Film deposition method and film deposition device

Abstract

To provide a technology that enables controlling the shape of a silicone-containing film embedded in a recess formed in a substrate.SOLUTION: A film forming method according to one embodiment of the present disclosure includes: (a) a step of supplying an aminosilane-based gas into a recess formed in a substrate and causing the aminosilane-based gas to be adsorbed by the inner face of the recess; (b) a step of supplying an oxidizing gas into the recess having adsorbed the aminosilane-based gas and causing the aminosilane-based gas and the oxidizing gas to react; (c) a step of exposing the substrate to a plasma generated from a reformed gas; (d) a step of repeating a first treatment including the step (a), the step (b), and the step (c) in this order to form a silicone-containing film. The step (d) includes changing the temperature of the substrate in the middle of repeating the first process.SELECTED DRAWING: Figure 9

Description

[Technical field]

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

[0002] There is known a technique for forming a film in a recess formed in a substrate from a reaction product of a first reactive gas and a second reactive gas that reacts with the first reactive gas (see, for example, Patent Document 1). In Patent Document 1, hydroxyl groups are adsorbed on the inner surface of the recess in a desired distribution, and then the first reactive gas and the second reactive gas are supplied in this order, thereby controlling the distribution of the thickness of the film formed in the recess. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2013-135154 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique capable of controlling the embedding shape of a silicon-containing film in a recess formed in a substrate. [Means for solving the problem]

[0005] A film formation method according to one embodiment of the present disclosure includes the steps of: (a) supplying an aminosilane-based gas to a recess formed in a substrate and causing the aminosilane-based gas to be adsorbed onto the inner surface of the recess; (b) supplying an oxidizing gas to the recess into which the aminosilane-based gas has been adsorbed and causing the aminosilane-based gas to react with the oxidizing gas; (c) exposing the substrate to plasma generated from a modifying gas; and (d) repeating a first process including steps (a), (b), and (c) in this order to form a silicon-containing film, wherein step (d) includes changing the temperature of the substrate during the repetition of the first process. Effect of the Invention

[0006] According to the present disclosure, it is possible to control the embedding shape of a silicon-containing film in a recess formed in a substrate. [Brief description of the drawings]

[0007] [Figure 1] 1 is a schematic cross-sectional view showing a film forming apparatus according to an embodiment. [Diagram 2] 2 is a schematic perspective view showing a configuration inside a vacuum chamber of the film forming apparatus of FIG. 1. [Diagram 3] 2 is a schematic plan view showing the configuration inside a vacuum chamber of the film forming apparatus of FIG. 1. [Figure 4] 2 is a schematic cross-sectional view taken along a concentric circle of a rotary table provided in a vacuum chamber of the film forming apparatus of FIG. 1. [Diagram 5] 2 is another schematic cross-sectional view of the film forming apparatus of FIG. 1. [Figure 6] 2 is a schematic cross-sectional view showing a plasma generation source provided in the film forming apparatus of FIG. 1. [Figure 7] 1. FIG. 4 is another schematic cross-sectional view showing the plasma generation source provided in the film forming apparatus of FIG. [Figure 8] 2 is a schematic top view showing a plasma generation source provided in the film forming apparatus of FIG. 1. [Figure 9] 2 is a flowchart illustrating a film forming method according to an embodiment. [Figure 10] FIG. 1 is a schematic diagram (1) for explaining a film forming method according to an embodiment. [Figure 11] FIG. 2 is a schematic diagram (2) for explaining the film forming method according to the embodiment. [Figure 12] FIG. 3 is a schematic diagram for explaining the film forming method according to the embodiment. [Figure 13] FIG. 4 is a schematic diagram for explaining the film forming method according to the embodiment; [Figure 14] FIG. 5 is a schematic diagram (5) for explaining the film forming method according to the embodiment. [Figure 15] FIG. 2 is a schematic diagram for explaining the reaction of 3DMAS gas on the surface of a substrate. [Figure 16] FIG. 13 is a diagram showing a thickness distribution of a silicon-containing film in the depth direction of a trench. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, non-limiting exemplary embodiments of the present disclosure will be described with reference to the accompanying drawings. In all of the accompanying drawings, the same or corresponding members or parts are designated by the same or corresponding reference numerals, and duplicated descriptions will be omitted.

[0009] [Film forming equipment] A film forming apparatus suitable for carrying out the film forming method according to the embodiment will be described. With reference to Fig. 1 to Fig. 3, the film forming apparatus includes a flat vacuum vessel 1 having a substantially circular planar shape, and a rotary table 2 provided inside the vacuum vessel 1 and having a rotation center at the center of the vacuum vessel 1. The vacuum vessel 1 includes a vessel body 12 having a cylindrical shape with a bottom, and a top plate 11 that is detachably and airtightly arranged on the upper surface of the vessel body 12 via a seal member 13 such as an O-ring.

[0010] The rotary table 2 is fixed at its center to a cylindrical core portion 21. The core portion 21 is fixed to the upper end of a rotary shaft 22 extending in the vertical direction. The rotary shaft 22 penetrates the bottom portion 14 of the vacuum vessel 1, and its lower end is attached to a drive portion 23 that rotates the rotary shaft 22 about the vertical axis. The rotary shaft 22 and the drive portion 23 are housed in a cylindrical case body 20 whose upper surface is open. A flange portion provided on the upper surface of the case body 20 is airtightly attached to the lower surface of the bottom portion 14 of the vacuum vessel 1, and an airtight state between the internal atmosphere of the case body 20 and the external atmosphere is maintained.

[0011] As shown in Figs. 2 and 3, a circular mounting portion 24 is provided on the surface of the turntable 2 along the rotation direction (circumferential direction) for mounting a plurality of substrates W (five substrates in the illustrated example). The substrates W may be semiconductor wafers such as silicon wafers. For convenience, Fig. 3 shows the substrate W on only one mounting portion 24. The mounting portion 24 has an inner diameter that is slightly larger than the diameter of the substrate W, for example, by 4 mm, and a depth that is approximately equal to the thickness of the substrate W. In this case, when the substrate W is accommodated on the mounting portion 24, the surface of the substrate W and the surface of the turntable 2 (an area on which the substrate W is not mounted) are at the same height. The bottom surface of the mounting portion 24 is formed with through holes (none of which are shown) through which, for example, three lift pins pass to support the back surface of the substrate W and lift the substrate W.

