JP6091940B2 - Semiconductor device manufacturing method, substrate processing apparatus, and program - Google Patents

Description

  The present invention relates to a semiconductor device manufacturing method, a substrate processing method, a substrate processing apparatus, and a program including a step of forming a thin film on a substrate.

  As a process of manufacturing a semiconductor device (device) such as a DRAM, a substrate processing process for forming a thin film such as a silicon oxide film (hereinafter also referred to as an SiO film) on a substrate on which a fine resist pattern is formed in advance. May be performed. The SiO film can be formed, for example, by performing a step of supplying a source gas containing silicon to a substrate in the processing chamber and a step of supplying an oxidizing gas to the substrate in the processing chamber.

  However, when the SiO film is formed, the resist pattern formed on the substrate may be oxidized and volatilized. Further, the resist pattern may be deformed or collapsed due to the stress caused by the film stress of the SiO film formed on the resist pattern.

  An object of the present invention is to provide a semiconductor device capable of suppressing oxidation of a resist pattern or suppressing deformation or collapse of a resist pattern when a thin film is formed on a substrate on which a resist pattern is formed in advance. The object is to provide a manufacturing method, a substrate processing method, a substrate processing apparatus, and a program.

According to one aspect of the invention,
Performing a step of supplying a source gas containing a predetermined element to a substrate in a processing chamber and a step of supplying a nitriding gas to the substrate in the processing chamber; Forming a first layer containing nitrogen;
The step of supplying a source gas containing the predetermined element to the substrate in the processing chamber and the step of supplying an oxidizing gas to the substrate in the processing chamber are performed on the first layer. And forming a second layer containing the predetermined element and oxygen,
By performing the above, a method for manufacturing a semiconductor device is provided in which a thin film containing the predetermined element, nitrogen and oxygen is formed on the substrate.

According to another aspect of the invention,
Performing a step of supplying a source gas containing a predetermined element to a substrate in a processing chamber and a step of supplying a nitriding gas to the substrate in the processing chamber; Forming a first layer containing nitrogen;
The step of supplying a source gas containing the predetermined element to the substrate in the processing chamber and the step of supplying an oxidizing gas to the substrate in the processing chamber are performed on the first layer. And forming a second layer containing the predetermined element and oxygen,
By performing the above, there is provided a substrate processing method for forming a thin film containing the predetermined element, nitrogen and oxygen on the substrate.

According to yet another aspect of the invention,
A processing chamber for processing the substrate;
A raw material gas supply system for supplying a raw material gas containing a predetermined element into the processing chamber;
A nitriding gas supply system for supplying a nitriding gas into the processing chamber;
An oxidizing gas supply system for supplying an oxidizing gas into the processing chamber,
By performing the process of supplying the source gas containing the predetermined element to the substrate in the processing chamber and the process of supplying the nitriding gas to the substrate in the processing chamber, Forming a first layer containing a predetermined element and nitrogen;
The first layer is obtained by performing a process of supplying a source gas containing the predetermined element to the substrate in the process chamber and a process of supplying the oxidizing gas to the substrate in the process chamber. A process for forming a second layer containing the predetermined element and oxygen;
Performing a source gas supply system containing the predetermined element, a source gas supply system containing the predetermined element, and a nitriding gas supply so as to form a thin film containing the predetermined element, nitrogen and oxygen on the substrate. There is provided a substrate processing apparatus having a system and a controller for controlling the oxidizing gas supply system.

According to yet another aspect of the invention,
By performing a procedure for supplying a source gas containing a predetermined element to a substrate in a processing chamber of the substrate processing apparatus and a procedure for supplying a nitriding gas to the substrate in the processing chamber, on the substrate, Forming a first layer containing the predetermined element and nitrogen;
By performing a procedure for supplying a source gas containing the predetermined element to the substrate in the processing chamber and a procedure for supplying an oxidizing gas to the substrate in the processing chamber, And forming a second layer containing the predetermined element and oxygen,
By performing the above, there is provided a program for causing a computer to execute a procedure for forming a thin film containing the predetermined element, nitrogen and oxygen on the substrate.

  ADVANTAGE OF THE INVENTION According to this invention, when forming a thin film on the board | substrate with which the resist pattern was previously formed, the oxidation of a resist pattern can be suppressed, or the deformation | transformation and collapse of a resist pattern can be suppressed. A manufacturing method, a substrate processing method, a substrate processing apparatus, and a program can be provided.

It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus used suitably by embodiment of this invention, and is a figure which shows a processing furnace part with a longitudinal cross-sectional view. It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus used suitably by embodiment of this invention, and is a figure which shows a processing furnace part with the sectional view on the AA line of FIG. It is a schematic block diagram of the controller of the substrate processing apparatus used suitably by embodiment of this invention. It is a figure which shows the film-forming flow in 1st Embodiment of this invention. It is a figure which shows the timing of the gas supply in the film-forming sequence of 1st Embodiment of this invention. It is a figure which shows the film-forming flow in 2nd Embodiment of this invention. It is a figure which shows the timing of the gas supply in the film-forming sequence of 2nd Embodiment of this invention. It is a figure which shows the modification of the film-forming flow in 2nd Embodiment of this invention. It is a figure which shows the modification of the timing of gas supply in the film-forming sequence of 2nd Embodiment of this invention.

<First Embodiment of the Present Invention>
Hereinafter, a first embodiment of the present invention will be described with reference to the drawings.

(1) Configuration of Substrate Processing Apparatus FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in the present embodiment, and shows a processing furnace 202 portion in a vertical sectional view. FIG. 2 is a schematic configuration diagram of a vertical processing furnace suitably used in the present embodiment, and shows a processing furnace 202 portion in a cross-sectional view taken along the line AA of FIG. FIG. 3 is a schematic configuration diagram of the controller 280 of the substrate processing apparatus preferably used in the present embodiment.

(Reaction tube)
As shown in FIGS. 1 and 2, the processing furnace 202 is provided with a heater 207 as a heating device (heating means) for heating the wafer 200. The heater 207 includes a cylindrical heat insulating member whose upper portion is closed and a plurality of heater wires, and has a unit configuration in which the heater wires are provided on the heat insulating member. A heating power source 250 for supplying heating power is connected to the heater 207. Inside the heater 207, a reaction tube 203 made of quartz (SiO ₂ ) for processing the wafer 200 is provided concentrically with the heater 207.

  Below the reaction tube 203, a seal cap 219 is provided as a furnace opening lid capable of airtightly closing the lower end opening of the reaction tube 203. The seal cap 219 comes into contact with the lower end of the reaction tube 203 from the lower side in the vertical direction. The seal cap 219 is made of a metal such as stainless steel and has a disk shape. An O-ring 220 as an airtight member is disposed between the annular flange provided at the lower opening end of the reaction tube 203 and the upper surface of the seal cap 219, so that the two can be hermetically sealed. It is configured. At least the processing chamber 201 is formed by the reaction tube 203 and the seal cap 219.

  A boat support 218 that supports the boat 217 is provided on the seal cap 219. The boat support 218 is made of a heat resistant material such as quartz or silicon carbide (SiC), for example, and functions as a heat insulating portion and also functions as a support that supports the boat 217. The boat 217 is erected on the boat support 218. The boat 217 includes a bottom plate 210 fixed to the boat support base 218 and a top plate 211 disposed above the bottom plate 210, and a plurality of support columns 212 are installed between the bottom plate 210 and the top plate 211. It has a configuration. On the support column 212 of the boat 217, a plurality of wafers 200 are stacked in multiple stages in the tube axis direction of the reaction tube 203 in a horizontal posture and with the centers aligned with each other at a constant interval. . The bottom plate 210, the top plate 211, and the support column 212 of the boat 217 are made of a heat-resistant material such as quartz or silicon carbide.

  A rotation mechanism 267 that rotates the boat 217 is provided on the side of the seal cap 219 opposite to the processing chamber 201. A rotation shaft 265 of the rotation mechanism 267 passes through the seal cap 219 and is connected to the boat support 218. The rotation mechanism 267 is configured to rotate the boat 217 and the wafer 200 via the boat support 218 by rotating the rotation mechanism 267.

  The seal cap 219 is configured to be moved up and down in the vertical direction by a boat elevator 115 as an elevating mechanism provided outside the reaction tube 203, and thereby, the boat 217 is carried into and out of the processing chamber 201. It is possible. That is, the boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers the boat 217, that is, the wafers 200 into and out of the processing chamber 201.

  In the processing furnace 202 described above, in a state where a plurality of wafers 200 to be batch-processed are stacked in multiple stages on the boat 217, the boat 217 is carried into the processing chamber 201 while being supported by the boat support 218, and the heater 207. However, the wafer 200 loaded into the processing chamber 201 can be heated to a predetermined temperature.

(Gas supply system)
In the processing chamber 201, nozzles 410, 420, and 430 are provided so as to penetrate the lower part of the reaction tube 203. Gas supply pipes 310, 320, and 330 that supply gas are connected to the nozzles 410, 420, and 430, respectively. As described above, the reaction tube 203 is provided with the three nozzles 410, 420, and 430 and the three gas supply tubes 310, 320, and 330. It is comprised so that a kind of gas can be supplied. A metal manifold that supports the reaction tube 203 may be provided below the reaction tube 203, and each nozzle may be provided so as to penetrate the side wall of the metal manifold. In this case, an exhaust pipe 231 to be described later may be further provided on the metal manifold. Even in this case, the exhaust pipe 231 may be provided below the reaction pipe 203 instead of the metal manifold. As described above, the furnace port portion of the processing furnace 202 may be made of metal, and a nozzle or the like may be attached to the metal furnace port portion.

(Raw gas supply system)
The gas supply pipe 310 includes, in order from the upstream side, a mass flow controller (MFC) 312 that is a flow rate control device (flow rate control unit), a valve 314 that is an on-off valve, a gas reservoir (gas reservoir) 315, and a valve that is an on-off valve. 313 is provided. An upstream end of a vent gas pipe 610 that bypasses and exhausts gas is connected between the mass flow controller 312 of the gas supply pipe 310 and the valve 314. The downstream end of the vent gas pipe 610 is connected to the downstream side of the APC valve 243 of the exhaust pipe 231 described later. The vent gas pipe 610 is provided with a valve 612. A downstream end of an inert gas supply pipe 510 that supplies an inert gas as a carrier gas or a purge gas is connected to the downstream side of the valve 313 of the gas supply pipe 310. The inert gas supply pipe 510 is provided with a mass flow controller 512 and a valve 513 in order from the upstream side.

  The downstream end of the gas supply pipe 310 is connected to the upstream end of the nozzle 410. The nozzle 410 is provided in an arc-shaped space between the inner wall of the reaction tube 203 and the wafer 200 so as to rise upward in the stacking direction of the wafer 200 along the lower portion and the upper portion of the inner wall of the reaction tube 203. Yes. The nozzle 410 is configured as an L-shaped long nozzle. A number of gas supply holes 411 for supplying gas are provided on the side surface of the nozzle 410. The gas supply hole 411 is opened to face the center of the reaction tube 203. The gas supply holes 411 have the same or inclined opening area from the lower part to the upper part, and are provided at the same pitch.

