Method for forming metal-containing film, method for manufacturing capacitor, and film forming device

Abstract

A method for forming a metal-containing film according to one embodiment of the present disclosure comprises: preparing a substrate having a high dielectric constant film; modifying the surface of the high dielectric constant film without supplying plasma to the high dielectric constant film in a state where the substrate is controlled at a first temperature; and forming a metal-containing film on the surface of the high dielectric constant film modified in a state where the substrate is controlled at a second temperature. The first temperature is equal to or lower than the second temperature.

Description

Method for forming a metal-containing film, method for manufacturing a capacitor, and film forming apparatus

[0001] The present disclosure relates to a method for forming a metal-containing film, a method for manufacturing a capacitor, and a film forming apparatus.

[0002] Patent Document 1 discloses a technique of disposing a barrier layer between a dielectric film and an upper electrode in a capacitor including a lower electrode, a dielectric film, and an upper electrode.

[0003] Japanese Patent Application Laid-Open No. 2004-266010

[0004] The present disclosure provides a technique capable of reducing damage to a high dielectric constant film when forming a metal-containing film.

[0005] A method for forming a metal-containing film according to an aspect of the present disclosure includes preparing a substrate having a high dielectric constant film, modifying a surface of the high dielectric constant film without supplying plasma to the high dielectric constant film while controlling the substrate at a first temperature, and forming a metal-containing film on the modified surface of the high dielectric constant film while controlling the substrate at a second temperature, wherein the first temperature is the same as or lower than the second temperature.

[0006] According to the present disclosure, damage to a high dielectric constant film when forming a metal-containing film can be reduced.

[0007] It is a flowchart showing a method for forming a metal-containing film according to an embodiment. It is a cross-sectional view (1) showing a method for forming a metal-containing film according to an embodiment. It is a cross-sectional view (2) showing a method for forming a metal-containing film according to an embodiment. It is a cross-sectional view (3) showing a method for forming a metal-containing film according to an embodiment. It is a diagram showing a first example of the gas supply sequence in step S12 of FIG. 1. It is a diagram showing a second example of the gas supply sequence in step S12 of FIG. 1. It is a diagram showing a third example of the gas supply sequence in step S12 of FIG. 1. It is a diagram showing a first example of the gas supply sequence in step S13 of FIG. 1. It is a diagram showing a second example of the gas supply sequence in step S13 of FIG. 1. It is a diagram for explaining the effect of the SiN cycle. It is a flowchart showing a method for manufacturing a capacitor according to an embodiment. It is a cross-sectional view (1) showing a method for manufacturing a capacitor according to an embodiment. It is a cross-sectional view (2) showing a method for manufacturing a capacitor according to an embodiment. It is a cross-sectional view (3) showing a method for manufacturing a capacitor according to an embodiment. It is a cross-sectional view (4) showing a method for manufacturing a capacitor according to an embodiment. It is a cross-sectional view (5) showing a method for manufacturing a capacitor according to an embodiment. It is a cross-sectional view showing a film-forming apparatus according to an embodiment. It is a diagram showing the amount of change in the thickness of the zirconium oxide film before and after forming a titanium nitride film. It is a diagram showing the amount of change in the thickness of the zirconium oxide film before and after forming a titanium silicon nitride film.

[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 members or components are denoted by the same or corresponding reference numerals, and redundant descriptions are omitted.

[0009] 〔Method for Forming Metal-Containing Film〕 Referring to FIGS. 1 to 10, a method for forming a metal-containing film according to an embodiment will be described. FIG. 1 is a flowchart showing a method for forming a metal-containing film according to an embodiment. FIGS. 2 to 4 are cross-sectional views showing a method for forming a metal-containing film according to an embodiment. The method for forming a metal-containing film according to the embodiment includes steps S11 to S13 shown in FIG. 1.

[0010] In step S11, the substrate 100 is prepared as shown in Figure 2. The substrate 100 has a silicon substrate 101 and a zirconium oxide film 103. The zirconium oxide film 103 is provided on the silicon substrate 101. The zirconium oxide film 103 is an example of a high dielectric constant (high-k) film.

