Tabernacle Method and Tabernacle Device

Abstract

A film formation method comprises the following (A) to (D): (A) Prepare a substrate having a first region on which a first film is exposed and a second region on which a second film formed of a material different from the first film is exposed. (B) Form a step on the surface such that the first region is higher than the second region. (C) Supply a liquid to the surface on which the step is formed. (D) Supply a processing gas that chemically changes the liquid to the surface, thereby moving the liquid from the second region to the first region through the reaction between the processing gas and the liquid, so as to selectively form a film on the first region relative to the second region.

Description

Technology Field

[0001] The present disclosure relates to a tabernacle method and a tabernacle apparatus. Background Technology

[0002] The film formation method described in Patent Document 1 includes a process of preparing a substrate having a first region in which a first material is exposed and a second region in which a second material different from the first material is exposed, a process of selectively forming a desired target film in the first region among the first region and the second region, and a process of removing a product formed in the second region during the formation of the target film by supplying ClF3 gas to the substrate. Prior art literature

[0003] Japanese Patent Publication No. 2020-147829 The problem to be solved

[0004] One aspect of the present disclosure provides a technique for selectively forming a film in a first region among a first region in which a first film is exposed and a second region in which a second film formed of a material different from the first film is exposed. means of solving the problem

[0005] A method for forming a film according to one embodiment of the present disclosure comprises the following (A) to (D): (A) A substrate is prepared having a first region on which a first film is exposed and a second region on which a second film formed of a material different from the first film is exposed. (B) A step is formed on the surface such that the first region is higher than the second region. (C) A liquid is supplied to the surface on which the step is formed. (D) A processing gas that chemically changes the liquid is supplied to the surface, and the liquid is moved from the second region to the first region by the reaction between the processing gas and the liquid, thereby selectively forming a film on the first region relative to the second region. Effects of the invention

[0006] According to one aspect of the present disclosure, among a first region in which a first film is exposed and a second region in which a second film formed of a material different from the first film is exposed, a film may be selectively formed in the first region. Brief explanation of the drawing

[0007] FIG. 1 is a flowchart illustrating a tabernacle method according to one embodiment. FIG. 2a is a cross-sectional view illustrating an example of step S1. FIG. 2b is a cross-sectional view illustrating an example of the first step of step S2. FIG. 2c is a cross-sectional view illustrating an example of the second step of step S2. FIG. 2d is a cross-sectional view illustrating an example of the third step of step S2. FIG. 3a is a cross-sectional view illustrating an example of step S3. FIG. 3b is a cross-sectional view illustrating an example of the first step of step S4. FIG. 3c is a cross-sectional view illustrating an example of the second step of step S4. FIG. 4a is a cross-sectional view illustrating an example immediately preceding step S7. FIG. 4b is a cross-sectional view illustrating an example immediately after step S7. FIG. 5a is a cross-sectional view illustrating a modified example of step S1. FIG. 5b is a cross-sectional view illustrating a modified example of step S2. FIG. 5c is a cross-sectional view illustrating a modified example of step S3. FIG. 5d is a cross-sectional view illustrating a variation of the first step of step S4. FIG. 6a is a cross-sectional view illustrating a variation of the second stage of step S4. FIG. 6b is a cross-sectional view illustrating an example of deformation immediately prior to step S7. FIG. 6c is a cross-sectional view illustrating an example of deformation immediately after step S7. FIG. 7 is a cross-sectional view illustrating a tabernacle apparatus according to one embodiment. Figure 8a is an SEM image of the substrate for Example 1, after step S3 and before step S4. Figure 8b is an SEM image of the substrate for Example 1, and an SEM image during step S4. Figure 8c is an SEM image of the substrate for Example 1 and an SEM image after step S4. Figure 9a is an SEM image of the substrate for Example 2, after step S3 and before S4. Figure 9b is an SEM image of the substrate for Example 2 and an SEM image after step S4. Figure 10 is a diagram illustrating the relationship between the processing time of Step S9 (Table 2) regarding Example 3 and the thickness of the liquid in the depression. Figure 11a is an SEM image of the substrate after processing for Example 4. Figure 11b is an SEM image of the substrate after processing for Example 5. Fig. 11c is an SEM image of the substrate after processing for Example 6. Fig. 11d is an SEM image of the substrate after processing for Example 7. Figure 12a is an SEM image of the substrate after processing for Example 8. Figure 12b is an SEM image of the substrate after processing for Example 9. Fig. 12c is an SEM image of the substrate after processing for Example 10. Figure 13a is an SEM image of the substrate after processing for Example 11. Figure 13b is an SEM image of the substrate after processing for Example 12. Figure 14a is an SEM image of the substrate after processing for Example 13. Figure 14b is an SEM image of the substrate after processing for Example 14. Figure 15 is an SEM image of the substrate after processing for Example 17. Figure 16 is an SEM image of the substrate after processing for Example 18. Specific details for implementing the invention

[0008] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In addition, in each drawing, identical or corresponding components are given the same reference numerals, and descriptions may be omitted.

[0009] Referring to FIG. 1 and others, an example of a tabernacle method is described. As illustrated in FIG. 1, the tabernacle method has, for example, steps S1 to S7. Additionally, the tabernacle method may have at least steps S1 to S4. Furthermore, the tabernacle method may have additional steps other than steps S1 to S7.

[0010] In step S1 of FIG. 1, a substrate (W) is prepared as shown in FIG. 2a. The substrate (W) is prepared having a first region (A1) on its surface where a first film (W1) is exposed, and a second region (A2) on which a second film (W2) formed of a material different from the first film (W1) is exposed. The first region (A1) and the second region (A2) are provided on one side of the substrate (W) in the plate thickness direction. The first region (A1) and the second region (A2) may not have a step at the boundary and may be flat.

[0011] The substrate (W) comprises, for example, a silicon wafer not illustrated, and a first film (W1) and a second film (W2) are formed on the silicon wafer. The substrate (W) may comprise a compound semiconductor wafer or a glass substrate instead of a silicon wafer. The compound semiconductor wafer is not particularly limited, but is, for example, a GaAs wafer, a SiC wafer, a GaN wafer, or an InP wafer.

[0012] The first film (W1) is, for example, an insulating film. The insulating film is, for example, a SiO film, a SiN film, a SiCO film, a SiCN film, a SiON film, or a SiC film. Here, a SiO film means a film containing silicon (Si) and oxygen (O). The atomic ratio of Si to O in the SiO film is not limited to 1:1. The same applies to SiO films, SiN films, SiCO films, SiCN films, SiON films, or SiC films.

[0013] Meanwhile, the second film (W2) is, for example, a conductive film. The conductive film is a metal film or a metal nitride film. The metal film is, for example, a Cu film, a Ru film, a Co film, a W film, or a Ti film. The metal nitride film is, for example, a TiN film or a TaN film. Here, a TiN film means a film containing titanium (Ti) and nitrogen (N). The atomic ratio of Ti to N in a TiN film is not limited to 1:1. The same applies to a TaN film.

[0014] In this embodiment, the first film (W1) is an insulating film and the second film (W2) is a conductive film, but the insulating film and the conductive film may be opposite, so the first film (W1) may be a conductive film and the second film (W2) may be an insulating film. Also, the number of first regions (A1) is one in FIG. 2a, but may be multiple. For example, two first regions (A1) may be arranged with a second region (A2) in between. The first region (A1) and the second region (A2) are adjacent in FIG. 2a, but may be spaced apart.

[0015] The substrate (W) may have a third region not illustrated on its surface in addition to the first region (A1) and the second region (A2). The third region is a region in which a third film of a material different from the first film (W1) and the second film (W2) is exposed. The third region may be positioned between the first region (A1) and the second region (A2), or outside the first region (A1) and the second region (A2).

[0016] For example, the substrate (W) may also have a third region on its surface in which a barrier film not illustrated is exposed. In this case, the third region is formed between the first region (A1) and the second region (A2). The barrier film is formed along the recess of the insulating film to suppress metal diffusion from the metal film embedded in the recess of the insulating film to the insulating film. The barrier film is not particularly limited, but is, for example, a TaN film or a TiN film.

[0017] Additionally, the substrate (W) may also have a fourth region on its surface where an unillustrated liner film is exposed. In this case, the fourth region is formed between the second region (A2) and the third region. The liner film is formed on the barrier film to support the formation of the metal film. The metal film is formed on the liner film. The liner film is not particularly limited, but is, for example, a Co film or a Ru film.

