Film formation method and film formation device

Abstract

To achieve improved uniformity of a polymer film.SOLUTION: This film formation method includes a first film formation step and a second film formation step. In the first film formation step, a film of a polymer is formed on the surface of a substrate in a chamber by supplying a gas of a first monomer and a gas of a second monomer into the chamber. In the second film formation step, a film of a polymer is additionally formed on the film of the polymer formed in the first film formation step, at a deposition rate higher than that in the first film formation step, by supplying the first monomer and the second monomer into the chamber.SELECTED DRAWING: Figure 10

Description

[Technical field]

[0001] Various aspects and embodiments of the present disclosure relate to a film formation method and a film formation apparatus. [Background technology]

[0002] For example, the following Patent Document 1 discloses that "the multiple types of raw materials used to form a film on the workpiece W are two types of raw materials, for example, raw material A as a first raw material and raw material B as a second raw material. For example, when forming a polyurea film on the workpiece W, raw material A and raw material B are, for example, a diisocyanate and a diamine. In the film forming apparatus 1, a polyurea film is formed on the surface of the workpiece W by vapor deposition polymerization of the diisocyanate and the diamine on the surface of the workpiece W." [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2019-218616 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a film formation method and a film formation apparatus capable of improving the uniformity of the film thickness of a polymer formed on a substrate. [Means for solving the problem]

[0005] One aspect of the present disclosure is a film formation method, including a first film formation step and a second film formation step. In the first film formation step, a polymer film is formed on a surface of a substrate in the chamber by supplying a gas of a first monomer and a gas of a second monomer into the chamber. In the second film formation step, a polymer film is further formed on the polymer film formed in the first film formation step at a higher deposition rate than in the first film formation step by supplying the first monomer and the second monomer into the chamber. Effect of the Invention

[0006] According to various aspects and embodiments of the present disclosure, it is possible to improve the uniformity of the film thickness of a polymer formed on a substrate. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic cross-sectional view illustrating an example of a film forming apparatus according to an embodiment of the present disclosure. [Diagram 2] FIG. 2 is a diagram showing an example of the relationship between the thickness and uniformity of a polymer film. [Diagram 3] FIG. 3 is a diagram showing an example of the relationship between the thickness and uniformity of a polymer film. [Figure 4] FIG. 4 is a diagram showing an example of the relationship between the thickness and uniformity of a polymer film. [Figure 5A] FIG. 5A is a schematic diagram showing an example of a process for forming a polymer film. [Figure 5B] FIG. 5B is a schematic diagram showing an example of a process for forming a polymer film. [Figure 5C] FIG. 5C is a schematic diagram showing an example of a process for forming a polymer film. [Figure 5D] FIG. 5D is a schematic diagram showing an example of a process for forming a polymer film. [Figure 6] FIG. 6 is a diagram showing an example of uniformity when the deposition rate is changed. [Figure 7] FIG. 7 is a diagram showing an example of the relationship between film thickness and uniformity in the comparative example and the embodiment. [Figure 8]FIG. 8 is a diagram showing an example of the relationship between film thickness and uniformity in the comparative example and the embodiment. [Figure 9] FIG. 9 is a flowchart showing an example of a film forming method. [Figure 10] FIG. 10 is a diagram showing an example of the relationship between the film thickness of the polymer and the deposition rate with respect to the treatment time. [Figure 11] FIG. 11 is a diagram showing an example of a film formed on surfaces with different wettability. [Figure 12] FIG. 12 is a diagram showing an example of a film formed on surfaces with different wettability. [Figure 13] FIG. 13 is a diagram showing an example of a film formed on surfaces with different wettability. [Figure 14A] FIG. 14A is a diagram showing an example of a process of film formation on a structure having surfaces with different wettability. [Figure 14B] FIG. 14B is a diagram showing an example of a process of film formation on a structure having surfaces with different wettability. [Figure 14C] FIG. 14C is a diagram showing an example of a process of film formation on a structure having surfaces with different wettability. [Figure 15A] FIG. 15A is a diagram showing an example of a process of film formation on a structure having surfaces with different wettability. [Figure 15B] FIG. 15B is a diagram showing an example of a process of film formation on a structure having surfaces with different wettability. [Figure 15C] FIG. 15C is a diagram showing an example of a process of film formation on a structure having surfaces with different wettability. [Figure 15D] FIG. 15D is a diagram showing an example of a process of film formation on a structure having surfaces with different wettability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, embodiments of the disclosed film forming method and film forming apparatus will be described in detail with reference to the drawings. Note that the disclosed film forming method and film forming apparatus are not limited to the following embodiments.