[0011] In step S12, the surface of the zirconium oxide film 103 is modified as shown in Figure 3. In Figure 3, the modified portion of the surface of the zirconium oxide film 103 is shown by the dashed line 103a. In step S12, the surface of the zirconium oxide film 103 is modified without supplying plasma to the zirconium oxide film 103 while the substrate 100 is controlled to a first temperature. Modifying the surface of the zirconium oxide film 103 involves, for example, applying monosilane (SiH) to the surface of the zirconium oxide film 103. ４ ) gas and ammonia (NH ３ This includes supplying at least one of the gases. Modifying the surface of the zirconium oxide film 103 may include generating Si-N bonds on the surface of the zirconium oxide film 103. The presence or absence of Si-N bonds can be measured, for example, by time-of-flight secondary ion mass spectrometry (TOF-SIMS). The first temperature is, for example, the same temperature as the second temperature described later, or a lower temperature than the second temperature. The first temperature is, for example, 400°C or higher and 550°C or lower.

[0012] Figure 5 shows a first example of the gas supply sequence in step S12 of Figure 1. In the first example, with the substrate 100 controlled to a first temperature, a SiN cycle is repeated in which monosilane gas is supplied to the substrate 100 and ammonia gas is supplied to the substrate 100 in that order. The SiN cycle is an example of the first cycle. In the first example, plasma is not generated from the monosilane gas and ammonia gas. The number of repetitions of the SiN cycle may be less than the number of repetitions of the TiN cycle described later. The number of repetitions of the SiN cycle may be less than the number of repetitions of the TSN cycle described later. The number of repetitions of the SiN cycle is, for example, 10 to 100 times. Purge may be performed when switching the gas supplied to the substrate 100. Monosilane gas is an example of a first silicon-containing gas, and ammonia gas is an example of a first nitride gas.

[0013] Figure 6 shows a second example of the gas supply sequence in step S12 of Figure 1. In the second example, with the substrate 100 controlled to a first temperature, the Si cycle is repeated in the order of supplying monosilane gas to the substrate 100 and then not supplying monosilane gas to the substrate 100. In the second example, with the substrate 100 controlled to a first temperature, monosilane gas is supplied to the substrate 100 intermittently without supplying ammonia gas to the substrate 100. In the second example, plasma is not generated from the monosilane gas. Purge may be performed during the period when monosilane gas is not supplied to the substrate 100.

[0014] Figure 7 shows a third example of the gas supply sequence in step S12 of Figure 1. In the third example, with the substrate 100 controlled to a first temperature, the process of supplying ammonia gas to the substrate 100 and then not supplying ammonia gas to the substrate 100 is repeated for N cycles. In the third example, with the substrate 100 controlled to a first temperature, ammonia gas is supplied to the substrate 100 intermittently without supplying monosilane gas to the substrate 100. In the third example, plasma is not generated from the ammonia gas. Purge may be performed during the period when ammonia gas is not supplied to the substrate 100.

[0015] In step S13, as shown in Figure 4, a metal-containing film 104 is formed on the surface of the zirconium oxide film 103. In step S13, the metal-containing film 104 is formed on the surface of the zirconium oxide film 103 while the substrate 100 is controlled to a second temperature. The metal-containing film 104 is, for example, a titanium nitride (TiN) film. The metal-containing film 104 may also be a titanium silicate (TiSiN) film. The second temperature is, for example, 400°C to 550°C. If the first temperature is the same as the second temperature, step S13 is performed, for example, in the same processing container as step S12. In this case, the surface modification of the zirconium oxide film 103 and the subsequent formation of the metal-containing film 104 on the surface of the zirconium oxide film 103 can be performed consecutively without changing the temperature of the substrate 100. If the first temperature is lower than the second temperature, step S13 is performed, for example, in a different processing container than that used in step S12.

[0016] Figure 8 shows a first example of the gas supply sequence in step S13 of Figure 1. In the first example, with the substrate 100 controlled to a second temperature, titanium tetrachloride (TiCl) is supplied to the substrate 100. ４ The TiN cycle is repeated in the order of supplying gas to the substrate 100 and supplying ammonia gas to the substrate 100. The TiN cycle is an example of the second cycle. As the TiN cycle is repeated, a titanium nitride film is formed on the surface of the zirconium oxide film 103. The number of repetitions of the TiN cycle is set in advance according to the thickness of the titanium nitride film formed in step S13. Purge may be performed when switching the gas supplied to the substrate 100. Titanium tetrachloride gas is an example of a metal raw material gas, and ammonia gas is an example of a second nitride gas.

