Film formation method and substrate processing apparatus

Abstract

To provide a method for forming a film containing silicon and oxygen with improved uniformity and a substrate processing device.SOLUTION: A film forming method for forming a film containing at least silicon and oxygen on a substrate includes a step S11 of supplying a metal-containing catalyst gas (TMA gas) to the substrate, a step S13 of applying RF power to the substrate to generate and supply hydrogen radicals from a hydrogen-containing gas (H2 gas), and a step S15 of supplying a silicon precursor gas (TPSOL gas) containing silanol in the substrate into a processing chamber, and each of the steps is performed non-simultaneously and repeated multiple times.SELECTED DRAWING: Figure 2

Description

Technical Field

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

Background Art

[0002] For example, a film forming method for forming a silicon-based film on a substrate is known.

[0003] Patent Document 1 discloses a method for depositing a thin film of silicon dioxide, including: a step of providing a gas-phase reactant pulse containing a metal precursor into a chamber of a reactant to form only a substantially monolayer of the metal precursor on a substrate; and a step of providing a gas-phase reactant pulse containing a silicon precursor into the chamber of the reactant to react the silicon precursor with the metal precursor on the substrate.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In the step of reacting a silicon precursor with a metal precursor on a substrate, the film formation amount may not saturate with respect to the time of supplying the silicon precursor. As a result, the uniformity of the film formed on the substrate may decrease.

[0006] On one aspect, the present disclosure provides a film forming method and a substrate processing apparatus that improve uniformity.

Means for Solving the Problems

[0007] To solve the above problems, according to one aspect, a film forming method for forming a film containing at least silicon and oxygen on a substrate, comprising: a) providing a metal-containing catalyst to the substrate Multiple units arranged with spacing along the vertical direction ​ From the outer periphery side of the aforementioned substrate The process of supplying, and a) applying hydrogen-containing gas to the substrate From the outer periphery side of the aforementioned substrate The process of supplying, and c) the silicon precursor containing silanol on the substrate From the outer periphery side of the aforementioned substrate A film formation method is provided, comprising a supply step. [Effects of the Invention]

[0008] In one aspect, it is possible to provide a film formation method and a substrate processing apparatus that improve uniformity. [Brief explanation of the drawing]

[0009] [Figure 1] A schematic diagram showing an example configuration of a substrate processing apparatus according to this embodiment. [Figure 2] A time chart showing an example of the film formation process according to this embodiment. [Figure 3] A time chart showing an example of the film formation process related to the first reference example. [Figure 4] An example of a graph showing the results of the film formation process according to this embodiment and reference example, specifically the average film thickness, film thickness uniformity within the substrate, and film thickness uniformity between substrates. [Figure 5] A figure showing an example of the film thickness distribution in this embodiment and the first reference example. [Figure 6] A graph showing an example of the results of secondary ion mass spectrometry of a film formed by the film formation process according to this embodiment. [Figure 7] An example graph showing the average film thickness results in a film formation process. [Figure 8] A time chart showing another example of the film formation process according to this embodiment. [Figure 9] A time chart showing another example of the film formation process according to this embodiment. [Figure 10] A time chart showing another example of the film formation process according to this embodiment. [Figure 11] An example graph showing the results of the average film thickness and film thickness uniformity within the substrate W during the film formation process. [Figure 12]A time chart showing another example of the film formation process according to this embodiment.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, embodiments for implementing the present disclosure will be described with reference to the drawings. In each drawing, the same reference numerals are assigned to the same components, and redundant descriptions may be omitted.

[0011] 〔Substrate Processing Apparatus〕 The substrate processing apparatus 100 according to this embodiment will be described with reference to FIG. 1. FIG. 1 is a schematic diagram showing a configuration example of the substrate processing apparatus 100 according to this embodiment.

[0012] The substrate processing apparatus 100 has a ceilinged cylindrical processing vessel 1 with an open lower end. The entire processing vessel 1 is formed of, for example, quartz. Near the upper end inside the processing vessel 1, a ceiling plate 2 formed of quartz is provided, and the region below the ceiling plate 2 is sealed. To the opening at the lower end of the processing vessel 1, a cylindrical metal manifold 3 is connected via a seal member 4 such as an O-ring.

[0013] The manifold 3 supports the lower end of the processing vessel 1, and a wafer boat 5 on which a large number (for example, 25 to 150) of semiconductor wafers (hereinafter referred to as "substrate W") are placed in multiple stages as substrates is inserted into the processing vessel 1 from below the manifold 3. Thus, a large number of substrates W are accommodated substantially horizontally in the processing vessel 1 at intervals along the vertical direction. The wafer boat 5 is formed of, for example, quartz. The wafer boat 5 has three rods 6 (two are shown in FIG. 1), and a large number of substrates W are supported by grooves (not shown) formed in the rods 6.