[0012] 2 and 3 are diagrams for explaining the structure inside the vacuum vessel 1, and for convenience of explanation, the top plate 11 is omitted. As shown in Fig. 2 and 3, above the turntable 2, reaction gas nozzles 31 and 32, separation gas nozzles 41 and 42, and a process gas nozzle 92 are arranged at intervals from each other in the circumferential direction of the vacuum vessel 1. In the illustrated example, the process gas nozzle 92, separation gas nozzle 41, reaction gas nozzle 31, separation gas nozzle 42, and reaction gas nozzle 32 are arranged in this order clockwise (the direction of rotation of arrow A in Fig. 3) from a transfer port 15 described later. The reaction gas nozzles 31 and 32, separation gas nozzles 41 and 42, and process gas nozzle 92 are examples of gas supply units, and are each formed of, for example, quartz. The reaction gas nozzles 31, 32, the separation gas nozzles 41, 42 and the process gas nozzle 92 have gas introduction ports 31a, 32a, 41a, 42a and 92a, which are their respective base ends, fixed to the outer circumferential wall of the vessel body 12. As a result, the reaction gas nozzles 31, 32, the separation gas nozzles 41, 42 and the process gas nozzle 92 are each introduced into the vacuum vessel 1 from the outer circumferential wall of the vacuum vessel 1, and are attached so as to extend horizontally with respect to the turntable 2 along the radial direction of the vessel body 12.

[0013] A plasma generation source 80 is provided above the processing gas nozzle 92, as simply shown by a dashed line in Fig. 3. The plasma generation source 80 will be described later.

[0014] A supply source GS1 filled with an aminosilane-based gas is connected to the reaction gas nozzle 31. The reaction gas nozzle 31 supplies the aminosilane-based gas from the supply source GS1 into the vacuum chamber 1. The flow rate of the aminosilane-based gas from the supply source GS1 is controlled by a flow rate controller FC1. The supply and stop of the aminosilane-based gas from the supply source GS1 into the vacuum chamber 1 is controlled by valves VA1 and VB1. The reaction gas nozzle 31 may be further connected to a supply source filled with another gas, for example, an inert gas.

[0015] The aminosilane gas may be, for example, trisdimethylaminosilane (3DMAS) gas. The aminosilane gas may be bisdimethylaminosilane (BDMAS) gas, bisdiethylaminosilane (BDEAS) gas, bistertiarybutylaminosilane (BTBAS) gas, diisopropylaminosilane (DIPAS) gas, or di-sec-butylaminosilane (DSBAS) gas.

[0016] A supply source GS3 filled with an oxidizing gas is connected to the reaction gas nozzle 32. The reaction gas nozzle 32 supplies the oxidizing gas from the supply source GS3 into the vacuum vessel 1. The flow rate of the oxidizing gas from the supply source GS3 is controlled by a flow rate controller FC3. The supply and stop of the oxidizing gas from the supply source GS3 into the vacuum vessel 1 is controlled by valves VA3 and VB3. A supply source filled with another gas, for example, an inert gas, may be further connected to the reaction gas nozzle 32. For example, the oxidizing gas is ozone (O3) gas. The oxidizing gas may be oxygen (O2) gas, water (H2O), or hydrogen peroxide (H2O2) gas.

[0017] The processing gas nozzle 92 is connected to a supply source GS4 filled with a modifying gas and a supply source GS5 filled with a dilution gas. The processing gas nozzle 92 supplies the modifying gas from the supply source GS4 and the dilution gas from the supply source GS5 into the vacuum vessel 1. The flow rates of the modifying gas and the dilution gas from the supply sources GS4 and GS5 are controlled by corresponding flow rate controllers FC4 and FC5. The supply and stop of the modifying gas and the dilution gas from the supply sources GS4 and GS5 into the vacuum vessel 1 is controlled by corresponding valves VA4, VB4, VA5, and VB5. The processing gas nozzle 92 may be further connected to a supply source filled with another gas. For example, the modifying gas is ammonia (NH3) gas. For example, the dilution gas is argon (Ar) gas.

[0018] A supply source GS6 filled with a separation gas is connected to the separation gas nozzle 41. The separation gas nozzle 41 supplies the separation gas from the supply source GS6 into the vacuum vessel 1. The flow rate of the separation gas from the supply source GS6 is controlled by a flow rate controller FC6. The supply and stop of the separation gas from the supply source GS6 into the vacuum vessel 1 is controlled by valves VA6 and VB6.

[0019] A supply source GS7 filled with a separation gas is connected to the separation gas nozzle 42. The separation gas nozzle 42 supplies the separation gas from the supply source GS7 into the vacuum vessel 1. The flow rate of the separation gas from the supply source GS7 is controlled by a flow rate controller FC7. The supply and stop of the separation gas from the supply source GS7 into the vacuum vessel 1 is controlled by valves VA7 and VB7.

[0020] For example, the separation gas is Ar gas. The separation gas may be any inert gas, such as nitrogen (N2) gas.

[0021] In the reactive gas nozzles 31, 32, a plurality of discharge holes 33 (FIG. 4) opening toward the turntable 2 are arranged at intervals of, for example, 10 mm along the longitudinal direction of the reactive gas nozzles 31, 32. The region below the reactive gas nozzle 31 becomes a first processing region P1 for adsorbing the silicon-containing gas onto the substrate W. The region below the reactive gas nozzle 32 becomes a second processing region P2 for oxidizing the silicon-containing gas adsorbed onto the substrate W in the first processing region P1.

[0022] 2 and 3, two convex portions 4 are provided in the vacuum vessel 1. The convex portions 4, together with the separation gas nozzles 41, 42, constitute a separation region D. For this reason, as described below, they are attached to the rear surface of the top plate 11 so as to protrude toward the turntable 2. The convex portions 4 have a fan-shaped planar shape with the top cut into an arc. The convex portions 4 are arranged, for example, so that the inner arc is connected to the protruding portion 5 (described below) and the outer arc is aligned along the inner circumferential surface of the vessel body 12 of the vacuum vessel 1.

[0023] FIG. 4 shows a cross section of the vacuum vessel 1 along the concentric circle of the turntable 2 from the reaction gas nozzle 31 to the reaction gas nozzle 32. As shown in the figure, the convex portion 4 is attached to the back surface of the top plate 11, so that in the vacuum vessel 1, there are a flat low ceiling surface 44 (first ceiling surface) which is the lower surface of the convex portion 4, and a ceiling surface 45 (second ceiling surface) which is higher than the ceiling surface 44 and is located on both sides of the ceiling surface 44 in the circumferential direction. The ceiling surface 44 has a fan-shaped planar shape with the top cut into an arc shape. As shown in the figure, the convex portion 4 has a groove portion 43 formed so as to extend in the radial direction at the center in the circumferential direction, and the separation gas nozzle 42 is accommodated in the groove portion 43. A similar groove portion 43 is also formed in the other convex portion 4, and the separation gas nozzle 41 is accommodated in the groove portion 43. The reaction gas nozzles 31 and 32 are provided in the spaces 481 and 482 below the high ceiling surface 45, respectively. The reaction gas nozzles 31 and 32 are provided in the vicinity of the substrate W and spaced apart from the ceiling surface 45 .