[0017] FIG. 9 is a diagram showing a second example of the gas supply sequence in step S13 of FIG. 1. In the second example, a TSN cycle is repeated in which a TiN cycle and a SiN cycle are performed in this order while the substrate 100 is controlled at the second temperature. The TiN cycle includes supplying titanium tetrachloride gas to the substrate 100 and supplying ammonia gas to the substrate 100 in this order. The TiN cycle is an example of the third cycle. The SiN cycle includes supplying monosilane gas to the substrate 100 and supplying ammonia gas to the substrate 100 in this order. The SiN cycle is an example of the fourth cycle. The TSN cycle is an example of the fifth cycle. By repeating the TSN cycle, a titanium silicon nitride film is formed on the surface of the zirconium oxide film 103. The number of repetitions of the TSN cycle is preset according to the thickness of the titanium silicon nitride film formed in step S13. When switching the gas supplied to the substrate 100, purging may be performed. The titanium tetrachloride gas and ammonia gas used in the TiN cycle are examples of a metal raw material gas and a second nitriding gas, respectively. The monosilane gas and ammonia gas used in the SiN cycle are examples of a second silicon-containing gas and a third nitriding gas, respectively.

[0018] Next, the surface reaction of the zirconium oxide film 103 when performing the SiN cycle and the TiN cycle in this order as the surface modification of the zirconium oxide film 103 will be described.

[0019] FIG. 10 is a diagram for explaining the effect of the SiN cycle. In the SiN cycle, as shown in (a) of FIG. 10, SiH ４ gas and NH ３ gas are supplied to the surface of the zirconium oxide film 103. As a result, as shown in (b) of FIG. 10, Si ３ N ４ , N, Si, Si ２ etc. bind to Zr on the surface of the zirconium oxide film 103. In the TiN cycle, as shown in (c) of FIG. 10, TiCl ４Gas is supplied. As a result, Si ３ N ４ N, Si, Si ２ Zr that is not bonded to TiCl ４ Reaction with gas results in ZrCl ４ As such, it desorbs from the surface of the zirconium oxide film 103. In contrast, as shown in Figure 10(d), Si ３ N ４ N, Si, Si ２ Zr to which these are bonded is TiCl ４ Because the reaction with the gas does not proceed easily, it does not desorb from the surface of the zirconium oxide film 103. As a result, the amount of Zr desorbed from the surface of the zirconium oxide film 103 is reduced, and damage to the zirconium oxide film 103 can be reduced. Damage to the zirconium oxide film 103 may include a decrease in the thickness of the zirconium oxide film 103 and an increase in the surface roughness of the zirconium oxide film 103.

[0020] The surface reaction of the zirconium oxide film 103 when the Si cycle and TiN cycle are performed in this order will be described. In the Si cycle, SiH ４ Gas is supplied. This causes Si to be added to Zr on the surface of the zirconium oxide film 103. ２ These are bonded together. In the TiN cycle, TiCl bonded to the surface of the zirconium oxide film 103. ４ Gas is supplied. This allows Si, Si ２ Zr that is not bonded to TiCl ４ Reaction with gas results in ZrCl ４ It is detached from the surface of the zirconium oxide film 103. In contrast, Si, Si ２ Zr to which these are bonded is TiCl ４ Because the reaction with the gas does not proceed easily, it does not desorb from the surface of the zirconium oxide film 103. As a result, the amount of Zr desorbed from the surface of the zirconium oxide film 103 is reduced, and damage to the zirconium oxide film 103 can be reduced.

[0021] The surface reaction of the zirconium oxide film 103 when the N cycle and TiN cycle are performed in this order will be explained. In the N cycle, the surface of the zirconium oxide film 103 undergoes NH ３ Gas is supplied. This causes N and other atoms to bond to Zr on the surface of the zirconium oxide film 103. In the TiN cycle, TiCl bonds to the surface of the zirconium oxide film 103. ４ Gas is supplied. This causes Zr that is not bonded to N etc. to TiCl ４ Reaction with gas results in ZrCl ４ It is detached from the surface of the zirconium oxide film 103. In contrast, Zr to which N etc. is bonded is detached from TiCl ４ Because the reaction with the gas does not proceed easily, it does not desorb from the surface of the zirconium oxide film 103. As a result, the amount of Zr desorbed from the surface of the zirconium oxide film 103 is reduced, and damage to the zirconium oxide film 103 can be reduced.