[0014] The wafer boat 5 is placed on a table 8 via a heat-insulating cylinder 7 formed of quartz. The table 8 is supported on a rotating shaft 10 that penetrates a metal (stainless steel) lid 9 that opens and closes the opening at the lower end of the manifold 3.

[0015] A magnetic fluid seal 11 is provided in the through-hole of the rotating shaft 10, which hermetically seals the rotating shaft 10 and supports it rotatably. A seal member 12 for maintaining the airtightness inside the processing vessel 1 is provided between the peripheral portion of the lid body 9 and the lower end of the manifold 3.

[0016] The rotating shaft 10 is attached to the tip of an arm 13 supported by a lifting mechanism (not shown) such as a boat elevator. The wafer boat 5 and the lid body 9 are lifted and lowered integrally and inserted into and removed from the processing vessel 1. Note that the table 8 may be fixed to the lid body 9 side and the substrate W may be processed without rotating the wafer boat 5.

[0017] Further, the substrate processing apparatus 100 has a gas supply unit 20 that supplies a predetermined gas such as a processing gas and a purge gas into the processing vessel 1.

[0018] The gas supply unit 20 has gas supply pipes 21 to 24. The gas supply pipes 21, 22, and 23 are formed of, for example, quartz, penetrate the side wall of the manifold 3 inward, bend upward, and extend vertically. A plurality of gas holes 21g, 22g, and 23g are formed at predetermined intervals over the vertical length corresponding to the wafer support range of the wafer boat 5 in the vertical portions of the gas supply pipes 21, 22, and 23. Each of the gas holes 21g, 22g, and 23g discharges gas in the horizontal direction. The gas supply pipe 24 is formed of, for example, quartz and consists of a short quartz pipe penetrating the side wall of the manifold 3.

[0019] The vertical portion (the vertical portion where the gas hole 21g is formed) of the gas supply pipe 21 is provided inside the processing vessel 1. A metal-containing catalyst gas is supplied to the gas supply pipe 21 from a gas supply source 21a through a gas pipe. A flow controller 21b and an on-off valve 21c are provided in the gas pipe. Thereby, the metal-containing catalyst gas from the gas supply source 21a is supplied into the processing vessel 1 through the gas pipe and the gas supply pipe 21.

[0020] Here, the gas supply source 21a supplies a metal-containing catalyst gas that forms a single molecular layer of the metal catalyst on the surface of the substrate W. The metal-containing catalyst gas includes gases of metals, metalloids, or compounds thereof that have Lewis acid properties. Specifically, the metal-containing catalyst gas can be an organic, inorganic, or halide precursor gas containing, for example, Al, Co, Hf, Ni, Pt, Ru, W, Zr, Ti, B, Ga, In, Zn, Mg, or Ta. The metal catalyst may be a substrate in which Al, Co, Hf, Ni, Pt, Ru, W, Zr, Ti, B, Ga, In, Zn, Mg, or Ta are exposed. In the following description, the metal-containing catalyst gas will be described as TMA (Trimethylaluminum) gas.

[0021] The gas supply pipe 22 has a vertical portion (the vertical portion where the gas holes 22g are formed) located inside the processing container 1. Silicon precursor gas is supplied to the gas supply pipe 22 from the gas supply source 22a via the gas piping. The gas piping is equipped with a flow controller 22b and an on / off valve 22c. As a result, the silicon precursor gas from the gas supply source 22a is supplied into the processing container 1 via the gas piping and the gas supply pipe 22.

[0022] Here, gas source 22a supplies a silicon precursor gas containing silanol. Examples of silicon precursor gases that can be used include TPSOL gas, Triethylsilanol, Methyl bis(tert-pentoxy)silanol, and Tris(tert-butoxy)silanol. In the following description, the silicon precursor gas will be described as TPSOL (Tris(tert-pentoxy)silanol).

[0023] The gas supply pipe 23 has a vertical portion (the vertical portion where the gas holes 23g are formed) located in the plasma generation space, which will be described later. Hydrogen-containing gas is supplied to the gas supply pipe 23 from the gas supply source 23a via gas piping. The gas piping is equipped with a flow controller 23b and an on-off valve 23c. As a result, the hydrogen-containing gas from the gas supply source 23a is supplied to the plasma generation space via the gas piping and the gas supply pipe 23, where it is plasma-generated and hydrogen radicals are supplied into the processing container 1.

[0024] Here, the gas supply source 23a supplies a hydrogen-containing gas. As the hydrogen-containing gas, it is possible to use gases that contain at least hydrogen (H) or deuterium (D), such as H2 gas, D2 gas, H2O gas, NH3 gas, silicon hydride gas, PH3 gas, B2H6 gas, and hydrocarbon gases. In the following explanation, the hydrogen-containing gas will be described as H2 gas.

[0025] Although the substrate processing apparatus 100 has been described as a plasma processing apparatus that generates hydrogen radicals from a hydrogen-containing gas and supplies them to the substrate W in the processing container 1, it is not limited to this. The substrate processing apparatus 100 may also be a substrate processing apparatus that performs thermal processing by supplying a hydrogen-containing gas (for example, NH3 gas, etc.) from a gas supply pipe 23 to the substrate W in the processing container 1 which has been heated to a desired temperature.