The gas reservoir 315 is configured as, for example, a gas tank or a spiral pipe having a larger gas capacity than a normal pipe. By opening and closing the upstream valve 314 and the downstream valve 313 of the gas reservoir 315, the gas supplied from the gas supply pipe 310 is filled in the gas reservoir 315, or the gas filled in the gas reservoir 315 is processed. It can be supplied into the chamber 201. It is preferable that the conductance between the gas reservoir 315 and the processing chamber 201 is, for example, 1.5 × 10 ⁻³ m ³ / s or more. Considering the ratio between the volume of the reaction tube 203 and the volume of the gas reservoir 315, when the volume of the reaction tube 203 is 100 L (liter), the volume of the gas reservoir 315 is preferably, for example, 100 to 300 cc. The volume of the reaction tube 203 is preferably 1/1000 to 3/1000 times, for example.

  By closing the valve 313 and the valve 612 and opening the valve 314, the gas whose flow rate is adjusted by the mass flow controller 312 can be filled in the gas reservoir 315. When the gas reservoir 315 is filled with a predetermined amount of gas and the pressure in the gas reservoir 315 reaches a predetermined pressure, the valve 314 is closed and the valve 313 is opened, whereby the high-pressure gas filled in the gas reservoir 315 is obtained. Can be supplied into the processing chamber 201 through the gas supply pipe 310 and the nozzle 410 at once (in a short time). At this time, an inert gas as a carrier gas (dilution gas, diffusion gas) whose flow rate is adjusted by the mass flow controller 512 is supplied into the processing chamber 201 through the gas supply pipe 310 and the nozzle 410 by opening the valve 513. can do. Further, by closing the valve 314 and opening the valve 612, the gas whose flow rate is adjusted by the mass flow controller 312 is bypassed without being supplied into the processing chamber 201, and is exhausted to the exhaust pipe 231 through the vent gas pipe 610. Can do. Further, by closing the valve 313 and opening the valve 513, an inert gas as a purge gas whose flow rate is adjusted by the mass flow controller 512 is supplied into the processing chamber 201 through the gas supply pipe 310 and the nozzle 410, and the processing chamber The inside of 201 can be purged.

  From the gas supply pipe 310, as a source gas containing a predetermined element, for example, a source gas containing silicon (Si) is passed through the mass flow controller 312, the valve 314, the gas reservoir 315, the valve 313, and the nozzle 410 into the processing chamber 201. To be supplied.

As a source gas containing Si, for example, tetrakisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₄ , abbreviation: 4DMAS), trisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₃ H, abbreviation: 3DMAS) , Bisdiethylaminosilane (Si [N (C ₂ H ₅ ) ₂ ] ₂ H ₂ , abbreviation: 2DEAS), trisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₃ H, abbreviation: TDMAS), binary butylaminosilane (Si [NH (C ₄ H ₉ )] ₂ H ₂ , abbreviation: BTBAS), bisdiethylaminosilane (Si [N (C ₂ H ₅ ) ₂ ] ₂ H ₂ , abbreviation: BDEAS), bisdiethylmethylaminosilane (Si _{[N (CH 3) 2]} 2 H 2, abbreviation: BDEMAS) for aminosilane-based precursor was vaporized gas, such as Rukoto can. The aminosilane-based raw material is a silane-based raw material having an amino group (also a silane-based raw material containing both a methyl group and an ethyl group), and at least silicon (Si), carbon (C), and nitrogen (N ).

Examples of source gas containing Si include dichlorosilane (SiH ₂ Cl ₂ , abbreviation: DCS), monochlorosilane (SiH ₃ Cl, abbreviation: MCS), hexachlorodisilane (Si ₂ Cl ₆ , abbreviation: HCDS), A gas obtained by vaporizing a chlorosilane-based material such as tetrachlorosilane, that is, silicon tetrachloride (SiCl ₄ , abbreviation: STC), trichlorosilane (SiHCl ₃ , abbreviation: TCS), or the like can also be used. The chlorosilane-based raw material is a silane-based raw material having a chloro group as a halogen group, and is a raw material containing at least silicon (Si) and chlorine (Cl).

Further, as the source gas containing Si, for example, a gas obtained by vaporizing a fluorosilane-based source such as tetrafluorosilane, that is, silicon tetrafluoride (SiF ₄ ) gas, hexafluorodisilane (Si ₂ F ₆ ) gas, or the like is used. You can also. Here, the fluorosilane-based material is a silane-based material having a fluoro group as a halogen group, and is a material containing at least a silicon (Si) element and a fluorine (F) element.

As the source gas containing Si, for example, an inorganic source such as trisilane (Si ₃ H ₈ , abbreviation: TS), disilane (Si ₂ H ₆ , abbreviation: DS), monosilane (SiH ₄ , abbreviation: MS), or the like is used. Vaporized gas can also be used.

  For example, when using a liquid material that is in a liquid state at normal temperature and pressure, such as BTBAS and DCS, the liquid material is vaporized by a vaporization system such as a vaporizer or a bubbler and used as a raw material gas (BTBAS gas, DCS gas). Will be supplied.

For example, nitrogen (N ₂ ) gas or rare gas such as Ar, He, Ne, and Xe is processed from the inert gas supply pipe 510 through the mass flow controller 512, the valve 513, the gas supply pipe 310, and the nozzle 410, respectively. It is supplied into the chamber 201.

  A source gas supply system 301 is mainly configured by the gas supply pipe 310, the mass flow controller 312, the valve 314, the gas reservoir 315, the valve 313, and the nozzle 410. The vent gas pipe 610 and the valve 612 may be included in the source gas supply system 301. Further, a first inert gas supply system (carrier and purge gas supply system) 501 is mainly configured by the inert gas supply pipe 510, the mass flow controller 512, and the valve 513. Note that the gas supply pipe 310 and the nozzle 410 may be included in the first inert gas supply system 501.

(Nitriding gas supply system)
The gas supply pipe 320 is provided with a mass flow controller (MFC) 322 that is a flow rate control device (flow rate control unit) and a valve 323 that is an on-off valve in order from the upstream side. An upstream end of a vent gas pipe 620 that bypasses and exhausts gas is connected between the mass flow controller 322 of the gas supply pipe 320 and the valve 323. The downstream end of the vent gas pipe 620 is connected to the downstream side of the APC valve 243 of the exhaust pipe 231 described later. The vent gas pipe 620 is provided with a valve 622. A downstream end of an inert gas supply pipe 520 that supplies an inert gas as a carrier gas or a purge gas is connected to the downstream side of the valve 323 of the gas supply pipe 320. The inert gas supply pipe 520 is provided with a mass flow controller 522 and a valve 523 in order from the upstream side.

  The downstream end of the gas supply pipe 320 is connected to the upstream end of the nozzle 420. The nozzle 420 is provided in a buffer chamber 423 which is a gas dispersion space (discharge chamber, discharge space). In the buffer chamber 423, electrode protection tubes 451 and 452 described later are further provided. In the buffer chamber 423, the nozzle 420, the electrode protection tube 451, and the electrode protection tube 452 are arranged in this order so as to follow the inner wall of the reaction tube 203.

  The buffer chamber 423 is formed by the inner wall of the reaction tube 203 and the buffer chamber wall 424. The buffer chamber wall 424 is provided in an arc-shaped space between the inner wall of the reaction tube 203 and the wafer 200 in a portion extending from the lower part to the upper part of the inner wall of the reaction tube 203 along the loading direction of the wafer 200. A gas supply hole 425 for supplying a gas is provided in a wall of the buffer chamber wall 424 adjacent to the wafer 200. The gas supply hole 425 is provided between the electrode protection tube 451 and the electrode protection tube 452. The gas supply hole 425 is opened so as to face the center of the reaction tube 203. A plurality of gas supply holes 425 are provided from the lower part to the upper part of the reaction tube 203, each having the same opening area, and further provided at the same pitch.

  The nozzle 420 is provided on one end side of the buffer chamber 423 so as to rise upward in the stacking direction of the wafer 200 along the lower portion of the inner wall of the reaction tube 203. The nozzle 420 is configured as an L-shaped long nozzle. A gas supply hole 421 for supplying gas is provided on the side surface of the nozzle 420. The gas supply hole 421 opens so as to face the center of the buffer chamber 423. A plurality of gas supply holes 421 are provided from the lower part to the upper part of the reaction tube 203, similarly to the gas supply holes 425 of the buffer chamber 423. Each of the gas supply holes 421 has the same opening area with the same opening area from the upstream side (lower part) to the downstream side (upper part) when the differential pressure in the buffer chamber 423 and the nozzle 420 is small. The pitch may be set, but when the differential pressure is large, the opening area may be sequentially increased from the upstream side toward the downstream side, or the pitch may be decreased.

  In this embodiment, by adjusting the opening area and the opening pitch of each of the gas supply holes 421 of the nozzle 420 from the upstream side to the downstream side as described above, first, the flow rate of each gas supply hole 421 is adjusted from each of the gas supply holes 421. Although there is a difference, the gas with the same flow rate is ejected. The gas ejected from each of the gas supply holes 421 is once introduced into the buffer chamber 423, and the difference in gas flow velocity is made uniform in the buffer chamber 423. That is, the gas ejected into the buffer chamber 423 from each of the gas supply holes 421 of the nozzle 420 is reduced in the particle velocity of each gas in the buffer chamber 423 and then into the processing chamber 201 from the gas supply hole 425 of the buffer chamber 423. To erupt. Thus, when the gas ejected into the buffer chamber 423 from each of the gas supply holes 421 of the nozzle 420 is ejected into the processing chamber 201 from each of the gas supply holes 425 of the buffer chamber 423, a uniform flow rate and flow velocity are obtained. It becomes gas which has.

  By opening the valve 323, the gas whose flow rate is adjusted by the mass flow controller 322 can be supplied into the processing chamber 201 through the gas supply pipe 320, the nozzle 420 and the buffer chamber 423. At this time, by opening the valve 523, the inert gas as the carrier gas (dilution gas, diffusion gas) whose flow rate is adjusted by the mass flow controller 522 is passed through the gas supply pipe 320, the nozzle 420 and the buffer chamber 423. 201 can be supplied. Further, by closing the valve 323 and opening the valve 622, the gas whose flow rate is adjusted by the mass flow controller 322 is bypassed without being supplied into the processing chamber 201, and is exhausted to the exhaust pipe 231 through the vent gas pipe 620. Can do. Further, by closing the valve 323 and opening the valve 523, an inert gas as a purge gas whose flow rate is adjusted by the mass flow controller 522 is supplied into the processing chamber 201 through the gas supply pipe 320, the nozzle 420 and the buffer chamber 423. Then, the inside of the processing chamber 201 can be purged.

From the gas supply pipe 320, a gas containing nitrogen (N) element as a nitriding gas (nitriding agent) is supplied into the processing chamber 201 through the mass flow controller 322, the valve 323, the nozzle 420 and the buffer chamber 423. . As the nitriding gas, for example, ammonia (NH ₃ ) gas, diazine (N ₂ H ₂ ) gas, hydrazine (N ₂ H ₄ ) gas, N ₃ H ₈ gas, or a gas containing these compounds can be used.