[0022] [Capacitor Manufacturing Method] A method for manufacturing a capacitor according to the embodiment will be described with reference to Figures 11 to 16. Figure 11 is a flowchart showing a method for manufacturing a capacitor according to the embodiment. Figures 12 to 16 are cross-sectional views showing a method for manufacturing a capacitor according to the embodiment. The method for manufacturing a capacitor according to the embodiment includes steps S21 to S25 shown in Figure 11.

[0023] In step S21, the substrate 200 is prepared as shown in Figure 12. The substrate 200 has a silicon substrate 201.

[0024] In step S22, as shown in Figure 13, a first metal-containing film 202 is formed on the silicon substrate 201. The first metal-containing film 202 functions as the lower electrode of the capacitor. The first metal-containing film 202 is, for example, a titanium nitride film. The first metal-containing film 202 may also be a titanium silicate film. The first metal-containing film 202 can be formed, for example, in the same manner as the metal-containing film 104 in step S13 described above.

[0025] In step S23, as shown in Figure 14, a zirconium oxide film 203 is formed on the first metal-containing film 202. The zirconium oxide film 203 can be formed, for example, by supplying a source gas containing zirconium (Zr) to the substrate 200 and repeatedly cycling the substrate 200 with an oxidizing gas. The zirconium oxide film 203 is an example of a high dielectric constant film.

[0026] In step S24, the surface of the zirconium oxide film 203 is modified as shown in Figure 15. In Figure 15, the modified portion of the surface of the zirconium oxide film 203 is shown by the dashed line 203a. Step S24 may be the same as step S12 described above.

[0027] In step S25, as shown in Figure 16, a second metal-containing film 204 is formed on the surface of the zirconium oxide film 203. The second metal-containing film 204 functions as the upper electrode of the capacitor. The second metal-containing film 204 is, for example, a titanium nitride film. The second metal-containing film 204 may also be a titanium silicate film. The second metal-containing film 204 can be formed, for example, in the same manner as the metal-containing film 104 in step S13 described above.

[0028] As described above, a capacitor having a structure in which a zirconium oxide film 203 is sandwiched between a first metal-containing film 202 and a second metal-containing film 204 can be manufactured.

[0029] According to the capacitor manufacturing method of the embodiment, damage to the zirconium oxide film 203 can be reduced for the same reasons as the method for forming the metal-containing film 104 according to the embodiment. As a result, a capacitor with low leakage can be manufactured.

[0030] [Film Deposition Apparatus] Referring to Figure 17, an example of a film deposition apparatus capable of carrying out steps S12 and S13 in the method for forming the metal-containing film 104 according to the embodiment, and steps S22 to S25 in the method for manufacturing the capacitor according to the embodiment will be described. Figure 17 is a cross-sectional view showing the film deposition apparatus according to the embodiment.

[0031] The film deposition apparatus comprises a processing container 1, a mounting table 2, a shower head 3, an exhaust unit 4, a gas supply unit 5, and a control circuit 9.

[0032] The processing container 1 is made of a metal such as aluminum and has a substantially cylindrical shape. The processing container 1 houses the substrate W. The substrate W corresponds to the aforementioned substrate 100 or substrate 200. An inlet / outlet 11 for loading or unloading the substrate W is formed in the side wall of the processing container 1. The inlet / outlet 11 is opened and closed by a gate valve 12. An annular exhaust duct 13 with a rectangular cross-section is provided on the main body of the processing container 1. A slit 13a is formed in the exhaust duct 13 along its inner circumference. An exhaust port 13b is formed in the outer wall of the exhaust duct 13. A top wall 14 is provided on the upper surface of the exhaust duct 13 so as to close the upper opening of the processing container 1 via an insulating member 16. The space between the exhaust duct 13 and the insulating member 16 is airtightly sealed with a sealing member 15. The sealing member 15 may be, for example, an O-ring. The partitioning member 17 divides the inside of the processing container 1 vertically when the mounting platform 2 (and cover member 22) rises to the processing position described later.