[0026] The gas supply pipe 24 is supplied with purge gas from a purge gas supply source (not shown) via gas piping. The gas piping (not shown) is equipped with a flow controller (not shown) and an on / off valve (not shown). As a result, the purge gas from the purge gas supply source is supplied into the processing container 1 via the gas piping and gas supply pipe 24. As the purge gas, an inert gas such as argon (Ar) or nitrogen (N2) can be used. Although the case in which the purge gas is supplied from the purge gas supply source to the processing container 1 via the gas piping and gas supply pipe 24 has been described, the system is not limited to this, and the purge gas may be supplied from any of the gas supply pipes 21 to 23.

[0027] A plasma generation mechanism 30 is formed in a part of the side wall of the processing container 1. The plasma generation mechanism 30 generates hydrogen (H) radicals by plasmaizing a hydrogen-containing gas (for example, H2 gas).

[0028] The plasma generation mechanism 30 comprises a plasma compartment wall 32, a pair of plasma electrodes 33 (one is shown in Figure 1), a power supply line 34, a high-frequency power supply 35, and an insulating protective cover 36.

[0029] The plasma compartment wall 32 is hermetically welded to the outer wall of the processing vessel 1. The plasma compartment wall 32 is made of, for example, quartz. The plasma compartment wall 32 has a concave cross-section and covers an opening 31 formed in the side wall of the processing vessel 1. The opening 31 is elongated in the vertical direction so as to cover all the substrates W supported on the wafer boat 5 in the vertical direction. A gas supply pipe 23 for discharging hydrogen-containing gas (for example, H2 gas) is arranged in the inner space defined by the plasma compartment wall 32 and communicating with the inside of the processing vessel 1, i.e., the plasma generation space.

[0030] A pair of plasma electrodes 33 (one is shown in Figure 1) each have an elongated shape and are arranged facing each other vertically on the outer surfaces of the walls on both sides of the plasma compartment wall 32. Each plasma electrode 33 is held by a holding part (not shown) provided, for example, on the side of the plasma compartment wall 32. A power supply line 34 is connected to the lower end of each plasma electrode 33.

[0031] The power supply line 34 electrically connects each plasma electrode 33 to the high-frequency power supply 35. In the illustrated example, one end of the power supply line 34 is connected to the lower end of each plasma electrode 33, and the other end is connected to the high-frequency power supply 35.

[0032] The high-frequency power supply 35 is connected to the lower end of each plasma electrode 33 via a power supply line 34 and supplies high-frequency power of, for example, 13.56 MHz to the pair of plasma electrodes 33. This applies high-frequency power to the plasma generation space defined by the plasma partition wall 32. The hydrogen-containing gas (e.g., H2 gas) discharged from the gas supply pipe 23 is plasma-generated in the plasma generation space to which high-frequency power is applied, and the hydrogen radicals generated are supplied to the inside of the processing container 1 through the opening 31.

[0033] The insulating protective cover 36 is attached to the outside of the plasma compartment wall 32 so as to cover the plasma compartment wall 32. A refrigerant passage (not shown) is provided in the inner portion of the insulating protective cover 36, and the plasma electrode 33 is cooled by flowing a refrigerant such as cooled nitrogen (N2) gas through the refrigerant passage. A shield (not shown) may also be provided between the plasma electrode 33 and the insulating protective cover 36 so as to cover the plasma electrode 33. The shield is made of a good conductor such as metal and is grounded.

[0034] An exhaust port 40 for evacuating the inside of the processing container 1 is provided on the side wall portion of the processing container 1 facing the opening 31. The exhaust port 40 is formed to be long and narrow vertically, corresponding to the wafer boat 5. An exhaust port cover member 41, which is formed in a U-shape in cross-section, is attached to the portion of the processing container 1 corresponding to the exhaust port 40. The exhaust port cover member 41 extends upward along the side wall of the processing container 1. An exhaust pipe 42 for evacuating the processing container 1 through the exhaust port 40 is connected to the lower part of the exhaust port cover member 41. An exhaust device 44, which includes a pressure control valve 43 for controlling the pressure inside the processing container 1 and a vacuum pump, is connected to the exhaust pipe 42, and the inside of the processing container 1 is evacuated by the exhaust device 44 through the exhaust pipe 42.

[0035] Furthermore, a cylindrical heating mechanism 50 is provided that surrounds the outer circumference of the processing container 1 and heats the processing container 1 and the substrate W inside it.

[0036] The substrate processing apparatus 100 also has a control unit 60. The control unit 60 controls the operation of each part of the substrate processing apparatus 100, for example, the supply and cessation of gases by opening and closing valves 21c to 23c, the control of gas flow rate by flow controllers 21b to 23b, and exhaust control by exhaust device 44. The control unit 60 also controls the on / off of high-frequency power by high-frequency power supply 35 and the temperature of the substrate W by heating mechanism 50.