[0024] The separation gas nozzle 42 has a plurality of discharge holes 42h (see FIG. 4) that open toward the turntable 2 and are arranged at intervals of, for example, 10 mm along the length direction of the separation gas nozzle 42. Similarly to the separation gas nozzle 42, the separation gas nozzle 41 also has a plurality of discharge holes (not shown) that open toward the turntable 2 and are arranged at intervals of, for example, 10 mm along the length direction of the separation gas nozzle 41.

[0025] The ceiling surface 44 forms a narrow separation space H with respect to the turntable 2. When the separation gas is supplied from the discharge hole 42h of the separation gas nozzle 42, the separation gas flows through the separation space H toward the space 481 and the space 482. At this time, the volume of the separation space H is smaller than the volume of the spaces 481 and 482. Therefore, the pressure of the separation space H can be made higher than the pressure of the spaces 481 and 482 by the separation gas. That is, a separation space H with a high pressure is formed between the spaces 481 and 482. In addition, the separation gas flowing out from the separation space H to the spaces 481 and 482 acts as a counter flow to the aminosilane gas from the first processing region P1 and the oxidizing gas from the second processing region P2. As a result, the aminosilane gas from the first processing region P1 and the oxidizing gas from the second processing region P2 are separated by the separation space H. Therefore, the aminosilane gas and the oxidizing gas are prevented from mixing and reacting in the vacuum vessel 1.

[0026] The height h1 of the ceiling surface 44 relative to the upper surface of the turntable 2 is set to a height suitable for making the pressure in the separation space H higher than the pressure in the spaces 481 and 482, taking into consideration the pressure inside the vacuum vessel 1 when processing the substrate, the rotation speed of the turntable 2, the amount of separation gas supplied, etc.

[0027] A protruding portion 5 (FIGS. 2 and 3) is provided on the underside of the top plate 11, surrounding the outer periphery of the core portion 21 to which the turntable 2 is fixed. The protruding portion 5 is continuous with, for example, a portion of the convex portion 4 on the rotation center side, and the underside is formed at the same height as the ceiling surface 44.

[0028] FIG. 1, which was referred to above, is a cross-sectional view taken along line I-I' in FIG. 3, showing the area where the ceiling surface 45 is provided. Meanwhile, FIG. 5 is a cross-sectional view showing the area where the ceiling surface 44 is provided. As shown in FIG. 5, a bent portion 46 is formed in the peripheral portion (the portion on the outer edge side of the vacuum vessel 1) of the fan-shaped convex portion 4, which is bent in an L-shape so as to face the outer end surface of the turntable 2. The bent portion 46, like the convex portion 4, suppresses the intrusion of the aminosilane-based gas and the oxidizing gas from both sides of the separation region D, and suppresses the mixing of the aminosilane-based gas and the oxidizing gas. The fan-shaped convex portion 4 is provided on the top plate 11, and the top plate 11 is detachable from the vessel body 12. For this reason, there is a slight gap between the outer peripheral surface of the bent portion 46 and the vessel body 12. The gap between the inner peripheral surface of the bent portion 46 and the outer end surface of the turntable 2, and the gap between the outer peripheral surface of the bent portion 46 and the vessel body 12 are set to, for example, the same dimensions as the height of the ceiling surface 44 relative to the upper surface of the turntable 2.

[0029] In the separation region D, the inner peripheral wall of the container body 12 is formed in a vertical plane close to the outer peripheral surface of the bent portion 46 as shown in FIG. 5. In the portion other than the separation region D, the inner wall of the container body 12 is recessed outward from the portion facing the outer end surface of the turntable 2 to the bottom portion 14 as shown in FIG. 1. Hereinafter, for convenience of explanation, the recessed portion having a generally rectangular cross-sectional shape is referred to as the exhaust region E. Specifically, the exhaust region communicating with the first processing region P1 is referred to as the first exhaust region E1, and the region communicating with the second processing region P2 is referred to as the second exhaust region E2. At the bottoms of the first exhaust region E1 and the second exhaust region E2, a first exhaust port 61 and a second exhaust port 62 are formed, respectively, as shown in FIGS. 1 to 3. The first exhaust port 61 and the second exhaust port 62 are connected to a vacuum pump 64 via an exhaust pipe 63, respectively, as shown in FIG. 1. The exhaust pipe 63 is provided with a pressure regulator 65 .

[0030] As shown in FIG. 1 and FIG. 5, a heater unit 7 is provided in the space between the turntable 2 and the bottom 14 of the vacuum vessel 1. The heater unit 7 heats the substrate W on the turntable 2 to a temperature determined by a process recipe via the turntable 2. An annular cover member 71 is provided on the lower side near the periphery of the turntable 2 (FIG. 5). The cover member 71 divides the atmosphere from the space above the turntable 2 to the exhaust regions E1 and E2 from the atmosphere in which the heater unit 7 is placed, thereby suppressing the intrusion of gas into the region below the turntable 2. The cover member 71 includes an inner member 71a provided to face the outer periphery of the turntable 2 and the outer periphery side from the lower side, and an outer member 71b provided between the inner member 71a and the inner wall surface of the vacuum vessel 1. The outer member 71b is provided below the bent portion 46 formed on the outer periphery of the convex portion 4 in the separation region D and in close proximity to the bent portion 46. The inner member 71a surrounds the heater unit 7 all around below the outer edge of the turntable 2 (and below a portion slightly outside the outer edge).

[0031] The bottom 14 at a portion closer to the center of rotation than the space in which the heater unit 7 is disposed protrudes upward to approach the core 21 near the center of the lower surface of the turntable 2, forming a protruding portion 12a. A narrow space is formed between the protruding portion 12a and the core 21, and a narrow gap is formed between the inner peripheral surface of the through hole of the rotary shaft 22 penetrating the bottom 14 and the rotary shaft 22, and these narrow spaces communicate with the case body 20. The case body 20 is provided with a purge gas supply pipe 72 for supplying a purge gas into the narrow space to purge it. The purge gas is, for example, Ar gas. The purge gas may be N2 gas. A plurality of purge gas supply pipes 73 for purging the space in which the heater unit 7 is disposed are provided at a predetermined angular interval in the circumferential direction below the heater unit 7 in the bottom 14 of the vacuum vessel 1. FIG. 5 shows one purge gas supply pipe 73. A lid member 7a is provided between the heater unit 7 and the turntable 2 to cover the area from the inner peripheral wall of the outer member 71b (the upper surface of the inner member 71a) to the upper end of the protruding portion 12a in the circumferential direction in order to prevent gas from entering the area where the heater unit 7 is provided. The lid member 7a can be made of, for example, quartz.

