositing a semiconductor nitride film as the first film on the inner side and bottom surface of the third insulating film in the hole; and performing the aforementioned free radical oxidation system to generate the aforementioned processing gas plasma, thereby causing the exposed surface of the aforementioned semiconductor nitride film to be oxidized by free radicals.

15. A method for manufacturing a semiconductor device as described in claim 1, wherein, The aforementioned free radical oxidation system is carried out by uniformly supplying plasma generated from the aforementioned processing gas containing hydrogen isotope gas to the surface of the aforementioned first membrane, thereby causing the aforementioned first membrane to undergo free radical oxidation.

16. A substrate processing apparatus, characterized by comprising: a platform disposed in a processing chamber, on which a substrate is placed, and including a first electrode; a gas supply system capable of supplying a processing gas containing a hydrogen isotope to the platform in the processing chamber; a second electrode disposed outside the processing chamber at a position away from the platform; and an exhaust system capable of adjusting the pressure inside the processing chamber; wherein the flow rate ratio is the ratio of the flow rate of the hydrogen isotope gas to the flow rate of the processing gas; the gas supply system is capable of supplying the processing gas to the platform in the processing chamber, the processing gas containing the hydrogen isotope gas at a flow rate ratio of 5% to 95%; and wherein a high-frequency voltage is applied between the first electrode and the second electrode to generate plasma in the processing chamber.

17. The substrate processing apparatus as described in claim 16, wherein, The aforementioned gas supply system is capable of supplying the aforementioned processing gas, which contains the aforementioned hydrogen isotope gas and oxygen isotope gas, to the aforementioned platform in the aforementioned processing chamber.

18. The substrate processing apparatus as described in claim 16, wherein, The aforementioned gas supply system is capable of supplying the aforementioned processing gas, which includes the aforementioned hydrogen isotope, oxygen, and rare gases, to the aforementioned platform in the aforementioned processing chamber.

19. The substrate processing apparatus as described in claim 16, wherein, The aforementioned gas supply system is capable of supplying the aforementioned processing gas, which includes the aforementioned hydrogen isotope gas, the aforementioned oxygen isotope gas, and the aforementioned rare gas, to the aforementioned platform in the aforementioned processing chamber.