From the inert gas supply pipe 520, for example, nitrogen (N ₂ ) gas or a rare gas such as Ar, He, Ne, or Xe passes through the mass flow controller 522, the valve 523, the gas supply pipe 320, the nozzle 420, and the buffer chamber 423. Is supplied into the processing chamber 201.

  A nitriding gas supply system 302 is mainly configured by the gas supply pipe 320, the mass flow controller 322, the valve 323, the nozzle 420 and the buffer chamber 423. The vent gas pipe 620 and the valve 622 may be included in the nitriding gas supply system 302. In addition, a second inert gas supply system (carrier and purge gas supply system) 502 is mainly configured by the inert gas supply pipe 520, the mass flow controller 522, and the valve 523. The gas supply pipe 320, the nozzle 420, and the buffer chamber 423 may be included in the second inert gas supply system 502.

(Oxidizing gas supply system)
The gas supply pipe 330 is provided with a mass flow controller (MFC) 332 that is a flow rate control device (flow rate control unit) and a valve 333 that is an on-off valve in order from the upstream side. An upstream end of a vent gas pipe 630 that bypasses and exhausts gas is connected between the mass flow controller 332 and the valve 333 of the gas supply pipe 330. The downstream end of the vent gas pipe 630 is connected to the downstream side of the APC valve 243 of the exhaust pipe 231 described later. The vent gas pipe 630 is provided with a valve 632. A downstream end of an inert gas supply pipe 530 that supplies an inert gas as a carrier gas or a purge gas is connected to the downstream side of the valve 333 of the gas supply pipe 330. The inert gas supply pipe 530 is provided with a mass flow controller 532 and a valve 533 in order from the upstream side.

  The downstream end of the gas supply pipe 330 is connected to the upstream end of the nozzle 430. The nozzle 430 is provided in a buffer chamber 433 that is a gas dispersion space (discharge chamber, discharge space). In the buffer chamber 433, electrode protection tubes 461 and 462, which will be described later, are further provided. In the buffer chamber 433, the nozzle 430, the electrode protection tube 461, and the electrode protection tube 462 are arranged in this order so as to follow the inner wall of the reaction tube 203.

  The buffer chamber 433 is formed by the inner wall of the reaction tube 203 and the buffer chamber wall 434. The buffer chamber wall 434 is provided in an arc-shaped space between the inner wall of the reaction tube 203 and the wafer 200 in a portion extending from the lower part to the upper part of the inner wall of the reaction tube 203 along the loading direction of the wafer 200. A gas supply hole 435 for supplying a gas is provided on the wall of the buffer chamber wall 434 adjacent to the wafer 200. The gas supply hole 435 is provided between the electrode protection tube 461 and the electrode protection tube 462. The gas supply hole 435 is opened to face the center of the reaction tube 203. A plurality of gas supply holes 435 are provided from the lower part to the upper part of the reaction tube 203, each having the same opening area, and further provided at the same pitch.

  The nozzle 430 is provided on one end side of the buffer chamber 433 so as to rise upward in the stacking direction of the wafer 200 along the upper portion from the lower portion of the inner wall of the reaction tube 203. The nozzle 430 is configured as an L-shaped long nozzle. A gas supply hole 431 for supplying a gas is provided on a side surface of the nozzle 430. The gas supply hole 431 is opened to face the center of the buffer chamber 433. Similar to the gas supply hole 435 of the buffer chamber 433, a plurality of gas supply holes 431 are provided from the lower part to the upper part of the reaction tube 203. Each of the gas supply holes 431 has the same opening area from the upstream side (lower part) to the downstream side (upper part) with the same opening area when the differential pressure between the buffer chamber 433 and the nozzle 430 is small. The pitch may be set, but when the differential pressure is large, the opening area may be sequentially increased from the upstream side toward the downstream side, or the pitch may be decreased.

  In the present embodiment, by adjusting the opening area and the opening pitch of each of the gas supply holes 431 of the nozzle 430 from the upstream side to the downstream side as described above, first, the flow rate from each of the gas supply holes 431 is adjusted. Although there is a difference, the gas with the same flow rate is ejected. The gas ejected from each of the gas supply holes 431 is once introduced into the buffer chamber 433, and the difference in gas flow velocity is made uniform in the buffer chamber 433. That is, the gas ejected into the buffer chamber 433 from each of the gas supply holes 431 of the nozzle 430 is reduced in the particle velocity of each gas in the buffer chamber 433, and then the gas supply holes 435 in the buffer chamber 433 enter the processing chamber 201. To erupt. As a result, when the gas ejected into the buffer chamber 433 from each of the gas supply holes 431 of the nozzle 430 is ejected into the processing chamber 201 from each of the gas supply holes 435 of the buffer chamber 433, a uniform flow rate and flow rate are obtained. It becomes gas which has.

  By opening the valve 333, the gas whose flow rate is adjusted by the mass flow controller 332 can be supplied into the processing chamber 201 through the gas supply pipe 330, the nozzle 430, and the buffer chamber 433. At this time, by opening the valve 533, the inert gas as the carrier gas (dilution gas, diffusion gas) whose flow rate is adjusted by the mass flow controller 532 is passed through the gas supply pipe 330, the nozzle 430 and the buffer chamber 433. 201 can be supplied. Further, by closing the valve 333 and opening the valve 632, the gas whose flow rate is adjusted by the mass flow controller 332 is bypassed without being supplied into the processing chamber 201, and is exhausted to the exhaust pipe 231 through the vent gas pipe 630. Can do. Further, by closing the valve 333 and opening the valve 533, the inert gas as the purge gas whose flow rate is adjusted by the mass flow controller 532 is supplied into the processing chamber 201 through the gas supply pipe 330, the nozzle 430 and the buffer chamber 433. Then, the inside of the processing chamber 201 can be purged.

From the gas supply pipe 330, a gas containing oxygen (O) element as an oxidizing gas (oxidant) is supplied into the processing chamber 201 through the mass flow controller 332, the valve 333, the nozzle 430 and the buffer chamber 433. . Examples of the oxidizing gas include oxygen (O ₂ ) gas, mixed gas of oxygen gas and hydrogen gas (O ₂ + H ₂ ), nitrogen dioxide (N ₂ O) gas, nitrogen monoxide (NO) gas, ozone (O _3). ) Gas, water vapor (H ₂ O), hydrogen peroxide (H ₂ O ₂ ) gas, or the like can be used.

From the inert gas supply pipe 530, for example, nitrogen (N ₂ ) gas or a rare gas such as Ar, He, Ne, or Xe passes through the mass flow controller 532, the valve 533, the gas supply pipe 330, the nozzle 430, and the buffer chamber 433. Is supplied into the processing chamber 201.

  An oxidizing gas supply system 303 is mainly configured by the gas supply pipe 330, the mass flow controller 332, the valve 333, the nozzle 430, and the buffer chamber 433. The vent gas pipe 630 and the valve 632 may be included in the oxidizing gas supply system 303. In addition, a third inert gas supply system (carrier and purge gas supply system) 503 is mainly configured by the inert gas supply pipe 530, the mass flow controller 532, and the valve 533. The gas supply pipe 330, the nozzle 430, and the buffer chamber 433 may be included in the third inert gas supply system 503.

(First and second plasma sources)
In the buffer chamber 423, as shown in FIG. 2, rod-like electrodes 471 and rod-like electrodes 472 having an elongated structure are arranged along the stacking direction of the wafers 200 from the lower part to the upper part of the reaction tube 203. The rod-shaped electrode 471 and the rod-shaped electrode 472 are each provided in parallel with the nozzle 420. The rod-shaped electrode 471 and the rod-shaped electrode 472 are protected by being covered with electrode protection tubes 451 and 452 which are protection tubes that protect the electrode from the upper part to the lower part, respectively. The rod-shaped electrode 471 is connected to a radio frequency (RF) power source 270 via a matching unit 271, and the rod-shaped electrode 472 is connected to a ground 272 that is a reference potential. By applying high-frequency power between the rod-shaped electrode 471 and the rod-shaped electrode 472 from the high-frequency power source 270 via the matching device 271, plasma is generated in the plasma generation region between the rod-shaped electrode 471 and the rod-shaped electrode 472. The first plasma generation structure 429 is mainly configured by the rod-shaped electrode 471, the rod-shaped electrode 472, the electrode protection tube 451, the electrode protection tube 452, and the buffer chamber 423. The rod-shaped electrode 471, the rod-shaped electrode 472, the electrode protection tube 451, and the electrode protection tube 452 mainly constitute a first plasma source as a plasma generator (plasma generator). Note that the matching device 271 and the high-frequency power source 270 may be included in the first plasma source. The first plasma source functions as an activation mechanism that activates gas with plasma. The buffer chamber 423 functions as a plasma generation chamber.

  In the buffer chamber 433, as in the buffer chamber 423, rod-like electrodes 481 and rod-like electrodes 482 having an elongated structure are disposed along the stacking direction of the wafers 200 from the lower part to the upper part of the reaction tube 203. Each of the rod-shaped electrode 481 and the rod-shaped electrode 482 is provided in parallel with the nozzle 430. The rod-shaped electrode 481 and the rod-shaped electrode 482 are protected by being covered with electrode protection tubes 461 and 462 that are protection tubes that protect the electrode from the upper part to the lower part, respectively. The rod-shaped electrode 481 is connected to the high-frequency power source 270 via the matching unit 271, and the rod-shaped electrode 482 is connected to the ground 272 that is a reference potential. By applying high-frequency power between the rod-shaped electrode 481 and the rod-shaped electrode 482 from the high-frequency power source 270 via the matching device 271, plasma is generated in the plasma generation region between the rod-shaped electrode 481 and the rod-shaped electrode 482. The second plasma generation structure 439 is mainly configured by the rod-shaped electrode 481, the rod-shaped electrode 482, the electrode protection tube 461, the electrode protection tube 462, and the buffer chamber 433. The rod-shaped electrode 481, the rod-shaped electrode 482, the electrode protective tube 461, and the electrode protective tube 462 mainly constitute a second plasma source as a plasma generator (plasma generating unit). Note that the matching device 271 and the high-frequency power source 270 may be included in the second plasma source. The second plasma source functions as an activation mechanism that activates the gas with plasma. The buffer chamber 433 functions as a plasma generation chamber.

  The electrode protection tubes 451, 452, 461, and 462 are placed in the buffer chambers 423 and 433 through a through hole (not shown) provided in the reaction tube 203 at a height near the lower portion of the boat support 218. Each is inserted. The electrode protection tubes 451, 452, 461, and 462 are structured such that the rod-shaped electrodes 471, 472, 481, 482 can be inserted into the buffer chambers 423, 433 while being isolated from the atmosphere of the buffer chambers 423, 433, respectively. Here, if the insides of the electrode protection tubes 451, 452, 461, and 462 are substantially the same as the oxygen concentration in the outside air (atmosphere), the rod-shaped electrodes 471 and 472 inserted into the electrode protection tubes 451, 452, 461, and 462, respectively. , 481, 482 are oxidized by heat from the heater 207. Therefore, the inside of the electrode protection tubes 451, 452, 461, 462 is filled with an inert gas such as nitrogen gas, or the inside of the electrode protection tubes 451, 452, 461, 462 is nitrogenated using an inert gas purge mechanism. By purging with an inert gas such as a gas, the oxygen concentration inside the electrode protection tubes 451, 452, 461, and 462 can be reduced, and oxidation of the rod-shaped electrodes 471, 472, 481, and 482 can be prevented. It is configured.