[0032] A separation gas supply pipe 51 is connected to the center of the top plate 11 of the vacuum vessel 1. The separation gas supply pipe 51 supplies a separation gas to a space 52 between the top plate 11 and the core part 21. The separation gas supplied to the space 52 is discharged toward the periphery along the surface of the turntable 2 on the substrate placement region side through a narrow space 50 between the protrusion 5 and the turntable 2. The space 50 can be maintained at a higher pressure than the spaces 481 and 482 by the separation gas. Therefore, the space 50 prevents the aminosilane gas supplied to the first processing region P1 and the oxidizing gas supplied to the second processing region P2 from mixing through the central region C. That is, the space 50 (or the central region C) functions similarly to the separation space H (or the separation region D).

[0033] 2 and 3, a transfer port 15 is formed in the side wall of the vacuum vessel 1 for transferring the substrate W between an external transfer arm 10 and the turntable 2. The transfer port 15 is opened and closed by a gate valve (not shown). The substrate W is transferred between the transfer arm 10 at a position facing the transfer port 15. A transfer lift pin and a lift mechanism (neither shown) for penetrating the placement part 24 and lifting the substrate W from the back surface are provided at a position corresponding to the transfer position on the lower side of the turntable 2.

[0034] The plasma generation source 80 will be described with reference to Fig. 6 to Fig. 8. Fig. 6 is a schematic cross-sectional view of the plasma generation source 80 taken along the radial direction of the turntable 2. Fig. 7 is a schematic cross-sectional view of the plasma generation source 80 taken along a direction perpendicular to the radial direction of the turntable 2. Fig. 8 is a top view showing an outline of the plasma generation source 80. For ease of illustration, some members are simplified in these figures.

[0035] Referring to FIG. 6, the plasma generation source 80 includes a frame member 81, a Faraday shielding plate 82, an insulating plate 83, and an antenna 85. The frame member 81 is formed of a high-frequency transparent material. The frame member 81 has a recess recessed from the upper surface, and is fitted into an opening 11a formed in a top plate 11. The Faraday shielding plate 82 is housed in the recess of the frame member 81, and has a substantially box-like shape with an open top. The insulating plate 83 is disposed on the bottom surface of the Faraday shielding plate 82. The antenna 85 is supported above the insulating plate 83. The antenna 85 has a coil shape with a substantially octagonal upper surface shape.

[0036] The opening 11a of the top plate 11 has a plurality of steps. One of the steps has a groove formed around the entire circumference. A seal member 81a such as an O-ring is fitted into the groove. The frame member 81 has a plurality of steps corresponding to the steps of the opening 11a. When the frame member 81 is fitted into the opening 11a, the back surface of one of the steps contacts the seal member 81a fitted into the groove of the opening 11a. This maintains airtightness between the top plate 11 and the frame member 81. As shown in FIG. 6, a pressing member 81c is provided along the outer periphery of the frame member 81 fitted into the opening 11a of the top plate 11, and this presses the frame member 81 downward against the top plate 11. This more reliably maintains airtightness between the top plate 11 and the frame member 81.

[0037] The underside of frame member 81 faces turntable 2 in vacuum vessel 1, and a protrusion 81b is provided on the outer periphery of the underside, protruding downward (towards turntable 2) around the entire periphery. The underside of protrusion 81b is close to the surface of turntable 2. A space (hereinafter, internal space S) is defined above turntable 2 by protrusion 81b, the surface of turntable 2, and the underside of frame member 81. The distance between the underside of protrusion 81b and the surface of turntable 2 may be approximately the same as height h1 of top plate 11 relative to the upper surface of turntable 2 in separation space H (FIG. 4).

[0038] The process gas nozzle 92, which penetrates the protrusion 81b, extends into the internal space S. As described above, the process gas nozzle 92 supplies the modifying gas from the supply source GS4 and the dilution gas from the supply source GS5 into the vacuum vessel 1 (the internal space S).

[0039] The processing gas nozzle 92 has a plurality of discharge holes 92h formed at a predetermined interval (for example, 10 mm) along its longitudinal direction. The processing gas nozzle 92 discharges the reformed gas and the dilution gas from the discharge holes 92h. As shown in FIG. 7, the discharge holes 92h are inclined from a direction perpendicular to the turntable 2 toward the upstream side in the rotation direction of the turntable 2. Therefore, the reformed gas and the dilution gas supplied from the processing gas nozzle 92 are discharged in the direction opposite to the rotation direction of the turntable 2, specifically, toward the gap between the lower surface of the protrusion 81b and the surface of the turntable 2. This prevents the oxidizing gas and the separation gas from flowing into the internal space S from the space below the ceiling surface 45 located upstream of the plasma generation source 80 along the rotation direction of the turntable 2. As described above, the protrusion 81b formed along the outer periphery of the lower surface of the frame member 81 is close to the surface of the turntable 2. Therefore, the pressure in the internal space S can be easily maintained high by the reformed gas and the dilution gas from the processing gas nozzle 92. This also prevents the oxidizing gas and the separating gas from flowing into the internal space S.

[0040] The Faraday shield 82 is made of a conductive material such as a metal, and is grounded (not shown). As shown in Fig. 8, a plurality of slits 82s are formed in the bottom of the Faraday shield 82. Each of the slits 82s extends substantially perpendicular to a corresponding side of the antenna 85 having a substantially octagonal planar shape.

[0041] 7 and 8, the Faraday shield 82 has support portions 82a that are bent outward at two points on the upper end. The support portions 82a are supported on the upper surface of the frame member 81, whereby the Faraday shield 82 is supported at a predetermined position within the frame member 81.

[0042] The insulating plate 83 is formed of, for example, quartz glass. The insulating plate 83 has a size slightly smaller than the bottom surface of the Faraday shielding plate 82, and is placed on the bottom surface of the Faraday shielding plate 82. The insulating plate 83 insulates the Faraday shielding plate 82 from the antenna 85. The insulating plate 83 transmits high frequency waves radiated from the antenna 85 downward.

