JP2025078162A - Film forming method and film forming apparatus - Google Patents

Abstract

The present invention provides a method for improving the uniformity of a polymer film.
[Solution] The film formation method includes 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 deposition rate higher than that of the first film formation step by supplying the first monomer and the second monomer into the chamber.
[Selected figure] Figure 10

Description

Various aspects and embodiments of the present disclosure relate to a film forming method and a film forming apparatus.

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 the first raw material and raw material B as the second raw material. For example, when forming a polyurea film on the workpiece W, raw materials A and B are, for example, diisocyanate and diamine. In the film forming apparatus 1, the diisocyanate and diamine are vapor-deposition-polymerized on the surface of the workpiece W to form a polyurea film on the surface of the workpiece W."

JP 2019-218616 A

The present disclosure provides a film formation method and a film formation apparatus that can improve the uniformity of the film thickness of a polymer formed on a substrate.

One aspect of the present disclosure is a film formation method, which includes a first film formation step and a second film formation step. In the first film formation step, a polymer film is formed on the 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 the first film formation step by supplying the first monomer and the second monomer into the chamber.

Various aspects and embodiments of the present disclosure can improve the uniformity of the film thickness of the polymer formed on the substrate.

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

Below, embodiments of the disclosed film formation method and film formation apparatus will be described in detail with reference to the drawings. Note that the disclosed film formation method and film formation apparatus are not limited to the following embodiments.

However, when forming a polymer film on a substrate, if there is a bias in the thickness of the polymer film, this can lead to large variations in the characteristics of the semiconductor device fabricated using the polymer film. For this reason, it is important to increase the uniformity of the thickness of the polymer film formed on the substrate.

Therefore, the present disclosure provides a technology that can improve the uniformity of the film thickness of the polymer formed on the substrate.

[Configuration of Film Forming Apparatus 10]
1 is a schematic cross-sectional view illustrating 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.

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

A gas supply unit 13 that supplies multiple types of raw material monomers is connected to the chamber 11 via a shower head 16. In this embodiment, the multiple types of raw material monomers are, for example, isocyanate and amine. Isocyanate is an example of a first monomer, and 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.

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

The shower head 16 is provided, for example, at the top of the chamber 11, and has a number of outlets formed on the bottom surface. The shower head 16 ejects 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.

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 uses a temperature adjustment mechanism to control the temperature of the substrate W so that the temperature is 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 the range of 60°C to 100°C.

Using such a film forming apparatus 10, a vapor deposition polymerization reaction of two types of raw material monomers is caused on the surface of the substrate W, forming a polymer film on the surface of the substrate W. When the two types of raw material monomers are isocyanate and amine, a polyurea polymer film is laminated on the surface of the substrate W.

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 the 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.

[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.

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 values become smaller). Conversely, as the thickness of the polymer film decreases, the film thickness uniformity decreases.

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

Also, referring to Figure 2, the deposition rate (D/R) decreases as the film thickness increases.

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

In the early stages 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, an excessive amount of monomer molecules are adsorbed to the surface of the substrate W. Therefore, the distribution of monomer molecules on the surface of the substrate W is significantly affected by the uneven distribution of 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 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 stages of film formation.

Furthermore, as the film formation progresses, as shown in FIG. 5B, for example, monomer molecules are adsorbed to the surface of the substrate W and the surface of the polymer film 30. However, the surface of the polymer film 30 is less wettable (hydrophobic) than the surface of the substrate W. For example, the contact angle of the surface of silicon is approximately 31.2°, whereas the contact angle of the surface of the polyurea polymer film 30 is approximately 73.1°. As a result, more monomer molecules are adsorbed to the surface of the substrate W than to the polyurea polymer film 30. This is thought to improve the uniformity of the film.

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 approximately 29.0°, and the contact angle of the surface of a silicon oxide film is approximately 50.9°.

Furthermore, as the film formation progresses further, the surface of the substrate W is covered with a polymer film 30, as shown in Figures 5C and 5D, for example, 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 parts of the surface of the polymer film 30 are easy to detach, but the monomer molecules adsorbed to the concave parts 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 less pronounced, and it is believed that the uniformity of the film thickness is further improved.

[Relationship between deposition rate and uniformity]
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, condition 2 indicates a condition in which the deposition rate is relatively high, and condition 3 indicates a condition in which the deposition rate is relatively high after the deposition rate is relatively low. In addition, condition 3 indicates a condition in which the deposition rate is relatively high after the deposition rate is relatively low.

In condition 1, the pressure in the chamber 11 is set low as one of the conditions that results in a lower deposition rate than in condition 2. In addition to lowering the pressure, other conditions that can result in a lower deposition rate include, for example, increasing the temperature of the substrate W, lowering the flow rate of at least one type of monomer gas, and lowering the concentration of at least one type of monomer gas.