[0018] In step S2 of FIG. 1, as illustrated in FIG. 2b to 2d, a step is formed on the surface of the substrate (W) such that the first region (A1) is higher than the second region (A2). For example, first, as illustrated in FIG. 2b, an organic compound is supplied to the surface of the substrate (W) to selectively form a self-assembled monolayer (SAM) (W3) in the second region (A2) relative to the first region (A1). In this embodiment, the organic compound is supplied in a gaseous state, but it may be supplied in a liquid state.

[0019] The organic compound that serves as the raw material for the self-organizing monolayer (W3) is appropriately selected according to the materials of the first film (W1) and the second film (W2). When the first film (W1) is an insulating film and the second film (W2) is a conductive film, the organic compound is, for example, a thiol-based compound. The thiol-based compound is, for example, a compound represented by the general formula R-SH. The thiol group (SH) is more easily chemically adsorbed onto the conductive film compared to the insulating film.

[0020] Here, R is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and some of the hydrogen may be substituted with a halogen. Halogens include fluorine, chlorine, bromine, or iodine, etc. Thiol compounds are, for example, CF3(CF2) X (CH2)2SH(X=an integer from 0 to 17), or CH3(CH2) X SH is an integer from 1 to 19.

[0021] Additionally, step S2 includes forming a second insulating film (W4) in the first region (A1) while inhibiting the formation of the second insulating film (W4) in the second region (A2) using a self-organizing monolayer (W3) as illustrated in FIG. 2c. The second insulating film (W4) is formed, for example, by the Chemical Vapor Deposition (CVD) method or the Atmospheric Layer Deposition (ALD) method.

[0022] The second insulating film (W4) is, for example, a SiO film, an AlO film, a SiN film, a ZrO film, or an HfO film. Here, an AlO film means a film containing aluminum (Al) and oxygen (O). The atomic ratio of Al to O in the AlO film is not limited to 1:1. The same applies to SiO films, SiN films, ZrO films, and HfO films. The second insulating film (W4) may be a film of the same material as the first insulating film (W1), or it may be a film of a different material.

[0023] When forming an AlO film by the ALD method, an Al-containing gas such as TMA (trimethylaluminum) gas and an oxidizing gas such as water vapor (H2O gas) are alternately supplied to the surface of the substrate (W). Since water vapor is not adsorbed onto the hydrophobic self-organizing monolayer film (W3), AlO is selectively deposited in the first region (A1). In addition to the Al-containing gas and the oxidizing gas, a reforming gas such as hydrogen gas may be supplied to the substrate (W). These source gases may be plasmafied to promote a chemical reaction. Furthermore, these source gases may be heated to promote a chemical reaction.

[0024] When forming an HfO film by the ALD method, an Hf-containing gas, such as tetrakisdimethylamide hafnium (TDMAH: Hf[N(CH3)2]4) gas, and an oxidizing gas, such as water vapor (H2O gas), are alternately supplied to the surface of the substrate (W). Since water vapor is not adsorbed onto the hydrophobic self-organizing monolayer (W3), HfO is selectively deposited in the first region (A1). In addition to the Hf-containing gas and the oxidizing gas, a reforming gas, such as hydrogen gas, may be supplied to the substrate (W). These source gases may be plasmafied to promote a chemical reaction. Furthermore, these source gases may be heated to promote a chemical reaction.

[0025] Additionally, step S2 includes removing the self-organizing monolayer (W3) as illustrated in FIG. 2d. The removal method may be general, and, for example, an ashing method using ozone, etc. may be used. Additionally, it may be removed using plasma hydrogen, plasma oxygen, or plasma ammonia.

[0026] However, as shown in FIG. 2c, if the formation of the second insulating film (W4) in the second region (A2) is inhibited by using a self-organizing monolayer (W3), and the second insulating film (W4) is formed in the first region (A1), as shown in FIG. 2d, the second insulating film (W4) may protrude horizontally from the first region (A1). The thicker the film thickness of the second insulating film (W4), the more likely the second insulating film (W4) is to protrude horizontally. If the second insulating film (W4) is etched, the portion of the second insulating film (W4) that protrudes horizontally from the first region (A1) can be removed, but the film thickness of the second insulating film (W4) becomes thin.

[0027] Therefore, the film formation method of the present embodiment expands the step formed in step S2 as described below. The substrate surface (Wa) before expanding the step includes adjacent concave portions (Wb) and convex portions (Wc), as shown in FIG. 2d. The concave portion (Wb) is a trench or a hole, etc. The hole includes a via hole. The convex portion (Wc) may be a filler or a pin, etc.

[0028] The substrate surface (Wa) includes, for example, a concave bottom surface (Wb1), a concave side surface (Wb2), and a convex top surface (Wc1). For example, the convex top surface (Wc1) is a flat surface, and the concave portion (Wb) becomes concave from the convex top surface (Wc1). The depth of the concave portion (Wb) indicates the size of the step difference. The concave bottom surface (Wb1) is formed by a conductive film, which is a second film (W2). Meanwhile, the concave side surface (Wb2) and the convex top surface (Wc1) are formed by a second insulating film (W4).

[0029] In step S3 of FIG. 1, a liquid (L) is supplied to the substrate surface (Wa) as shown in FIG. 3a. In FIG. 3a, the liquid (L) is filled only in the concave portion (Wb) and does not cover the convex normal surface (Wc1), but it may overflow from the concave portion (Wb) and cover the convex normal surface (Wc1).

[0030] It is desirable for the liquid (L) to have strong intermolecular forces. The stronger the intermolecular forces, the stronger the cohesive force. If the cohesive force of the liquid (L) is high, the evaporation of the liquid (L) can be prevented. The intermolecular force of the liquid (L) is, for example, 30 kJ / mol or higher.

[0031] The liquid (L) is, for example, a halide. The liquid halide is formed, for example, by the reaction of a source gas of the halide and a reaction gas that reacts with the source gas. The formation of the liquid (L) may be facilitated by plasmaizing both the source gas and the reaction gas, or by plasmaizing the reaction gas. The source gas is, for example, TiCl4 gas, and the reaction gas is, for example, H2 gas.

[0032] TiCl4 gas and H2 gas are generally used for the formation of a Ti film, rather than for the formation of a liquid (L). The Ti film is formed, for example, by the CVD (Chemical Vapor Deposition) method or the ALD (Atmoic Layer Deposition) method. In the CVD method, TiCl4 gas and H2 gas are supplied simultaneously to the substrate (W). Meanwhile, in the ALD method, TiCl4 gas and H2 gas are supplied alternately to the substrate (W). According to the CVD or ALD method, it is presumed that the following equations (1) to (3) contribute to the formation of the Ti film.

[0033] TiCl4 + H2 → TiH x Cl y … (1)

[0034] TiH x Cl y →TiCl2+HCl … (2)

[0035] TiCl2+H2→Ti+HCl … (3)

[0036] In addition, in the above equations (2) and (3), TiCl2 may be TiCl or TiCl3.

[0037] In the formation of the Ti film, the temperature of the substrate (W) is controlled to be 400°C or higher. As a result, the reactions of the above formulas (1) to (3) proceed sequentially, and the Ti film is formed.

[0038] Meanwhile, in the formation of the liquid (L), the temperature of the substrate (W) is controlled to -100°C to 390°C, preferably 20°C to 350°C. As a result, the reaction of formula (2) and the reaction of (3) are suppressed, so TiH x Cl y A liquid (L) containing [the component] is formed. The liquid (L) may contain Ti, TiCl, TiCl2, TiCl3, or TiCl4. The temperature of the substrate (W) should be lower than the decomposition point of the liquid (L).

[0039] In addition, the source gas is not limited to TiCl4 gas. For example, the source gas may be a silicon halogenated gas such as SiCl4 gas, Si2Cl6 gas, SiHCl3 gas, or a metal halogenated gas such as WCl4 gas, VCl4 gas, AlCl3 gas, MoCl5 gas, SnCl4 gas, GeCl4 gas. The source gas may contain a halogen, and as the halogen, it may contain bromine (Br), iodine (I), or fluorine (F), etc., instead of chlorine (Cl). When the temperature of the substrate (W) is low, the reaction similar to that of Equation (1) above mainly proceeds with these source gases, so a liquid (L) of the halogenate is formed.