  The plasma generated by this embodiment is called remote plasma. Remote plasma is a plasma process in which plasma generated between electrodes is transported to the surface of an object by gas flow or the like. In this embodiment, since two rod-shaped electrodes 471 and 472 are accommodated in the buffer chamber 423 and the two rod-shaped electrodes 481 and 482 are accommodated in the buffer chamber 433, ions that cause damage to the wafer 200 are present. This structure is difficult to leak into the processing chamber 201 outside the buffer chambers 423 and 433. Further, an electric field is generated so as to surround the two rod-shaped electrodes 471 and 472 (that is, so as to surround the electrode protection tubes 451 and 452 in which the two rod-shaped electrodes 471 and 472 are respectively accommodated), and plasma is generated. An electric field is generated so as to surround the two rod-shaped electrodes 481 and 482 (that is, so as to surround the electrode protection tubes 461 and 462 in which the two rod-shaped electrodes 481 and 482 are accommodated, respectively), and plasma is generated. . The active species contained in the plasma is supplied from the outer periphery of the wafer 200 toward the center of the wafer 200 through the gas supply hole 425 of the buffer chamber 423 and the gas supply hole 435 of the buffer chamber 433. Further, in the case of a vertical batch apparatus in which a plurality of wafers 200 are stacked in a stack shape with the main surface parallel to a horizontal plane as in the present embodiment, the inner wall surface of the reaction tube 203, that is, close to the wafer 200 to be processed. As a result of the buffer chambers 423 and 433 being arranged at the positions, there is an effect that the generated active species can easily reach the surface of the wafer 200 without being deactivated.

(Exhaust system)
An exhaust port 230 is provided below the reaction tube 203. An exhaust pipe 231 that exhausts the atmosphere in the processing chamber 201 is connected to the exhaust port 230. The exhaust pipe 231 includes, in order from the upstream side, a pressure sensor 245 as a pressure detector (pressure detection unit) that detects the pressure in the processing chamber 201, and an APC (Auto Pressure Controller) as a pressure regulator (pressure adjustment unit). A valve 243 and a vacuum pump 246 as a vacuum exhaust device are provided. The exhaust pipe 231 on the downstream side of the vacuum pump 246 is connected to a waste gas treatment device (not shown) or the like. Note that the APC valve 243 can open and close the vacuum pump 246 in a state where the vacuum pump 246 is operated to perform vacuum exhaust and stop the vacuum exhaust in the processing chamber 201, and further, a state where the vacuum pump 246 is operated. The valve is configured so that the pressure in the processing chamber 201 can be adjusted by adjusting the valve opening degree. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. Note that the vacuum pump 246 may be included in the exhaust system. The exhaust system adjusts the opening degree of the APC valve 243 based on pressure information detected by the pressure sensor 245 while operating the vacuum pump 246, so that the pressure in the processing chamber 201 becomes a predetermined pressure (vacuum). It is configured so that it can be evacuated to a degree.

  The exhaust port 230 is provided at a position (on the opposite side of 180 degrees) facing the gas supply hole 411 of the nozzle 410 with the wafer 200 interposed therebetween. Thereby, the gas supplied from the gas supply hole 411 flows so as to cross the main surface of the wafer 200 carried into the processing chamber 201 in the direction of the exhaust pipe 231, and more efficiently on the entire surface of the wafer 200. In addition, the gas is supplied more uniformly, so that the processing efficiency for the wafer 200 can be improved and the in-plane uniformity can be improved. Further, the gas supply hole 425 of the first plasma generation structure 429 and the gas supply hole 435 of the second plasma generation structure 439 described above are the center of the wafer 200 (the center of the reaction tube 203) loaded into the processing chamber 201. Are provided at positions symmetrical with each other with respect to a straight line connecting the exhaust port 230 and the exhaust port 230. As a result, the gas (gas activated by plasma) supplied from the gas supply holes 425 and 435 is more uniformly supplied to the entire surface of the wafer 200 carried into the processing chamber 201. In-plane uniformity of processing on the wafer 200 can be further improved. Further, the distance between the gas supply hole 411 of the nozzle 410 and the gas supply hole 425 of the buffer chamber 423, the distance between the gas supply hole 411 of the nozzle 410 and the gas supply hole 435 of the buffer chamber 433, and the gas supply hole 425 of the buffer chamber 423. And the gas supply hole 435 of the buffer chamber 433 are configured to be equal to each other. In this way, the in-plane uniformity of processing on the wafer 200 can be further improved.

(Temperature sensor)
A temperature sensor 263 as a temperature detector is installed in the reaction tube 203. The temperature sensor 263 is configured in an L shape like the nozzles 410, 420, and 430, and is provided along the inner wall of the reaction tube 203. Based on the temperature information detected by the temperature sensor 263, the supply power to the heater 207 from the heating power source 250 is adjusted so that the temperature in the processing chamber 201 has a desired temperature distribution.

(controller)
As shown in FIG. 3, the controller 280, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 280a, a RAM (Random Access Memory) 280b, a storage device 280c, and an I / O port 280d. Has been. The RAM 280b, the storage device 280c, and the I / O port 280d are configured to exchange data with the CPU 280a via the internal bus 280e. For example, an input / output device 122 configured as a touch panel or the like is connected to the controller 280.

  The storage device 280c is configured by, for example, a flash memory, an HDD (Hard Disk Drive), or the like. In the storage device 280c, a control program that controls the operation of the substrate processing apparatus, a process recipe that describes the procedure and conditions of the substrate processing described later, and the like are stored in a readable manner. Note that the process recipe is a combination of the controller 280 so that predetermined procedures can be obtained by causing the controller 280 to execute each procedure in the substrate processing process described later, and functions as a program. Hereinafter, the process recipe, the control program, and the like are collectively referred to as simply a program. When the term “program” is used in this specification, it may include only a process recipe alone, may include only a control program alone, or may include both. The RAM 280b is configured as a memory area (work area) in which a program, data, and the like read by the CPU 280a are temporarily stored.

  The I / O port 280d includes the mass flow controllers 312, 322, 332, 512, 522, 532, the valves 313, 314, 323, 333, 513, 523, 533, 612, 622, 632, the pressure sensor 245, and the APC valve. 243, vacuum pump 246, heater 207, heating power supply 250, temperature sensor 263, high frequency power supply 270, matching unit 271, rotating mechanism 267, boat elevator 115, and the like.

  The CPU 280a is configured to read and execute a control program from the storage device 280c and to read a process recipe from the storage device 280c in response to an operation command input from the input / output device 282 or the like. Then, the CPU 280a adjusts the flow rates of various gases by the mass flow controllers 312, 322, 332, 512, 522, 532, valves 313, 314, 323, 333, 513, 523, in accordance with the contents of the read process recipe. 533, 612, 622, 632 opening / closing operation, APC valve 243 opening / closing operation, pressure adjustment operation by APC valve 243 based on pressure sensor 245, starting and stopping of vacuum pump 246, temperature adjustment of heater 207 based on temperature sensor 263 ( Output adjustment of heating power supply 250), power supply of high-frequency power supply 270, impedance adjustment operation by matching unit 271, rotation and rotation speed adjustment operation of boat 217 by rotating mechanism 267, raising / lowering operation of boat 217 by boat elevator 115, etc. Control It is configured to.

  The controller 280 is not limited to being configured as a dedicated computer, and may be configured as a general-purpose computer. For example, an external storage device storing the above-described program (for example, magnetic tape, magnetic disk such as a flexible disk or hard disk, optical disk such as CD or DVD, magneto-optical disk such as MO, semiconductor memory such as USB memory or memory card) The controller 280 according to the present embodiment can be configured by preparing 281 and installing a program in a general-purpose computer using the external storage device 281. The means for supplying the program to the computer is not limited to supplying the program via the external storage device 281. For example, the program may be supplied without using the external storage device 281 using communication means such as the Internet or a dedicated line. Note that the storage device 280c and the external storage device 281 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as a recording medium. Note that when the term “recording medium” is used in this specification, it may include only the storage device 280c alone, may include only the external storage device 281 alone, or may include both.

(2) Substrate Processing Step Next, a method of forming a thin film on the wafer 200 in the processing chamber 201 as one step of a semiconductor device (device) manufacturing process using the processing furnace 202 of the substrate processing apparatus described above. An example will be described. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 280.

  In the present embodiment, by performing a step of supplying a source gas containing a predetermined element to the wafer 200 in the processing chamber 201 and a step of supplying a nitriding gas to the wafer 200 in the processing chamber 201, A step of forming a first layer containing a predetermined element and nitrogen on the wafer 200, a step of supplying a source gas containing the predetermined element to the wafer 200 in the processing chamber 201, and a wafer 200 in the processing chamber 201 And a step of forming a second layer containing a predetermined element and oxygen on the first layer by performing a step of supplying an oxidizing gas to the substrate. A thin film containing elements, nitrogen and oxygen is formed.

  In the step of forming the first layer, a step of supplying a source gas containing a predetermined element and a step of supplying a nitriding gas are alternately performed a predetermined number of times. In the step of forming the second layer, the step of supplying the source gas containing the predetermined element and the step of supplying the oxidizing gas are alternately performed a predetermined number of times. Here, performing a predetermined number of times means performing one or more times, that is, performing one or more times.

Hereinafter, the film forming sequence of the present embodiment will be specifically described with reference to FIGS. FIG. 4 is a diagram showing a film formation flow in the present embodiment. FIG. 5 is a diagram showing gas supply timings in the film forming sequence of the present embodiment. Here, the step of supplying DCS gas, which is a chlorosilane-based source gas, to the wafer 200 in the processing chamber 201 and the step of supplying ammonia (NH ₃ ) gas as the nitriding gas are alternately performed. Performing a predetermined number of times (m times) to form a first layer (SiN layer) containing silicon and nitrogen on the wafer 200, and a BTBAS gas that is an aminosilane source gas for the wafer 200 in the processing chamber 201 And a step of supplying oxygen (O ₂ ) gas as an oxidizing gas to the wafer 200 in the processing chamber 201, whereby a _second layer containing silicon and oxygen is formed on the first layer. Forming a silicon oxynitride film (SiON film) containing silicon, nitrogen and oxygen on the wafer 200 by performing the step of forming a layer (SiO layer) Will be described.

(Wafer charge and boat load)
When a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the lower end opening of the reaction tube 203 is opened. As shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the reaction tube 203 via the O-ring 220. Note that a resist pattern formed by photolithography processing of a resist film is formed in advance on at least a part of the wafer 200. The resist pattern becomes a part of the base film when the SiON film is formed.

