Film deposition method and film deposition apparatus

Abstract

This invention provides a technology for forming a boron oxide film, which is used as an inhibitory film to hinder the formation of a target film in the selective deposition of a target film, using a simple process. [Solution] The film formation method comprises: preparing a substrate having an oxide film substantially free of boron and a non-oxide film substantially free of oxygen in different regions of its surface; supplying a modified gas containing boron to the substrate to modify at least the surface of the oxide film into a boron oxide film; and selectively forming a target film on the surface of the non-oxide film relative to the surface of the boron oxide film. The target film contains a desired element X. Forming the target film involves supplying a raw material gas containing a compound of element X and a halogen, and a reaction gas that reacts with adsorbents of the raw material gas, to the substrate.

Description

Technical Field

[0001] The present disclosure relates to a film forming method and a film forming apparatus.

Background Art

[0002] In the film forming method described in Patent Document 1, a boron-containing film is used as an inhibitory film that inhibits the film formation of a target film in order to selectively form the target film on a part of the substrate surface. On the other hand, in the film forming method described in Patent Document 2, a SAM (Self-Assembled Monolayer) is used as an inhibitory film that inhibits the film formation of a target film in order to selectively form the target film on a part of the substrate surface. In Patent Document 2, an oxide film is replaced with a boron oxide film before forming the SAM, and the unnecessary SAM attached to the boron oxide film is removed by removing the boron oxide film. That is, in Patent Document 2, the boron oxide film is not used as an inhibitory film, but is used for removing the inhibitory film.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] One embodiment of the present disclosure provides a technique for forming a boron oxide film used as an inhibitory film that inhibits the film formation of a target film in the selective film formation of the target film by a simple process.

Means for Solving the Problems

[0005] A film-forming method according to one embodiment of the present disclosure comprises: preparing a substrate having a substantially boron-free oxide film and a substantially oxygen-free non-oxide film in different regions of its surface; supplying a boron-containing modified gas to the substrate to modify at least the surface of the oxide film into a boron oxide film; and selectively forming a target film on the surface of the non-oxide film relative to the surface of the boron oxide film. The target film contains a desired element X. Forming the target film involves supplying a source gas containing a compound of element X and a halogen, and a reaction gas that reacts with adsorbents of the source gas, to the substrate. [Effects of the Invention]

[0006] According to one embodiment of the present disclosure, a boron oxide film can be formed by a simple process to be used as an inhibitory film to inhibit the formation of a target film in the selective deposition of a target film. [Brief explanation of the drawing]

[0007] [Figure 1] Figure 1 is a flowchart showing a film deposition method according to one embodiment. [Figure 2] Figure 2 is a flowchart showing an example of S103 in Figure 1. [Figure 3] Figure 3 is a cross-sectional view showing a film deposition method according to one embodiment. [Figure 4] Figure 4 is a flowchart showing a film deposition method related to a modified example. [Figure 5] Figure 5 is a flowchart showing an example of S107 in Figure 4. [Figure 6] Figure 6 is a cross-sectional view showing a film formation method according to a modified example. [Figure 7] Figure 7 is a cross-sectional view showing a modified film formation method following Figure 6. [Figure 8] Figure 8 is a cross-sectional view showing a modified example of S101 in Figure 4. [Figure 9] Figure 9 is a plan view showing a substrate processing apparatus according to one embodiment. [Figure 10]Figure 10 is a cross-sectional view showing an example of the first processing unit. [Modes for carrying out the invention]

[0008] Embodiments of this disclosure will be described below with reference to the drawings. In each drawing, identical or similar components are denoted by the same reference numerals, and their descriptions may be omitted. In this specification, the "~" indicating a numerical range means that the numbers before and after it are included as the lower and upper limits. Numerical ranges include rounded ranges. In this specification, the semiconductor element is Si or Ge.

[0009] First, a film deposition method according to one embodiment will be described with reference to Figures 1 to 3. The film deposition method includes, for example, steps S101 to S106 shown in Figure 1. However, the film deposition method only needs to include steps S101 to S104, and does not need to include steps S105 to S106. Furthermore, the film deposition method may include steps other than steps S101 to S106 shown in Figure 1.

[0010] Step S101 includes preparing the substrate W (see, for example, Figure 3). The substrate W has an oxide film W1 containing oxygen and a non-oxide film W2 substantially free of oxygen in different areas of its surface. The substrate W may be pre-cleaned so that both the oxide film W1 and the non-oxide film W2 are exposed in different areas of the substrate W's surface. In this embodiment, the surface of the substrate W is flat, but it may also be uneven. It is preferable that both the oxide film W1 and the non-oxide film W2 substantially do not contain boron (B). Substantially free of B means that the B content is 0 at% to 5 at%.

[0011] The oxide film W1 contains, for example, a compound of a semiconductor element and oxygen, or a compound of a metal and oxygen. The oxide film W1 preferably has an oxygen content of 20 at% to 60 at%. The oxide film W1 is not particularly limited, and examples thereof include a SiO film, a TiO film, a SnO film, a WO film, or a HfO film. Here, the 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 1:2. The same applies to the TiO film, SnO film, WO film, HfO film, etc. other than the SiO film, which means that they contain each element and are not limited to the stoichiometric ratio.

[0012] The non-oxide film W2 contains, for example, only a semiconductor element, a compound of a semiconductor element and nitrogen, only a metal, or a compound of a metal and nitrogen. The non-oxide film W2 preferably has an oxygen content of 0 at% to 10 at%. The non-oxide film W2 is not particularly limited, and examples thereof include a Si film, a SiN film, or a SiGe film. When the non-oxide film W2 is a semiconductor film, the semiconductor film may be an amorphous film, a polycrystalline film, or a single crystal film.

[0013] The oxide film W1 and the non-oxide film W2 are formed on a base substrate (not shown). The base substrate is a silicon wafer or a compound semiconductor wafer. The compound semiconductor wafer is, for example, a GaAs wafer, a SiC wafer, a GaN wafer, or an InP wafer. A functional film (not shown) may be formed between the oxide film W1 or the non-oxide film W2 and the base substrate (not shown). The oxide film W1 may be formed by naturally oxidizing the underlying film (for example, a metal film or a semiconductor film) due to contact with the atmosphere. The oxide film W1 may be formed by oxidizing the underlying film (for example, a metal film or a semiconductor film) by reaction with a reaction gas or the like.