[0040] In addition, the reaction gas is not limited to H2 gas. The reaction gas may be any gas capable of forming a liquid (L) upon reaction with the source gas. For example, the reaction gas may be D2 gas. The reaction gas may be supplied together with an inert gas such as argon gas.

[0041] Step S3 includes, for example, simultaneously supplying a source gas and a reaction gas to a substrate (W). In this case, Step S3 may also include plasmaizing both the source gas and the reaction gas. Plasmaization can promote the reaction between the source gas and the reaction gas. Additionally, plasmaization makes it easier to form a liquid (L) at a low substrate temperature.

[0042] Additionally, in this embodiment, Step S3 includes supplying the source gas and the reaction gas simultaneously to the substrate (W), but it may also include supplying the source gas and the reaction gas alternately to the substrate (W). In the latter case, Step S3 may also include plasmaizing the reaction gas. Plasmaization can promote the reaction between the source gas and the reaction gas. Additionally, plasmaization makes it easier to form the liquid (L) at a low substrate temperature. Additionally, Step S3 may include supplying only the source gas to the substrate (W).

[0043] The liquid (L) may be one having strong intermolecular forces and may be an ionic liquid, a metal in a liquid state, or a polymer in a liquid state. The metal may be a pure metal or an alloy. The polymer may be, for example, Si2Cl6 gas, SiCl4 gas, SiHCl3 gas, SiH2Cl2 gas, SiH3Cl gas, SiH4 gas, Si2H6 gas, Si3H8 gas, Si4H 10The oligomer or polymer formed by polymerizing two or more molecules of gas, cyclohexasilane gas, tetraethoxysilane (TEOS) gas, dimethyldiethoxysilane (DMDEOS) gas, 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS) gas, or trisilylamine (TSA) gas may be, for example, polysiloxane, polysilane, or polysilazane. Additionally, the liquid (L) may be silanol, etc. These liquids (L) are supplied to the concave portion (Wb) of the substrate (W) by a spin coating method, or synthesized inside a processing vessel that accommodates the substrate (W) and supplied to the concave portion (Wb) of the substrate (W).

[0044] In step S4 of FIG. 1, as shown in FIG. 3b, a treatment gas (G) that chemically changes the liquid (L) is supplied to the substrate surface (Wa), and the liquid (L) is moved from the concave portion (Wb) to the convex normal surface (Wc1) by the reaction between the treatment gas (G) and the liquid (L), and the step of the substrate surface (Wa) is expanded by forming a film (W5) on the convex normal surface (Wc1) as shown in FIG. 3c. The size of the step is represented by the depth of the concave portion (Wb).

[0045] The film (W5) may also be formed on the concave side (Wb2) as shown in FIG. 3c. If the thickness of the film (W5) on the concave side (Wb2) is thinner than the thickness of the film (W5) on the convex normal surface (Wc1), for example, even if the film (W5) is isotropically etched, the step difference of the substrate surface (Wa) can be expanded by the formation of the film (W5).

[0046] Additionally, although not shown, the film (W5) may also be formed on the bottom surface of the concave portion (Wb1). If the thickness of the film (W5) on the bottom surface of the concave portion (Wb1) is thinner than the thickness of the film (W5) on the top surface of the convex portion (Wc1), the step difference of the substrate surface (Wa) can be expanded.

[0047] The film (W5) may be a solid or a viscous material. The thickness of the film (W5) can be controlled by the amount of liquid (L) supplied. The film (W5) may have insulating properties. The insulating film (W5) is hereinafter also referred to as the third insulating film (W5). The third insulating film (W5) is, for example, a metal oxide film or a metal nitride film.

[0048] The processing gas (G) is supplied, for example, from above the substrate surface (Wa) and reacts with the liquid (L). The liquid (L) reacts with the processing gas (G) and undergoes a chemical change. Since the chemical change proceeds slowly from the surface of the liquid (L), a difference in surface tension occurs, and volume expansion or contraction occurs from the surface of the liquid (L), causing the liquid (L) to become unstable and convection to occur. As the surface of the liquid (L) changes into a material with high surface tension due to the reaction with the processing gas (G), the liquid (L) moves toward the convex normal surface (Wc1). Additionally, the liquid (L) moves toward the convex normal surface (Wc1) driven by the increase or decrease in volume caused by the chemical change on the surface of the liquid (L). Although not illustrated, all of the liquid (L) may eventually move to the convex normal surface (Wc1) through the reaction with the processing gas (G).

[0049] In addition, during the chemical change of the liquid (L), degassing occurs from the liquid (L) due to the reaction between the liquid (L) and the processing gas (G). The movement of the liquid (L) caused by the generation of degassing is also considered to be a factor contributing to the movement of the liquid (L). Furthermore, minute vibrations of the substrate (W) are also considered to be a factor contributing to the movement of the liquid (L).

[0050] The treatment gas (G) contains elements that are introduced into the liquid (L) by, for example, through a reaction with the liquid (L). That is, the treatment gas (G) contains elements that are introduced into the membrane (W5). For example, oxygen from the treatment gas (G) is introduced into the liquid (L) to obtain a membrane (W5) that is an oxide. Or, nitrogen from the treatment gas (G) is introduced into the liquid (L) to obtain a membrane (W5) that is a nitride. It is sufficient that elements in the treatment gas (G) are introduced into the liquid (L), and in the process, elements constituting the liquid (L) may be degassed.

[0051] For example, the treatment gas (G) includes an oxygen-containing gas. The oxygen-containing gas includes oxygen as an element introduced into the liquid (L). The oxygen-containing gas may also include nitrogen as an element introduced into the liquid (L). The oxygen-containing gas includes, for example, O2 gas, O3 gas, H2O gas, NO gas, or N2O gas.

[0052] The treatment gas (G) may include a nitrogen-containing gas. The nitrogen-containing gas includes nitrogen as an element introduced into the liquid (L). The nitrogen-containing gas includes, for example, N2 gas, NH3 gas, N2H4 gas, or N2H2 gas.

[0053] The treatment gas (G) may include a hydride gas. The hydride gas includes an element bonded to hydrogen, such as Si, Ge, B, C, or P, as an element introduced into the liquid (L). The hydride gas includes, for example, a hydrocarbon gas such as SiH4 gas, Si2H6 gas, GeH4 gas, B2H6 gas, C2H4 gas, or PH3 gas.

[0054] The treatment gas (G) may degas the elements constituting the liquid (L) by reacting with the liquid (L). For example, the treatment gas (G) includes a reducing gas. The reducing gas is, for example, hydrogen (H2) gas or deuterium (D2) gas.

[0055] The treatment gas (G) may be supplied together with an inert gas such as argon gas.

[0056] Step S4 may include plasmaizing the treatment gas (G). Plasmaization can promote the reaction between the treatment gas (G) and the liquid (L).

[0057] In step S5 of FIG. 1, the film (W5) formed in step S4 is modified. The film (W5) after modification has superior chemical resistance compared to the film (W5) before modification. For example, the film (W5) after modification has a lower etching rate with respect to dilute hydrofluoric acid (DHF) compared to the film (W5) before modification.

[0058] The modification of the membrane (W5) comprises, for example, at least one of the following (A) to (B). (A) Reduce the halogen element or hydrogen element in the membrane (W5). (B) Densify the membrane (W5). Densification of the membrane (W5) can be achieved, for example, by terminating the unbonded loss of the membrane (W5) with an element contained in the modification gas, or by promoting the bonding of existing elements in the membrane (W5).

[0059] In step S5, a reforming gas may be supplied to the membrane (W5). If the reforming gas of S5 and the treatment gas (G) of S4 are the same gas, they are supplied under different conditions. Specifically, for example, while the reforming gas is plasmafied, the treatment gas (G) is not plasmafied. Alternatively, the reforming gas is supplied at a higher temperature or higher pressure compared to the treatment gas (G).

[0060] However, the reforming gas of S5 and the treatment gas (G) of S4 may be different gases. For example, the treatment gas (G) is nitrogen gas and is plasmafied, whereas the reforming gas is ammonia (NH3) gas and is plasmafied, or hydrazine (N2H4) gas. Alternatively, the treatment gas (G) is oxygen (O2) gas, while the reforming gas is ozone (O3) gas or water vapor (H2O).

[0061] In step S6 of FIG. 1, it is checked whether the first cycle has been performed M times (M is an integer greater than or equal to 1). One first cycle includes steps S3 to S5. Additionally, the first cycle may include at least steps S3 to S4 and may not include step S5. M may be an integer greater than or equal to 2.