(Pressure adjustment and temperature adjustment)
The processing chamber 201 is evacuated by a vacuum pump 246 so that a desired pressure (degree of vacuum) is obtained. At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 is feedback-controlled based on the measured pressure information (pressure adjustment). Note that the vacuum pump 246 keeps being operated at least until the processing on the wafer 200 is completed. Further, the processing chamber 201 is heated by the heater 207 so as to have a desired temperature. At this time, the power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution (temperature adjustment). Note that the heating of the processing chamber 201 by the heater 207 is continuously performed at least until the processing on the wafer 200 is completed. Subsequently, the rotation mechanism 267 starts to rotate the boat 217 and the wafer 200. Note that the rotation of the boat 217 and the wafers 200 by the rotation mechanism 267 is continuously performed at least until the processing on the wafers 200 is completed.

[SiON film formation process]
Thereafter, a SiON film is formed on the wafer 200 by sequentially executing a SiN layer forming step and a SiO layer forming step described later.

[SiN layer forming step]
In the SiN layer forming step, the following step 1a and step 2a are alternately performed a predetermined number of times (m times). That is, step 1a and step 2a are defined as one cycle, and this cycle is performed a predetermined number of times (m times).

(Step 1a)
With the valve 313 of the gas supply pipe 310 and the valve 612 of the vent gas pipe 610 closed, the valve 314 of the gas supply pipe 310 is opened to fill the gas reservoir 315 with the DCS gas whose flow rate has been adjusted by the mass flow controller 312. To do. The gas reservoir 315 is filled with DCS gas so that the pressure in the gas reservoir 315 is, for example, 20000 Pa or more. The amount of DCS gas filled in the gas reservoir 315 is, for example, 100 to 1000 cc. When a predetermined pressure and a predetermined amount of DCS gas are filled in the gas reservoir 315, the supply of DCS gas into the gas supply pipe 310 is continued by closing the upstream valve 314 and opening the valve 612 of the vent gas pipe 610. You may make it do.

  While the gas reservoir 315 is filled with the DCS gas, the inside of the processing chamber 201 is exhausted by the vacuum pump 246 so that the pressure in the processing chamber 201 becomes 20 Pa or less. When the filling of the DCS gas into the gas reservoir 315 and the exhaust of the processing chamber 201 are completed, the APC valve 243 is closed to stop the exhaust of the processing chamber 201, and then the valve 313 of the gas supply pipe 310 is opened. As a result, the high-pressure DCS gas stored in the gas reservoir 315 is supplied into the processing chamber 201 at once (pulse-like). At this time, since the APC valve 243 of the exhaust pipe 231 is closed, the pressure in the processing chamber 201 rapidly increases and is increased to, for example, 931 Pa (7 Torr). Thereafter, the pressure rising state in the processing chamber 201 is maintained for a predetermined time (for example, 1 to 10 seconds), and the wafer 200 is exposed to a high-pressure DCS gas atmosphere (DCS supply).

At this time, the valve 513 may be opened at the same time so that N ₂ gas as a carrier gas flows in the inert gas supply pipe 510. In this case, N ₂ gas is supplied into the processing chamber 201 together with NH ₃ gas, and is exhausted from the exhaust pipe 231. At this time, in order to prevent the DCS gas from entering the nozzles 420 and 430 and the buffer chambers 423 and 433, the valves 523 and 533 are opened so that the N ₂ gas flows through the inert gas supply pipes 520 and 530. It may be. In this case, the N ₂ gas is supplied into the processing chamber 201 through the gas supply pipes 320 and 330, the nozzles 420 and 430, and the buffer chambers 423 and 433.

  Thus, when the DCS gas is supplied at once using the gas reservoir 315, the DCS gas ejected from the nozzle 410 into the processing chamber 201 due to a pressure difference between the gas reservoir 315 and the processing chamber 201 is, for example, the speed of sound (340 m / Sec) and the speed of the DCS gas on the wafer 200 is increased to about several tens of m / sec. As a result, the DCS gas is efficiently supplied to the central portion of the wafer 200. Hereinafter, this supply method is also referred to as a flash flow.

  By supplying the DCS gas, a silicon-containing layer is formed on the wafer 200 (surface underlayer film).

The temperature of the heater 207 is preferably set to such a temperature that the temperature of the wafer 200 is in the range of room temperature to 200 ° C., for example, 200 ° C. When the temperature of the wafer 200 exceeds 200 ° C., the resist pattern formed in advance on the wafer 200 may be oxidized and volatilized when performing Step 2b (O ₂ gas supply) described later. . If the temperature of the wafer 200 is too low, it is difficult to form a source gas (DCS) gas molecular layer on the wafer 200, and a practical film formation rate may not be obtained. Therefore, the temperature of the wafer 200 is a temperature within the range of room temperature to 200 ° C., and is preferably set to 200 ° C., for example.

After the silicon-containing layer is formed, the valve 313 of the gas supply pipe 310 is closed and the supply of DCS gas is stopped. Then, the APC valve 243 of the exhaust pipe 231 is opened, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the DCS gas remaining in the processing chamber 201 or contributing to formation of the silicon-containing layer is treated with the processing chamber 201. Eliminate from inside (residual gas removal). At this time, the valves 513, 523, and 533 are opened, and N ₂ gas as an inert gas is supplied into the processing chamber 201. The N ₂ gas acts as a purge gas, which can enhance the effect of removing unreacted or residual DCS gas remaining in the processing chamber 201 from the processing chamber 201. At this time, the gas remaining in the processing chamber 201 may not be completely removed, and the inside of the processing chamber 201 may not be completely purged. If the amount of gas remaining in the processing chamber 201 is very small, no adverse effects will occur in the subsequent step 2a. At this time, the flow rate of the N ₂ gas supplied into the processing chamber 201 does not need to be a large flow rate. For example, by supplying an amount similar to the volume of the reaction tube 203 (processing chamber 201), adverse effects are caused in step 2a. Purging to such an extent that no occurrence occurs can be performed. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. In addition, consumption of N ₂ gas can be minimized.

(Step 2a)
After step 1 a is completed and residual gas in the processing chamber 201 is removed, the valve 323 of the gas supply pipe 320 is opened, and NH ₃ gas is allowed to flow into the gas supply pipe 320. The flow rate of the NH ₃ gas flowing through the gas supply pipe 320 is adjusted by the mass flow controller 322. The NH ₃ gas whose flow rate has been adjusted is supplied into the buffer chamber 423 from the gas supply hole 421 of the nozzle 420. At this time, by applying high frequency power from the high frequency power supply 270 via the matching unit 271 between the rod-shaped electrodes 471 and 472, the NH ₃ gas supplied into the buffer chamber 423 is plasma-excited, and a gas supply hole is used as an active species. 425 is supplied into the processing chamber 201 and is exhausted from the exhaust pipe 231. At this time, NH ₃ gas activated by plasma is supplied to the wafer 200 (NH ₃ ^* supply).

At the same time, the valve 523 is opened and N ₂ gas is allowed to flow into the inert gas supply pipe 520. The N ₂ gas is supplied into the processing chamber 201 together with the NH ₃ gas, and is exhausted from the exhaust pipe 231. At this time, in order to prevent the NH ₃ gas from entering the nozzles 410 and 430 and the buffer chamber 433, the valves 513 and 533 are opened, and the N ₂ gas is caused to flow into the inert gas supply pipes 510 and 530. N ₂ gas is supplied into the processing chamber 201 through the gas supply pipes 310 and 330, the nozzles 410 and 430, and the buffer chamber 433, and is exhausted from the exhaust pipe 231.

When flowing NH ₃ gas as an active species by plasma excitation, the APC valve 243 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 10 to 100 Pa. By using plasma, the NH ₃ gas can be activated even when the pressure in the processing chamber 201 is set to such a relatively low pressure zone. The partial pressure of NH ₃ gas in the processing chamber 201 is, for example, a pressure in the range of 6 to 100 Pa. The supply flow rate of NH ₃ gas controlled by the mass flow controller 322 is, for example, a flow rate in the range of 100 to 10,000 sccm. The supply flow rate of N ₂ gas controlled by the mass flow controllers 512, 522, and 532 is set to a flow rate in the range of, for example, 100 to 10,000 sccm. The time for supplying the active species obtained by plasma-exciting NH ₃ gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, 1 to 120 seconds, preferably 1 to 60 seconds. Time. The temperature of the heater 207 at this time is set to a temperature in which the temperature of the wafer 200 is in the range of room temperature to 200 ° C., for example, 200 ° C., as in step 1a. The high frequency power applied between the high frequency power source 270 and the rod-shaped electrodes 471 and 472 is set so as to be, for example, a power in the range of 50 to 1000 W.

At this time, the gas flowing in the processing chamber 201 is an active species obtained by plasma-exciting NH ₃ gas, and no DCS gas is flowing in the processing chamber 201. Therefore, the NH ₃ gas does not cause a gas phase reaction, and the NH ₃ gas that has become an active species reacts with at least a part of the silicon-containing layer formed on the wafer 200 in step 1a. As a result, the silicon-containing layer is nitrided and modified into a first layer containing Si and N, that is, a silicon nitride layer (SiN layer).

As described above, by flowing the activated species obtained by exciting the NH ₃ gas into the processing chamber 201, the silicon-containing layer can be plasma-nitrided to be modified (changed) into the SiN layer.

After the SiN layer is formed, the valve 323 of the gas supply pipe 320 is closed and the supply of NH ₃ gas is stopped. At this time, the supply of NH ₃ gas into the gas supply pipe 320 may be continued by opening the valve 622 of the vent gas pipe 620. At this time, the APC valve 243 of the exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and NH ₃ after remaining in the processing chamber 201 or contributing to formation of the SiN layer is exhausted. Gases and reaction byproducts are excluded from the processing chamber 201 (residual gas removal). At this time, the valves 513, 523, and 533 are opened, and N ₂ gas as an inert gas is supplied into the processing chamber 201. The N ₂ gas acts as a purge gas, which can enhance the effect of removing the NH ₃ gas remaining in the processing chamber 201 or contributing to the formation of the SiN layer from the processing chamber 201. At this time, the gas remaining in the processing chamber 201 may not be completely removed, and the inside of the processing chamber 201 may not be completely purged. If the amount of gas remaining in the processing chamber 201 is very small, no adverse effect will occur in the subsequent step 1a. At this time, the flow rate of the N ₂ gas supplied into the processing chamber 201 does not have to be a large flow rate. Purging to such an extent that no occurrence occurs can be performed. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. In addition, consumption of N ₂ gas can be minimized.

  Step 1a and step 2a described above are alternately performed a predetermined number of times (m times), that is, step 1a and step 2a are set as one cycle, and this cycle is performed a predetermined number of times (m times). A SiN layer having a predetermined composition and a predetermined thickness can be formed as a first layer on a base film including a resist pattern formed in advance. The above cycle is preferably repeated a plurality of times. That is, it is preferable that the thickness of the SiN layer formed per cycle is made smaller than the desired film thickness and the above-described cycle is repeated a plurality of times until the desired film thickness is obtained. The thickness of the SiN layer as the first layer is preferably 0.5 nm or more and 5.0 nm or less, for example.

[SiO layer forming step]
When an SiN layer having a predetermined composition and thickness is formed on the wafer 200, an SiO layer forming process is performed. In the SiO layer forming step, Step 1b and Step 2b described later are alternately performed a predetermined number of times (n times). That is, step 1b and step 2b are set as one cycle, and this cycle is performed a predetermined number of times (n times). Hereinafter, these steps will be described in order.