[0043] The antenna 85 is formed by winding a hollow copper tube (pipe) three times, for example, so that the planar shape is approximately octagonal. Cooling water can be circulated inside the pipe, which prevents the antenna 85 from being heated to a high temperature by the high frequency waves supplied to the antenna 85. The antenna 85 is provided with an erected portion 85a, and a support portion 85b is attached to the erected portion 85a. The support portion 85b maintains the antenna 85 at a predetermined position within the Faraday shield 82. A high frequency power source 87 is connected to the support portion 85b via a matching box 86. The high frequency power source 87 generates a high frequency wave having a frequency of, for example, 13.56 MHz.

[0044] According to the plasma generation source 80 having such a configuration, when high frequency power is supplied from the high frequency power supply 87 to the antenna 85 via the matching box 86, an electromagnetic field is generated by the antenna 85. The electric field component of the electromagnetic field cannot propagate downward because it is shielded by the Faraday shield 82. On the other hand, the magnetic field component propagates to the internal space S through the multiple slits 82s of the Faraday shield 82. The magnetic field component generates plasma from the modifying gas and dilution gas supplied from the processing gas nozzle 92 to the internal space S.

[0045] The film forming apparatus includes a control unit 100. The control unit 100 controls the operation of each unit of the film forming apparatus. The control unit 100 is, for example, a computer. A program for causing the film forming apparatus to perform a film forming method described later under the control of the control unit 100 is stored in the memory of the control unit 100. The program is organized into a group of steps for executing the film forming method described later. The program is stored in a medium 102 such as a hard disk, compact disk, magneto-optical disk, memory card, or flexible disk, and is read into the storage unit 101 by a predetermined reading device and installed in the control unit 100.

[0046] [Film formation method] The film forming method according to the embodiment will be described by taking the case where the film forming apparatus described above is used as an example. The film forming method according to the embodiment is performed by a control unit 100 controlling the operation of each unit of the film forming apparatus.

[0047] 10(a), a trench T is formed on a surface U of a substrate W. In the embodiment, the aminosilane-based gas is 3DMAS gas, the oxidizing gas is O gas, the modifying gas is NH gas, and the dilution gas is Ar gas.

[0048] First, in step S11, a gate valve (not shown) is opened, and the substrate W is transferred from the outside to the mounting parts 24 of the turntable 2 via the transfer port 15 (FIGS. 2 and 3) by the transfer arm 10 (FIG. 3). The transfer of the substrate W is performed by lifting pins (not shown) moving up and down from the bottom side of the vacuum vessel 1 through through holes in the bottom surface of the mounting part 24 when the mounting part 24 stops at a position facing the transfer port 15. The transfer of the substrate W is performed by intermittently rotating the turntable 2, and the substrate W is placed on each of the five mounting parts 24 of the turntable 2.

[0049] Next, in step S12, the gate valve is closed, and the vacuum chamber 1 is evacuated to an achievable vacuum level by the vacuum pump 64. Thereafter, Ar gas is discharged from the separation gas nozzles 41 and 42 at a predetermined flow rate, and Ar gas is also discharged from the separation gas supply pipe 51 and the purge gas supply pipes 72 and 72 at a predetermined flow rate. Accordingly, the pressure controller 65 (FIG. 1) controls the inside of the vacuum chamber 1 to a preset processing pressure. Next, the substrate W is heated to a first temperature by the heater unit 7 while rotating the turntable 2 clockwise at a predetermined rotation speed. The first temperature is, for example, 620° C.

[0050] Next, in step S13, while maintaining the temperature of the substrate W at the first temperature, 3DMAS gas is supplied from the reactive gas nozzle 31 (FIGS. 2 and 3), and O3 gas is supplied from the reactive gas nozzle 32. Also, a mixed gas of Ar gas and NH3 gas (hereinafter referred to as "Ar / NH3 gas") is supplied from the process gas nozzle 92, and high frequency power is supplied to the antenna 85 of the plasma generation source 80. As a result, plasma (hereinafter referred to as "Ar / NH3 plasma") is generated from the Ar / NH3 gas in the internal space S between the plasma generation source 80 (FIG. 6) and the turntable 2.

[0051] By the rotation of the turntable 2, the substrate W passes through the first processing region P1, the separation region D, the second processing region P2, the internal space S (the region below it), and the separation region D in this order repeatedly (see FIG. 3). In the first processing region P1, as shown in FIG. 10(b), the molecules Ms of the 3DMAS gas are adsorbed on the surface U of the substrate W and the inner surface of the trench T, forming a molecular layer 201 of 3DMAS. After passing through the separation region D, in the second processing region P2, as shown in FIG. 10(c), the 3DMAS gas adsorbed on the surface U of the substrate W and the inner surface of the trench T is oxidized by the O3 gas molecules Mo. As a result, as shown in FIG. 11(a), a silicon-containing film 202 containing oxygen atoms is formed along the inner surface of the trench T. When the 3DMAS gas is oxidized, OH groups Hy are generated as by-products, and the generated OH groups Hy are adsorbed on the surface of the silicon-containing film 202.

[0052] Next, when the substrate W reaches the internal space S of the plasma generation source 80, the substrate W is exposed to the Ar / NH3 plasma PS as shown in FIG. 11(b). At this time, some of the OH groups Hy adsorbed on the silicon-containing film 202 are desorbed from the silicon-containing film 202 due to collision of, for example, high-energy particles in the Ar / NH3 plasma PS. The Ar / NH3 plasma PS reaches the surface U of the substrate W and the vicinity of the opening of the trench T, but has difficulty reaching the vicinity of the bottom of the trench T. Therefore, a relatively large amount of OH groups Hy are desorbed from the surface U of the substrate W and the side surface near the opening of the trench T. As a result, as shown in FIG. 11(b), the OH groups Hy are distributed so that the density of the OH groups Hy is high at the bottom and the side surface near the bottom of the trench T, and the density decreases toward the opening of the trench T and the surface U of the substrate W. The silicon-containing film 202 becomes a silicon oxynitride (SiON) film containing oxygen atoms and nitrogen atoms by being exposed to the Ar / NH3 plasma.

[0053] Next, when the substrate W reaches the first processing region P1 again by the rotation of the turntable 2, the 3DMAS gas molecules Ms supplied from the reaction gas nozzle 31 are adsorbed onto the surface U of the substrate W and the inner surface of the trench T. At this time, the 3DMAS gas molecules Ms are easily adsorbed by OH groups Hy, and therefore are adsorbed onto the surface U of the substrate W and the inner surface of the trench T in a distribution according to the distribution of the OH groups Hy, as shown in Fig. 11(c) . That is, the 3DMAS gas molecules Ms are adsorbed onto the inner surface of the trench T so that the density is high at the bottom and the side surfaces near the bottom of the trench T and the density decreases toward the opening of the trench T.