[0037] The control unit 60 may be, for example, a computer. Furthermore, the computer program that controls the operation of each part of the substrate processing device 100 is stored in a storage medium. The storage medium may be, for example, a flexible disk, compact disk, hard disk, flash memory, DVD, etc.

[0038] Next, an example of a film formation process using the substrate processing apparatus 100 will be described. Figure 2 is a time chart showing an example of a film formation process according to this embodiment. In the film formation process according to this embodiment, a film containing at least silicon and oxygen is formed on the substrate W. Here, the case of forming an SiO2 film or a metal-containing SiO2 film will be described as an example.

[0039] The film formation process according to this embodiment, shown in Figure 2, is a process in which an SiO2 film or a metal-containing SiO2 film is formed on a substrate W by repeating a predetermined number of cycles, with each cycle consisting of steps S11 (supplying a metal-containing catalyst gas (TMA gas)), S12 (purging), S13 (supplying a hydrogen-containing gas (H2 gas)), S14 (purging), S15 (supplying a silicon precursor gas (TPSOL gas)), and S16 (purging). In Figure 2, one cycle is shown in parentheses. Furthermore, in steps S11 to S16, N2 gas, which is a purging gas, is continuously supplied from the gas supply pipe 24 throughout the film formation process.

[0040] Step S11, which involves supplying the metal-containing catalyst gas, is a step in which the metal-containing catalyst gas (TMA gas) is supplied into the processing container 1. In step S11, first, the on / off valve 21c is opened to supply the metal-containing catalyst gas from the gas supply source 21a to the processing container 1 via the gas supply pipe 21. As a result, the metal-containing catalyst gas is adsorbed onto the surface of the substrate W, forming a single molecular layer of the metal catalyst.

[0041] The purging step S12 is a step in which excess metal-containing catalyst gas etc. is purged from the processing container 1. In step S12, the on-off valve 21c is closed to stop the supply of metal-containing catalyst gas. As a result, the purge gas that is constantly supplied from the gas supply pipe 24 purges the excess metal-containing catalyst gas etc. from the processing container 1.

[0042] Step S13, which supplies hydrogen-containing gas, is a step in which hydrogen-containing gas (H2 gas) is supplied into the plasma generation space. In step S13, first, by opening the on / off valve 23c, hydrogen-containing gas is supplied from the gas supply source 23a through the gas supply pipe 23 into the plasma compartment wall 32. In addition, high-frequency power (RF) is applied to the plasma electrode 33 by the high-frequency power supply 35 to generate plasma in the plasma compartment wall 32. The generated hydrogen (H) radicals are supplied into the processing container 1 from the opening 31. By supplying hydrogen (H) radicals, the amount of SiO2 film deposited on the surface of the substrate W per cycle in step S15 is suppressed; in other words, a modification is made that reduces the saturation deposition amount at which the amount of SiO2 film deposited becomes saturated.

[0043] The purging step S14 is a step in which excess hydrogen-containing gas etc. is purged from the processing container 1. In step S14, the on-off valve 23c is closed to stop the supply of hydrogen-containing gas. As a result, the purge gas that is constantly supplied from the gas supply pipe 24 purges the excess hydrogen-containing gas etc. from the processing container 1.

[0044] Step S15, which involves supplying silicon precursor gas, is a step in which silicon precursor gas (TPSOL gas) is supplied into the processing container 1. In step S15, first, the on / off valve 22c is opened to supply silicon precursor gas from the gas supply source 22a to the processing container 1 via the gas supply pipe 22. This causes it to react with the metal catalyst on the surface of the substrate W to form an SiO2 film.

[0045] The purging step S16 is a step in which excess silicon precursor gas, etc., in the processing container 1 is purged. In step S16, the on-off valve 22c is closed to stop the supply of silicon precursor gas. As a result, the purge gas that is constantly supplied from the gas supply pipe 24 purges the excess silicon precursor gas, etc., in the processing container 1.

[0046] By repeating the above cycle, a SiO2 film of the desired thickness, or a metal-containing SiO2 film, is formed on the substrate W.

[0047] Although the steps of supplying the metal-containing catalyst gas (TMA gas) S11, supplying the hydrogen-containing gas (H2 gas) S13, and supplying the silicon precursor gas (TPSOL gas) S15 were described as being performed sequentially (non-simultaneously), this is not the only way in which they may be performed. Parts of the steps of supplying the metal-containing catalyst gas (TMA gas) S11, supplying the hydrogen-containing gas (H2 gas) S13, and supplying the silicon precursor gas (TPSOL gas) S15 may overlap.