[0014] Step S102 includes modifying the surface of the oxide film W1 into a boron oxide film WA with a reforming gas so as to selectively form a film of the target film WB in a desired region in step S103 (see FIG. 3). The reforming gas selectively modifies the surface of the oxide film W1 into a boron oxide film WA with respect to the surface of the non-oxide film W2. The reforming gas contains boron, and the boron takes oxygen from the oxide film W1 to form the boron oxide film WA. At this time, the semiconductor element or metal element contained in the oxide film W1 becomes a volatile compound and desorbs from the surface of the oxide film W1. As a result, it is considered that a highly pure boron oxide film WA is formed. The surface of the non-oxide film W2 is hardly modified.

[0015] The reforming gas contains boron and modifies at least the surface of the oxide film W1 into a boron oxide film WA. In this case, the reforming gas is BCl3, B(CH3)3, B2H6, BF3, BBr3, BI3, C9H 24 BN3, C3H9B, C6H 15 and preferably contains at least one of B3N3H6.

[0016] When the oxide film W1 is a TiO film and the reforming gas is BCl3 gas, a reforming reaction represented by the following reaction formula (1) proceeds. (1) TiO2 + 4 / 3 BCl3(g) → 2 / 3 B2O3 + TiCl4(g) The change in Gibbs energy in the reforming reaction represented by the above reaction formula (1) is -27.0 kcal / mol at 100°C.

[0017] When the oxide film W1 is a SiO film and the reforming gas is BCl3 gas, a reforming reaction represented by the following reaction formula (2) proceeds. (2) SiO2 + 4 / 3 BCl3(g) → 2 / 3 B2O3 + SiCl4(g) The change in Gibbs energy in the reforming reaction represented by the above reaction formula (2) is -9.8 kcal / mol at 100°C.

[0018] When the oxide film W1 is a SnO film and the reforming gas is BCl3 gas, the reforming reaction represented by the following reaction equation (3) proceeds. (3)SnO2+4 / 3BCl3(g)→2 / 3B2O3+SnCl4(g) The change in Gibbs free energy in the reforming reaction represented by the above reaction equation (3) is -46.2 kcal / mol at 100°C.

[0019] When the oxide film W1 is a WO film and the reforming gas is BCl3 gas, the reforming reaction represented by the following reaction equation (4) proceeds. (4)WO3+2BCl3(g)→B2O3+WCl6(g) The change in Gibbs free energy in the reforming reaction represented by the above reaction equation (4) is -13.3 kcal / mol at 100°C.

[0020] When the oxide film W1 is an HfO film and the reformed gas is BCl3 gas, the reforming reaction represented by the following reaction equation (5) proceeds. (5)HfO2+4 / 3BCl3(g)→2 / 3B2O3+HfCl4(g) The change in Gibbs free energy in the reforming reaction represented by the above reaction equation (5) is -16.4 kcal / mol at 100°C.

[0021] When the oxide film W1 is a SnO film and the reformed gas is B(CH3)3 gas, the reforming reaction represented by the following reaction equation (6) proceeds. (6)SnO2+4 / 3B(CH3)3(g)→2 / 3B2O3+Sn(CH3)4(g) The change in Gibbs free energy in the reforming reaction represented by the above reaction equation (6) is -28.2 kcal / mol at 100°C.

[0022] When the oxide film W1 is a SnO film and the reformed gas is B(C2H5)3 gas, the reforming reaction represented by the following reaction equation (7) proceeds. (7)SnO2+4 / 3B(C2H5)3(g)→2 / 3B2O3+Sn(C2H5)4(g) The change in Gibbs free energy in the reforming reaction represented by the above reaction equation (7) is -24.5 kcal / mol at 100°C.

[0023] When the oxide film W1 is a SnO film and the reformed gas is BBr3 gas, the reforming reaction represented by the following reaction equation (8) proceeds. (8)SnO2+4 / 3BBr3(g)→2 / 3B2O3+SnBr4(g) The change in Gibbs free energy in the reforming reaction represented by the above reaction equation (8) is -72.1 kcal / mol at 100°C.

[0024] When the oxide film W1 is a SnO film and the reforming gas is BI3 gas, the reforming reaction represented by the following reaction equation (9) proceeds. (9)SnO2+4 / 3BI3(g)→2 / 3B2O3+SnI4(g) The change in Gibbs free energy in the reforming reaction represented by the above reaction equation (9) is -113.4 kcal / mol at 100°C.

[0025] The more negative and larger the absolute value of the change in Gibbs free energy, the more easily the reforming reaction proceeds. To accelerate reforming, the reformed gas may be plasma-activated. Note that the above values ​​for the change in Gibbs free energy are for the case where the reformed gas is not plasma-activated.

[0026] In step S102 above, the temperature of the substrate W may be controlled to 100°C or higher in order to promote the reaction of the reforming gas on the surface of the oxide film W1 and to promote the desorption of volatile compounds (e.g., metal compounds) produced as byproducts of the reforming. If the temperature of the substrate W is below 100°C, the reaction of the reforming gas will not occur sufficiently, and the desorption of compounds (e.g., metal compounds) will be insufficient, making it difficult to selectively form the boron oxide film WA. The temperature of the substrate W is preferably 200°C or higher. The temperature of the substrate W is preferably 800°C or lower.

[0027] The boron oxide film WA is used as an inhibitory film that inhibits the formation of the target film WB. Alternatively, one could selectively adsorb the inhibitor onto the surface of the oxide film W1 to form the inhibitory film on the surface of the oxide film W1. However, the selectivity of the adsorption reaction may be insufficient. In this embodiment, the selectivity of the modification reaction is utilized, allowing the inhibitory film to be formed only on the surface of the oxide film W1, and the target film WB to be selectively formed on the surface of the non-oxide film W2.

[0028] Step S103 includes selectively forming a target film WB on the surface of a non-oxide film W2 on the surface of an oxide film W1 modified to a boron oxide film WA in step S102 (see Figure 3). Step S103 includes supplying a source gas containing a compound of a desired element X and a halogen, and a reaction gas that reacts with adsorbents of the source gas, to the substrate W. The source gas and reaction gas are supplied alternately or simultaneously. In this case, the target film WB contains element X.

[0029] Step S103 includes, for example, steps S103a to S103e, as shown in Figure 2. Step S103 only needs to include at least steps S103a, S103c, and S103e; it does not need to include steps S103b and S103d. Steps S103a to S103e will be described below.