[0062] If the number of times the first cycle is performed is less than M (step S6, "No"), the first cycle is performed again because the magnitude of the step difference on the substrate surface (Wa) is less than the target value. M is not particularly limited, but is, for example, 2 to 30, and preferably 5 to 20.

[0063] During the first cycle, which is performed M times, adjacent concave sides (Wb2) must not be connected to each other, and the concave (Wb) must not be blocked. This is because if the concave (Wb) becomes blocked, the step difference disappears. An upper limit value of M is set so that the concave (Wb) does not become blocked.

[0064] Meanwhile, when the number of times the first cycle is performed reaches M (Step S6, "Yes"), the magnitude of the step difference on the substrate surface (Wa) has reached the target value, so the processing after Step S7 is performed. An example of the substrate (W) immediately before Step S7 is shown in FIG. 4a, and an example of the substrate (W) immediately after Step S7 is shown in FIG. 4b.

[0065] In step S7 of FIG. 1, a portion of the film (W5) is etched. By etching, the portions of the second insulating film (W4) and the third insulating film (W5) that protrude from the first region (A1) can be removed, as shown in FIG. 4b. After etching, the bottom surface of the concave portion (Wb1) is formed by the conductive film, which is the second film (W2), the side surface of the concave portion (Wb2) is formed by the second insulating film (W4) and the third insulating film (W5), and the top surface of the convex portion (Wc1) is formed by the third insulating film (W5).

[0066] According to the present embodiment, a third insulating film (W5) is formed on the second insulating film (W4) before etching the portion protruding from the first region (A1) of the second insulating film (W4). The thickness of the insulating film can be increased by the third insulating film (W5), thereby allowing for a reduction in the thickness of the insulating film due to etching. As a result, the thickness of the insulating film can be increased without causing the insulating film to protrude from the first region (A1).

[0067] The etching may be either isotropic etching or anisotropic etching. A combination of isotropic etching and anisotropic etching may also be used. Isotropic etching can etch not only the bottom surface of the concave part (Wb1) and the top surface of the convex part (Wc1), but also the side surface of the concave part (Wb2), thereby removing the portion protruding from the first region (A1). Meanwhile, anisotropic etching can selectively etch the bottom surface of the concave part (Wb1) and the top surface of the convex part (Wc1) with respect to the side surface of the concave part (Wb2).

[0068] Etching can be either dry etching or wet etching, but preferably dry etching. In dry etching, an etching gas is supplied to the substrate surface (Wa). In dry etching, H2 gas, O2 gas, or NH3 gas, etc., may be supplied to the substrate surface (Wa) along with the etching gas.

[0069] When dry etching is thermal etching, for example, Cl2 gas, ClF3 gas, F2 gas, or HF gas is used as the etching gas. On the other hand, when dry etching is plasma etching, for example, Cl2 gas, CF4 gas, CHF3 gas, C4F8 gas, or SF6 gas is used as the etching gas to be plasmafied.

[0070] Etching may be performed by alternately supplying etching gas and reaction gas, as in ALE (Atomic Layer Etching). Examples of etching gases used include Cl2 gas, CF4 gas, C4F8 gas, WF6 gas, etc. As reaction gases, Ar gas, He gas, H2 gas, BCl3 gas, etc. are used. The reaction gas may be supplied in a plasma form.

[0071] The second cycle is composed of a first cycle of M times and a step S7 performed after the first cycle of M times. Although the second cycle is performed only once in FIG. 1, it may be performed multiple times. Additionally, etching may be performed after the second cycle is performed multiple times. Finally, the portion of the second insulating film (W4) and the third insulating film (W5) that protrudes from the first region (A1) must be removed.

[0072] However, step S2 of the above embodiment includes selectively forming a second insulating film (W4) on the first region (A1) with respect to the second region (A2). Meanwhile, step S2 of the following modified example includes selectively etching the second region (A2) with respect to the first region (A1) as shown in FIGS. 5a and 5b.

[0073] In this variation as well, the step formed in step S2 is extended. The substrate surface (Wa) before extending the step includes adjacent concave portions (Wb) and convex portions (Wc), as shown in FIG. 5b. The concave portion (Wb) is a trench or a hole, etc. The hole includes a via hole. The convex portion (Wc) may be a filler or a pin, etc.

[0074] The substrate surface (Wa) includes, for example, a concave bottom surface (Wb1), a concave side surface (Wb2), and a convex top surface (Wc1). For example, the convex top surface (Wc1) is a flat surface, and the concave portion (Wb) is concave from the convex top surface (Wc1). The depth of the concave portion (Wb) indicates the size of the step difference. The concave bottom surface (Wb1) is formed by a conductive film, which is a second film (W2). Meanwhile, the concave side surface (Wb2) and the convex top surface (Wc1) are formed by an insulating film, which is a first film (W1).

[0075] Steps S3 to S7 are similar to the above embodiment, so a detailed description is omitted and they are described simply. In Step S3, as shown in FIG. 5c, a liquid (L) is supplied to the substrate surface (Wa). In Step S4, as shown in FIG. 5d, a processing gas (G) that chemically changes the liquid (L) is supplied to the substrate surface (Wa), and the liquid (L) is moved from the concave portion (Wb) to the convex normal surface (Wc1) by the reaction between the processing gas (G) and the liquid (L), and the step difference of the substrate surface (Wa) is expanded by forming a third insulating film (W5) on the convex normal surface (Wc1) as shown in FIG. 6a. In Step S5, the third insulating film (W5) formed in Step S4 is modified. In Step S6, it is checked whether the first cycle has been performed M times (M is an integer greater than or equal to 1). If the number of times the first cycle is performed is less than M (Step S6, "No"), the first cycle is performed again because the magnitude of the step difference on the substrate surface (Wa) is less than the target value. On the other hand, if the number of times the first cycle is performed reaches M (Step S6, "Yes"), the magnitude of the step difference on the substrate surface (Wa) has reached the target value, so the processing after Step S7 is performed. An example of the substrate (W) immediately before Step S7 is shown in FIG. 6b, and an example of the substrate (W) immediately after Step S7 is shown in FIG. 6c. In Step S7, a portion of the third insulating film (W5) is etched. By etching, the portion protruding from the first region (A1) of the third insulating film (W5) can be removed, as shown in FIG. 6c. After etching, the bottom surface of the concave portion (Wb1) is formed by a conductive film which is the second film (W2), the side surface of the concave portion (Wb2) is formed by an insulating film which is the first film (W1) and a third insulating film (W5), and the top surface of the convex portion (Wc1) is formed by the third insulating film (W5).

[0076] Next, with reference to FIG. 7, a membrane device (1) will be described. The membrane device (1) comprises a roughly cylindrical, airtight processing vessel (2). An exhaust chamber (21) is provided in the center of the bottom wall of the processing vessel (2). The exhaust chamber (21) has, for example, a roughly cylindrical shape that protrudes downward. An exhaust pipe (22) is connected to the exhaust chamber (21), for example, from the side of the exhaust chamber (21).

[0077] An exhaust section (24) is connected to the exhaust pipe (22) through a pressure regulating section (23). The pressure regulating section (23) is equipped with a pressure regulating valve, such as a butterfly valve. The exhaust pipe (22) is configured to reduce the pressure inside the processing vessel (2) by means of the exhaust section (24). A return port (25) is provided on the side of the processing vessel (2). The return port (25) is opened and closed by a gate valve (26). The transfer of a substrate (W) between the processing vessel (2) and the return chamber (not shown) is carried out through the return port (25).

[0078] A stage (3) is provided within the processing container (2). The stage (3) is a holding support that holds and supports the substrate (W) horizontally with the surface (Wa) of the substrate (W) facing upward. The stage (3) is formed in a roughly circular shape when viewed in a planar view and is supported by a support member (31). On the surface of the stage (3), a roughly circular concave portion (32) is formed for loading, for example, a substrate (W) with a diameter of 300 mm. The concave portion (32) has an inner diameter slightly larger than the diameter of the substrate (W). The depth of the concave portion (32) is configured to be, for example, approximately equal to the thickness of the substrate (W). The stage (3) is formed by a ceramic material such as aluminum nitride (AlN). Additionally, the stage (3) may be formed by a metal material such as nickel (Ni). In addition, instead of the concave portion (32), a guide ring that guides the substrate (W) may be provided on the periphery of the surface of the stage (3).