[0009] However, when a polymer film is formed on a substrate, if there is a deviation in the thickness of the polymer film, the characteristics of a semiconductor device fabricated using the polymer film may vary significantly, and therefore it is important to increase the uniformity of the thickness of the polymer film formed on the substrate.

[0010] Therefore, the present disclosure provides a technique capable of improving the uniformity of the film thickness of a polymer formed on a substrate.

[0011] [Configuration of Film Forming Apparatus 10] 1 is a schematic cross-sectional view showing an example of a film formation apparatus 10 according to an embodiment of the present disclosure. The film formation apparatus 10 includes a chamber 11, an exhaust mechanism 12, a gas supply unit 13, a shower head 16, a stage 17, and a control unit 20. In this embodiment, the film formation apparatus 10 is, for example, a chemical vapor deposition (CVD) apparatus.

[0012] The exhaust mechanism 12 has a vacuum pump that exhausts gas inside the chamber 11, and a pressure adjustment valve that adjusts the pressure inside the chamber 11. The inside of the chamber 11 is controlled by the exhaust mechanism 12 to a vacuum atmosphere of a predetermined pressure.

[0013] A gas supply unit 13 that supplies a plurality of types of raw material monomers is connected to the chamber 11 via a shower head 16. In this embodiment, the plurality of types of raw material monomers are, for example, isocyanate and amine. The isocyanate is an example of a first monomer, and the amine is an example of a second monomer. The gas supply unit 13 has a raw material supply source 130a, a raw material supply source 130b, a vaporizer 131a, and a vaporizer 131b. The raw material supply source 130a contains an isocyanate liquid. The raw material supply source 130b contains an amine liquid.

[0014] The vaporizer 131a vaporizes the isocyanate liquid supplied from the raw material supply source 130a. The vapor of the isocyanate vaporized by the vaporizer 131a is introduced into the shower head 16 via the pipe 14a. The vaporizer 131b vaporizes the amine liquid supplied from the raw material supply source 130b. The vapor of the amine vaporized by the raw material supply source 130b is introduced into the shower head 16 via the pipe 14b.

[0015] The shower head 16 is provided, for example, in the upper part of the chamber 11, and has a large number of outlets formed on the lower surface. The shower head 16 discharges the isocyanate vapor introduced via the pipe 14a and the amine vapor introduced via the pipe 14b in a shower-like manner from separate outlets into the chamber 11.

[0016] A stage 17 is provided within the chamber 11. The stage 17 has a temperature adjustment mechanism (not shown). A substrate W on which a film is to be formed is placed on the stage 17. In this embodiment, the substrate W has a surface made of, for example, silicon. The stage 17 controls the temperature of the substrate W by the temperature adjustment mechanism so that the temperature becomes suitable for vapor deposition polymerization of the raw material monomer supplied from the gas supply unit 13. The temperature suitable for vapor deposition polymerization can be determined depending on the type of raw material monomer. The temperature suitable for vapor deposition polymerization is, for example, within a range of 60°C to 100°C.

[0017] By using such a film forming apparatus 10, a vapor deposition polymerization reaction of two kinds of raw material monomers occurs on the surface of the substrate W, thereby forming a polymer film on the surface of the substrate W. When the two kinds of raw material monomers are isocyanate and amine, a polyurea polymer film is laminated on the surface of the substrate W.

[0018] The control unit 20 has a processor, a memory, and an input / output interface. The memory stores a program executed by the processor and a recipe including conditions for each process. The processor executes the program read from the memory, and controls each part of the film forming apparatus 10 via the input / output interface based on the recipe stored in the memory, thereby performing a process for forming a polymer film on the substrate W.