[0030] Step S103a includes supplying a raw material gas to the substrate W. The raw material gas contains a compound of element X and a halogen. The halogen is fluorine, chlorine, bromine, or iodine. Element X is not particularly limited, but is preferably a metallic element, and more preferably a transition metal element. Element X is, for example, Ti, W, V, Al, Mo, Sn, Hf, Ta, Nb, Zr, In, Ga, or Sb. Specific examples of raw material gases include TiCl4, WCl6, WF6, VCl4, AlCl3, MoCl5, SnCl4, HfCl4, TaCl5, NbCl5, ZrCl4, InCl3, GaCl3, or SbCl3. Element X may also be a semiconductor element, specifically Si or Ge. The raw material gas is a silicon halide gas or a germanium halide gas. Specific examples of silicon halide gases include SiCl4, SiHCl3, SiH2Cl2, SiH3Cl, and Si2Cl 6、 Examples include Si2HCl5, Si2Cl3CH3, SiCl3CCl3, SiCl3CH3, or SiH2I2. Specific examples of germanium halide gases include GeCl4. The raw material gas may be supplied together with a diluent gas. The diluent gas is, for example, Ar gas or N2 gas.

[0031] Step S103b includes supplying a purge gas to the substrate W. The purge gas purges any excess raw material gas that was not adsorbed on the substrate W in step S103a. As the purge gas, for example, a noble gas such as Ar gas or N2 gas can be used.

[0032] Step S103c includes supplying a reaction gas to the substrate W. The reaction gas reacts with element X contained in the adsorbed material of the raw material gas to form the target film WB. The target film WB contains element X. Examples of reaction gases include oxygen-containing gases, nitrogen-containing gases, or hydrogen-containing gases. Oxygen-containing gases contain oxygen and form an oxide film of element X. Examples of oxygen-containing gases include O2, O3, CO2, N2O, NO, or H2O. Nitrogen-containing gases contain nitrogen and form a nitride film of element X. Examples of nitrogen-containing gases include NH3 or N2H4. Hydrogen-containing gases contain hydrogen and form a film (e.g., a metal film or a semiconductor film) mainly composed of element X. Examples of hydrogen-containing gases include H2 or H2S. The reaction gas may be supplied together with a diluent gas. Examples of diluent gases include Ar or N2.

[0033] Step S103c may include plasmaizing the reaction gas, and may also include supplying the plasmaized reaction gas to the substrate W. Plasmaizing the reaction gas can accelerate the formation of the target film WB.

[0034] The reaction gas may be supplied not only in step S103c, but also in all of steps S103a to S103d. However, plasma formation of the reaction gas is performed only in step S103c. This is because plasma formation of the reaction gas makes it easier to react with adsorbed material of the raw material gas on the substrate W.

[0035] Step S103c may also include supplying O3 to the substrate W as a reaction gas without plasma formation.

[0036] Step S103d includes supplying a purge gas to the substrate W. The purge gas purges any excess reaction gas that did not react with the substrate W in step S103c. As the purge gas, for example, a noble gas such as Ar gas or N2 gas can be used.

[0037] Step S103e includes checking whether the fourth cycle has been performed N times (where N is an integer greater than or equal to 1). The fourth cycle includes steps S103a to S103d. N may be an integer greater than or equal to 2, and the fourth cycle may be performed repeatedly multiple times. The film thickness of the target film WB can be increased.

[0038] If the number of cycles of the fourth cycle is less than N (step S103e, NO), the film thickness of the target film WB is less than the target value, so the fourth cycle is repeated. N is preferably 200 or more, more preferably 300 or more. N is preferably 1000 or less.

[0039] On the other hand, if the number of times the fourth cycle is performed reaches N (step S103e, YES), the film thickness of the target film WB has reached the target value, and the current process is terminated.

[0040] The film deposition method shown in Figure 2 is the ALD (Atomic Layer Deposition) method, but the CVD (Chemical Vapor Deposition) method may also be used. In the ALD method, the supply of raw material gas (step S103a) and the supply of reaction gas (step S103c) are performed alternately. On the other hand, in the CVD method, the supply of raw material gas and reaction gas is performed simultaneously.

[0041] To inhibit the formation of the target film WB on the surface of the boron oxide film WA, it is important that the adsorption of the source gas onto the boron oxide film WA is weak, and as a result, the adsorbed source gases on the surface of the boron oxide film WA desorb without advancing the film formation reaction (formation of the target film WB). Alternatively, it is important that the adsorption of the source gas onto the surface of the boron oxide film WA does not occur, or that the dissociation of the source gas on the surface of the boron oxide film WA is unlikely to occur. If the dissociation of the source gas occurs, the substrate processing reaction will proceed easily.

[0042] Since the boron oxide film WA contains boron, it is thought that adsorption of halides does not occur, or if it does occur, it is weak, or that dissociation of halides is unlikely to occur on the surface of the boron oxide film WA. As a result, the formation of the target film WB is inhibited on the surface of the boron oxide film WA.

[0043] On the other hand, since the non-oxide film W2 is substantially free of boron, it is thought that halides are strongly adsorbed on the surface of the non-oxide film W2, or that dissociation of halides is likely to occur. As a result, it is thought that the formation of the target film WB progresses on the surface of the non-oxide film W2.

[0044] Furthermore, halides such as TiCl4 are less susceptible to decomposition by the heat of the substrate W compared to organometallic complexes such as Ti[N(CH3)2]4. If the source gas decomposes after being adsorbed onto the boron oxide film WA, the formation of the target film WB will proceed. Therefore, to inhibit the formation of the target film WB on the surface of the boron oxide film WA, a halogen-containing gas is suitable as the source gas for the target film WB.

[0045] Furthermore, in plasma CVD, where both the halide and the reaction gas are plasma-activated, reactive species such as ions or radicals are generated from the dissociation of the halide. These reactive species generated from the halide are highly reactive, and it is thought that the substrate processing reaction will proceed more easily not only on the surface of the non-oxide film W2 but also on the surface of the boron oxide film WA. Therefore, it is preferable not to plasma-activate the source gas, and it is important to use thermal ALD, plasma ALD, or thermal CVD.

[0046] In steps S103a to S103d above, the temperature of the substrate W may be controlled to 100°C or higher in order to promote the desorption of the raw material gas on the surface of the boron oxide film WA. If the temperature of the substrate W is below 100°C, the desorption of the raw material gas will not occur sufficiently on the surface of the boron oxide film WA, and the raw material gas will be physically adsorbed, resulting in the formation of the target film WB on the surface of the boron oxide film WA as well. The temperature of the substrate W is preferably 200°C or higher. The temperature of the substrate W is preferably 800°C or lower.

[0047] Step S104 includes confirming whether the first cycle has been performed K times (where K is an integer greater than or equal to 1). The first cycle includes supplying reformed gas (step S102) and forming the target film WB (step S103). K may be an integer greater than or equal to 2, and the first cycle may be repeated multiple times. The thickness of the target film WB can be increased. In step S103, if the boron oxide film WA is damaged by plasma or the like before the thickness of the target film WB reaches the target value, and the surface of the oxide film W1 is exposed, it is effective to repeat the first cycle.