[0033] The mounting table 2 horizontally supports the substrate W within the processing container 1. The mounting table 2 has a disc shape. The outer diameter of the mounting table 2 is larger than, for example, the outer diameter of the substrate W. The mounting table 2 is made of a ceramic material such as AlN, or a metallic material such as aluminum or nickel alloy. A heater 21 for heating the substrate W is embedded inside the mounting table 2. The heater 21 is powered by a heater power supply (not shown) and generates heat. A thermocouple (not shown) is provided near the upper surface of the mounting table 2. By controlling the output of the heater 21 using the temperature signal of the thermocouple, the substrate W is controlled to a predetermined temperature. The heater 21 is an example of a temperature control unit. The mounting table 2 is provided with a cover member 22 made of ceramic material such as alumina so as to cover the outer peripheral region of the upper surface and the sides.

[0034] A support member 23 is provided on the bottom surface of the mounting table 2. The support member 23 supports the mounting table 2. The support member 23 extends from the center of the bottom surface of the mounting table 2, through a hole formed in the bottom wall of the processing container 1, and downward to the processing container 1. The lower end of the support member 23 is connected to a lifting mechanism 24. The lifting mechanism 24 raises and lowers the mounting table 2 via the support member 23 between the processing position shown in Figure 17 and the transport position below it, indicated by the dashed line, where the substrate W can be transported. A flange portion 25 is attached to the lower part of the support member 23 below the processing container 1. A bellows 26 is provided between the bottom surface of the processing container 1 and the flange portion 25. The bellows 26 partitions the atmosphere inside the processing container 1 from the outside air and expands and contracts in accordance with the lifting and lowering operation of the mounting table 2.

[0035] Three support pins (only two are shown) are provided near the bottom surface of the processing container 1, protruding upward from the lifting plate 27a. The support pins 27 are raised and lowered via the lifting plate 27a by a lifting mechanism 28 located below the processing container 1. The support pins 27 are inserted through holes 2a provided in the mounting table 2 at the transport position, and are able to protrude and retract relative to the upper surface of the mounting table 2. By raising and lowering the support pins 27, the substrate W is transferred between the transport device (not shown) and the mounting table 2.

[0036] The shower head 3 supplies processing gas into the processing container 1 in a shower-like manner. The shower head 3 is made of metal and is installed facing the mounting base 2. The shower head 3 has approximately the same diameter as the mounting base 2. The shower head 3 has a main body 31 and a shower plate 32. The main body 31 is fixed to the top wall 14 of the processing container 1. The shower plate 32 is connected below the main body 31. A gas diffusion space 33 is formed between the main body 31 and the shower plate 32. A gas introduction hole 36 is provided in the gas diffusion space 33 so as to penetrate the top wall 14 and the center of the main body 31. An annular projection 34 that protrudes downward is formed on the periphery of the shower plate 32. A gas discharge hole 35 is formed in the flat part inside the annular projection 34. When the mounting table 2 is in the processing position, a processing space 38 is formed between the mounting table 2 and the shower plate 32, and the upper surface of the cover member 22 and the annular projection 34 are in close proximity to form an annular gap 39.

[0037] The exhaust unit 4 exhausts the inside of the processing container 1. The exhaust unit 4 has an exhaust pipe 41 and an exhaust mechanism 42. The exhaust pipe 41 is connected to the exhaust port 13b. The exhaust mechanism 42 has a vacuum pump connected to the exhaust pipe 41 and a pressure control valve. During processing, the gas inside the processing container 1 reaches the exhaust duct 13 through the slit 13a, and is exhausted from the exhaust duct 13 through the exhaust pipe 41 by the exhaust mechanism 42.

[0038] The gas supply unit 5 supplies various processing gases to the shower head 3. The gas supply unit 5 includes a gas source 51 and a gas line 52. The gas source 51 includes a source for various processing gases, a mass flow controller, and a valve. The various processing gases include gases used in the method for forming the metal-containing film 104 and the method for manufacturing the capacitor according to the embodiment. The various gases are introduced from the gas source 51 into the gas diffusion space 33 via the gas line 52 and the gas introduction hole 36.

[0039] The control circuit 9 is an electronic circuit such as a CPU (Central Processing Unit), FPGA (Field Programmable Gate Array), or ASIC (Application Specific Integrated Circuit). The control circuit 9 performs the various control operations described in this specification by executing instruction codes stored in memory or by being designed as a circuit for special applications.

[0040] [Experimental Results] (Experiment 1) In Experiment 1, the damage to the zirconium oxide film when forming a titanium nitride film on the surface of the zirconium oxide film was evaluated.