(Step 1b)
In step 1b, the BTBAS gas is supplied to the wafer 200 in the processing chamber 201 by the above-described flash flow to form a silicon-containing layer on the wafer 200 (on the SiN layer). Note that the BTBAS gas may be supplied to the wafer 200 in the processing chamber 201 without performing the flash flow. Thereafter, the inside of the processing chamber 201 is evacuated, and the BTBAS gas remaining in the processing chamber 201 or contributing to the formation of the silicon-containing layer is removed from the processing chamber 201. Step 1b can be performed by the same procedure and the same conditions as the above-mentioned step 1a. In step 1b, the source gas used in step 1a, that is, the DCS gas can be used as the source gas containing Si.

(Step 2b)
After step 1 b is completed and residual gas in the processing chamber 201 is removed, the valve 333 of the gas supply pipe 330 is opened, and O ₂ gas is allowed to flow into the gas supply pipe 330. The flow rate of the O ₂ gas that has flowed through the gas supply pipe 330 is adjusted by the mass flow controller 332. The O ₂ gas whose flow rate has been adjusted is supplied into the buffer chamber 433 from the gas supply hole 431 of the nozzle 430. At this time, by applying high-frequency power from the high-frequency power source 270 via the matching unit 271 between the rod-shaped electrodes 481 and 482, the O ₂ gas supplied into the buffer chamber 433 is plasma-excited and used as a gas supply hole as an active species 435 is supplied into the processing chamber 201 and is exhausted from the exhaust pipe 231. At this time, O ₂ gas activated by plasma is supplied to the wafer 200 (O ₂ ^* supply).

At the same time, the valve 533 is opened, and N ₂ gas is allowed to flow into the inert gas supply pipe 530. The N ₂ gas is supplied into the processing chamber 201 together with the NH ₃ gas, and is exhausted from the exhaust pipe 231. At this time, in order to prevent the O ₂ gas from entering the nozzles 410 and 420 and the buffer chamber 423, the valves 513 and 523 are opened, and the N ₂ gas is allowed to flow into the inert gas supply pipes 510 and 520. The N ₂ gas is supplied into the processing chamber 201 through the gas supply pipes 310 and 320, the nozzles 410 and 420, and the buffer chamber 423, and is exhausted from the exhaust pipe 231.

When flowing O ₂ gas as an active species by plasma excitation is to properly adjust the APC valve 243, the pressure in the processing chamber 201, for example a pressure in the range of 10-100 Pa. By using plasma, the O ₂ gas can be activated even when the pressure in the processing chamber 201 is set to such a relatively low pressure zone. The partial pressure of O ₂ gas in the processing chamber 201 is, for example, a pressure in the range of 6 to 100 Pa. The supply flow rate of the O ₂ gas controlled by the mass flow controller 322 is, for example, a flow rate in the range of 100 to 10,000 sccm. The supply flow rate of N ₂ gas controlled by the mass flow controllers 512, 522, and 532 is set to a flow rate in the range of, for example, 100 to 10,000 sccm. The time for supplying the active species obtained by plasma excitation of the O ₂ gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, in the range of 1 to 120 seconds, preferably 1 to 60 seconds. Time. The temperature of the heater 207 at this time is set to a temperature in which the temperature of the wafer 200 is within a range of room temperature to 200 ° C., for example, 200 ° C., as in step 1b. The high-frequency power applied between the high-frequency power source 270 and the rod-shaped electrodes 481 and 482 is set so as to be, for example, in the range of 50 to 1000 W.

At this time, the gas flowing in the processing chamber 201 is an active species obtained by exciting the O ₂ gas with plasma, and no BTBAS gas is flowing in the processing chamber 201. Therefore, the O ₂ gas does not cause a gas phase reaction, and the O ₂ gas that has become an active species reacts with at least a part of the silicon-containing layer formed on the wafer 200 in Step 1b. As a result, the silicon-containing layer is oxidized and modified into a second layer containing Si and O, that is, a silicon oxide layer (SiO layer).

As described above, the active species obtained by plasma excitation of the O ₂ gas are allowed to flow into the processing chamber 201, whereby the silicon-containing layer can be plasma oxidized and modified (changed) into the SiO layer. At this time, the silicon-containing layer can be modified into the SiO layer by increasing the proportion of the O component in the silicon-containing layer and detaching the C component in the silicon-containing layer by the energy of the active species. At this time, the Si—O bond in the SiO layer is increased by the action of the plasma oxidation by the O ₂ gas, while the Si—C bond and the Si—Si bond are decreased, and the ratio of the C component and the Si component in the SiO layer are reduced. The proportion will decrease. In particular, most of the C component is reduced to the impurity level by being substantially eliminated, or substantially disappears. That is, the silicon-containing layer can be reformed into the SiO layer while changing the composition ratio in the direction of increasing the oxygen concentration and in the direction of decreasing the carbon concentration and the silicon concentration. Furthermore, by controlling the processing conditions such as the pressure in the processing chamber 201 and the gas supply time at this time, the ratio of the O component in the SiO layer, that is, the oxygen concentration can be finely adjusted, and the composition ratio of the SiO layer can be adjusted. It can be controlled more strictly.

After the SiO layer is formed, the valve 333 of the gas supply pipe 330 is closed and the supply of O ₂ gas is stopped. At this time, the supply of O ₂ gas into the gas supply pipe 330 may be continued by opening the valve 632 of the vent gas pipe 630. At this time, the APC valve 243 of the exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and O ₂ after remaining in the processing chamber 201 or contributing to formation of the SiO layer. Gases and reaction byproducts are excluded from the processing chamber 201 (residual gas removal). At this time, the valves 513, 523, and 533 are opened, and N ₂ gas as an inert gas is supplied into the processing chamber 201. The N ₂ gas acts as a purge gas, which can enhance the effect of removing the unreacted O ₂ gas remaining in the processing chamber 201 or after contributing to the formation of the SiO layer from the processing chamber 201. At this time, the gas remaining in the processing chamber 201 may not be completely removed, and the inside of the processing chamber 201 may not be completely purged. If the amount of gas remaining in the processing chamber 201 is very small, there will be no adverse effect in the subsequent step 1b. At this time, the flow rate of the N ₂ gas supplied into the processing chamber 201 does not need to be a large flow rate. Purging to such an extent that no occurrence occurs can be performed. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. In addition, consumption of N ₂ gas can be minimized.

  Step 1b and step 2b described above are alternately performed a predetermined number of times (n times), that is, step 1b and step 2b are set as one cycle, and this cycle is performed a predetermined number of times (n times). On the formed SiN layer, a SiO layer having a predetermined composition and a predetermined thickness can be laminated as the second layer. Then, a SiON film that is a thin film containing Si, N, and O can be formed. The above cycle is preferably repeated a plurality of times. That is, it is preferable that the thickness of the SiO layer formed per cycle is made smaller than the desired film thickness and the above-described cycle is repeated a plurality of times until the desired film thickness is obtained.

(Purge and return to atmospheric pressure)
When the formation of the SiON film on the wafer 200 is completed, the valves 513, 523 and 533 are opened, and N ₂ gas as an inert gas is supplied into the processing chamber 201 from each of the inert gas supply pipes 510, 520 and 530. Supply and exhaust from the exhaust pipe 231. The N ₂ gas acts as a purge gas, whereby the inside of the processing chamber 201 is purged with an inert gas, and the gas and reaction byproducts remaining in the processing chamber 201 are removed from the processing chamber 201 (purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

(Boat unload and wafer discharge)
Thereafter, the seal cap 219 is lowered by the boat elevator 115 to open the lower end of the reaction tube 203, and the processed wafer 200 is supported by the boat 217 from the lower end of the reaction tube 203 to the outside of the reaction tube 203. Unloaded (boat unload). Thereafter, the processed wafer 200 is taken out from the boat 217 (wafer discharge).

(3) Effects according to the present embodiment According to the present embodiment, the following one or more effects are achieved.

(A) According to the present embodiment, the SiON film is formed by forming the SiN layer as the first layer on the wafer 200 and then forming the SiO layer as the second layer. . That is, the SiON film is formed in two stages. As a result, the oxidation or volatilization of the resist pattern (a part of the base film) formed in advance on the wafer 200 can be suppressed. This is because the SiN layer formed before forming the SiO layer acts to suppress (block) the supply of the oxidizing gas (O ₂ ^* gas) to the resist pattern. Note that, by setting the thickness of the SiN layer formed on the wafer 200 to a thickness of, for example, 0.5 nm or more, the supply of the oxidizing gas to the resist pattern can be avoided more reliably, and the oxidation of the resist pattern can be further improved. It becomes possible to suppress it reliably.

(B) According to the present embodiment, by using the active species (NH ₃ ^* ) obtained by plasma excitation of NH ₃ gas, the temperature of the wafer 200 is set to a low temperature within a range of room temperature to 200 ° C., for example. Even in this case, the silicon-containing layer can be modified into a SiN layer. By forming the SiN layer in such a low temperature region, oxidation, volatilization, and the like of the resist pattern formed on the wafer 200 can be suppressed.

(C) According to the present embodiment, by using the active species (O ₂ ^* ) obtained by plasma-exciting O ₂ gas, the temperature of the wafer 200 is set to a low temperature within a range of room temperature to 200 ° C., for example. Even in this case, the silicon-containing layer can be modified into a SiO layer. By forming the SiO layer in such a low temperature region, it becomes possible to suppress oxidation or volatilization of the resist pattern formed on the wafer 200.

(D) According to the present embodiment, the composition of the SiON film can be set to a desired composition by adjusting the ratio of the thickness of the SiN layer and the thickness of the SiO layer. That is, the ratio of the N component and the O component contained in the SiON film can be set to a desired ratio. For example, the thickness of the SiN layer is set to, for example, 5 nm or less, and thereafter, the SiO layer is formed until the SiON film reaches a desired thickness, whereby the amount of O component in the SiON film is set to a predetermined amount or more. Therefore, the physical properties of the SiON film can be set to desired physical properties.

(E) According to the present embodiment, when the SiN layer is formed, a step of supplying DCS gas to the wafer 200 in the processing chamber 201 (Step 1a), and NH for the wafer 200 in the processing chamber 201 are performed. _The process of supplying _three gases (step 2a) is alternately performed. Further, when forming the SiO layer, a step of supplying BTBAS gas to the wafer 200 in the processing chamber 201 (step 1b) and a step of supplying O ₂ gas to the wafer 200 in the processing chamber 201 (step) 2b) are alternately performed. As described above, by performing the film forming process by alternately supplying the gas, the film thickness of the SiON film can be easily adjusted. Further, the step coverage of the SiON film, the film thickness uniformity within the wafer 200 surface, and the film thickness uniformity between the wafers 200 can be improved.

(F) According to the present embodiment, by forming an SiN layer using activated species (NH ₃ ^* ) obtained by plasma excitation of NH ₃ gas, impurities (particularly, C component) in the SiN layer are formed. It becomes possible to reduce the density | concentration of. Moreover, it is possible to reduce the concentration of impurities (especially C component) in the SiN layer by forming the SiO layer using the active species (O ₂ ^* ) obtained by exciting the O ₂ gas with plasma. It becomes. As a result, the quality of the SiON film can be improved.