[0054] Subsequently, when the substrate W passes through the second processing region P2, the 3DMAS gas adsorbed on the surface U of the substrate W and the inner surface of the trench T is oxidized by the O3 gas, and the silicon-containing film 202 is further formed as shown in Fig. 12(a). At this time, the density of the 3DMAS gas adsorbed on the inner surface of the trench T is reflected in the film thickness distribution of the silicon-containing film 202. That is, the silicon-containing film 202 is thicker at the bottom of the trench T and on the side surfaces near the bottom, and is thinner toward the opening of the trench T. Then, OH groups generated by the oxidation of the 3DMAS gas are adsorbed on the surface of the silicon-containing film 202.

[0055] Next, when the substrate W reaches the internal space S of the plasma generation source 80 again, as described above, the density of OH groups is high at the bottom of the trench T and on the side surfaces near the bottom, and the density decreases toward the opening of the trench T.

[0056] Thereafter, when the above-mentioned process (hereinafter referred to as the "first process") is repeated, the silicon-containing film 202 becomes thicker from the bottom of the trench T as shown in FIG. 12(b).

[0057] While the first process is being repeated, the control unit 100 determines whether the supply of 3DMAS gas from the reaction gas nozzle 31, the supply of O3 gas from the reaction gas nozzle 32, and the supply of Ar / NH3 gas from the process gas nozzle 92 have been performed for a predetermined time (step S14). In the determination of step S14, the control unit 100 may determine whether the number of rotations of the turntable 2 has reached a predetermined number, instead of the gas supply time. The predetermined time and the predetermined number of rotations can be determined based on the depth of the trench T, the opening width of the trench T, etc.

[0058] If the predetermined time has not elapsed (NO in step S14), the first process is repeated. If the predetermined time has elapsed (YES in step S14), the control unit 100 stops the supply of 3DMAS gas from the reaction gas nozzle 31, the supply of O3 gas from the reaction gas nozzle 32, and the supply of Ar / NH3 gas from the process gas nozzle 92. The control unit 100 also stops the supply of high-frequency power to the antenna 85 of the plasma generation source 80. Next, the control unit 100 changes the temperature of the substrate W from the first temperature to the second temperature by the heater unit 7 while rotating the turntable 2 (step S15). The second temperature is, for example, 400°C.

[0059] Next, in step S16, while maintaining the temperature of the substrate W at the second temperature, 3DMAS gas is supplied from the reactive gas nozzle 31 (FIGS. 2 and 3), and O3 gas is supplied from the reactive gas nozzle 32. Also, Ar / NH3 gas is supplied from the process gas nozzle 92, and high frequency power is supplied to the antenna 85 of the plasma generation source 80. As a result, Ar / NH3 plasma is generated in the internal space S between the plasma generation source 80 (FIG. 6) and the turntable 2.

[0060] By the rotation of the turntable 2, the substrate W passes through the first processing region P1, the separation region D, the second processing region P2, the internal space S (the region below it), and the separation region D in this order repeatedly (see FIG. 3). In the first processing region P1, as shown in FIG. 12(c), the molecules Ms of the 3DMAS gas are adsorbed on the surface U of the substrate W and the inner surface of the trench T, forming a molecular layer 203 of 3DMAS. After passing through the separation region D, in the second processing region P2, as shown in FIG. 13(a), the 3DMAS gas adsorbed on the surface U of the substrate W and the inner surface of the trench T is oxidized by the O3 gas molecules Mo. As a result, as shown in FIG. 13(b), a silicon-containing film 204 containing oxygen atoms is formed along the inner surface of the trench T. When the 3DMAS gas is oxidized, OH groups Hy are generated as by-products, and the generated OH groups Hy are adsorbed on the surface of the silicon-containing film 204.

[0061] Next, when the substrate W reaches the internal space S of the plasma generation source 80, the substrate W is exposed to the Ar / NH3 plasma PS as shown in FIG. 13(c). At this time, some of the OH groups Hy adsorbed on the silicon-containing film 204 are desorbed from the silicon-containing film 204 due to collision of, for example, high-energy particles in the Ar / NH3 plasma PS. The Ar / NH3 plasma PS reaches the surface U of the substrate W and the vicinity of the opening of the trench T, but has difficulty reaching the vicinity of the bottom of the trench T. Therefore, a relatively large amount of OH groups Hy are desorbed from the surface U of the substrate W and the side surface near the opening of the trench T. As a result, as shown in FIG. 13(c), the OH groups Hy are distributed so that the density of the OH groups Hy is high at the bottom of the trench T and the side surface near the bottom, and the density decreases toward the opening of the trench T and the surface U of the substrate W. The silicon-containing film 204 becomes a SiON film containing oxygen atoms and nitrogen atoms by being exposed to the Ar / NH3 plasma.

[0062] Next, when the substrate W reaches the first processing region P1 again by the rotation of the turntable 2, the 3DMAS gas molecules Ms supplied from the reaction gas nozzle 31 are adsorbed onto the surface U of the substrate W and the inner surface of the trench T. At this time, the 3DMAS gas molecules Ms are easily adsorbed by OH groups Hy, and therefore are adsorbed onto the surface U of the substrate W and the inner surface of the trench T in a distribution according to the distribution of the OH groups Hy, as shown in Fig. 14(a). That is, the 3DMAS gas molecules Ms are adsorbed onto the inner surface of the trench T so that the density is high at the bottom and the side surfaces near the bottom of the trench T and the density decreases toward the opening of the trench T.

[0063] Subsequently, when the substrate W passes through the second processing region P2, the 3DMAS gas adsorbed on the surface U of the substrate W and the inner surface of the trench T is oxidized by the O3 gas, and a silicon-containing film 204 is further formed as shown in Fig. 14(b). At this time, the density of the 3DMAS gas adsorbed on the inner surface of the trench T is reflected in the film thickness distribution of the silicon-containing film 204. That is, the silicon-containing film 204 is thicker at the bottom and the side surfaces near the bottom of the trench T and becomes thinner toward the opening of the trench T. Then, OH groups generated by the oxidation of the 3DMAS gas are adsorbed on the surface of the silicon-containing film 204.

[0064] Next, when the substrate W reaches the internal space S of the plasma generation source 80 again, as described above, the density of OH groups is high at the bottom of the trench T and on the side surfaces near the bottom, and the density decreases toward the opening of the trench T.

[0065] Thereafter, when the above-mentioned process (hereinafter referred to as the “second process”) is repeated, the silicon-containing film 204 thickens from the bottom of the trench T as shown in FIG. 14(c), and the trench T is filled with silicon oxide without forming voids, thereby completing the filling of the trench T.