[0048] In the film formation process shown in Figure 2, step S13, which involves supplying hydrogen-containing gas, has been described as a step in which RF power is applied to the plasma electrode 33 to generate hydrogen radicals from the hydrogen-containing gas, and the generated hydrogen radicals are supplied into the processing container 1 to perform plasma treatment on the substrate W in the processing container 1. However, the process is not limited to this. Step S13, which involves supplying hydrogen-containing gas (e.g., NH3 gas) from the gas supply pipe 23 to the substrate W in the processing container 1, which has been heated to a desired temperature, to perform thermal treatment. In this case, it is not necessary to apply RF power.

[0049] Here, the film formation process according to this embodiment will be further explained in comparison with the film formation process according to the reference example.

[0050] First, the film formation process according to the first reference example will be explained using Figure 3. Figure 3 is a time chart showing an example of the film formation process according to the first reference example. The film formation process according to the reference example forms an SiO2 film or a metal-containing SiO2 film, similar to the film formation process according to this embodiment.

[0051] The film formation process according to the first reference example shown in Figure 3 is a process in which a predetermined number of cycles are repeated to form an SiO2 film or a metal-containing SiO2 film on a substrate W, with one cycle consisting of the steps of supplying a metal-containing catalyst gas (TMA gas) in step S21, purging in step S22, supplying a silicon precursor gas (TPSOL gas) in step S23, and purging in step S24. Note that steps S21, S22, S23, and S24 shown in Figure 3 are the same as steps S11, S12, S15, and S16 shown in Figure 2, and redundant explanations are omitted.

[0052] Figure 4 is an example of a graph showing the results of the film formation process according to this embodiment and reference example, specifically the average film thickness, film thickness uniformity within the substrate W, and film thickness uniformity between substrates W.

[0053] (a)PE-H2 shows the film formation result in the film formation process according to this embodiment (see Figure 2). (b)Ref shows the film formation result in the film formation process according to the first reference example (see Figure 3). (c)Th-O2 shows the film formation result in the film formation process according to the second reference example, in which step S13 (see Figure 2) is changed to a step of supplying O2 gas without applying RF power. (d)PE-O2 shows the film formation result in the film formation process according to the third reference example, in which step S13 (see Figure 2) is changed to a step of supplying O2 gas with RF power applied.

[0054] Furthermore, Top shows the result for the uppermost substrate W among the substrates W placed in multiple layers within the processing container 1. Cnt shows the result for the middle substrate W among the substrates W placed in multiple layers within the processing container 1. Btm shows the result for the lowermost substrate W among the substrates W placed in multiple layers within the processing container 1.

[0055] Furthermore, the average film thickness (thickness) in each layer of substrate W is shown in a bar graph. The non-uniformity of film thickness (NU) within each layer of substrate W (WIW Unif.) is shown with a white triangle symbol. The non-uniformity of film thickness (NU) between substrate W of Top, Cnt, and Btm (WtW Unif.) is shown with a black diamond symbol.

[0056] Figure 5 shows an example of the film thickness distribution in this embodiment and the first reference example. Figure 5(a) shows an example of the film thickness distribution of the top substrate W in the film formation process according to this embodiment. Figure 5(b) shows an example of the film thickness distribution of the top substrate W in the film formation process according to the first reference example. In Figure 5, the film thickness is indicated by the intensity of the dots.

[0057] In the film formation process according to the first reference example, the average film thickness varies in the substrates W of Top, Cnt, and Btm, as shown in the bar graph in Figure 4(b). Furthermore, as shown by the diamond symbols in Figure 4(b), the non-uniformity of film thickness between the substrates W is large. That is, non-uniformity of film thickness occurs in the height direction of the substrates W arranged in multiple stages within the processing container 1.

[0058] Furthermore, in the film formation process according to the first reference example, as shown in Figure 5(b), the film thickness is thicker on the outer periphery of the substrate W and thinner towards the center. As a result, as shown by the triangular symbol in Figure 4(b), the non-uniformity of the film thickness within the substrate W at Top is large. Similarly, as shown by the triangular symbol in Figure 4(b), the non-uniformity of the film thickness within the substrate W is also large at Cnt and Btm. In other words, non-uniformity of the film thickness occurs in the radial direction within the substrate W.

[0059] This is because, in a substrate processing apparatus 100 that batch processes multiple substrates W simultaneously as shown in Figure 1, the process gas is supplied to the substrates W via side flow, resulting in a faster film deposition rate and thicker film thickness towards the outer periphery of the substrate W, and a slower film deposition rate and thinner film thickness towards the center. Furthermore, the film formation process according to the first reference example shows that the amount of SiO2 film deposited is not saturated in step S23, where silicon precursor gas (TPSOL gas) is supplied.

[0060] In the film formation process according to the second reference example where O2 gas is supplied (see Figure 4(c)), and in the film formation process according to the third reference example where RF power is applied to supply O2 gas (see Figure 4(d)), non-uniformity of film thickness occurred in the height direction and the radial direction within the multi-stage substrate W, similar to the film formation process according to the first reference example (see Figure 4(b)). In other words, neither the supply of O2 gas nor the supply of O2 gas with applied RF power resulted in any improvement in film thickness uniformity.