[0079] For example, a grounded lower electrode (33) is embedded in the stage (3). A heating mechanism (34) is embedded below the lower electrode (33). The heating mechanism (34) heats the substrate (W) loaded on the stage (3) to a set temperature by being supplied from a power supply unit (not shown) based on a control signal from the control unit (100). If the entire stage (3) is made of metal, the entire stage (3) functions as a lower electrode, so the lower electrode (33) does not need to be embedded in the stage (3). The stage (3) is provided with a plurality (e.g., three) of lifting pins (41) for holding and supporting the substrate (W) loaded on the stage (3) and for lifting and lowering it. The material of the lifting pins (41) may be ceramics such as alumina (Al2O3) or quartz. The lower end of the lifting pins (41) is installed on a support plate (42). The support plate (42) is connected to a lifting mechanism (44) provided on the outside of the processing container (2) via a lifting shaft (43).

[0080] The lifting mechanism (44) is installed, for example, at the bottom of the exhaust chamber (21). A bellows (45) is provided between the opening (211) for the lifting shaft (43) formed on the lower surface of the exhaust chamber (21) and the lifting mechanism (44). The shape of the support plate (42) may be such that it can be lifted without interfering with the support member (31) of the stage (3). The lifting pin (41) is configured to be able to be lifted between the upper surface of the stage (3) and the lower surface of the stage (3) by the lifting mechanism (44).

[0081] A gas supply unit (5) is provided in the ceiling wall (27) of the processing vessel (2) via an insulating member (28). The gas supply unit (5) forms an upper electrode and faces the lower electrode (33). A high-frequency power source (512) is connected to the gas supply unit (5) through a matching device (511). By supplying high-frequency power of 450 kHz to 2.45 GHz, preferably 450 kHz to 100 MHz, from the high-frequency power source (512) to the upper electrode (gas supply unit (5)), a high-frequency electric field is generated between the upper electrode (gas supply unit (5)) and the lower electrode (33), thereby generating a capacitively coupled plasma. The plasma generation unit (51) includes a matching device (511) and a high-frequency power source (512). Additionally, the plasma generating unit (51) is not limited to capacitively coupled plasma and may generate other plasmas such as inductively coupled plasma.

[0082] The gas supply unit (5) is provided with a hollow gas supply chamber (52). On the lower surface of the gas supply chamber (52), a plurality of holes (53) are evenly arranged, for example, to distribute and supply the processing gas into the processing container (2). A heating mechanism (54) is installed above the gas supply chamber (52), for example, in the gas supply unit (5). The heating mechanism (54) is heated to a set temperature by being supplied with power from a power supply unit (not shown) based on a control signal from the control unit (100).

[0083] A gas supply channel (6) is provided in the gas supply room (52). The gas supply channel (6) is connected to the gas supply room (52). Upstream of the gas supply channel (6), gas sources (G61, G62, G63, G64, G65, G66) are connected through gas lines (L61, L62, L63, L64, L65, L66), respectively.

[0084] The gas source (G61) is a gas source of TiCl4 and is connected to the gas supply line (6) through the gas line (L61). In the gas line (L61), a mass flow controller (M61), a storage tank (T61), and a valve (V61) are provided in this order from the gas source (G61) side. The mass flow controller (M61) controls the flow rate of the TiCl4 gas flowing through the gas line (L61). The storage tank (T61) can increase the pressure of the TiCl4 gas within the storage tank (T61) by storing the TiCl4 gas supplied from the gas source (G61) through the gas line (L61) when the valve (V61) is closed. The valve (V61) performs the supply and blocking of the TiCl4 gas to the gas supply line (6) through opening and closing operations.

[0085] The gas source (G62) is an Ar gas source and is connected to the gas supply line (6) through the gas line (L62). In the gas line (L62), a mass flow controller (M62) and a valve (V62) are provided in this order from the gas source (G62) side. The mass flow controller (M62) controls the flow rate of Ar gas flowing through the gas line (L62). The valve (V62) supplies and cuts off Ar gas to the gas supply line (6) by opening and closing operations.

[0086] The gas source (G63) is an O2 gas source and is connected to the gas supply path (6) through the gas line (L63). In the gas line (L63), a mass flow controller (M63) and a valve (V63) are provided in this order from the gas source (G63) side. The mass flow controller (M63) controls the flow rate of O2 gas flowing through the gas line (L63). The valve (V63) supplies and cuts off O2 gas to the gas supply path (6) through opening and closing operations.

[0087] The gas source (G64) is an H2 gas source and is connected to the gas supply line (6) through the gas line (L64). In the gas line (L64), a mass flow controller (M64) and a valve (V64) are provided in this order from the gas source (G64) side. The mass flow controller (M64) controls the flow rate of H2 gas flowing through the gas line (L64). The valve (V64) controls the supply and cutoff of H2 gas to the gas supply line (6) through opening and closing operations.

[0088] The gas source (G65) is a gas source of ClF3 and is connected to the gas supply line (6) through the gas line (L65). In the gas line (L65), a mass flow controller (M65) and a valve (V65) are provided in this order from the gas source (G65) side. The mass flow controller (M65) controls the flow rate of the ClF3 gas flowing through the gas line (L65). The valve (V65) controls the supply and cutoff of ClF3 gas to the gas supply line (6) through opening and closing operations.

[0089] The gas source (G66) is a gas source for the step gas and is connected to the gas supply path (6) through the gas line (L66). In the gas line (L66), a mass flow controller (M66) and a valve (V66) are provided in this order from the gas source (G66) side. The mass flow controller (M66) controls the flow rate of the step gas flowing through the gas line (L66). The valve (V66) supplies and cuts off the step gas to the gas supply path (6) through opening and closing operations.

[0090] The step gas is a gas used to form a step. The step gas is used in combination with, for example, an organic compound that is a raw material for the self-organizing monolayer (W3) and a metal-containing gas or an oxidizing gas (or nitride gas, etc.) that is a raw material for the second insulating film (W4). Alternatively, the step gas is an etching gas that etches the conductive film, which is the first film (W1). If there are multiple step gases, a gas source (G66) and a gas line (L66) are provided for each step gas.

[0091] The film deposition device (1) is equipped with a control unit (100) and a memory unit (101). The control unit (100) is equipped with a CPU, RAM, ROM, etc. (not all shown), and controls the film deposition device (1) comprehensively by executing, for example, a computer program stored in the ROM or memory unit (101) on the CPU. Specifically, the control unit (100) executes a control program stored in the memory unit (101) on the CPU to control the operation of each component of the film deposition device (1), thereby performing film deposition processing on the substrate (W).

[0092] Next, referring again to FIG. 7, the operation of the film formation device (1) will be described. First, the control unit (100) opens the gate valve (26) to transport the substrate (W) into the processing container (2) by means of a transport mechanism and loads it onto the stage (3). The substrate (W) is loaded horizontally with its surface (Wa) facing upward. The control unit (100) withdraws the transport mechanism from the processing container (2) and closes the gate valve (26). Subsequently, the control unit (100) heats the substrate (W) to a predetermined temperature by means of a heating mechanism (34) of the stage (3) and adjusts the pressure inside the processing container (2) to a predetermined pressure by means of a pressure adjustment unit (23). For example, bringing the substrate (W) into the processing container (2) is included in step S1 of FIG. 1.

[0093] Next, in step S2 of FIG. 1, the control unit (100) opens the valve (V66) to supply the step-type gas into the processing vessel (2). The valves (V61, V62, V63, V64, V65) are closed. Additionally, along with the step-type gas, Ar gas or O2 gas, etc., may be supplied into the processing vessel (2). Due to the step-type gas, a concave portion (Wb) and a convex portion (Wc) are formed on the surface (Wa) of the substrate.

[0094] Next, in step S3 of FIG. 1, the control unit (100) opens valves (V61, V62, V64) to simultaneously supply TiCl4 gas, Ar gas, and H2 gas into the treatment vessel (2). Valves (V63, V65, V66) are closed. Due to the reaction between TiCl4 gas and H2 gas, TiH x Cl y Liquid (L) is supplied to the concave portion (Wb) of the substrate (W).

[0095] The specific processing conditions for Step S3 are, for example, as follows.