In the example of FIG. 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 condition is switched to condition 2 to form a further 15.0 nm film.

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 deposition is performed under condition 1, where the deposition rate is low at the beginning of film deposition, 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 of condition 1.

In addition, because condition 3 has a higher deposition rate than condition 1, it is possible to achieve a higher throughput than condition 1 while maintaining the same uniformity as condition 1. In this embodiment, as in condition 3, film formation is performed under conditions with a low deposition rate at the beginning of film formation, and then film formation is performed under conditions with a high deposition rate. Therefore, in this embodiment, it is possible to improve the uniformity of the film thickness, and to shorten the time required to form a polymer film of a predetermined thickness on the substrate W, compared to the case where film formation is continued under conditions with a low deposition rate.

Figures 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 Figures 7 and 8, the results of film formation under conditions of a high deposition rate are shown as a comparative example, and the results of film formation under conditions of a low deposition rate at the beginning of film formation and then under conditions of a high deposition rate are shown as an embodiment.

As shown in Figures 7 and 8, for all film thicknesses, the present embodiment has better (smaller) film thickness uniformity (WiW ± [%]) than the comparative example. For example, as shown in Figure 8, the film formation method of the present embodiment can suppress the film thickness uniformity (WiW ± [%]) to 5% or less.

In addition, in this embodiment, although film formation is performed under conditions with a low deposition rate in the early stages of film formation, the time for film formation under conditions with a low deposition rate is not very long, so the overall deposition rate is not significantly different from that of the comparative example. Therefore, in this embodiment, it is possible to improve the uniformity of the film thickness while suppressing a decrease in throughput.

Figure 9 is a flowchart showing an example of a film formation method. The film formation method illustrated in Figure 9 is realized by the control unit 20 controlling each part of the film formation apparatus 10.

First, the substrate W is loaded into the chamber 11 (step S10). In step S10, the control unit 20 controls, for example, a lift pin drive mechanism (not shown) so that the tip of the lift pin (not shown) protrudes from the upper surface of the stage 17. The control unit 20 then controls a gate valve (not shown) that opens and closes an opening (not shown) formed in the side wall of the chamber 11 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 pin. The control unit 20 then controls the lift pin drive mechanism so that the lift pin descends. As a result, the lift pin descends and the substrate W is placed on the stage 17. The control unit 20 then controls the gate valve to close the gate valve.

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° C.
Flow rate of isocyanate vapor: 10 sccm
Amine vapor flow rate: 20 sccm
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

Here, the relationship between the polymer film thickness and deposition rate 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. It is preferable that the deposition rate of the polymer film in the first film formation process is, for example, 5 nm/min or less.

Next, a second film forming process is performed (step S12). The second film forming process in step S12 is performed under a condition 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° C.
Flow rate of isocyanate vapor: 10 sccm
Amine vapor flow rate: 20 sccm
Pressure in chamber 11: 1.0 Torr (about 133.3 Pa)
Flow rate of additive gas (e.g., nitrogen gas) in chamber 11: 400 sccm
Processing time: 43 seconds

Next, the substrate W is removed 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. The control unit 20 then controls a gate valve (not shown) to open it, and the substrate W is removed from the chamber 11 by a transfer robot (not shown) through an opening formed in the side wall of the chamber 11. The control unit 20 then controls the gate valve to close it, and controls the lift pin drive mechanism to lower the lift pins. The film formation method shown in this flowchart then ends.

The above describes the embodiment. As described above, the film formation method in the embodiment includes a first film formation process and a second film formation process. In the first film formation process, 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 formation process, a polymer film is further formed on the polymer film formed in the first film formation process at a higher deposition rate than the first film formation process 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.

In addition, in the above embodiment, the pressure in the chamber in the first film formation process is lower than the pressure in the chamber in the second film formation process. This can improve the uniformity of the film thickness of the polymer formed on the substrate.

In addition, in the above embodiment, the temperature of the substrate in the first film formation process is higher than the temperature of the substrate in the second film formation process. This can improve the uniformity of the film thickness of the polymer formed on the substrate.

In addition, in the above-described embodiment, the flow rates of the first monomer and second monomer gases in the first film-forming process are less than the flow rates of the first monomer and second monomer gases in the second film-forming process. This can improve the uniformity of the film thickness of the polymer formed on the substrate.

In addition, in the above-described embodiment, the concentrations of the first monomer and second monomer gases supplied into the chamber in the first film-forming process are lower than the concentrations of the first monomer and second monomer gases supplied into the chamber in the second film-forming process. This can improve the uniformity of the film thickness of the polymer formed on the substrate.

In addition, in the above embodiment, the deposition rate in the first film formation process is 5 nm/min or less. This can improve the uniformity of the film thickness of the polymer formed on the substrate.