(E) According to the present embodiment, since the DCS gas and the BTBAS gas are supplied by the flash flow in steps 1a and 1b, the DCS gas and the BTBAS gas can be efficiently supplied to the central portion of the wafer 200. . As a result, the film thickness uniformity and film quality uniformity of the SiON film formed on the wafer 200 within the wafer 200 surface can be improved.

<Second Embodiment>
As described above, when a silicon oxide film is formed on the wafer 200, the resist pattern may be stressed and deformed or collapsed due to the film stress of the silicon oxide film. Therefore, in this embodiment, such a problem is solved by reducing the film stress of the thin film formed on the wafer 200.

  Specifically, a step of supplying a source gas containing a predetermined element to the wafer 200 in the processing chamber 201, a step of supplying a nitriding gas to the wafer 200 in the processing chamber 201, By performing a cycle including the step of supplying an oxidizing gas to the wafer 200 a predetermined number of times, a thin film containing a predetermined element, nitrogen and oxygen is formed on the wafer 200, thereby solving the problem. ing. Here, performing a predetermined number of times means performing one or more times, that is, performing one or more times.

Hereinafter, the film forming sequence of the present embodiment will be specifically described with reference to FIGS. FIG. 6 is a diagram showing a film forming flow in the present embodiment. FIG. 7 is a diagram illustrating gas supply timings in the film forming sequence of the present embodiment. Here, the step of supplying BTBAS gas, which is an aminosilane-based source gas, as the source gas to the wafer 200 in the processing chamber 201, the step of supplying ammonia (NH ₃ ) gas as the nitriding gas, and the processing chamber 201 And a step of supplying oxygen (O ₂ ) gas as an oxidizing gas to the inner wafer 200 by performing a predetermined number of times (N times), a silicon acid containing silicon, nitrogen and oxygen on the wafer 200 An example of forming a nitride film (SiON film) will be described.

(Wafer charge to pressure and temperature adjustment)
Wafer charging, boat loading, pressure adjustment, and temperature adjustment are performed in the same procedure as in the first embodiment.

[SiON film formation process]
Thereafter, a cycle including steps 1c to 3c described later is defined as one cycle, and this cycle is performed a predetermined number of times (N times), thereby forming a SiON film on the wafer 200.

(Step 1c)
BTBAS gas is supplied to the wafer 200 in the processing chamber 201 by the above-described flash flow to form a silicon-containing layer on the wafer 200 (on the base film including the resist pattern). Thereafter, the inside of the processing chamber 201 is evacuated, and the BTBAS gas remaining in the processing chamber 201 or contributing to the formation of the silicon-containing layer is removed from the processing chamber 201. Step 1c can be performed by the same procedure and the same conditions as step 1a of the first embodiment described above.

(Step 2c)
Next, NH ₃ gas activated by plasma is supplied to the wafer 200 in the processing chamber 201, and the silicon-containing layer formed on the wafer 200 is nitrided to form a silicon nitride layer containing Si and N ( SiN layer). Thereafter, the inside of the processing chamber 201 is evacuated, and the NH ₃ gas remaining in the processing chamber 201 or contributing to the formation of the SiN layer is removed from the processing chamber 201. Step 2c can be performed by the same procedure and the same conditions as step 2a of the first embodiment described above.

(Step 3c)
Next, O ₂ gas activated by plasma is supplied to the wafer 200 in the processing chamber 201 to oxidize the SiN layer formed on the wafer 200, and silicon oxynitride containing Si, N, and O Modification into a layer (SiON layer). Thereafter, the inside of the processing chamber 201 is evacuated, and the O ₂ gas remaining in the processing chamber 201 or contributed to the formation of the SiON layer is removed from the processing chamber 201. Step 3c can be performed by the same procedure and the same conditions as step 2b of the first embodiment described above.

  By performing the cycle including the steps 1c to 3c described above a predetermined number of times (N times), a SiON film that is a thin film containing Si, N, and O can be formed on the wafer 200. The above cycle is preferably repeated a plurality of times. That is, it is preferable that the thickness of the SiON layer formed per cycle is made smaller than the desired film thickness and the above cycle is repeated a plurality of times until the desired film thickness is obtained.

  When the cycle including steps 1c to 3c is repeated a plurality of times, step 2c and step 3c may be thinned at a predetermined frequency. For example, in the initial stage of forming the SiON film, the SiON layer (or the SiN layer not containing the O component) with a relatively small O component content may be formed by thinning out step 3c at a predetermined frequency. . Further, in the middle stage to the latter stage of the formation of the SiON film, the SiON layer having a small N component content (or the SiO layer not containing the N component) may be formed by thinning out step 2c at a predetermined frequency. .

  According to the present embodiment, one or more effects shown below are produced.

(A) According to the present embodiment, the SiO film is not formed on the wafer 200 but is formed in advance on the wafer 200 by forming the SiON film to which the N component is added in the SiO film. Deformation or collapse of the resist pattern (a part of the base film) can be suppressed. This is because the SiON film to which the N component is added has less film stress and less stress applied to the resist pattern than the SiO film.

(B) According to this embodiment, when the cycle including steps 1c to 3c is repeated a plurality of times, step 2c and step 3c are thinned out at a predetermined frequency, so that the composition of the SiON film is densely distributed in the thickness direction. It becomes possible to control. For example, in the initial stage of formation of the SiON film, by thinning out step 3c at a predetermined frequency, the lower layer of the SiON film can be made an SiON layer (or SiN layer) with a low content of O component. Further, in the middle stage to the latter stage of the formation of the SiON film, the middle layer to the upper layer of the SiON film can be made into a SiON layer (or SiO layer) with a low N component content by thinning out step 2c at a predetermined frequency. . Thus, when the N component in the layer (lower layer) close to the resist pattern in the SiON film is increased, the stress applied to the resist pattern can be further reduced, and the deformation and collapse of the resist pattern can be further suppressed. It becomes like this. In addition, by thinning out step 3c at a predetermined frequency in the initial stage of forming the SiON film, the supply amount of the oxidizing gas (O ₂ ^* gas) to the resist pattern can be reduced, and the oxidation and volatilization of the resist pattern are further suppressed. become able to.

(C) According to the present embodiment, by using the activated species (NH ₃ ^* ) obtained by plasma excitation of NH ₃ gas, the temperature of the wafer 200 is set to a low temperature within a range of room temperature to 200 ° C., for example. Even in this case, the silicon-containing layer can be modified into a SiN layer. By forming the SiN layer in such a low temperature region, oxidation, volatilization, and the like of the resist pattern formed on the wafer 200 can be suppressed.

(D) According to the present embodiment, by using the active species (O ₂ ^* ) obtained by plasma-exciting O ₂ gas, the temperature of the wafer 200 is set to a low temperature within a range of room temperature to 200 ° C., for example. Even in this case, the silicon-containing layer can be modified into a SiO layer. By forming the SiO layer in such a low temperature region, it becomes possible to suppress oxidation or volatilization of the resist pattern formed on the wafer 200.

(E) According to this embodiment, the cycle including steps 1c to 3c is performed a predetermined number of times. By performing the film forming process by such a gas supply sequence, the step coverage of the SiON film, the film thickness uniformity within the wafer 200 surface, and the film thickness uniformity between the wafers 200 can be improved. .

(F) According to the present embodiment, by forming an SiN layer using activated species (NH ₃ ^* ) obtained by plasma excitation of NH ₃ gas, impurities (particularly, C component) in the SiN layer are formed. It becomes possible to reduce the density | concentration of. Further, by forming the SiON layer using the active species (O ₂ ^* ) obtained by plasma excitation of O ₂ gas, it is possible to reduce the concentration of impurities (particularly C component) in the SiON layer. Become. As a result, the quality of the SiON film can be improved.

(E) According to this embodiment, since the BTBAS gas is supplied by the flash flow in step 1c, the BTBAS gas can be efficiently supplied to the central portion of the wafer 200. As a result, the film thickness uniformity and film quality uniformity of the SiON film formed on the wafer 200 within the wafer 200 surface can be improved.

(Modification)
The present embodiment can be modified as shown in FIGS. 8 and 9, for example.

FIG. 8 is a diagram showing a modification of the film forming flow in the present embodiment. FIG. 9 is a diagram showing a modification of the gas supply timing in the film forming sequence of the present embodiment. Here, a step of supplying BTBAS gas, which is an aminosilane-based source gas, as a source gas to the wafer 200 in the processing chamber 201, a step of supplying ammonia (NH ₃ ) gas as a nitriding gas, A cycle including a step of supplying BTBAS gas as a source gas to the wafer 200 and a step of supplying oxygen (O ₂ ) gas as an oxidizing gas to the wafer 200 in the processing chamber 201 is repeated a predetermined number of times (N times). This shows an example in which a silicon oxynitride film (SiON film) containing silicon, nitrogen and oxygen is formed on the wafer 200 by performing the above.

  In this modification, a cycle including step 1d to step 4d is defined as one cycle, and this cycle is performed a predetermined number of times (N times), thereby forming a SiON film including Si, N, and O on the wafer 200. Step 1d and step 3d can be performed by the same procedure and the same conditions as step 1a of the first embodiment described above. Step 2d can be performed by the same procedure and the same conditions as Step 2a of the first embodiment described above. Step 4d can be performed by the same procedure and the same conditions as step 2b of the first embodiment described above.

  Also in this modification, when the cycle is repeated a plurality of times, step 2d and step 4d may be thinned at a predetermined frequency. For example, in the initial stage of formation of the SiON film, the SiON layer (or SiN layer) with a small content of O component may be formed by thinning out steps 3d and 4d at a predetermined frequency. Further, in the middle stage to the latter stage of the formation of the SiON film, the SiON layer (or SiO layer) having a small N component content may be formed by thinning out steps 1d and 2d at a predetermined frequency.

  Also in this modification, the same effect as the film-forming sequence shown in FIGS.

<Third embodiment of the present invention>
Next, a third embodiment of the present invention will be described.

  In the present embodiment, the SiON film is formed by a combination of the first embodiment and the second embodiment described above. That is, after the SiN layer as the first layer is formed on the wafer 200 by the film formation flow of the first embodiment, the SiON layer as the second layer is formed on the SiN layer by the film formation flow of the second embodiment. Form. Specifically, after steps 1a and 2a of the first embodiment are alternately performed a predetermined number of times (m times) to form a SiN layer on the wafer 200, steps 1c to 3c (or steps of the second embodiment) are performed. A SiON layer is formed on the SiN layer by performing a cycle including 1d to 4d) a predetermined number of times (n times). Thereby, a SiON film which is a thin film containing Si, N and O is formed on the wafer 200. Also in this embodiment, when the SiON layer is formed by repeating the cycle a plurality of times, step 2c and step 3c (or step 2d and step 4d) may be thinned at a predetermined frequency.