[0019] [Relationship between film thickness and uniformity] Figures 2 to 4 are diagrams showing an example of the relationship between the thickness and uniformity of a polymer film. Figure 4 shows the difference in uniformity between adjacent film thicknesses in Figure 3. In Figures 2 to 4, film formation is continued under the same conditions until a predetermined thickness is reached.

[0020] For example, as shown in Figures 2 and 3, as the thickness of the polymer film increases, the film thickness uniformity (WiW± [%] and WiW1σ [%]) improves (the value decreases). Conversely, as the thickness of the polymer film decreases, the film thickness uniformity decreases.

[0021] In addition, in FIG. 4, the difference in uniformity between the film thicknesses of 0 nm and 5 nm is defined as the first uniformity, the difference in uniformity between the film thicknesses of 5 nm and 10 nm is defined as the second uniformity, and the difference in uniformity between the film thicknesses of 10 nm and 15 nm is defined as the third uniformity. The difference in uniformity between the film thicknesses of 15 nm and 30 nm is defined as the fourth uniformity, and the difference in uniformity between the film thicknesses of 30 nm and 60 nm is defined as the fifth uniformity. Among the first to fifth uniformities, the first uniformity is the worst. There is not much difference in uniformity among the second to fifth uniformities.

[0022] Furthermore, referring to FIG. 2, the deposition rate (D / R) decreases as the film thickness increases.

[0023] From the results of Figures 2 to 4, the film formation process can be inferred as shown in Figures 5A to 5D, for example. Figures 5A to 5D are schematic diagrams showing an example of the process of forming a polymer film.

[0024] In the early stage of film formation, when monomer molecules collide with the surface of the substrate W, they stay on the highly wettable (hydrophilic) surface of the substrate W for a long time, and as shown in FIG. 5A, for example, the monomer molecules are excessively adsorbed to the surface of the substrate W. Therefore, the distribution of the monomer molecules on the surface of the substrate W is significantly affected by the uneven distribution of the monomer gas in the chamber 11. For example, more monomer molecules are adsorbed on the surface of the substrate W near the monomer gas outlet than on the surface of the substrate W at a position away from the monomer gas outlet. This is thought to result in a deterioration in the uniformity of the polymer film 30 in the early stage of film formation.

[0025] Furthermore, as the film formation progresses, monomer molecules are adsorbed onto the surface of the substrate W and onto the surface of the polymer film 30, as shown in FIG. 5B for example. However, the surface of the polymer film 30 has lower wettability (hydrophobicity) than the surface of the substrate W. For example, the contact angle of the silicon surface is about 31.2°, whereas the contact angle of the polyurea polymer film 30 surface is about 73.1°. As a result, more monomer molecules are adsorbed onto the surface of the substrate W than onto the polyurea polymer film 30. This is believed to improve the uniformity of the film.

[0026] The surface of the substrate W on which the polymer film 30 is formed may be a silicon nitride film, a silicon oxide film, or the like, in addition to silicon. The contact angle of the surface of a silicon nitride film is about 29.0°, and the contact angle of the surface of a silicon oxide film is about 50.9°.

[0027] 5C and 5D, the surface of the substrate W is covered with a polymer film 30, and the monomer molecules are adsorbed only to the surface of the polymer film 30. In this case, the monomer molecules adsorbed to the convex portions of the surface of the polymer film 30 are easy to detach, but the monomer molecules adsorbed to the concave portions of the surface of the polymer film 30 are difficult to detach. Therefore, as the thickness of the polymer film 30 increases, the unevenness of the surface becomes gentler, and it is considered that the uniformity of the film thickness is further improved.

[0028] [Relationship between deposition rate and uniformity] Fig. 6 is a diagram showing an example of uniformity when the deposition rate is changed. In Fig. 6, condition 1 indicates a condition in which the deposition rate is relatively low, and condition 2 indicates a condition in which the deposition rate is relatively high. Condition 3 indicates a condition in which a film is formed under condition 1 followed by a film is formed under condition 2.