[0048] If the number of times the first cycle is performed is less than K (step S104, NO), the film thickness of the target film WB is less than the target value, so the first cycle is performed again. K is preferably 1 or more, more preferably 2 or more. K is preferably 10 or less.

[0049] On the other hand, when the number of times the first cycle is performed reaches K (step S104, YES), the thickness of the target film WB has reached the target value, so step S105 is performed. Note that if K is an integer of 2 or more, that is, if the first cycle is performed repeatedly, the target film WB is preferably a non-oxide film that substantially does not contain oxygen. The non-oxide film preferably has an oxygen content of 0 at% to 10 at%. If the target film WB is a non-oxide film, the reformed gas does not replace the target film WB with a boron oxide film WA in step S102 from the second time onward.

[0050] Step S105 includes etching the boron oxide film WA, which has been reformed with a reforming gas, with an etching gas (see Figure 3). The etching gas is not particularly limited, but is preferably a plasma-generated noble gas. The plasma-generated noble gas sputters the boron oxide film WA, promoting its volatilization. As a result, etching of the boron oxide film WA progresses. The noble gas includes He, Ne, Ar, Kr, or Xe.

[0051] The etching gas is not limited to plasma-generated noble gases. The etching gas may include H2, O2, COS, NH3, SO2, CO2, CO, CH4, NO2, NO, or N2, etc. The etching gas may also include Cl2, F2, HF, XeF2, ClF3, BrF3, HCl, Br2, HBr, I2, HI, SOCl2, SO2Cl2, or SF6. The etching gas may also include CF4, CH3F, CHF3, C4F6, C4F8, CH3Cl, or CH3Br. These etching gases may be plasma-generated.

[0052] The etching gas can remove the target film WB that adhered to the boron oxide film WA in step S103 by etching the boron oxide film WA, and selectively leave the target film WB on the non-oxide film W2. The etching gas may also etch a portion of the target film WB formed on the non-oxide film W2, not just the boron oxide film WA.

[0053] Step S106 includes confirming whether the second cycle has been performed L times (where L is an integer greater than or equal to 1). The second cycle includes supplying reforming gas (step S102), forming the target film WB (step S103), and supplying etching gas (step S105). L may be an integer greater than or equal to 2, and the second cycle may be repeated multiple times. The film thickness of the target film WB can be increased while maintaining the selectivity of the target film WB.

[0054] If the number of times the second cycle is performed is less than L (step S106, NO), the film thickness of the target film WB is less than the target value, so the second cycle is performed again. L is preferably 2 or more, more preferably 5 or more. L is preferably 10 or less.

[0055] On the other hand, when the number of times the second cycle is performed reaches L (step S106, YES), the film thickness of the target film WB has reached the target value, and the process is terminated. Note that if L is an integer of 2 or more, that is, if the second cycle is repeated, the target film WB is preferably a non-oxide film that substantially does not contain oxygen. The non-oxide film preferably has an oxygen content of 0 at% to 10 at%. If the target film WB is a non-oxide film, the reformed gas does not replace the target film WB with a boron oxide film WA in step S102 from the second time onward.

[0056] As described above, the substrate processing method of this embodiment comprises steps S101 to S103. Step S103 is the selective deposition of the target film WB. In the selective deposition of the target film WB, a boron oxide film WA is used as an inhibitory film that inhibits the deposition of the target film WB. Step S102 is the supply of a modified gas containing boron to the substrate W, thereby modifying the surface of the oxide film W1 into a boron oxide film WA. Thus, the boron oxide film WA can be formed in a simple process.

[0057] Furthermore, the substrate processing method of this embodiment includes step S105 in addition to steps S101 to S103. Step S105 involves etching the boron oxide film WA with an etching gas. After the thickness of the target film WB reaches the target value, the unnecessary boron oxide film WA can be removed. Also, by removing the boron oxide film WA, the oxide film W1 is exposed, and the boron oxide film WA can be formed again on the oxide film W1.

[0058] In step S103, the target film WB is selectively formed on the non-oxide film W2 relative to the boron oxide film WA. However, growth nuclei for the target film WB may also be generated on the boron oxide film WA. In addition, a portion of the boron oxide film WA may be lost, exposing the surface of the oxide film W1. In other words, if the time in step S103 is long, the inhibitory effect of the boron oxide film WA may be impaired. By removing the boron oxide film WA in step S105 to expose the oxide film W1, and then forming the boron oxide film WA again on the oxide film W1 in step S103, the inhibitory effect of the boron oxide film WA can be restored.

[0059] Next, a modified film formation method will be described with reference to Figures 4 to 8. The differences from the above embodiment will be described below. In the above embodiment, a substrate W is used to form a boron oxide film WA on a part of the substrate surface, and the oxide film W1 and the non-oxide film W2 are on different regions of the surface. In this modified film formation method, a substrate W is used to form a boron oxide film WA on a part of the substrate surface, and the oxide film W1 has a top surface W1a of a convex portion and a recess W1b that is recessed from the top surface W1a of the convex portion. As previously described, in the above embodiment, the surface of the substrate W may be an uneven surface, and it is also possible to combine the above embodiment and this modified embodiment.

[0060] Furthermore, the film deposition method includes, for example, steps S101 to S109 shown in Figure 4. Note that the film deposition method only needs to include steps S101 to S106, and does not need to include steps S107 to S109. Also, the film deposition method may include steps other than those S101 to S109 shown in Figure 4.

[0061] Step S101 includes preparing the substrate W. The substrate W has a top surface W1a of the protrusion and a recess W1b that is recessed from the top surface W1a of the protrusion on the surface of the oxide film W1. The recess W1b has a side surface W1b1 and a bottom surface W1b2. In this modified example, the formation of the surface irregularities of the oxide film W1 is performed when the oxide film W1 is formed, as shown in Figure 6, but it may also be performed after the formation of the oxide film W1, as shown in Figure 8. In the former case, the oxide film W1 is formed along the irregularities of the substrate W0. The substrate W0 may be an oxide film.

[0062] Step S102 includes modifying the surface of the oxide film W1 with a modifying gas. The modifying gas selectively modifies the top surface W1a of the protrusion and its vicinity with respect to the bottom surface W1b2 of the recess W1b and its vicinity. The modifying gas contains boron and modifies a portion of the oxide film W1 into a boron oxide film WA. The deeper the depth from the top surface W1a of the protrusion, the more difficult it is for the modifying gas to penetrate, and the less likely it is for the boron oxide film WA to form. Almost no boron oxide film WA is formed on the bottom surface W1b2 of the recess W1b and its vicinity.