[0041] First, a substrate having a zirconium oxide film on its surface was prepared. Next, a titanium nitride film was formed on the surface of the zirconium oxide film by performing steps S12 and S13 of the metal-containing film formation method according to the embodiment.

[0042] In step S12, the surface of the zirconium oxide film was modified by a SiN cycle. The number of SiN cycle repetitions was set to 10, 50, and 100. The case without a SiN cycle was used as a comparative example.

[0043] In step S13, a titanium nitride film was formed on the surface of the zirconium oxide film by a TiN cycle.

[0044] X-ray fluorescence (XRF) analysis was used to measure the thickness of the zirconium oxide film before and after steps S12 and S13. The change in the thickness of the zirconium oxide film was calculated by subtracting the thickness of the zirconium oxide film after steps S12 and S13 from the thickness of the zirconium oxide film before steps S12 and S13. A larger change in the thickness of the zirconium oxide film indicates greater damage to the zirconium oxide film when the titanium nitride film is formed on the surface of the zirconium oxide film.

[0045] Figure 18 shows the change in thickness of the zirconium oxide film before and after the formation of the titanium nitride film. In Figure 18, the horizontal axis represents the number of SiN cycle repetitions [cycles], and the vertical axis represents the change in thickness of the zirconium oxide film [Å]. In Figure 18, open circles indicate the results when the SiN cycle was performed, and filled circles indicate the results when the SiN cycle was not performed.

[0046] As shown in Figure 18, the change in thickness of the zirconium oxide film when no SiN cycle was performed was 2.36 Å. The changes in thickness of the zirconium oxide film when the number of SiN cycles was 10, 50, and 100 were 1.27 Å, 0.52 Å, and 0.30 Å, respectively. From these results, it can be said that performing a SiN cycle can reduce damage to the zirconium oxide film when forming a titanium nitride film on the surface of the zirconium oxide film. From the viewpoint of particularly minimizing the change in thickness of the zirconium oxide film, the number of SiN cycles is preferably 10 or more, more preferably 50 or more, and even more preferably 100 or more.

[0047] (Experiment 2) In Experiment 2, the damage to the zirconium oxide film when forming a titanium silicate film on the surface of the zirconium oxide film was evaluated.

[0048] First, a substrate having a zirconium oxide film on its surface was prepared. Next, a titanium silicate film was formed on the surface of the zirconium oxide film by performing steps S12 and S13 of the metal-containing film formation method according to the embodiment.

[0049] In step S12, the surface of the zirconium oxide film was modified by SiN cycle, Si cycle, and N cycle. The number of repetitions for the SiN cycle was set to 10, 50, and 100. The number of repetitions for the Si cycle was set to 10 and 50. The number of repetitions for the N cycle was set to 10 and 50. A comparative example was provided in the case where the SiN cycle, Si cycle, and N cycle were not performed.

[0050] In step S13, a titanium silicate film was formed on the surface of the zirconium oxide film by the TSN cycle.

[0051] The thickness of the zirconium oxide film before and after steps S12 and S13 was measured using X-ray fluorescence analysis. The change in the thickness of the zirconium oxide film was calculated by subtracting the thickness of the zirconium oxide film after steps S12 and S13 from the thickness of the zirconium oxide film before steps S12 and S13. A larger change in the thickness of the zirconium oxide film indicates greater damage to the zirconium oxide film when the titanium silicate film is formed on the surface of the zirconium oxide film.

[0052] Figure 19 shows the change in the thickness of the zirconium oxide film before and after the formation of the titanium silicate film. In Figure 19, the horizontal axis represents the number of cycles [times], and the vertical axis represents the change in the thickness of the zirconium oxide film [Å]. In Figure 19, the black circles indicate the results when the SiN cycle, Si cycle, and N cycle were not performed, while the white circles, triangles, and diamonds indicate the results when the SiN cycle, Si cycle, and N cycle were performed, respectively.