[0096] TiCl4 gas flow rate: 1 sccm to 100 sccm

[0097] Ar gas flow rate: 10 sccm to 100,000 sccm, preferably 100 sccm to 20,000 sccm

[0098] H2 gas flow rate: 1 sccm to 50,000 sccm, preferably 10 sccm to 10,000 sccm

[0099] Processing time: 1 second to 1800 seconds

[0100] Treatment temperature: -100℃ to 390℃, preferably 20℃ to 350℃

[0101] Processing pressure: 0.1 Pa to 10,000 Pa, preferably 0.1 Pa to 2,000 Pa

[0102] In step S3, the control unit (100) may generate plasma by the plasma generation unit (51) to promote the reaction between TiCl4 gas and H2 gas. When the control unit (100) supplies TiCl4 gas and H2 gas simultaneously, it plasmaizes both TiCl4 gas and H2 gas.

[0103] Additionally, in step S3, the control unit (100) may supply TiCl4 gas and H2 gas alternately instead of supplying them simultaneously into the treatment vessel (2). In this case, the control unit (100) may plasmaize only the H2 gas among the TiCl4 gas and H2 gas.

[0104] After Step S3, valves (V61, V64) are closed. At this time, since valve (V62) is open, Ar is supplied into the treatment vessel (2), and the gas remaining inside the treatment vessel (2) is discharged through the exhaust pipe (22), thereby replacing the atmosphere inside the treatment vessel (2) with Ar.

[0105] Next, in step S4 of FIG. 1, the control unit (100) opens the valve (V63) to supply O2 gas together with Ar gas into the processing vessel (2). Due to the reaction between the O2 gas and the liquid (L), the liquid (L) moves from the concave portion (Wb) to the convex normal surface (Wc1), and a third insulating film (W5) is formed on the convex normal surface (Wc1). As a result, the step height of the substrate surface (Wa) is expanded.

[0106] The specific processing conditions for Step S4 are, for example, as follows.

[0107] O2 gas flow rate: 1 sccm to 100,000 sccm, preferably 1 sccm to 10,000 sccm

[0108] Ar gas flow rate: 10 sccm to 100,000 sccm, preferably 100 sccm to 20,000 sccm

[0109] Processing time: 1 second to 1800 seconds

[0110] Treatment temperature: -100℃ to 390℃, preferably 20℃ to 350℃

[0111] Processing pressure: 0.1 Pa to 10,000 Pa, preferably 0.1 Pa to 2,000 Pa

[0112] Next, in step S5 of FIG. 1, just as in step S4, the control unit (100) supplies O2 gas together with Ar gas into the processing vessel (2). Also, in step S5, unlike in step S4, the control unit (100) generates plasma by the plasma generation unit (51) to modify the third insulating film (W5). The specific processing conditions of step S5 are the same as those of step S4, except for generating plasma, so the description is omitted.

[0113] After step S5, the valve (V63) is closed. At this time, since the valve (V62) is open, Ar is supplied into the treatment vessel (2), and the gas remaining inside the treatment vessel (2) is discharged through the exhaust pipe (22), thereby replacing the atmosphere inside the treatment vessel (2) with Ar.

[0114] Next, in step S6 of FIG. 1, the control unit (100) checks whether the first cycle has been performed M times (M is a natural number greater than or equal to 1). One first cycle includes steps S3 to S5. Additionally, the first cycle may include at least steps S3 to S4 and may not include step S5.

[0115] If the number of times the first cycle is executed is less than M (step S6, "No"), the control unit (100) executes the first cycle again. Meanwhile, if the number of times the first cycle is executed reaches M (step S6, "Yes"), the control unit (100) executes step S7.

[0116] Next, in step S7 of FIG. 1, the control unit (100) opens the valve (V65) to supply ClF3 gas together with Ar gas into the processing vessel (2). A portion of the second insulating film (W4) and a portion of the third insulating film (W5) are etched by the ClF3 gas. Also, in step S7, the control unit (100) may generate plasma by the plasma generation unit (51) or may plasmaize the ClF3 gas.

[0117] The specific processing conditions for Step S7 are, for example, as follows.

[0118] ClF3 gas flow rate: 1 sccm to 100 sccm

[0119] Ar gas flow rate: 10 sccm to 100,000 sccm, preferably 100 sccm to 20,000 sccm

[0120] Processing time: 1 second to 1800 seconds

[0121] Processing temperature: 30℃ to 350℃, preferably 80℃ to 200℃

[0122] Processing pressure: 0.1 Pa to 10,000 Pa, preferably 0.1 Pa to 2,000 Pa

[0123] After step S7, the valve (V65) is closed. At this time, since the valve (V62) is open, Ar is supplied into the treatment vessel (2), and the gas remaining inside the treatment vessel (2) is discharged through the exhaust pipe (22), thereby replacing the atmosphere inside the treatment vessel (2) with Ar.

[0124] Additionally, Step S7 and Steps S3 to S5 are performed inside the same processing container (2) in this embodiment, but may be performed inside a different processing container (2).

[0125] After step S7, the control unit (100) removes the substrate (W) from the processing container (2) in the reverse order of bringing the substrate (W) into the processing container (2).

[0126] [Example]

[0127] Next, examples and the like will be described. Among the following Examples 1 to 18, Example 12 is an example, and Examples 1 to 11 and Examples 13 to 18 are reference examples. In the following Examples 1 to 18, before introducing the substrate (W) into the processing vessel (2) shown in FIG. 7, a concave portion and a convex portion were formed in advance on the surface (Wa) of the substrate. The pre-formed convex portion normal surface (Wc1) is hereinafter also referred to as the convex portion normal surface (Wd).

[0128] <Examples 1 to 2>

[0129] In Examples 1 and 2, steps S1 to S4 and S6 were performed using the film formation device (1) shown in FIG. 7 under the processing conditions shown in Table 1, and steps S5 and S7 were not performed. Additionally, as described above, before introducing the substrate (W) into the processing container (2), concave and convex portions were formed in advance on the surface (Wa) of the substrate.

[0130]

[0131] In Table 1, the "convex normal surface" is the material of the convex normal surface (Wd) formed in advance before Step S3. The material of the concave side surface formed in advance before Step S3 is the same as the material of the convex normal surface (Wd). The "concave bottom surface" is the material of the concave bottom surface formed in advance before Step S3. In addition, "○" in various gases means that various gases have been supplied, and "ON" in "RF" means that the gas has been plasmafied by high-frequency power. In addition, "cycle count" is the number of repetitions of Steps S3 and S4 (i.e., M in Step S6). The same applies to Tables 2 to 8 described later.

[0132] FIGS. 8a to 8c show SEM images of a substrate (W-1) according to Example 1. As shown in FIG. 8a, liquid (L-1) was supplied to the concave portion (Wb-1) by step S3. The amount of liquid (L-1) supplied was such that it entered the interior of the concave portion (Wb-1). In addition, as shown in FIG. 8b, when the process was stopped during step S4, specifically when the processing time of step S4 was 10 seconds, a similar appearance to FIG. 3b was observed, that is, the liquid (L-1) was seen rising from the concave portion (Wb-1) toward the convex normal surface (Wd-1). In addition, as shown in FIG. 8c, a film (W5-1) was selectively formed on the convex normal surface (Wd-1) by step S4.

[0133] FIGS. 9a and 9b show SEM images of a substrate (W-2) according to Example 2. As shown in FIG. 9a, liquid (L-2) was supplied to the concave portion (Wb-2) by step S3. In Example 2, the processing time of step S3 was longer than in Example 1, so the amount of liquid (L-2) supplied was large; thus, liquid (L-2) was supplied not only to the concave portion (Wb-2) but also to the convex normal surface (Wd-2). Additionally, as shown in FIG. 9b, a film (W5-2) was selectively formed on the convex normal surface (Wd-2) by step S4.

[0134] <Example 3>

[0135] In Example 3, using the film-forming device (1) shown in FIG. 7, steps S1 to S3 were performed under the processing conditions shown in Table 2, and then steps S4 to S7 were not performed, and step S9 was performed under the processing conditions shown in Table 2. In step S9, only Ar gas was supplied into the processing vessel (2), and the change in the liquid (L) in the concave portion (Wb) was observed.

[0136]

[0137] FIG. 10 shows the relationship between the processing time of Step S9 of Example 3 and the thickness of the liquid (L) in the depression (Wb). As is evident from FIG. 10, no movement or reduction of the liquid (L) in the depression (Wb) was observed even when left for a long time under a reduced pressure atmosphere. This means that there is no movement of the liquid (L) until the reaction between the liquid (L) and the processing gas (G) begins, and that the liquid (L) is difficult to evaporate because it has strong intermolecular forces and strong cohesive forces.