[0063] Step S103 includes selectively forming a target film WB on the bottom surface W1b2 of the recess W1b and its vicinity on the top surface W1a and its vicinity of the convex portion modified to a boron oxide film WA in step S102 (see Figure 6). Step S103 includes supplying a raw material gas containing a compound of a desired element X and a halogen, and a reaction gas that reacts with adsorbed substances of the raw material gas, to the substrate W. The raw material gas and the reaction gas are supplied alternately or simultaneously. In this case, the target film WB contains element X. The target film WB is not particularly limited, but it is preferably an oxide film having a similar composition to the oxide film W1. Note that the target film WB does not have to be an oxide film, and may be a non-oxide film.

[0064] Step S104 includes confirming whether the first cycle has been performed K times (where K is an integer greater than or equal to 1). The first cycle includes supplying reformed gas (step S102) and forming the target film WB (step S103). K may be an integer greater than or equal to 2, and the first cycle may be repeated multiple times. The thickness of the target film WB can be increased. In step S103, if the boron oxide film WA is damaged by plasma or the like before the thickness of the target film WB reaches the target value, and the surface of the oxide film W1 (the top surface W1a of the convex portion and its vicinity) is exposed, it is effective to repeat the first cycle.

[0065] If K in the first cycle is an integer of 2 or more, that is, if the first cycle is repeated, the target film WB is preferably an oxide film. If the target film WB is an oxide film, in the second and subsequent steps S102, the reformed gas can replace a portion of the target film WB (the portion close to the top surface W1a of the convex part) with the boron oxide film WA. This allows the target film WB to be selectively embedded in the deeper parts of the concave parts in the second and subsequent steps S103.

[0066] Step S105 includes etching the boron oxide film WA, which has been reformed with a reforming gas, with an etching gas (see Figure 6). The etching gas is not particularly limited, but is preferably a plasma-generated noble gas. The plasma-generated noble gas sputters the boron oxide film WA, promoting its volatilization. As a result, etching of the boron oxide film WA progresses. The noble gas includes He, Ne, Ar, Kr, or Xe.

[0067] The etching gas is not limited to plasma-generated noble gases. The etching gas may include H2, O2, COS, NH3, SO2, CO2, CO, CH4, NO2, NO, or N2, etc. The etching gas may also include Cl2, F2, HF, XeF2, ClF3, BrF3, HCl, Br2, HBr, I2, HI, SOCl2, SO2Cl2, or SF6. The etching gas may also include CF4, CH3F, CHF3, C4F6, C4F8, CH3Cl, or CH3Br. These etching gases may be plasma-generated. The etching gas may etch not only the boron oxide film WA, but also a portion of the target film WB.

[0068] Step S106 includes confirming whether the second cycle has been performed L times (where L is an integer greater than or equal to 1). The second cycle includes supplying reformed gas (step S102), forming the target film WB (step S103), and supplying etching gas (step S105). L may be an integer greater than or equal to 2, and the second cycle may be repeated multiple times. When embedding the target film WB inside the recess W1b, the generation of seams and voids can be suppressed.

[0069] If L in the second cycle is an integer of 2 or more, that is, if the second cycle is repeated, it is preferable that the target film WB is an oxide film. If the target film WB is an oxide film, in the second and subsequent steps S102, the reformed gas can replace a portion of the target film WB (the portion close to the top surface W1a of the convex part) with the boron oxide film WA (see Figure 7). This allows the target film WB to be selectively embedded in the depth of the recess W1b in the second and subsequent steps S103. In addition, the opening of the recess W1b can be widened before the second and subsequent steps S103, and the generation of seams and voids can be suppressed in the second and subsequent steps S103.

[0070] Step S107 includes, for example, steps S107a to S107e, as shown in Figure 5. Step S107 only needs to include at least steps S107a, S107c, and S107e; steps S107b and S107d are not required. Steps S107a to S107e will be described below.

[0071] The purpose of performing step S107 is at least one of the following: (1) to widen the opening of the recess W1b, and (2) to widen the opening of the target film WB if the target film WB is an oxide film.

[0072] Step S107a includes supplying a reformed gas to the substrate W, similar to step S102. The reformed gas is preferably the same as the reformed gas used in S102. The reformed gas may be BCl3, B(CH3)3, B2H6, BF3, BBr3, BI3, C9H 24 BN3, C3H9B, C6H 15 It is preferable that the mixture contains at least one of B and B3N3H6. The reformed gas selectively reforms the top surface W1a of the convex portion and its vicinity with respect to the bottom surface W1b2 of the recess W1b and its vicinity. The reformed gas contains boron and reforms a portion of the oxide film W1 into a boron oxide film WA. The greater the depth from the top surface W1a of the convex portion, the more difficult it is for the reformed gas to penetrate, and the less likely it is for the boron oxide film WA to form. Almost no boron oxide film WA is formed on the bottom surface W1b2 of the recess W1b and its vicinity.

[0073] Step S107b includes supplying a purge gas to the substrate W. The purge gas purges any excess reforming gas that was not used to reform the substrate W in step S107a. As the purge gas, for example, a noble gas such as Ar gas or N2 gas may be used.

[0074] Step S107c, similar to step S105, includes supplying an etching gas to the substrate W. The etching gas is preferably the same etching gas used in S105. The etching gas is not particularly limited, but for example, it may be a plasma-formed noble gas. The plasma-formed noble gas sputters the boron oxide film WA, promoting its volatilization. As a result, etching of the boron oxide film WA progresses. The noble gas may include He, Ne, Ar, Kr, or Xe.

[0075] The etching gas is not limited to plasma-generated noble gases. The etching gas may include H2, O2, COS, NH3, SO2, CO2, CO, CH4, NO2, NO, or N2, etc. The etching gas may also include Cl2, F2, HF, XeF2, ClF3, BrF3, HCl, Br2, HBr, I2, HI, SOCl2, SO2Cl2, or SF6. The etching gas may also include CF4, CH3F, CHF3, C4F6, C4F8, CH3Cl, or CH3Br. These etching gases may be plasma-generated. The etching gas may etch not only the boron oxide film WA, but also a portion of the target film WB.

[0076] Step S107d includes supplying a purge gas to the substrate W. The purge gas purges any excess etching gas that did not react with the substrate W in step S107c. As the purge gas, for example, a noble gas such as Ar gas or N2 gas can be used.