[0053] As shown in Figure 19, the change in thickness of the zirconium oxide film when the SiN cycle, Si cycle, and N cycle were not performed was 1.69 Å. The change in thickness of the zirconium oxide film when the SiN cycle was repeated 10, 50, and 100 times was 0.68 Å, 0.23 Å, and 0.054 Å, respectively. The change in thickness of the zirconium oxide film when the Si cycle was repeated 10 and 50 times was 1.28 Å and 1.14 Å, respectively. The change in thickness of the zirconium oxide film when the N cycle was repeated 10 and 50 times was 1.54 Å and 1.45 Å, respectively. From these results, it can be said that performing the SiN cycle, Si cycle, and N cycle can reduce damage to the zirconium oxide film when forming a titanium silicate film on the surface of the zirconium oxide film. When forming a titanium silicate film on the surface of a zirconium oxide film, performing the SiN cycle is preferable from the viewpoint of particularly reducing the change in thickness of the zirconium oxide film. From the viewpoint of particularly minimizing the change in the thickness of the zirconium oxide film, the number of SiN cycles is preferably 10 or more, more preferably 50 or more, and even more preferably 100 or more.

[0054] The embodiments disclosed herein should be considered in all respects to be illustrative and not restrictive. The above embodiments may be omitted, replaced, or modified in various ways without departing from the scope and spirit of the appended claims.

[0055] In the above embodiments, the case where the high dielectric constant film is a zirconium oxide film was described, but the disclosure is not limited thereto. The material of the high dielectric constant film can be any material having a relative permittivity higher than silicon oxide. Examples of high dielectric constant films include HfSiO, HfSiON, and ZrO ２ , ZrSiO, ZrSiON, Ta ２ O ５ , Nb ２ O ５ Al ２ O ３ , HfO ２ , ScO ３ , Y ２ O ３ La ２ O ３ , CEO ３ , Pr ２ O ３ , Nd ２ O ３ Sm ２ O ３ , Eu ２ O ３ , Gd ２ O ３ , Tb ２ O ３ , Dy ２ O ３ Ho ２ O ３ Er ２ O ３ , Tm ２ O ３ Yb ２ O ３ and Lu ２ O ３ It may include at least one insulating material selected from the group consisting of the following.

[0056] In the embodiments described above, the case in which the metal-containing film, the first metal-containing film, and the second metal-containing film are titanium nitride films or titanium silicate films has been explained, but the disclosure is not limited thereto. The metal-containing film, the first metal-containing film, and the second metal-containing film may be metal oxides, metal nitrides, or metal oxynitrides formed from a precursor containing a halogen and a metal and a reaction gas (e.g., an oxygen-containing gas, a nitrogen-containing gas). The metal may be, for example, one of molybdenum (Mo), ruthenium (Ru), or tungsten (W).

[0057] In the embodiments described above, the case in which the first silicon-containing gas and the second silicon-containing gas are monosilane gases was explained, but the disclosure is not limited thereto. The first silicon-containing gas and the second silicon-containing gas are, for example, the same gas. In this case, the number of gases used can be reduced. The first silicon-containing gas and the second silicon-containing gas may be different gases. The first silicon-containing gas and the second silicon-containing gas are, for example, halogen-free gases. In this case, the high dielectric constant film is less likely to be etched when modifying the surface of the high dielectric constant film. The materials of the first silicon-containing gas and the second silicon-containing gas may include at least one selected from the group consisting of silicon hydride and organosilicon compounds. Silicon hydride is SiH ４ Yes, Si ２ H ６ Si ３ H ８ Si ４ H １０ It may contain higher-order silanes such as [specific examples of higher-order silanes]. Furthermore, silicon hydride may contain halogens. For example, silicon hydride containing halogens is [specific example of a halogen-containing silicon hydride]. ２ Cl ２ (DCS) is also acceptable.

[0058] In the embodiments described above, the case in which the metal source gas is titanium tetrachloride gas was explained, but the disclosure is not limited thereto. The metal source gas may be any gas containing a first metal and a halogen. The first metal may include molybdenum (Mo), ruthenium (Ru), and tungsten (W). The halogen may include at least one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and element (I).

[0059] In the embodiments described above, the case where the first nitride gas, second nitride gas, and third nitride gas are ammonia gas was explained, but this disclosure is not limited thereto. The first nitride gas, second nitride gas, and third nitride gas are, for example, the same gas. In this case, the number of types of gas used can be reduced.

[0060] 100 Substrate 103 Zirconium oxide film 104 Metal-containing film 200 Substrate 201 Silicon substrate 202 First metal-containing film 203 Zirconium oxide film 204 Second metal-containing film

Claims

1. A method for forming a metal-containing film, comprising: preparing a substrate having a high dielectric constant film; modifying the surface of the high dielectric constant film without supplying plasma to the high dielectric constant film while the substrate is controlled to a first temperature; and forming a metal-containing film on the surface of the modified high dielectric constant film while the substrate is controlled to a second temperature, wherein the first temperature is the same as or lower than the second temperature.