[0138] <Examples 4 to 7>

[0139] In Examples 4 to 7, steps S1 to S4 and S6 were performed using the film formation device (1) shown in FIG. 7 under the processing conditions shown in Table 3, and steps S5 and S7 were not performed. Additionally, as described above, before introducing the substrate (W) into the processing container (2), concave and convex portions were formed in advance on the surface (Wa) of the substrate.

[0140]

[0141] Figure 11a shows an SEM image of the substrate (W-4) after processing according to Example 4. In Example 4, steps S3 and S4 were performed once each, as in Example 1. As a result, among the concave portion (Wb-4) and the convex normal surface (Wd-4), a film (W5-4) was selectively formed on the convex normal surface (Wd-4).

[0142] Figure 11b shows an SEM image of the substrate (W-5) after processing according to Example 5. In Example 5, unlike Example 1, steps S3 and S4 were performed 10 times each. As a result, among the concave portion (Wb-5) and the convex normal surface (Wd-5), a film (W5-5) was selectively formed on the convex normal surface (Wd-5).

[0143] FIG. 11c shows an SEM image of the substrate (W-6) after processing for Example 6. In Example 6, unlike Example 1, H2O gas was supplied into the processing vessel (2) instead of O2 gas in step S4. As a result, among the concave portion (Wb-6) and the convex portion normal surface (Wd-6), a film (W5-6) was selectively formed on the convex portion normal surface (Wd-6).

[0144] FIG. 11d shows an SEM image of the substrate (W-7) after processing for Example 7. In Example 7, unlike Example 1, N2 gas was supplied into the processing vessel (2) instead of O2 gas in step S4. Additionally, the N2 gas was plasmafied. As a result, among the concave portion (Wb-7) and the convex portion normal surface (Wd-7), a film (W5-7) was selectively formed on the convex portion normal surface (Wd-7).

[0145] As is evident from Examples 4 to 7, by using various types of processing gas (G), a film (W5) could be selectively formed on the normal surface (Wd) of the convex portion.

[0146] <Examples 8 to 12>

[0147] In Examples 8 to 12, steps S1 to S4 and S6 were performed using the film formation device (1) shown in FIG. 7 under the processing conditions shown in Table 4, and steps S5 and S7 were not performed. Additionally, as described above, before introducing the substrate (W) into the processing container (2), concave and convex portions were formed in advance on the surface (Wa) of the substrate.

[0148]

[0149] Figure 12a shows an SEM image of the substrate (W-8) after processing according to Example 8. In Example 8, steps S3 and S4 were performed once each under the same conditions as Example 4, except that the material of the convex normal surface and the concave bottom surface was changed to titanium oxide (TiO2). As a result, among the concave portion (Wb-8) and the convex normal surface (Wd-8), a film (W5-8) was selectively formed on the convex normal surface (Wd-8).

[0150] FIG. 12b shows an SEM image of the substrate (W-9) after processing according to Example 9. In Example 9, steps S3 and S4 were performed once each under the same conditions as Example 4, except that the material of the convex normal surface and the concave bottom surface was changed to silicon nitride (SiN). As a result, among the concave portion (Wb-9) and the convex normal surface (Wd-9), a film (W5-9) was selectively formed on the convex normal surface (Wd-9).

[0151] FIG. 12c shows an SEM image of the substrate (W-10) after processing according to Example 10. In Example 10, steps S3 and S4 were performed once each under the same conditions as Example 4, except that the material of the convex normal surface and the concave bottom surface was changed to silicon (Si). As a result, among the concave portion (Wb-10) and the convex normal surface (Wd-10), a film (W5-10) was selectively formed on the convex normal surface (Wd-10).

[0152] Figure 13a shows an SEM image of the substrate (W-11) after processing according to Example 11. In Example 11, steps S3 and S4 were performed once each under the same conditions as Example 4, except that the material of the convex normal surface and the concave bottom surface was changed to carbon (C). As a result, among the concave portion (Wb-11) and the convex normal surface (Wd-11), a film (W5-11) was selectively formed on the convex normal surface (Wd-11).

[0153] Figure 13b shows an SEM image of the substrate (W-12) after processing according to Example 12. In Example 12, steps S3 and S4 were performed once each under the same conditions as Example 4, except that the material of the normal surface of the convex portion was changed to ruthenium (Ru). As a result, among the concave portion (Wb-12) and the normal surface of the convex portion (Wd-12), a film (W5-12) was selectively formed on the normal surface of the convex portion (Wd-12).

[0154] As is evident from Examples 8 to 12, a film (W5) could be selectively formed on the normal surface (Wd) of the convex portion using a substrate (W) of various materials.

[0155] <Examples 13 to 14>

[0156] In Examples 13 and 14, steps S1 to S4 and S6 were performed using the film formation device (1) shown in FIG. 7 under the processing conditions shown in Table 5, and steps S5 and S7 were not performed. Additionally, as described above, before introducing the substrate (W) into the processing container (2), concave and convex portions were formed in advance on the surface (Wa) of the substrate.

[0157]

[0158] Figure 14a shows an SEM image of the substrate (W-13) after processing according to Example 13. In Example 13, steps S3 and S4 were performed once each under the same conditions as Example 4, except that the substrate temperature was changed to 80°C. As a result, among the concave portion (Wb-13) and the convex portion normal surface (Wd-13), a film (W5-13) was selectively formed on the convex portion normal surface (Wd-13).

[0159] Figure 14b shows an SEM image of the substrate (W-14) after processing according to Example 14. In Example 14, steps S3 and S4 were performed once each under the same conditions as Example 4, except that the substrate temperature was changed to 200°C. As a result, among the concave portion (Wb-14) and the convex portion normal surface (Wd-14), a film (W5-14) was selectively formed on the convex portion normal surface (Wd-14).

[0160] As is evident from Examples 13 to 14, a film (W5) could be selectively formed on the normal surface (Wd) of the convex portion at various substrate temperatures.

[0161] <Examples 15 to 16>

[0162] In Example 15, steps S1 to S4 and S6 were performed under the processing conditions shown in Table 6 using the film-forming device (1) shown in FIG. 7, and steps S5 and S7 were not performed. Meanwhile, in Example 16, steps S1 to S6 were performed under the processing conditions shown in Table 6 using the film-forming device (1) shown in FIG. 7, and step S7 was not performed. Additionally, as described above, before introducing the substrate (W) into the processing container (2), concave and convex portions were formed in advance on the surface (Wa) of the substrate.

[0163]

[0164] In Example 15, the film (W5) formed on the convex normal surface (Wd) was etched with an aqueous solution having an HF concentration of 0.5 mass%, and the etching rate was 762.8 Å / min. Meanwhile, in Example 16, the film (W5) formed on the convex normal surface (Wd) was etched with an aqueous solution having an HF concentration of 0.5 mass%, and the etching rate was 81.3 Å / min. Therefore, the film (W5) could be modified by step S5.

[0165] <Example 17>

[0166] In Example 17, steps S1 to S4 and S6 were performed using the film-forming device (1) shown in FIG. 7 under the processing conditions shown in Table 7, and steps S5 and S7 were not performed. Additionally, as described above, before introducing the substrate (W) into the processing container (2), concave and convex portions were formed in advance on the surface (Wa) of the substrate.

[0167]

[0168] FIG. 15 shows an SEM image of the substrate (W-17) after processing according to Example 17. In Example 17, unlike Example 1, Si2Cl6 (HCD) was supplied into the processing vessel (2) instead of TiCl4 as the source gas in Step S3. Also, in Step S4, Ar gas and O2 gas were plasma-formed. Additionally, Steps S3 and S4 were performed twice each. Also, the material of the convex normal surface and the concave bottom surface was changed to TiO2. As a result, among the concave portion (Wb-17) and the convex normal surface (Wd-17), a film (W5-17) was selectively formed on the convex normal surface (Wd-17). Also, the same result was obtained when the material of the convex normal surface and the concave bottom surface was changed to SiO2.

[0169] <Example 18>

[0170] In Example 18, steps S1 to S4 and S6 were performed using the film-forming device (1) shown in FIG. 7 under the processing conditions shown in Table 8, and steps S5 and S7 were not performed. Additionally, as described above, before introducing the substrate (W) into the processing container (2), concave and convex portions were formed in advance on the surface (Wa) of the substrate.