[0077] Step S107e includes checking whether the fifth cycle has been performed J times (where J is an integer greater than or equal to 1). The fifth cycle includes steps S107a to S107d. J may be an integer greater than or equal to 2, and the fifth cycle may be repeated multiple times. The amount of etching of the oxide film W1 can be increased.

[0078] If the number of times the fifth cycle is performed is less than J (step S107e, NO), the opening of the recess W1b has not been expanded to the desired width, or, if the embedded target film WB is an oxide film, the opening of the target film WB has not been expanded to the desired width, so the fifth cycle is performed again. J is preferably 5 or more, more preferably 10 or more. J is preferably 100 or less.

[0079] On the other hand, if the number of executions of the fifth cycle reaches J (step S107e, YES), the current process is terminated. Reaching J executions of the fifth cycle may include (1) the opening of the recess W1b reaching a desired size, or (2) if the target film WB is an oxide film, the opening of the target film WB reaching a desired size.

[0080] In step S107, the supply of reforming gas (step S107a) and etching gas (step S107c) is carried out without the formation of the target film WB in between. As long as the oxide film W1 and the target film WB remain, etching of the oxide film W1 can be advanced. By performing step S107, the opening of the recess W1b can be widened. Furthermore, if the target film WB is an oxide film, the opening of the target film WB can be widened. This makes it possible to suppress the generation of seams and voids when filling the recess W1b with the target film WB in step S109.

[0081] Step S108 includes confirming whether the third cycle has been performed M times (where M is an integer greater than or equal to 1). The third cycle includes supplying reformed gas (step S102), forming the target film WB (step S103), and supplying etching gas (step S105), and thereafter including supplying reformed gas (step S107a) and etching gas (step S107c) without intervening the formation of the target film WB. M may be an integer greater than or equal to 2, and the third cycle may be repeated multiple times. When embedding the target film WB inside the recess W1b, the generation of seams and voids can be suppressed.

[0082] If M in the third cycle is an integer of 2 or more, that is, if the third cycle is repeated, the target film WB is preferably an oxide film. If the target film WB is an oxide film, in the second and subsequent steps S102, the reformed gas can replace a portion of the target film WB (the portion close to the top surface W1a of the convex part) with a boron oxide film WA. This allows the target film WB to be selectively embedded in the depth of the recess W1b in the second and subsequent steps S103. In addition, the opening of the recess W1b can be widened before the second and subsequent steps S103, and the generation of seams and voids can be suppressed in the second and subsequent steps S103.

[0083] Step S109 includes filling the recess W1b with the target film WB. The target film WB is formed by CVD, ALD, or plating. Preferably, the target film WB is formed not only on the recess W1b but also on the top surface W1a of the protrusion. Although not shown, the substrate processing method may include a step of polishing the target film WB after step S109. Note that step S109 may be performed after step S106 instead of after step S108.

[0084] As described above, the substrate processing method of this modified example has steps S101 to S103, similar to the substrate processing method of the above embodiment. Step S103 is the selective deposition of the target film WB. In the selective deposition of the target film WB, a boron oxide film WA is used as an inhibitory film that inhibits the deposition of the target film WB. Step S102 is the supply of a modified gas containing boron to the substrate W, thereby modifying a portion of the oxide film W1 into a boron oxide film WA. Thus, the boron oxide film WA can be formed in a simple process.

[0085] Furthermore, the substrate processing method of this modified example, like the substrate processing method of the above embodiment, includes step S105 in addition to steps S101 to S103. Step S105 involves etching the boron oxide film WA with an etching gas. This allows for the removal of the unwanted boron oxide film WA. Additionally, when the second cycle is repeated, the opening of the recess W1b can be widened.

[0086] Furthermore, this modified substrate processing method differs from the substrate processing method of the above embodiment in that, in addition to steps S101 to S105, it includes step S107. Step S107a includes supplying a modified gas to the substrate W. Step S107c includes supplying an etching gas to the substrate W. Step S107 can widen the opening of the recess W1b.

[0087] Next, with reference to Figure 9, a substrate processing apparatus 100 for carrying out the above-described film deposition method will be explained. As shown in Figure 9, the substrate processing apparatus 100 has a first processing unit 200A, a second processing unit 200B, a third processing unit 200C, a transport unit 400, and a control unit 500. The first processing unit 200A carries out step S102 in Figure 1. The second processing unit 200B carries out step S103 in Figure 1. The third processing unit 200C carries out step S105 in Figure 1. It is also possible for the first processing unit 200A to carry out all of steps S102, S103, and S105 in Figure 1.

[0088] The substrate processing apparatus 100 can also perform the film deposition method shown in Figure 4 instead of the film deposition method shown in Figure 1. For example, the first processing unit 200A performs steps S102 and S107a in Figure 4. Steps S102 and S107a may be performed in separate processing units. The second processing unit 200B performs step S103 in Figure 4. The third processing unit 200C performs steps S105 and S107c in Figure 4. Steps S105 and S107c may be performed in separate processing units. The first processing unit 200A can also perform all of steps S102, S103, S105, S107a and S107c in Figure 4. Step S109 in Figure 4 may be performed by an external device to the substrate processing apparatus 100.

[0089] The transport unit 400 transports the substrate W to the first processing unit 200A, the second processing unit 200B, and the third processing unit 200C. The transport unit 400 has a first transport chamber 401 and a first transport mechanism 402. The internal atmosphere of the first transport chamber 401 is an atmospheric atmosphere. The first transport mechanism 402 is provided inside the first transport chamber 401. The first transport mechanism 402 includes an arm 403 for holding the substrate W and travels along a rail 404. The rail 404 extends in the direction of the arrangement of the carriers C.

[0090] Furthermore, the transport unit 400 includes a second transport chamber 411 and a second transport mechanism 412. The internal atmosphere of the second transport chamber 411 is a vacuum atmosphere. The second transport mechanism 412 is provided inside the second transport chamber 411. The second transport mechanism 412 includes an arm 413 for holding the substrate W, and the arm 413 is arranged to be movable in the vertical and horizontal directions and rotatable around a vertical axis. The first processing unit 200A, the second processing unit 200B, and the third processing unit 200C are connected to the second transport chamber 411 via different gate valves G.

[0091] Furthermore, the conveying section 400 has a load lock chamber 421 between the first conveying chamber 401 and the second conveying chamber 411. The internal atmosphere of the load lock chamber 421 is switched between a vacuum atmosphere and an atmospheric atmosphere by a pressure regulating mechanism (not shown). This allows the inside of the second conveying chamber 411 to always be maintained in a vacuum atmosphere. It also prevents gas from flowing from the first conveying chamber 401 into the second conveying chamber 411. Gate valves G are provided between the first conveying chamber 401 and the load lock chamber 421, and between the second conveying chamber 411 and the load lock chamber 421.