[0066] While repeating the second process, the control unit 100 determines whether the supply of 3DMAS gas from the reaction gas nozzle 31, the supply of O3 gas from the reaction gas nozzle 32, and the supply of Ar / NH3 gas from the process gas nozzle 92 have been performed for a predetermined time (step S17). In the determination in step S17, the control unit 100 may determine whether the number of rotations of the turntable 2 has reached a predetermined number, instead of the gas supply time. The predetermined time and the predetermined number of rotations can be determined based on the depth of the trench T, the opening width of the trench T, etc.

[0067] If the predetermined time has not elapsed (NO in step S17), the second process is repeated. If the predetermined time has elapsed (YES in step S17), the process is terminated. As a result, as shown in FIG. 14(c), the trench T is filled with the silicon-containing films 202 and 204 without creating voids.

[0068] According to the embodiment, the OH groups generated by oxidation of the aminosilane gas and adsorbed to the silicon-containing films 202, 204 are distributed by the Ar / NH3 plasma so that the density is high at the bottom and the side near the bottom of the trench T and the density is low toward the opening of the trench T. The OH groups act as adsorption sites for the aminosilane gas, and the aminosilane gas is adsorbed according to the distribution of the OH groups. Therefore, the aminosilane gas is also distributed so that the density is high at the bottom and the side near the bottom of the trench T and the density is low toward the opening of the trench T. Therefore, the silicon-containing films 202, 204 are formed so that they are thick at the bottom and the side near the bottom of the trench T and are thin toward the opening of the trench T.

[0069] Furthermore, according to the embodiment, the temperature of the substrate W is changed from the first temperature to the second temperature during the formation of the silicon-containing films 202, 204. In this case, it is possible to control the embedding shape of the silicon-containing films 202, 204 in the trenches T. The reason why it is possible to control the embedding shape of the silicon-containing films 202, 204 in the trenches T is considered as follows.

[0070] Fig. 15 is a schematic diagram for explaining the reaction of the 3DMAS gas on the surface of the substrate W. As shown in Fig. 15, when the 3DMAS gas is supplied to the surface of the substrate W, the 3DMAS gas is adsorbed to OH groups on the surface of the substrate W, and hydrogen (H) atoms bonded to silicon (Si) atoms (hereinafter referred to as "silicon-bonded hydrogen atoms") are generated on the surface of the substrate W.

[0071] Silicon-bonded hydrogen atoms present on the surface of the substrate W may be desorbed during the formation of the silicon-containing films 202, 204. The amount of silicon-bonded hydrogen atoms that are desorbed increases as the temperature of the substrate W decreases. If silicon-bonded hydrogen atoms are desorbed while the aminosilane-based gas is being supplied, adsorption of the aminosilane-based gas to the surface of the substrate W is promoted, and the formation rate of the silicon-containing films 202, 204 increases. For this reason, if the temperature of the substrate W is lowered, the amount of silicon-bonded hydrogen atoms that are desorbed increases, and the formation rate of the silicon-containing films 202, 204 increases.

[0072] The change in the deposition rate of the silicon-containing films 202, 204 is greater at the bottom and side surfaces near the bottom of the trench T, where a greater amount of aminosilane-based gas is adsorbed, than near the opening of the trench T, where a smaller amount of aminosilane-based gas is adsorbed. For this reason, when the temperature of the substrate W is changed, the film thickness of the silicon-containing films 202, 204 formed on the bottom and side surfaces near the bottom of the trench T changes more than the film thickness of the silicon-containing films 202, 204 formed near the opening of the trench T. As a result, the embedding shape of the silicon-containing films 202, 204 in the trench T is controlled.

[0073] In the above embodiment, the first temperature is 620° C. and the second temperature is 400° C., but the present invention is not limited thereto. The first temperature and the second temperature may be different from each other. The first temperature and the second temperature can be selected according to a target embedding shape when embedding the silicon-containing films 202 and 204 in the trench T.

[0074] The first and second temperatures are, for example, temperatures at which the aminosilane gas is not decomposed. The temperature at which the 3DMAS gas is not decomposed is, for example, 760° C. or lower. The temperature at which the DIPAS gas is not decomposed is, for example, 600° C. or lower.

[0075] For example, the first temperature may be higher than the second temperature. In this case, in the first half of the film formation, bottom-up film formation can be maintained, and the thickness of the silicon-containing film 202 formed on the bottom of the trench T and the side surface near the bottom can be made thin. Therefore, in the first half of the film formation, it is easy to prevent the vicinity of the opening of the trench T from being blocked by the silicon-containing film 202. Also, in the second half of the film formation, the silicon-containing film 204, which has a high bottom-up property, can be filled in. Therefore, it is easy to fill the trench T with the silicon-containing film 204 without voids.

[0076] In the above embodiment, the temperature of the substrate W is changed once during the formation of the silicon-containing film, but the present invention is not limited to this. For example, the temperature of the substrate W may be changed two or more times during the formation of the silicon-containing film. For example, during the formation of the silicon-containing film, the temperature of the substrate W may be maintained at a first temperature first, then at a second temperature, and finally at the first temperature. For example, during the formation of the silicon-containing film, the temperature of the substrate W may be maintained at a first temperature first, then at a second temperature, and finally at a third temperature. In this case, the first temperature may be higher than the second temperature, and the second temperature may be higher than the third temperature. This makes it easier to improve the embedding characteristics of the silicon-containing film in deep trenches.

[0077] In the above embodiment, the oxidizing gas is O3 gas, but is not limited thereto. For example, the oxidizing gas may be O2 gas, H2O, or H2O2 gas.

[0078] Furthermore, every time the first process is repeated for a predetermined time, the supply of 3DMAS gas from the reactive gas nozzle 31 may be stopped while continuing the supply of O3 gas from the reactive gas nozzle 32 and the supply of Ar / NH3 gas from the process gas nozzle 92. In this case, the substrate W is exposed to Ar / NH3 gas without being supplied with 3DMAS gas. This makes it possible to suppress the increase in the thickness of the silicon-containing film caused by the detachment of silicon-bonded hydrogen atoms present on the surfaces of the silicon-containing films 202, 204.

[0079] Furthermore, every time the second process is repeated for a predetermined time, the supply of 3DMAS gas from the reactive gas nozzle 31 may be stopped while continuing the supply of O3 gas from the reactive gas nozzle 32 and the supply of Ar / NH3 gas from the process gas nozzle 92. In this case, the substrate W is exposed to Ar / NH3 gas without being supplied with 3DMAS gas. This makes it possible to suppress the increase in the thickness of the silicon-containing film caused by the detachment of silicon-bonded hydrogen atoms present on the surfaces of the silicon-containing films 202 and 204.