[0061] In contrast, in the film formation process according to this embodiment, as shown in the bar graph in Figure 4(a), the variation in average film thickness between the multi-tiered substrates W is reduced. Furthermore, as shown by the diamond symbols in Figure 4(a), the uniformity of film thickness between the substrates W is improved.

[0062] Furthermore, in the film formation process according to this embodiment, as shown in Figure 5(a), the variation in film thickness between the outer periphery and the center of the substrate W is reduced. As a result, as shown by the triangular symbol in Figure 4(a), the uniformity of film thickness within the substrate W at Top is improved. Similarly, as shown by the triangular symbol in Figure 4(a), the uniformity of film thickness within the substrate W at Cnt and Btm is also improved.

[0063] This is because the addition of step S13, which supplies hydrogen-containing gas, modifies the surface of the substrate W and allows control of the saturated film deposition amount of the SiO2 film. As a result, even in a configuration where the process gas is supplied to the substrate W via side flow, saturating the amount of SiO2 film deposition in step S15, which supplies silicon precursor gas (TPSOL gas), reduces the variation in film thickness between the outer and central parts of the substrate W, thereby improving the uniformity of the film thickness. Furthermore, even between substrates W placed in multiple stages, saturating the amount of SiO2 film deposition in step S15, which supplies silicon precursor gas (TPSOL gas), reduces the variation in film thickness between substrates W, thereby improving the uniformity of the film thickness.

[0064] Furthermore, in the film formation process according to this embodiment, an SiO2 film can be formed without using oxidizing agents such as O3 and O2. For example, when forming an SiO2 film on a metal film, oxidation of the metal film can be suppressed.

[0065] Figure 6 is a graph showing an example of the results of secondary ion mass spectrometry (SIMS) of a film formed by the film formation process according to this embodiment. The horizontal axis represents the depth from the film surface, and the vertical axis represents the amount of Al detected.

[0066] According to the film formation process of this embodiment, the addition of step S13, which involves supplying a hydrogen-containing gas, allows for control of the saturation film deposition amount of the SiO2 film. In other words, the amount of SiO2 film deposited per cycle can be controlled. By reducing the amount of SiO2 film deposited per cycle, the number of times the metal-containing catalyst gas is supplied can be increased, and as shown in Figure 6, the amount of Al element contained in the SiO2 film can be increased. This makes it possible to form a metal-containing SiO2 film.

[0067] Furthermore, by using a metal-containing catalyst gas containing Hf or Zr, HfSiO films and ZrSiO films can be formed.

[0068] Figure 7 is an example of a graph showing the average film thickness results in the film formation process. In Figure 7, the average film thickness (thickness) of the SiO2 film applied to the substrate W by each process is illustrated in a bar graph. (a) Ref shows the film formation results in the film formation process according to the first reference example (see Figure 3). (b) PE-H2 shows the film formation results in the film formation process (see Figure 2). Here, the film formation results are shown when H2 gas is used as the hydrogen-containing gas in step S13, and hydrogen radicals generated from the hydrogen-containing gas are supplied to the substrate W in the processing container 1 by applying RF power. (c) PE-NH3 shows other film formation results in the film formation process (see Figure 2). Here, the film formation results are shown when NH3 gas is used instead of H2 gas as the hydrogen-containing gas in step S13, and hydrogen radicals generated from the hydrogen-containing gas are supplied to the substrate W in the processing container 1 by applying RF power. (d) th-NH3 shows other film formation results in the film formation process (see Figure 2). Here, we show the film deposition results when NH3 gas is used as the hydrogen-containing gas in step S13, no RF power is applied, and the hydrogen-containing gas is supplied to the substrate W in the processing container 1 heated to a desired temperature for thermal processing.

[0069] As shown by comparing (a)Ref and (b)PE-H2 in Figure 7, the amount of SiO2 film deposited in (b)PE-H2 is reduced compared to (a)Ref. In other words, the addition of step S13, which supplies hydrogen-containing gas, in (b)PE-H2 modifies the surface of the substrate W and controls the saturation amount of SiO2 film deposited.

[0070] Furthermore, in (c)PE-NH3, the amount of SiO2 film deposited is reduced compared to (a)Ref. In other words, in (c)PE-NH3, even when NH3 gas is used as the hydrogen-containing gas in step S13, the surface of the substrate W is modified and the saturation amount of SiO2 film deposited is controlled, similar to (b)PE-H2.

[0071] Furthermore, in (d)th-NH3, the amount of SiO2 film deposited is reduced compared to (a)Ref. In other words, in (d)th-NH3, even when NH3 gas is used as the hydrogen-containing gas in step S13, and the plasma treatment is changed to a thermal treatment, the surface of the substrate W is modified and the saturation amount of SiO2 film deposited is controlled, similar to (b)PE-H2.