[0092] The control unit 500 is, for example, a computer and has an arithmetic unit 501 such as a CPU (Central Processing Unit) and a storage unit 502 such as memory. The storage unit 502 stores programs that control various processes performed in the substrate processing apparatus 100. The control unit 500 controls the operation of the substrate processing apparatus 100 by causing the arithmetic unit 501 to execute the programs stored in the storage unit 502. The control unit 500 controls the first processing unit 200A, the second processing unit 200B, the third processing unit 200C and the transport unit 400 to carry out the above-described film deposition method.

[0093] The control unit 500 includes an electronic circuit such as a CPU, FPGA (Field Programmable Gate Array), or ASIC (Application Specific Integrated Circuit), and performs various control operations described in this specification by executing instruction codes stored in memory or by designing the circuit for special applications.

[0094] Next, the operation of the substrate processing apparatus 100 will be described. First, the first transport mechanism 402 takes the substrate W from the carrier C, transports the removed substrate W to the load lock chamber 421, and exits the load lock chamber 421. Next, the internal atmosphere of the load lock chamber 421 is switched from an atmospheric atmosphere to a vacuum atmosphere. After that, the second transport mechanism 412 takes the substrate W from the load lock chamber 421 and transports the removed substrate W to the first processing unit 200A.

[0095] Next, the first processing unit 200A performs step S102 in Figure 1. After that, the second transport mechanism 412 removes the substrate W from the first processing unit 200A and transports the removed substrate W to the second processing unit 200B. During this time, the substrate W is protected in a vacuum atmosphere, and contamination of the substrate W by organic compounds in the atmosphere is suppressed.

[0096] Next, the second processing unit 200B performs step S103 in Figure 1. Then, the control unit 500 performs step S104 in Figure 1. If the number of times the first cycle has been performed has not reached K (step S104, NO), the second transport mechanism 412 removes the substrate W from the second processing unit 200B and transports the removed substrate W to the first processing unit 200A. After that, the first cycle is performed again.

[0097] On the other hand, when the number of executions of the first cycle reaches K (step S104, YES), the second transport mechanism 412 removes the substrate W from the second processing unit 200B and transports the removed substrate W to the third processing unit 200C. During this time, the substrate W can be protected in a vacuum atmosphere, and contamination of the substrate W by organic compounds in the atmosphere can be suppressed.

[0098] Next, the third processing unit 200C performs step S105 in Figure 1. Then, the control unit 500 performs step S106 in Figure 1. If the number of times the second cycle has been performed has not reached L (step S106, NO), the second transport mechanism 412 removes the substrate W from the third processing unit 200C and transports the removed substrate W to the first processing unit 200A. After that, the second cycle is performed again.

[0099] On the other hand, when the number of executions of the second cycle reaches L (step S106, YES), the second transport mechanism 412 removes the substrate W from the third processing unit 200C, transports the removed substrate W to the load lock chamber 421, and exits the load lock chamber 421. Subsequently, the internal atmosphere of the load lock chamber 421 is switched from a vacuum atmosphere to an atmospheric atmosphere. After that, the first transport mechanism 402 removes the substrate W from the load lock chamber 421 and places the removed substrate W into the carrier C. Then, the processing of the substrate W is completed.

[0100] Next, the first processing unit 200A will be described with reference to Figure 10. Note that the configurations of the second processing unit 200B and the third processing unit 200C are the same as those of the first processing unit 200A, so their illustrations and descriptions are omitted.

[0101] The first processing unit 200A includes a substantially cylindrical, airtight processing container 210. An exhaust chamber 211 is provided in the center of the bottom wall of the processing container 210. The exhaust chamber 211 has a shape that protrudes downward, for example, a substantially cylindrical shape. An exhaust pipe 212 is connected to the exhaust chamber 211, for example, on the side of the exhaust chamber 211.

[0102] An exhaust source 272 is connected to the exhaust piping 212 via a pressure controller 271. The pressure controller 271 includes a pressure regulating valve, such as a butterfly valve. The exhaust piping 212 is configured to reduce the pressure inside the processing container 210 by the exhaust source 272. The pressure controller 271 and the exhaust source 272 constitute a gas discharge mechanism 270 that discharges gas from inside the processing container 210.

[0103] A transport port 215 is provided on the side of the processing container 210. The transport port 215 is opened and closed by a gate valve G. The substrate W is loaded and unloaded between the processing container 210 and the second transport chamber 411 (see Figure 9) through the transport port 215.

[0104] A stage 220, which is a holding part for holding the substrate W, is provided inside the processing container 210. The stage 220 holds the substrate W horizontally with the surface to be etched facing upwards. The stage 220 is formed in a substantially circular shape in plan view and is supported by a support member 221. A substantially circular recess 222 is formed on the surface of the stage 220 for placing a substrate W, for example, with a diameter of 300 mm. The recess 222 has an inner diameter slightly larger than the diameter of the substrate W. The depth of the recess 222 is set to be approximately the same as the thickness of the substrate W, for example. The stage 220 is made of a ceramic material such as aluminum nitride (AlN). Alternatively, the stage 220 may be made of a metallic material such as nickel (Ni). Instead of the recess 222, a guide ring for guiding the substrate W may be provided on the peripheral edge of the surface of the stage 220.

[0105] A lower electrode 223, for example, grounded, is embedded in the stage 220. A heating mechanism 224 is embedded below the lower electrode 223. The heating mechanism 224 is powered by a power supply unit (not shown) based on a control signal from the control unit 500 (see Figure 9), and heats the substrate W placed on the stage 220 to a set temperature. If the entire stage 220 is made of metal, the entire stage 220 functions as the lower electrode, so the lower electrode 223 does not need to be embedded in the stage 220. The stage 220 is provided with a plurality (e.g., three) of lifting pins 231 for holding and raising and lowering the substrate W placed on the stage 220. The material of the lifting pins 231 may be, for example, ceramics such as alumina (Al2O3) or quartz. The lower ends of the lifting pins 231 are attached to a support plate 232. The support plate 232 is connected via a lifting shaft 233 to a lifting mechanism 234 located outside the processing container 210.

[0106] The lifting mechanism 234 is installed, for example, at the bottom of the exhaust chamber 211. The bellows 235 is provided between the opening 219 for the lifting shaft 233 formed on the lower surface of the exhaust chamber 211 and the lifting mechanism 234. The shape of the support plate 232 may be such that it can move up and down without interfering with the support member 221 of the stage 220. The lifting pin 231 is configured to move up and down between the upper surface of the stage 220 and the lower surface of the stage 220 by the lifting mechanism 234.