[0080] In the above embodiment, the first process is repeatedly performed in one vacuum vessel 1, the temperature of the substrate W is then changed from the first temperature to the second temperature, and the second process is then repeatedly performed. However, the present invention is not limited to this. For example, the first process may be repeatedly performed in a first vacuum vessel in which the substrate W is adjusted to have the first temperature, and then the second process may be repeatedly performed in a second vacuum vessel in which the substrate W is adjusted to have the second temperature. In this case, the time required to change the temperature of the substrate W from the first temperature to the second temperature can be shortened. For example, the first vacuum vessel and the second vacuum vessel may be connected to a common vacuum transfer chamber. In this case, the substrate W can be transferred from the first vacuum vessel to the second vacuum vessel via the vacuum transfer chamber. Therefore, after the first process is repeatedly performed, the second process can be continuously performed repeatedly without exposing the substrate W to the atmosphere. The configurations of the first vacuum vessel and the second vacuum vessel may be the same as the configuration of the vacuum vessel 1 described above.

[0081] [Example] In the examples, the film thickness distribution of the silicon-containing film in the depth direction of the trench was measured when the temperature of the substrate during the formation of the silicon-containing film was changed.

[0082] First, a substrate having a trench formed on its surface was prepared. The depth of the trench was 7.2 μm. Next, steps S11, S12, S13, and S14 were performed on the prepared substrate in this order. In step S12, the substrate was heated to a predetermined temperature by the heater unit 7 while rotating the turntable 2 clockwise at a rotation speed of 10 rpm. In step S13, 3DMAS gas was supplied from the reaction gas nozzle 31, and O3 gas was supplied from the reaction gas nozzle 32. In addition, Ar / NH3 gas was supplied from the process gas nozzle 92, and a high frequency wave having a frequency of 13.56 MHz was supplied to the antenna 85 of the plasma generation source 80 with a power of 2 kW.

[0083] In the examples, the thickness distribution of the silicon-containing film in the depth direction of the trench was compared when the temperature of the substrate during deposition of the silicon-containing film was changed. The temperature of the substrate during deposition of the silicon-containing film was adjusted to 400°C and 620°C.

[0084] Fig. 16 is a diagram showing the film thickness distribution of the silicon-containing film in the depth direction of the trench. In Fig. 16, the vertical axis indicates the trench depth [μm], and the horizontal axis indicates the film thickness of the silicon-containing film. In Fig. 16, the circles indicate the results when the substrate temperature was 400°C, and the diamonds indicate the results when the substrate temperature was 620°C.

[0085] 16, it can be seen that the film thickness distribution of the silicon-containing film in the depth direction of the trench is different when the substrate temperature is 400° C. and when the substrate temperature is 620° C. From this result, it can be said that the embedding shape of the silicon-containing film in the trench can be controlled by changing the substrate temperature when forming the silicon-containing film.

[0086] For example, by increasing the substrate temperature to 620°C instead of 400°C, it is possible to maintain the V-shape in which the film thickness decreases from the bottom of the trench to the opening, while still reducing the film thickness at the bottom of the trench.

[0087] The embodiments disclosed herein should be considered to be illustrative and not restrictive in all respects. The above-described embodiments may be omitted, substituted, or modified in various forms without departing from the scope and spirit of the appended claims.

[0088] In the above embodiment, the case where the plasma generation source is an inductively coupled plasma (ICP) source having an antenna has been described, but the present disclosure is not limited to this. For example, the plasma generation source 80 may be a capacitively coupled plasma (CCP) source that generates plasma by applying a high frequency wave between two rod electrodes extending parallel to each other.

[0089] In the above embodiment, the film forming apparatus is an apparatus that processes a substrate while revolving the substrate placed on the turntable, but the present disclosure is not limited thereto. For example, the film forming apparatus may be an apparatus that has a rotation mechanism that rotates a substrate placement portion on the turntable so that the substrate placed on the turntable rotates on its axis while revolving, and processes the substrate while revolving the substrate placed on the turntable. In this case, the uniformity of the processing within the surface of the substrate is improved.

[0090] In the above embodiment, the film forming apparatus is a semi-batch type apparatus, but the present disclosure is not limited thereto. For example, the film forming apparatus may be a single-wafer type apparatus that processes substrates one by one. For example, the film forming apparatus may be a batch type apparatus that processes multiple substrates at once. [Explanation of symbols]

[0091] T-Trench W substrate

Claims

1. (a) supplying an aminosilane-based gas into a recess formed in a substrate and causing the aminosilane-based gas to be adsorbed onto an inner surface of the recess; (b) supplying an oxidation gas to the recesses to which the aminosilane-based gas has been adsorbed, and reacting the aminosilane-based gas with the oxidation gas; (c) exposing the substrate to a plasma generated from a modifying gas; (d) repeating a first process including the steps (a), (b), and (c) in this order to form a silicon-containing film; having The step (d) includes changing a temperature of the substrate during the repetition of the first process. Film formation method.

2. The step (d) includes changing a temperature of the substrate from a first temperature to a second temperature during the repetition of the first process; The first temperature is higher than the second temperature. The film forming method according to claim 1 .

3. the temperature of the substrate is maintained at the first temperature during the first process iteration; The film forming method according to claim 2 .

4. the first temperature and the second temperature are both temperatures at which the aminosilane-based gas does not decompose; The film forming method according to claim 2 .

5. The aminosilane gas is trisdimethylaminosilane (3DMAS) gas. The film forming method according to claim 1 .

6. (e) supplying the oxidizing gas to the recess; (f) exposing the substrate to a plasma generated from a diluent gas; (g) repeating a second process including the steps (e) and (f) in this order; and The step (d) includes performing the step (g) during the repetition of the first treatment. The film forming method according to claim 1 .

7. The step (d) includes changing the temperature of the substrate by transferring the substrate from one of two vacuum chambers maintained at different temperatures to the other. The film forming method according to claim 1 .

8. a vacuum vessel for housing the substrate; a gas supply unit for supplying a processing gas into the vacuum chamber; A control unit; Equipped with The control unit is (a) supplying an aminosilane-based gas into a recess formed in the substrate and causing the aminosilane-based gas to be adsorbed onto an inner surface of the recess; (b) supplying an oxidation gas to the recesses to which the aminosilane-based gas has been adsorbed, and reacting the aminosilane-based gas with the oxidation gas; (c) exposing the substrate to a plasma generated from a modifying gas; (d) repeating a first process including the steps (a), (b), and (c) in this order to form a silicon-containing film; configured to run The control unit is configured to change a temperature of the substrate during the repetition of the first process in the step (d). Film deposition equipment.

Images