In the above-described embodiment, at least a portion of the surface of the substrate is silicon, a silicon nitride film, or a silicon oxide film. This can improve the uniformity of the film thickness of the polymer formed on the substrate.

In addition, in the above embodiment, a polymer film having a thickness of 0.6 nm to 5 nm is formed in the first film formation process. This can improve the uniformity of the polymer film thickness formed on the substrate.

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 a first monomer and a second monomer gas 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 the first monomer and the second monomer gas 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.

[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.

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 also be applied to the case of forming a polymer film on the surfaces of two members having surfaces with different surface wettability.

Consider the case where a polymer film is formed on a substrate W having a member 40 with a surface that is relatively highly wettable (hydrophilic) and a member 41 with a surface that is relatively lowly wettable (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, the monomer is excessively adsorbed onto the surface of the member 40 in the early stages of film formation, and as shown in FIG. 11, for example, the film 30 on the surface of the member 40 becomes thick. This reduces the uniformity of the thickness of the polymer film 30 across the entire substrate W.

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 the 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 (hydrophobic) property, the surface of the member 40 is covered with the polymer film 30, and therefore the difference in surface wettability is reduced across the entire substrate W. Furthermore, by forming the film under conditions of a high deposition rate, the difference in thickness between the polymer film 30 formed on the member 40 and 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 across the entire substrate W can be improved.

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).

When a polymer film 30 is formed on a substrate W having the structure 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 stages of film formation, as shown in FIG. 14B, for example. Therefore, if film formation of the polymer film 30 continues under the same conditions, voids 31 may be formed between the structures, as shown in FIG. 14C, for example.

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 member 50 having a highly wettable (hydrophilic) surface and the surface of the substrate W 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 is small. Then, by forming the film under conditions of a high deposition rate, 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.

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 approximately 56.2°, and the contact angle of the surface of the carbon-containing silicon oxide film is approximately 129.1°.

In the above embodiment, a polymer film having a urea bond (-NH-CO-NH-) is formed on the surface of the substrate W using isocyanate as the first monomer and 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 epoxide as the first monomer and 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 isocyanate as the first monomer and 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 acyl halide as the first monomer and 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 carboxylic anhydride as the first monomer and amine as the second monomer.

The embodiments disclosed herein should be considered as illustrative in all respects and not restrictive. 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.

The following additional notes are provided with respect to the above embodiment:

(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;
and a second film formation process for further forming a polymer film on the polymer film formed in the first film formation process at a deposition rate higher than that of the first film formation process by supplying the first monomer and the second monomer into the chamber.
(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 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.
(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 method according to claim 1, wherein a deposition rate in the first film formation step is 5 nm/min or less.
(Appendix 7)
7. The method of 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 method for forming a film according to claim 1, wherein the first film-forming step forms a film of the polymer having a thickness of 0.6 nm to 5 nm.
(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 first monomer gas and a second monomer gas into the chamber;
A control unit.
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 formation process for further forming a polymer film on the polymer film formed in the first film formation process at a deposition rate higher than that of the first film formation process by supplying gases of the first monomer and the second monomer into the chamber by controlling the gas supply unit.

W substrate 10 film forming apparatus 11 chamber 12 exhaust mechanism 13 gas supply unit 130 source material supply source 131 vaporizer 14 pipe 16 shower head 17 stage 20 control unit 30 film 31 void 40 member 41 member 50 member 51 member

Claims (14)

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;
and a second film formation process for further forming a polymer film on the polymer film formed in the first film formation process at a deposition rate higher than that of the first film formation process by supplying the first monomer and the second monomer into the chamber. The film forming method according to claim 1, wherein 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. The film formation method according to claim 1 or 2, wherein the temperature of the substrate in the first film formation process is higher than the temperature of the substrate in the second film formation process. The film forming method according to claim 1 or 2, wherein the flow rates of the first monomer and the second monomer gas in the first film forming process are less than the flow rates of the first monomer and the second monomer gas in the second film forming process. The film forming method according to claim 1 or 2, wherein the concentration of the first monomer and the second monomer gas supplied into the chamber in the first film forming process is lower than the concentration of the first monomer and the second monomer gas supplied into the chamber in the second film forming process. The film formation method according to claim 1 or 2, wherein the deposition rate in the first film formation step is 5 nm/min or less. The film forming method according to claim 1 or 2, wherein at least a portion of the surface of the substrate is silicon, a silicon nitride film, or a silicon oxide film. The film forming method according to claim 1 or 2, wherein in the first film forming step, a film of the polymer having a thickness of 0.6 nm to 5 nm is formed. 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. 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. 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. 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. 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. 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;
A control unit.
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 formation process for further forming a polymer film on the polymer film formed in the first film formation process at a deposition rate higher than that of the first film formation process by supplying gases of the first monomer and the second monomer into the chamber by controlling the gas supply unit.

Images