[0072] Note that the time chart for the film formation process according to this embodiment is not limited to that shown in Figure 2. Another example of the film formation process using the substrate processing apparatus 100 will be described. This will be explained using Figures 8 to 10 and Figure 12. Figures 8 to 12 are time charts showing another example of the film formation process according to this embodiment.

[0073] The film formation process shown in Figure 8 is a process in which a predetermined number of cycles are repeated, with each cycle being defined as 100, and an SiO2 film or a metal-containing SiO2 film being formed on a substrate W. This process consists of a step 110 for supplying a metal-containing catalyst gas (TMA gas), a step 121 for supplying a silicon precursor gas (TPSOL gas), and a step 122 for supplying a hydrogen-containing gas (H2 gas). A purging step may be included before and after the gas supply step. In the example shown in Figure 8, the hydrogen-containing gas supply step 122 involves supplying a hydrogen-containing gas (H2 gas) and applying RF power to the plasma electrode 33 to generate hydrogen radicals from the hydrogen-containing gas, which are then supplied into the processing container 1.

[0074] The film formation process shown in Figure 9 is a process in which a predetermined number of cycles are repeated, with each cycle consisting of a step 210 of supplying a metal-containing catalyst gas (TMA gas), a step 221 of supplying a hydrogen-containing gas (H2 gas), and a step 222 of supplying a silicon precursor gas (TPSOL gas), and this is repeated for a predetermined number of cycles to form an SiO2 film or a metal-containing SiO2 film on a substrate W. The process may include purging steps before and after the gas supply steps. In the example shown in Figure 9, the step 221 of supplying the hydrogen-containing gas involves supplying the hydrogen-containing gas (H2 gas) and applying RF power to the plasma electrode 33 to generate hydrogen radicals from the hydrogen-containing gas, and supplying the generated hydrogen radicals into the processing container 1.

[0075] The film formation process shown in Figure 10 is a process in which a predetermined number of cycles are repeated, consisting of a step 310 in which a metal-containing catalyst gas (TMA gas) is supplied 311 and a step 312 in which a hydrogen-containing gas (H2 gas) is supplied, and a step 320 in which a silicon precursor gas (TPSOL gas) is supplied, with each cycle 300 being repeated to form an SiO2 film or a metal-containing SiO2 film on a substrate W. A purging step may be included before and after the gas supply step. In the example shown in Figure 10, the hydrogen-containing gas supply step 312 involves supplying a hydrogen-containing gas (H2 gas) and applying RF power to the plasma electrode 33 to generate hydrogen radicals from the hydrogen-containing gas, and supplying the generated hydrogen radicals into the processing container 1.

[0076] Here, the effects of the film formation process shown in Figure 10 will be explained using Figure 11. Figure 11 is a graph showing the results of the average film thickness and film thickness uniformity within the substrate W during the film formation process. In Figure 11, the average film thickness (thickness) of the SiO2 film applied to the substrate W by each process is shown as a bar graph. In addition, the non-uniformity of the film thickness (NU) within the substrate W (WIW) is shown as a white triangle symbol. (a) PE-H2 shows the film formation result in the film formation process (see Figure 2). (b) PE-H2×5 shows the film formation result in the film formation process (see Figure 10). Here, process 310 is defined as repeating the process of supplying a metal-containing catalyst gas (TMA gas) in process 311 and a hydrogen-containing gas (H2 gas) in process 312 for 5 cycles.

[0077] As shown in Figure 11, (b) in PE-H2×5, the non-uniformity of film thickness (NU) within the substrate W (WIW) is reduced. In other words, the uniformity of film thickness can be improved.

[0078] The film formation process shown in Figure 12 is a process in which a predetermined number of cycles are repeated, with one cycle 400 consisting of steps 410, which include supplying a hydrogen-containing gas (H2 gas) in step 411, supplying a metal-containing catalyst gas (TMA gas) in step 412, and supplying a hydrogen-containing gas (H2 gas) in step 413, and supplying a silicon precursor gas (TPSOL gas) in step 420, to form an SiO2 film or a metal-containing SiO2 film on a substrate W. The process may include purging steps before and after the gas supply steps. In the example shown in Figure 12, steps 411 and 413, which supply the hydrogen-containing gas, supply the hydrogen-containing gas (H2 gas) and apply RF power to the plasma electrode 33 to generate hydrogen radicals from the hydrogen-containing gas, and supply the generated hydrogen radicals into the processing container 1.

[0079] In the film formation processes shown in Figures 8 to 10 and Figure 12, the saturation film deposition amount can be controlled, similar to the film formation process shown in Figure 2. This improves the uniformity of the film thickness. Furthermore, by reducing the film deposition amount per cycle, the amount of Al element contained in the SiO2 film can be increased, allowing for the formation of an SiO2 film or a metal-containing SiO2 film.