[0171]

[0172] FIG. 16 shows an SEM image of the substrate (W-18) after processing for Example 18. In Example 18, unlike Example 1, SnCl4 was supplied into the processing vessel (2) instead of TiCl4 as the source gas in step S3. As a result, among the concave portion (Wb-18) and the convex portion normal surface (Wd-18), a film (W5-18) was selectively formed on the convex portion normal surface (Wd-18).

[0173] As is evident from Examples 17 to 18, a film (W5) could be selectively formed on the normal surface (Wd) of the convex portion using various raw gases.

[0174] Regarding the above embodiment, the following supplementary information is disclosed.

[0175] [Appendix 1]

[0176] (A) Preparing a substrate having a first region on the surface in which a first film is exposed and a second region in which a second film formed of a material different from the first film is exposed, and

[0177] (B) forming a step on the surface such that the first region is higher than the second region, and

[0178] (C) supplying liquid to the surface on which the step is formed, and

[0179] (D) A method for forming a film having a process gas that chemically changes the liquid and supplies the liquid to the surface, thereby moving the liquid from the second region to the first region by means of a reaction between the process gas and the liquid, and selectively forming a film on the first region relative to the second region.

[0180] [Book 2]

[0181] A film formation method described in Appendix 1, wherein the first film is an insulating film and the second film is a conductive film.

[0182] [Book 3]

[0183] The above (B) is a film formation method described in Appendix 1 or 2, comprising selectively forming a self-organizing monolayer in the second region with respect to the first region, and forming the second insulating film in the first region while inhibiting the formation of the second insulating film in the second region using the self-organizing monolayer.

[0184] [Book 4]

[0185] The above (B) is a film formation method described in Appendix 1 or 2, comprising selectively etching the second region with respect to the first region.

[0186] [Book 5]

[0187] A film formation method described in any one of Appendix 1 to 4, comprising etching a portion of the above film.

[0188] [Book 6]

[0189] The above liquid is a halogenated film forming method described in any one of Appendix 1 to 5.

[0190] [Book 7]

[0191] The above (C) is a film formation method described in Appendix 6, comprising forming the liquid by a reaction between a source gas that is a source of the above halide and a reaction gas that reacts with the above source gas.

[0192] [Book 8]

[0193] The above liquid is a liquid polymer, a film formation method described in any one of Appendix 1 to 5.

[0194] [Book 9]

[0195] The above liquid is synthesized in a processing vessel that accommodates the substrate and supplied to the surface of the substrate, a film formation method described in Appendix 8.

[0196] [Book 10]

[0197] A film formation method described in any one of Appendix 1 to 9, wherein the treatment gas that chemically changes the liquid in (D) above comprises an element introduced into the liquid.

[0198] [Book 11]

[0199] The treatment gas that chemically changes the above liquid comprises an oxygen-containing gas, a film formation method described in Appendix 10.

[0200] [Book 12]

[0201] The treatment gas that chemically changes the above liquid comprises a nitrogen-containing gas, a film formation method described in Appendix 10.

[0202] [Appendix 13]

[0203] The treatment gas that chemically changes the above liquid comprises a hydride gas, a film formation method described in Appendix 10.

[0204] [Book 14]

[0205] The treatment gas that chemically changes the liquid degasses the elements constituting the liquid, a film formation method described in any one of Appendix 1 to 9.

[0206] [Book 15]

[0207] The treatment gas that chemically changes the above liquid comprises a reducing gas, a film formation method described in Appendix 14.

[0208] [Appendix 16]

[0209] The above reducing gas is hydrogen gas or deuterium gas, a method for forming a film as described in Appendix 15.

[0210] [Appendix 17]

[0211] The above (D) is a film formation method described in any one of Appendix 1 to 16, comprising plasmaizing the treatment gas that chemically changes the liquid.

[0212] [Appendix 18]

[0213] A method for forming a membrane as described in any one of Appendix 1 to 17, comprising modifying the above membrane.

[0214] Although embodiments of the film-forming method and film-forming apparatus according to the present disclosure have been described above, the present disclosure is not limited to the above embodiments. Various changes, modifications, substitutions, additions, deletions, and combinations are possible within the scope described in the claims. These also naturally fall within the technical scope of the present disclosure.

[0215] This application claims priority based on Japanese Patent Application No. 2021-093208 filed with the Japan Patent Office on June 2, 2021, and incorporates the entire contents of Japanese Patent Application No. 2021-093208 into this application. Explanation of the symbols

[0216] A1: Area 1 A2: Area 2 L: Liquid W: Substrate W1: Act 1 W2: Act 2 W5: Film (Third insulating film)

Claims

Claim 1 (A) preparing a substrate having a first region on which a first film is exposed and a second region on which a second film formed of a material different from the first film is exposed; (B) forming a step on the surface such that the first region is higher than the second region; (C) supplying a liquid to the surface on which the step is formed; and (D) supplying a treatment gas that chemically changes the liquid to the surface, thereby moving the liquid from the second region to the first region by utilizing the change in surface tension caused by the reaction between the treatment gas and the liquid, so as to selectively form a film on the first region relative to the second region. Claim 2 A film formation method according to claim 1, wherein the first film is an insulating film and the second film is a conductive film. Claim 3 A method for forming a film according to claim 1, wherein (B) comprises selectively forming a self-organizing monolayer in the second region with respect to the first region, and forming the second insulating film in the first region while inhibiting the formation of the second insulating film in the second region using the self-organizing monolayer. Claim 4 A method for forming a film according to claim 1, wherein (B) comprises selectively etching the second region with respect to the first region. Claim 5 A method for forming a film according to claim 1, comprising etching a portion of the film formed in (D). Claim 6 In claim 1, the liquid is a halide, a film formation method. Claim 7 A method for forming a film according to claim 6, wherein (C) comprises forming the liquid by a reaction between a raw material gas that is a raw material for the halide and a reaction gas that reacts with the raw material gas. Claim 8 A film formation method according to claim 1, wherein the liquid is a polymer in a liquid state. Claim 9 A film formation method according to claim 8, wherein the liquid is synthesized in a processing vessel containing the substrate and supplied to the surface of the substrate. Claim 10 A method for forming a film according to claim 1, wherein the treatment gas that chemically changes the liquid in (D) comprises an element introduced into the liquid. Claim 11 In claim 10, the treatment gas that chemically changes the liquid comprises an oxygen-containing gas, in a film formation method. Claim 12 In claim 10, the treatment gas that chemically changes the liquid comprises a nitrogen-containing gas, in a film formation method. Claim 13 In claim 10, the treatment gas that chemically changes the liquid comprises a hydride gas, in a film formation method. Claim 14 A film formation method according to claim 1, wherein the treatment gas that chemically changes the liquid degass the elements constituting the liquid. Claim 15 In claim 14, the treatment gas that chemically changes the liquid comprises a reducing gas, in a film formation method. Claim 16 In paragraph 15, the reducing gas is hydrogen gas or deuterium gas, a method for forming a film. Claim 17 A method for forming a film according to claim 1, wherein (D) comprises plasmaizing the treatment gas that chemically changes the liquid. Claim 18 A method for forming a film according to claim 1, comprising modifying the film formed in (D) above. Claim 19 A conveying unit for conveying a substrate having a first region where a first film is exposed and a second region where a second film formed of a material different from the first film is exposed on the surface; a processing vessel into which the substrate is introduced by the conveying unit; a holding support unit that holds and supports the substrate horizontally with the surface of the substrate facing upward inside the processing vessel; a gas supply unit that supplies a gas forming a step on the surface of the substrate held and supported by the holding support unit, a raw material gas supplied to the surface where the step is formed, a reaction gas that reacts with the raw material gas, and a processing gas that chemically changes a liquid formed by the reaction of the raw material gas and the reaction gas; and a control unit that controls the conveying unit and the gas supply unit, wherein the control unit comprises: (A) introducing the substrate into the processing vessel; (B) forming the step on the surface such that the first region is higher than the second region; and (C) supplying the liquid formed by the reaction of the raw material gas and the reaction gas to the surface where the step is formed. A film forming apparatus comprising: (D) supplying the treatment gas to the surface, and using the change in surface tension generated by the reaction between the treatment gas and the liquid to move the liquid from the second region to the first region, thereby selectively forming a film on the first region relative to the second region.

Images