2. The method for forming a metal-containing film according to claim 1, wherein modifying the surface of the high dielectric constant film includes supplying at least one of a first silicon-containing gas and a first nitride gas to the substrate.

3. The method for forming a metal-containing film according to claim 2, wherein modifying the surface of the high dielectric constant film includes repeating a first cycle in which the first silicon-containing gas is supplied to the substrate and the first nitride gas is supplied to the substrate in this order.

4. The method for forming a metal-containing film according to claim 3, wherein forming the metal-containing film comprises repeating a second cycle in which the following steps are performed in this order: supplying a metal raw material gas containing a first metal and a halogen to the substrate, and supplying a second nitride gas to the substrate.

5. The method for forming a metal-containing film according to claim 4, wherein the number of repetitions of the first cycle is less than the number of repetitions of the second cycle.

6. The method for forming a metal-containing film according to claim 4, wherein the second nitriding gas is the same as the first nitriding gas.

7. A method for forming a metal-containing film according to claim 3, comprising: repeating a third cycle in which a metal raw material gas containing a first metal and a halogen is supplied to the substrate and a second nitride gas is supplied to the substrate in this order; repeating a fourth cycle in which a second silicon-containing gas is supplied to the substrate and a third nitride gas is supplied to the substrate in this order; and repeating a fifth cycle in which the third cycle and the fourth cycle are repeated in this order.

8. The method for forming a metal-containing film according to claim 7, wherein the number of repetitions of the first cycle is less than the number of repetitions of the fifth cycle.

9. The method for forming a metal-containing film according to claim 7, wherein the second nitride gas and the third nitride gas are the same as the first nitride gas.

10. The method for forming a metal-containing film according to claim 7, wherein the second silicon-containing gas is the same as the first silicon-containing gas.

11. The method for forming a metal-containing film according to any one of claims 2 to 10, wherein the first silicon-containing gas is a halogen-free gas.

12. The method for forming a metal-containing film according to any one of claims 4 to 10, wherein the first silicon-containing gas is monosilane gas, the first nitride gas is ammonia gas, and the metal raw material gas is titanium tetrachloride gas.

13. The method for forming a metal-containing film according to any one of claims 1 to 10, wherein the high dielectric constant film is a zirconium oxide film.

14. The method for forming a metal-containing film according to any one of claims 1 to 10, wherein the metal-containing film is a titanium nitride film or a titanium silicate film.

15. The method for forming a metal-containing film according to any one of claims 1 to 10, wherein the surface modification of the high dielectric constant film is performed in the same processing vessel used to form the metal-containing film.

16. The method for forming a metal-containing film according to any one of claims 3 to 10, wherein the number of repetitions of the first cycle is 10 or more and 100 or less.

17. A method for manufacturing a capacitor, comprising: preparing a substrate; forming a first metal-containing film on the substrate; forming a high dielectric constant film on the first metal-containing film; modifying the surface of the high dielectric constant film without supplying plasma to the high dielectric constant film while the substrate is controlled to a first temperature; and forming a second metal-containing film on the surface of the modified high dielectric constant film while the substrate is controlled to a second temperature, wherein the first temperature is the same as or lower than the second temperature.

18. The method for manufacturing a capacitor according to claim 17, wherein the second metal-containing film is the same film as the first metal-containing film.

19. The method for manufacturing a capacitor according to claim 18, wherein the first metal-containing film and the second metal-containing film are a titanium nitride film or a titanium silicate film.

20. A film deposition apparatus comprising: a processing container for housing a substrate; a gas supply unit for supplying gas into the processing container; a temperature control unit for controlling the temperature of the substrate in the processing container; and a control circuit, wherein the control circuit is configured to control the gas supply unit and the temperature control unit to perform the following: housing a substrate having a high dielectric constant film in the processing container; modifying the surface of the high dielectric constant film without supplying plasma to the high dielectric constant film while the substrate is controlled to a first temperature in the processing container; and forming a metal-containing film on the surface of the modified high dielectric constant film while the substrate is controlled to a second temperature in the processing container, wherein the first temperature is the same as or lower than the second temperature.

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