[0029] In condition 1, the pressure inside the chamber 11 is set low as one of the conditions for lowering the deposition rate compared to condition 2. Note that other than lowering the pressure, other possible conditions for lowering the deposition rate include, for example, increasing the temperature of the substrate W, decreasing the flow rate of at least one type of monomer gas, decreasing the concentration of at least one type of monomer gas, etc.

[0030] 6, under condition 1, film formation is performed under the same conditions from the initial stage until the film thickness reaches 4.2 nm. Under condition 2, film formation is performed under the same conditions from the initial stage until the film thickness reaches 15.0 nm. Under condition 3, film formation is performed under the same conditions as condition 1 from the initial stage until the film thickness reaches 4.2 nm, and then the conditions are switched to condition 2 to form a film of another 15.0 nm.

[0031] Under condition 1, where the deposition rate is relatively low, the film thickness uniformity (WiW±[%]) is better (smaller value) than under condition 2, where the deposition rate is relatively high. Also, under condition 3, where film formation is performed under condition 1, where the deposition rate is low at the beginning of film formation, and then under condition 2, where the deposition rate is high, the film thickness uniformity is better than that under condition 2 and is equivalent to that under condition 1.

[0032] Moreover, under condition 3, the deposition rate is higher than under condition 1, and therefore a higher throughput than under condition 1 can be achieved while maintaining the same uniformity as under condition 1. In this embodiment, as under condition 3, film formation is performed under conditions with a low deposition rate in the early stage of film formation, and then film formation is performed under conditions with a high deposition rate. Therefore, in this embodiment, the uniformity of the film thickness can be improved, and the time required to form a polymer film of a predetermined thickness on the substrate W can be shortened, compared to the case where film formation is continued under conditions with a low deposition rate.

[0033] 7 and 8 are diagrams showing an example of the relationship between film thickness and uniformity in a comparative example and an embodiment. In the examples of Fig. 7 and Fig. 8, a result of film formation under conditions of a high deposition rate is shown as a comparative example, and a result of film formation under conditions of a low deposition rate in the early stage of film formation and then under conditions of a high deposition rate is shown as an embodiment.

[0034] 7 and 8, for any thickness, the present embodiment has better (smaller) thickness uniformity (WiW±[%]) than the comparative example. For example, as shown in FIG. 8, the film forming method of the present embodiment can suppress the thickness uniformity (WiW±[%]) to 5% or less.

[0035] In addition, in this embodiment, although the deposition rate is low in the early stage of the deposition, the deposition time under the low deposition rate is not so long, so that the overall deposition rate is not so different from that of the comparative example. Therefore, in this embodiment, the uniformity of the film thickness can be improved while suppressing the decrease in throughput.

[0036] 9 is a flow chart showing an example of a film forming method. The film forming method shown in FIG.

[0037] First, the substrate W is loaded into the chamber 11 (step S10). In step S10, the control unit 20 controls, for example, a drive mechanism for the lift pins (not shown) so that the tips of the lift pins (not shown) protrude from the upper surface of the stage 17. Then, the control unit 20 controls a gate valve (not shown) that opens and closes an opening (not shown) formed in the side wall of the chamber 11 so as to open the gate valve. The substrate W is loaded into the chamber 11 by a transfer robot (not shown) through the opening in the side wall of the chamber 11 and placed on the lift pins. Then, the control unit 20 controls the drive mechanism for the lift pins so that the lift pins are lowered. As a result, the lift pins are lowered, and the substrate W is placed on the stage 17. Then, the control unit 20 controls the gate valve so as to close the gate valve.