[0107] A gas supply unit 240 is provided on the top wall 217 of the processing container 210 via an insulating member 218. The gas supply unit 240 forms the upper electrode and faces the lower electrode 223. A high-frequency power supply 252 is connected to the gas supply unit 240 via a matching unit 251. By supplying high-frequency power of 100kHz to 2.45GHz, preferably 450kHz to 100MHz, from the high-frequency power supply 252 to the upper electrode (gas supply unit 240), a high-frequency electric field is generated between the upper electrode (gas supply unit 240) and the lower electrode 223, and a capacitively coupled plasma is generated. The plasma generation unit 250 that generates the plasma includes a matching unit 251 and a high-frequency power supply 252. Note that the plasma generation unit 250 is not limited to generating a capacitively coupled plasma, but may generate other plasmas such as inductively coupled plasma or remote plasma. Note that in steps where plasma is not generated, it is not necessary for the gas supply unit 240 to form the upper electrode, and the lower electrode 223 is also unnecessary.

[0108] The gas supply unit 240 includes a hollow gas supply chamber 241. On the lower surface of the gas supply chamber 241, numerous holes 242 are evenly arranged, for example, to distribute and supply the processing gas into the processing container 210. Above the gas supply chamber 241 in the gas supply unit 240, for example, a heating mechanism 243 is embedded. The heating mechanism 243 is heated to a set temperature by being powered from a power supply unit (not shown) based on a control signal from the control unit 500.

[0109] A gas supply mechanism 260 is connected to the gas supply chamber 241 via a gas supply passage 261. The gas supply mechanism 260 supplies the gas used in the desired step of Figure 1 or Figure 4 to the gas supply chamber 241 via the gas supply passage 261. The gas supply mechanism 260, although not shown, includes individual piping for each type of gas, on-off valves installed in the middle of the individual piping, and flow controllers installed in the middle of the individual piping. When the on-off valve opens the individual piping, gas is supplied from the supply source to the gas supply passage 261. The amount of gas supplied is controlled by the flow controller. On the other hand, when the on-off valve closes the individual piping, the supply of gas from the supply source to the gas supply passage 261 is stopped.

[0110] While embodiments of the film deposition method and film deposition apparatus relating to this disclosure have been described above, this disclosure is not limited to the above embodiments. Various changes, modifications, substitutions, additions, deletions, and combinations are possible within the scope of the claims. These also naturally fall within the technical scope of this disclosure. [Explanation of Symbols]

[0111] W board W1 Oxide film W2 Non-oxide film WA boron oxide film WB Target membrane

Claims

1. The method involves preparing a substrate having an oxide film substantially free of boron and a non-oxide film substantially free of oxygen in different regions of its surface, The process involves supplying a boron-containing modified gas to the substrate and modifying at least the surface of the oxide film into a boron oxide film. The process involves selectively forming a target film on the surface of the non-oxide film relative to the surface of the boron oxide film, It has, The aforementioned target film contains the desired element X, A film-forming method comprising supplying a source gas containing a compound of element X and a halogen, and a reaction gas that reacts with adsorbed substances of the source gas, to the substrate for forming the target film.

2. The method for forming a film according to claim 1, wherein the oxide film comprises a compound of a metal and oxygen or a compound of a semiconductor element and oxygen.

3. The method for forming a film according to claim 1, wherein the non-oxide film has an oxygen content of 0 at% to 10 at%.

4. The modified gas is BCl ３ , B(CH ３ ) ３ , B ２ H ６ , BF ３ , BBr ３ , BI ３ , C ９ H ２４ BN ３ , C ３ H ９ B, C ６ H １５ B, and B ３ N ３ H ６ The film forming method according to claim 1, comprising at least one of

5. The aforementioned membrane is substantially free of oxygen, The film formation method according to claim 1, wherein the film formation method is repeated multiple times, the first cycle including the supply of the reformed gas and the formation of the target film.

6. The film formation method according to claim 1, further comprising etching the boron oxide film with an etching gas after forming the target film.

7. The aforementioned membrane is substantially free of oxygen, The film formation method according to claim 6, wherein the film formation method is repeated multiple times through a second cycle that includes supplying the modified gas, forming the target film, and supplying the etching gas.

8. A substrate is prepared having an oxide film substantially free of boron on its surface, and the oxide film surface having a top surface of a convex portion and a recess extending from the top surface of the convex portion. A modified gas containing boron is supplied to the substrate, and the top surface and vicinity of the protrusions are selectively modified to form a boron oxide film relative to the bottom surface and vicinity of the recesses. The target film is selectively formed on the bottom surface of the recess and its vicinity on the top surface of the convex portion and its vicinity, which has been modified with the boron oxide film. It has, The aforementioned target film contains the desired element X, A film-forming method comprising supplying a source gas containing a compound of element X and a halogen, and a reaction gas that reacts with adsorbed substances of the source gas, to the substrate for forming the target film.

9. The method for forming a film according to claim 8, wherein the oxide film comprises a compound of a metal and oxygen or a compound of a semiconductor element and oxygen.

10. The reformed gas is BCl ３ , B (CH ３ ) ３ , B ２ H ６ BF ３ , C ９ H ２４ BN ３ , C ３ H ９ B, C ６ H １５ B, and B ３ N ３ H ６ The film formation method according to claim 8, comprising at least one of the above.

11. The film formation method according to claim 8, wherein the film formation method is repeated multiple times, the first cycle including the supply of the reformed gas and the formation of the target film.

12. The film formation method according to claim 8, further comprising etching the boron oxide film with an etching gas after forming the target film.

13. The film formation method according to claim 12, wherein the film formation method is repeated multiple times through a second cycle that includes the supply of the modified gas, the formation of the target film, and the supply of the etching gas.

14. The film formation method according to claim 12, wherein, after supplying the reformed gas, forming the target film, and supplying the etching gas, the supplying of the reformed gas and the supplying of the etching gas are performed once or more times without intervening the formation of the target film.

15. The film formation method according to claim 14, comprising supplying the reforming gas, forming the target film, and supplying the etching gas, and thereafter repeatedly performing a third cycle multiple times, which includes supplying the reforming gas and supplying the etching gas once or more times without intervening the formation of the target film.

16. A processing container for housing the aforementioned substrate, The processing container includes a holding section for holding the substrate inside, A supply unit that supplies gas to the substrate held in the holding unit, A control unit that controls the supply unit, Equipped with, The control unit performs control for carrying out the film deposition method described in any one of claims 1 to 15, wherein the film deposition apparatus.

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