[0080] In the film formation process shown in Figures 8 to 10 and Figure 12, the steps 122, 221, 312, 411, and 413 for supplying hydrogen-containing gas were described as steps for applying RF power to the plasma electrode 33 to generate hydrogen radicals from the hydrogen-containing gas and supplying the generated hydrogen radicals into the processing container 1 to perform plasma treatment on the substrate W in the processing container 1. However, the process is not limited to this. The steps 122, 221, 312, 411, and 413 for supplying hydrogen-containing gas may also be steps for supplying hydrogen-containing gas (e.g., NH3 gas, etc.) from the gas supply pipe 22 to the substrate W in the processing container 1, which has been heated to a desired temperature, to perform thermal treatment. In this case, it is not necessary to apply RF power.

[0081] The film formation method of this embodiment using the substrate processing apparatus 100 has been described above, but this disclosure is not limited to the above embodiments, and various modifications and improvements are possible within the scope of the gist of this disclosure as described in the claims.

[0082] The film formation process shown in Figures 2, 8 to 10, and 12 has been described assuming a batch-type substrate processing apparatus 100 that performs film formation on multiple substrates W, but it is not limited to this. The film formation process of this embodiment may also be applied to a single-wafer substrate processing apparatus. [Explanation of symbols]

[0083] W board 100 Substrate Processing Equipment 1. Processing container 2 Ceiling panels 3 Manifold 4. Sealing member 5 wafer boats 6 rods 7 Heat insulation cylinder 8 tables 9 Lid 10 Rotation axis 20 Gas Supply Department 21. Gas supply pipe (metal-containing catalyst supply section) 22. Gas supply pipe (silicon precursor supply section) 23. Gas supply pipes (hydrogen-containing gas supply section, hydrogen radical supply section) 24 Gas supply pipes 21a Gas supply source (metal-containing catalyst supply unit) 22a Gas supply source (silicon precursor supply section) 23a Gas supply source (hydrogen-containing gas supply unit, hydrogen radical supply unit) 30 Plasma generation mechanism (hydrogen radical supply unit) 40 Exhaust vents 50 Heating mechanism 60 Control Unit

Claims

1. A film forming method for forming films containing at least silicon and oxygen on a plurality of substrates arranged with spacing along the vertical direction, a) A step of supplying a metal-containing catalyst to the substrate from the outer peripheral side of the substrate, b) A step of supplying a hydrogen-containing gas to the substrate from the outer periphery of the substrate, c) A step of supplying a silicon precursor containing silanol to the substrate from the outer peripheral side of the substrate, Film formation method.

2. The above a), b), and c) are performed non-simultaneously. The film formation method according to claim 1.

3. A first step of performing the above a), After the first step described above, a second step is performed in which step b) described above, After the second step described above, the third step of performing step c) described above is repeated multiple times. A film formation method according to claim 1 or claim 2.

4. A first step of performing the above a), After the first step described above, a second step is performed, in which steps b) and c) are repeated alternately, and this process is repeated multiple times. A film formation method according to claim 1 or claim 2.

5. A first step of alternately repeating the above a) and b), After the first step described above, the second step of performing step c) described above is repeated multiple times. A film formation method according to claim 1 or claim 2.

6. The metal-containing catalyst comprises a metal, a metalloid, or a compound thereof having Lewis acid properties. A film formation method according to any one of claims 1 to 5.

7. The metal contained in the aforementioned metal-containing catalyst is It contains at least one of Al, Co, Hf, Ni, Pt, Ru, W, Zr, Ti, B, Ga, In, Zn, Mg, and Ta. The film formation method according to claim 6.

8. The above b) is, The process involves generating hydrogen radicals from the hydrogen-containing gas and supplying the hydrogen radicals to the substrate. A film formation method according to any one of claims 1 to 7.

9. The hydrogen-containing gas is H ２ Gas, D ２ Gas, H ２ O gas, NH ３ Gas, silicon hydride gas, PH ３ Gas, B ２ H ６ A gas containing at least one of a hydrocarbon gas, A film formation method according to any one of claims 1 to 8.

10. A processing container for housing a plurality of substrates arranged with spacing along the vertical direction, A metal-containing catalyst supply unit that supplies a metal-containing catalyst into the processing container, A silicon precursor supply unit that supplies a silicon precursor containing silanol into the processing container, A hydrogen-containing gas supply unit that supplies hydrogen-containing gas into the processing container, It comprises a control unit and, The control unit, a) A step of controlling the metal-containing catalyst supply unit to supply the metal-containing catalyst to the substrate in the processing container from the outer periphery of the substrate, b) A step of controlling the hydrogen-containing gas supply unit to supply the hydrogen-containing gas to the substrate in the processing container from the outer periphery of the substrate, c) A step of controlling the silicon precursor supply unit to supply the silicon precursor to the substrate in the processing container from the outer periphery of the substrate, and executing the following: Circuit board processing equipment.

11. The processing container accommodates and processes multiple substrates. The substrate processing apparatus according to claim 10.

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