[0038] Next, a first film formation process is performed (step S11). The first film formation process in step S11 is performed under the following conditions, for example. Temperature of substrate W: 80℃ Isocyanate vapor flow rate: 10sccm Amine vapor flow rate: 20sccm Pressure in chamber 11: 0.25 Torr (approximately 33.3 Pa) Flow rate of additive gas (e.g., nitrogen gas) in chamber 11: 400 sccm Processing time: 60 seconds

[0039] Here, the relationship between the film thickness and deposition rate of the polymer relative to the processing time in the first film formation process in step S11 is, for example, as shown in FIG. 10. For example, as shown in FIG. 10, the deposition rate is high from the start of polymer film formation until the film thickness reaches 0.6 nm, but when the film thickness exceeds this value, it takes time to form the film. Therefore, the film thickness of the polymer formed in the first film formation process is preferably 0.6 nm to 5 nm. Note that the deposition rate of the polymer film in the first film formation process is preferably, for example, 5 nm / min or less.

[0040] Next, a second film forming process is performed (step S12). The second film forming process in step S12 is performed under conditions with a lower deposition rate than the first film forming process in step S11. The second film forming process in step S12 is performed under the following conditions, for example. Temperature of substrate W: 80℃ Isocyanate vapor flow rate: 10sccm Amine vapor flow rate: 20sccm Pressure in chamber 11: 1.0 Torr (approximately 133.3 Pa) Flow rate of additive gas (e.g., nitrogen gas) in chamber 11: 400 sccm Processing time: 43 seconds

[0041] Next, the substrate W is unloaded from the chamber 11 (step S13). In step S13, the control unit 20 controls a lift pin drive mechanism (not shown) so that the tips of the lift pins (not shown) protrude from the upper surface of the stage 17, thereby lifting the substrate W from the stage 17. Then, the control unit 20 controls a gate valve (not shown) to open it, and the substrate W is unloaded from the chamber 11 by a transfer robot (not shown) through an opening formed in a side wall of the chamber 11. Then, the control unit 20 controls the gate valve to close it, and controls the lift pin drive mechanism to lower the lift pins. Then, the film forming method shown in this flowchart is completed.

[0042] The embodiment has been described above. As described above, the film forming method in the embodiment includes a first film forming step and a second film forming step. In the first film forming step, a polymer film (film 30) is formed on the surface of a substrate (substrate W) in the chamber (chamber 11) by supplying a gas of a first monomer and a gas of a second monomer into the chamber. In the second film forming step, a polymer film is further formed on the polymer film formed in the first film forming step at a higher deposition rate than the first film forming step by supplying the first monomer and the second monomer into the chamber. This can improve the uniformity of the film thickness of the polymer formed on the substrate.

[0043] In the above embodiment, the pressure in the chamber in the first film-forming step is lower than the pressure in the chamber in the second film-forming step, thereby improving the uniformity of the film thickness of the polymer formed on the substrate.

[0044] In the above embodiment, the temperature of the substrate in the first film-forming step is higher than the temperature of the substrate in the second film-forming step, thereby improving the uniformity of the film thickness of the polymer formed on the substrate.

[0045] In the above embodiment, the flow rates of the first and second monomer gases in the first film-forming step are smaller than the flow rates of the first and second monomer gases in the second film-forming step, thereby improving the uniformity of the film thickness of the polymer formed on the substrate.

[0046] In the above embodiment, the concentrations of the first and second monomer gases supplied into the chamber in the first film-forming step are lower than the concentrations of the first and second monomer gases supplied into the chamber in the second film-forming step, thereby improving the uniformity of the film thickness of the polymer formed on the substrate.

[0047] In the above embodiment, the deposition rate in the first film-forming step is 5 nm / min or less, which can improve the uniformity of the film thickness of the polymer formed on the substrate.

[0048] In the above-described embodiment, at least a part of the surface of the substrate is made of silicon, a silicon nitride film, or a silicon oxide film, which can improve the uniformity of the film thickness of the polymer formed on the substrate.

[0049] In the above embodiment, a polymer film having a thickness of 0.6 nm to 5 nm is formed in the first film-forming step, which can improve the uniformity of the thickness of the polymer film formed on the substrate.

[0050] The film forming apparatus (film forming apparatus 10) in the above embodiment includes a chamber (chamber 11), a stage (stage 17), a gas supply unit (gas supply unit 13), and a control unit (control unit 20). The stage is provided in the chamber, and a substrate is placed on the stage. The gas supply unit supplies gases of a first monomer and a second monomer into the chamber. The control unit executes a first film forming process and a second film forming process. In the first film forming process, the gas supply unit is controlled to supply gases of the first monomer and the second monomer into the chamber, and a polymer film is formed on the surface of the substrate in the chamber. In the second film forming process, the gas supply unit is controlled to supply the first monomer and the second monomer into the chamber, and a polymer film is further formed on the polymer film formed in the first film forming process at a deposition rate higher than that of the first film forming process. This can improve the uniformity of the film thickness of the polymer formed on the substrate.

[0051] [others] It should be noted that the technology disclosed in the present application is not limited to the above-described embodiment, and various modifications are possible within the scope of the gist thereof.

[0052] For example, in the above embodiment, a polymer film is formed on a substrate W having a silicon surface, but the disclosed technology is not limited to this. For example, the disclosed technology can be applied to a case where a polymer film is formed on the surfaces of two members having surfaces with different surface wettability.

[0053] Here, consider the case where a polymer film is formed on a substrate W having a member 40 with a surface having relatively high wettability (hydrophilic) and a member 41 with a surface having relatively low wettability (hydrophobic), as shown in Fig. 11. When a polymer film is formed on such a substrate W under conditions that result in a constant deposition rate, monomers are excessively adsorbed on the surface of the member 40 in the early stage of film formation, and therefore the film 30 on the surface of the member 40 becomes thick, as shown in Fig. 11. This reduces the uniformity of the thickness of the polymer film 30 over the entire substrate W.

[0054] In contrast, in this embodiment, the film is formed under conditions of a low deposition rate in the early stage of film formation. As a result, in the early stage of film formation, the surface of a member 40 having a highly wettable (hydrophilic) surface is covered with a thin polymer film 30, for example, as shown in FIG. 12. Since the surface of the polymer film 30 has a low wettability (hydrophobicity), the surface of the member 40 is covered with the polymer film 30, and the difference in surface wettability is reduced in the entire substrate W. Then, the film is formed under conditions of a high deposition rate, so that the difference between the thickness of the polymer film 30 formed on the member 40 and the thickness of the polymer film 30 formed on the member 41 can be reduced, for example, as shown in FIG. 13. As a result, the uniformity of the thickness of the polymer film 30 can be improved in the entire substrate W.

[0055] Also, consider the case where a polymer film is formed on the surface of a structure having surfaces with different wettabilities, as shown in Fig. 14A. In the example of Fig. 14A, a structure is formed on a substrate W, the structure having a member 50 having a surface with relatively high wettability (hydrophilic) and a member 51 having a surface with relatively low wettability (hydrophobic).

[0056] When a polymer film 30 is formed on a substrate W having the structures illustrated in Fig. 14A under conditions of a constant deposition rate, a larger amount of the polymer film 30 is formed on the surface of the member 50 and the substrate W in the early stage of film formation, as shown in Fig. 14B for example. Therefore, if film formation of the polymer film 30 is continued under the same conditions, voids 31 may be formed between the structures, as shown in Fig. 14C for example.

[0057] In contrast, in this embodiment, when forming a polymer film 30 on a substrate W having a structure as exemplified in FIG. 15A, the film is formed under conditions of a low deposition rate in the early film formation stage. As a result, in the early film formation stage, the surface of the substrate W and the member 50 having a highly wettable (hydrophilic) surface are covered with a thin polymer film 30, as shown in FIG. 15B, for example. As a result, the surface of the polymer film 30 has a low wettability (hydrophobic), so that the difference in wettability of the surface of the substrate W as a whole becomes small. Thereafter, the film is formed under conditions of a high deposition rate, so that the thickness of the polymer film 30 can be increased in a state where the difference between the thickness of the polymer film 30 on the member 40 and the thickness of the polymer film 30 on the member 41 is small, as shown in FIG. 15C, for example. As a result, it is possible to suppress the formation of voids 31 in the polymer film 30, as shown in FIG. 15D, for example.

[0058] In the substrate W having the structure illustrated in Fig. 15A, the member 50 may be, for example, a silicon nitride film, the member 51 may be, for example, ruthenium, and the substrate W may be, for example, silicon. Alternatively, in the substrate W having the structure illustrated in Fig. 15A, the member 50 may be, for example, a titanium nitride film, the member 51 may be, for example, a carbon-containing silicon oxide film (SiOC film), and the substrate W may be, for example, silicon. The contact angle of the surface of titanium nitride is about 56.2°, and the contact angle of the surface of the carbon-containing silicon oxide film is about 129.1°.

[0059] In the above embodiment, a polymer film having a urea bond (-NH-CO-NH-) is formed on the surface of the substrate W using an isocyanate as the first monomer and an amine as the second monomer, but the disclosed technology is not limited to this. For example, a polymer film having a 2-aminoethanol bond (-NH-CH2-CH(OH)-) may be formed on the surface of the substrate W using an epoxide as the first monomer and an amine as the second monomer. Alternatively, a polymer film having a urethane bond (-NH-CO-O-) may be formed on the surface of the substrate W using an isocyanate as the first monomer and an alcohol as the second monomer. Alternatively, a polymer film having an amide bond (-NH-CO-) may be formed on the surface of the substrate W using an acyl halide as the first monomer and an amine as the second monomer. Alternatively, a polymer film having an imide bond (-CO-N(-)-CO-) may be formed on the surface of the substrate W using a carboxylic anhydride as the first monomer and an amine as the second monomer.

[0060] It should be noted that the embodiments disclosed herein are illustrative in all respects and should not be construed as limiting. Indeed, the above-described embodiments may be embodied in various forms. Furthermore, the above-described embodiments may be omitted, substituted, or modified in various forms without departing from the scope and spirit of the appended claims.

[0061] Furthermore, the following supplementary notes are disclosed regarding the above embodiment.

[0062] (Appendix 1) a first film-forming step of supplying a gas of a first monomer and a gas of a second monomer into a chamber to form a polymer film on a surface of a substrate in the chamber; a second film-forming step of further forming a polymer film on the polymer film formed in the first film-forming step at a deposition rate higher than that of the first film-forming step by supplying the first monomer and the second monomer into the chamber; A film formation method for performing the above. (Appendix 2) 2. The film forming method according to claim 1, wherein a pressure in the chamber in the first film forming step is lower than a pressure in the chamber in the second film forming step. (Appendix 3) 3. The film forming method according to claim 1, wherein a temperature of the substrate in the first film forming step is higher than a temperature of the substrate in the second film forming step. (Appendix 4) 4. The film formation method according to claim 1, wherein a flow rate of the gas of the first monomer and the gas of the second monomer in the first film formation process is lower than a flow rate of the gas of the first monomer and the gas of the second monomer in the second film formation process. (Appendix 5) 5. The film formation method according to claim 1, wherein a concentration of the first monomer and the second monomer gas supplied into the chamber in the first film formation step is lower than a concentration of the first monomer and the second monomer gas supplied into the chamber in the second film formation step. (Appendix 6) 6. The film forming method according to claim 1, wherein a deposition rate in the first film forming step is 5 nm / min or less. (Appendix 7) 7. The film forming method according to claim 1, wherein at least a portion of the surface of the substrate is silicon, a silicon nitride film, or a silicon oxide film. (Appendix 8) 8. The film forming method according to claim 1, wherein in the first film forming step, a film of the polymer having a thickness of 0.6 nm to 5 nm is formed. (Appendix 9) the first monomer is an isocyanate; the second monomer is an amine; 9. The method for forming a film according to any one of claims 1 to 8, wherein the polymer film contains a urea bond. (Appendix 10) the first monomer is a carboxylic acid anhydride; the second monomer is an amine; 9. The method for forming a film according to any one of claims 1 to 8, wherein the polymer film contains an imide bond. (Appendix 11) the first monomer is an epoxide; the second monomer is an amine; 9. The method for forming a film according to any one of claims 1 to 8, wherein the polymer film contains a 2-aminoethanol bond. (Appendix 12) the first monomer is an isocyanate; the second monomer is an alcohol; 9. The method for forming a film according to any one of claims 1 to 8, wherein the polymer film contains a urethane bond. (Appendix 13) the first monomer is an acyl halide; the second monomer is an amine; 9. The method for forming a film according to any one of claims 1 to 8, wherein the polymer film contains an amide bond. (Appendix 14) A chamber; a stage provided within the chamber and on which a substrate is placed; a gas supply unit that supplies a gas of a first monomer and a gas of a second monomer into the chamber; Control unit and Equipped with The control unit is a first film formation step of supplying gases of the first monomer and the second monomer into the chamber by controlling the gas supply unit to form a polymer film on the surface of the substrate in the chamber; a second film-forming step of further forming a polymer film on the polymer film formed in the first film-forming step at a deposition rate higher than that of the first film-forming step by supplying gases of the first monomer and the second monomer into the chamber by controlling the gas supply unit; A deposition apparatus that performs the above. [Explanation of symbols]

[0063] W substrate 10 Film deposition equipment 11. Chamber 12 Exhaust system 13 Gas supply section 130 Raw material sources 131 Carburetor 14 Piping 16. Shower Head 17 Stages 20 Control section 30 membrane 31 Void 40 Materials 41 Materials 50 Materials 51 Materials

Claims

1. a first film-forming step of supplying a gas of a first monomer and a gas of a second monomer into a chamber to form a polymer film on a surface of a substrate in the chamber; a second film-forming step of further forming a polymer film on the polymer film formed in the first film-forming step at a deposition rate higher than that of the first film-forming step by supplying the first monomer and the second monomer into the chamber; A film formation method for performing the above.

2. 2. The film forming method according to claim 1, wherein a pressure in the chamber in the first film forming step is lower than a pressure in the chamber in the second film forming step.

3. 3. The film forming method according to claim 1, wherein a temperature of the substrate in the first film forming step is higher than a temperature of the substrate in the second film forming step.

4. 3. The film forming method according to claim 1, wherein a flow rate of the gas of the first monomer and the gas of the second monomer in the first film forming step is lower than a flow rate of the gas of the first monomer and the gas of the second monomer in the second film forming step.

5. 3. The film forming method according to claim 1, wherein a concentration of the first monomer and the second monomer gas supplied into the chamber in the first film forming step is lower than a concentration of the first monomer and the second monomer gas supplied into the chamber in the second film forming step.

6. 3. The film forming method according to claim 1, wherein a deposition rate in the first film forming step is 5 nm / min or less.

7. 3. The film forming method according to claim 1, wherein at least a part of the surface of the substrate is made of silicon, a silicon nitride film, or a silicon oxide film.

8. 3. The film forming method according to claim 1, wherein in the first film forming step, a film of the polymer having a thickness of 0.6 nm to 5 nm is formed.

9. the first monomer is an isocyanate; the second monomer is an amine; 3. The method of claim 1, wherein the polymer film contains a urea bond.

10. the first monomer is a carboxylic acid anhydride; the second monomer is an amine; 3. The method of claim 1, wherein the polymer film contains an imide bond.

11. the first monomer is an epoxide; the second monomer is an amine; 3. The method of claim 1, wherein the polymer film contains a 2-aminoethanol bond.

12. the first monomer is an isocyanate; the second monomer is an alcohol; 3. The method of claim 1, wherein the polymer film contains a urethane bond.

13. the first monomer is an acyl halide; the second monomer is an amine; 3. The method of claim 1, wherein the polymer film contains an amide bond.

14. A chamber; a stage provided within the chamber and on which a substrate is placed; a gas supply unit that supplies a first monomer gas and a second monomer gas into the chamber; Control unit and Equipped with The control unit is a first film formation step of supplying gases of the first monomer and the second monomer into the chamber by controlling the gas supply unit to form a polymer film on the surface of the substrate in the chamber; a second film-forming step of further forming a polymer film on the polymer film formed in the first film-forming step at a deposition rate higher than that of the first film-forming step by supplying gases of the first monomer and the second monomer into the chamber by controlling the gas supply unit; A deposition apparatus that performs the above.

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