According to this modification, the effects of the above-described first embodiment and the effects of the second embodiment are simultaneously achieved. That is, the SiN layer formed before forming the SiO layer can suppress (block) the supply of the oxidizing gas (O ₂ ^* gas) to the resist pattern, thereby suppressing the oxidation and volatilization of the resist pattern. Become. Further, by forming a SiON layer with little film stress on the SiN layer, it is possible to reduce the stress applied to the resist pattern and to suppress the deformation and collapse of the resist pattern.

<Other Embodiments of the Present Invention>
As mentioned above, although embodiment of this invention was described concretely, this invention is not limited to the above-mentioned embodiment, It can change variously in the range which does not deviate from the summary.

  For example, in the first embodiment described above, an example in which different types of source gases (DCS gas, BTBAS gas) are used in the SiN layer forming step and the SiO layer forming step has been described. However, the present invention is not limited to such a form. The same kind of source gas may be used. In addition, for example, BTBAS gas is used as a source gas in the SiN layer forming step, and in the other step, an aminosilane-based source gas other than BTBAS gas, a halogen-based material such as a chlorosilane-based source gas or a fluorosilane-based source gas is used as the source gas. Alternatively, a silane-based source gas having the above ligand or a silane-based gas obtained by vaporizing an inorganic source may be used. As the type of the source gas, an appropriate one may be selected as appropriate in accordance with the nitriding or oxidizing treatment conditions. Similarly, in the second embodiment, the type of the source gas may be switched during the cycle including steps 1c to 3c (or steps 1d to 4d). Similarly, in the third embodiment, different source gases may be used in the SiN layer forming step and the SiON layer forming step.

  By using the silicon insulating film formed by the method of each of the above-described embodiments and modifications as a sidewall spacer, it is possible to provide a device forming technique with less leakage current and excellent workability.

  In addition, by using the silicon insulating film formed by the method of each of the above-described embodiments and modifications as an etch stopper, it is possible to provide a device forming technique with excellent workability.

  In the above-described embodiment, an example in which a silicon-based insulating film (SiON film) containing silicon as a semiconductor element is formed as the oxynitride film has been described. However, the present invention can be applied to, for example, titanium (Ti), zirconium (Zr). ), Hafnium (Hf), tantalum (Ta), aluminum (Al), molybdenum (Mo), and other metal-based thin films containing metal elements can also be applied. That is, the present invention provides, for example, a titanium oxynitride film (TiON film), a zirconium oxynitride film (ZrON film), a hafnium oxynitride film (HfON film), a tantalum oxynitride film (TaON film), and an aluminum oxynitride film (AlON). Film) and a metal oxynitride film such as a molybdate oxynitride film (MoON film).

  In this case, instead of the silane-based source gas in the above-described embodiment, a source gas containing a metal element can be used to form a film in the same sequence as in the above-described embodiment.

For example, when forming a metal-based thin film (TiON film) containing Ti, the raw material gas includes Ti and amino groups such as tetrakisdimethylaminotitanium (Ti [N (CH ₃ ) ₂ ] ₄ , abbreviation: TDMAT). A gas, a gas containing Ti and a chloro group such as titanium tetrachloride (TiCl ₄ ), or a gas containing Ti and a fluoro group such as titanium tetrafluoride (TiF ₄ ) can be used. As the nitriding gas and the oxidizing gas, the same gas as that in the above-described embodiment can be used. Note that the processing conditions at this time can be the same processing conditions as in the above-described embodiment, for example.

For example, when forming a metal-based thin film (ZrON film) containing Zr, tetrakisdimethylaminozirconium (Zr [N (CH ₃ ) ₂ ] ₄ , abbreviation: TDMAZ), tetrakisethylmethylaminozirconium ( Zr [N (CH ₃ ) CH ₂ CH ₃ ] ₄ , gas containing Zr and amino groups such as TEMAZ), gas containing Zr and chloro groups such as zirconium tetrachloride (ZrCl ₄ ), zirconium tetrafluoro A gas containing Zr and a fluoro group such as a ride (ZrF ₄ ) can be used. As the nitriding gas and the oxidizing gas, the same gas as that in the above-described embodiment can be used. Note that the processing conditions at this time can be the same processing conditions as in the above-described embodiment, for example.

For example, in the case of forming a metal-based thin film containing Hf (HfON film), tetrakisdimethylaminohafnium (Hf [N (CH ₃ ) ₂ ] ₄ , abbreviation: TDMAHf), tetrakisethylmethylaminohafnium (HfON film) Gas containing Hf and amino groups such as Hf [N (CH ₃ ) CH ₂ CH ₃ ] ₄ , abbreviation: TEMAHf), gas containing Hf and chloro groups such as hafnium tetrachloride (HfCl ₄ ), hafnium tetrafluor A gas containing Hf and a fluoro group such as a ride (HfF ₄ ) can be used. As the nitriding gas and the oxidizing gas, the same gas as that in the above-described embodiment can be used. Note that the processing conditions at this time can be the same processing conditions as in the above-described embodiment, for example.

For example, when forming a metal-based thin film (TaON film) containing Ta, as a source gas, trisdiethylaminotertiarybutyliminotantalum (Ta [N (C ₂ H ₅ ) ₂ ] ₃ [= NC (CH ₃ ) ₃ ], abbreviation: TBTDET), trisethylmethylamino tertiary butylimino tantalum (Ta [NC (CH ₃ ) ₃ ] [N (C ₂ H ₅ ) CH ₃ ] ₃ ), abbreviation TBTEMT) and the like and amino groups , A gas containing Ta and a chloro group such as tantalum pentachloride (TaCl ₅ ), and a gas containing Ta and a fluoro group such as tantalum pentafluoride (TaF ₅ ) can be used. As the nitriding gas and the oxidizing gas, the same gas as that in the above-described embodiment can be used. Note that the processing conditions at this time can be the same processing conditions as in the above-described embodiment, for example.

Further, for example, in the case of forming a metal-based thin film (AlON film) containing Al, as a raw material gas, a gas containing Al and an amino group such as trimethylaluminum (Al (CH ₃ ) ₃ , abbreviation: TMA) or aluminum tri A gas containing Al and a chloro group such as chloride (AlCl ₃ ) or a gas containing Al and a fluoro group such as aluminum trifluoride (AlF ₃ ) can be used. As the nitriding gas and the oxidizing gas, the same gas as that in the above-described embodiment can be used. Note that the processing conditions at this time can be the same processing conditions as in the above-described embodiment, for example.

Further, for example, when forming a metal-based thin film (MoON film) containing Mo, as a source gas, a gas containing Mo and a chloro group such as molybdenum pentachloride (MoCl ₅ ), molybdenum pentafluoride (MoF ₅ ), etc. A gas containing Mo and a fluoro group can be used. As the nitriding gas and the oxidizing gas, the same gas as that in the above-described embodiment can be used. Note that the processing conditions at this time can be the same processing conditions as in the above-described embodiment, for example.

  In the above-described embodiment, an example in which a thin film is formed using a batch-type substrate processing apparatus that processes a plurality of substrates at a time has been described. However, the present invention is not limited to this, and one substrate at a time. Alternatively, the present invention can be suitably applied to the case where a thin film is formed using a single wafer processing apparatus that processes several substrates.

  Moreover, the above-described embodiments, modifications, application examples, and the like can be used in appropriate combination.

  The present invention can also be realized by changing a process recipe of an existing substrate processing apparatus, for example. When changing a process recipe, the process recipe according to the present invention is installed in an existing substrate processing apparatus via a telecommunication line or a recording medium recording the process recipe, or input / output of the existing substrate processing apparatus It is also possible to operate the apparatus and change the process recipe itself to the process recipe according to the present invention.

<Preferred embodiment of the present invention>
Hereinafter, preferred embodiments of the present invention will be additionally described.

(Appendix 1)
According to one aspect of the invention,
Performing a step of supplying a source gas containing a predetermined element to a substrate in a processing chamber and a step of supplying a nitriding gas to the substrate in the processing chamber; Forming a first layer containing nitrogen;
The step of supplying a source gas containing the predetermined element to the substrate in the processing chamber and the step of supplying an oxidizing gas to the substrate in the processing chamber are performed on the first layer. And forming a second layer containing the predetermined element and oxygen,
By performing the above, a method for manufacturing a semiconductor device is provided in which a thin film containing the predetermined element, nitrogen and oxygen is formed on the substrate.

(Appendix 2)
A method of manufacturing a semiconductor device according to appendix 1, preferably,
In the step of forming the first layer,
The step of supplying the source gas containing the predetermined element and the step of supplying the nitriding gas are alternately performed a predetermined number of times (m times).

(Appendix 3)
A method of manufacturing a semiconductor device according to appendix 1 or 2, preferably,
In the step of forming the second layer,
The step of supplying the source gas containing the predetermined element and the step of supplying the oxidizing gas are alternately performed a predetermined number of times (n times).

(Appendix 4)
A method of manufacturing a semiconductor device according to appendix 1 or 2, preferably,
In the step of forming the second layer,
A cycle including a step of supplying a source gas containing the predetermined element, a step of supplying the nitriding gas, and a step of supplying the oxidizing gas is performed a predetermined number of times (n times).

(Appendix 5)
A method of manufacturing a semiconductor device according to appendix 1 or 2, preferably,
In the step of forming the second layer,
A cycle including a step of supplying a raw material gas containing the predetermined element, a step of supplying the nitriding gas, a step of supplying a raw material gas containing the predetermined element, and a step of supplying the oxidizing gas a predetermined number of times (N times).

(Appendix 6)
A method of manufacturing a semiconductor device according to any one of appendices 1 to 5, preferably,
The thickness of the first layer is 0.5 nm or more and 5.0 nm or less.

(Appendix 7)
According to another aspect of the invention,
Supplying a source gas containing a predetermined element to a substrate in the processing chamber;
Supplying a nitriding gas to the substrate in the processing chamber;
And a step of supplying an oxidizing gas to the substrate in the processing chamber, a thin film containing the predetermined element, nitrogen and oxygen is formed on the substrate by performing a cycle including a predetermined number of times. Is provided.

(Appendix 8)
According to yet another aspect of the invention,
Supplying a source gas containing a predetermined element to a substrate in the processing chamber;
Supplying a nitriding gas to the substrate in the processing chamber;
Supplying a source gas containing the predetermined element to the substrate in the processing chamber;
And a step of supplying an oxidizing gas to the substrate in the processing chamber, a thin film containing the predetermined element, nitrogen and oxygen is formed on the substrate by performing a cycle including a predetermined number of times. Is provided.

(Appendix 9)
A method for manufacturing a semiconductor device according to any one of appendices 1 to 8, preferably,
The temperature of the substrate when forming the thin film is set to a temperature of 200 ° C. or lower.

(Appendix 10)
A method of manufacturing a semiconductor device according to any one of appendices 1 to 9, preferably,
In the step of supplying the nitriding gas, the nitriding gas activated by plasma is supplied to the substrate.

(Appendix 11)
A method of manufacturing a semiconductor device according to any one of appendices 1 to 10, preferably,
In the step of supplying the oxidizing gas, the oxidizing gas activated by plasma is supplied to the substrate.

(Appendix 12)
A method for manufacturing a semiconductor device according to any one of appendices 1 to 11, preferably,
The predetermined element includes a semiconductor element or a metal element.

(Appendix 13)
A method for manufacturing a semiconductor device according to any one of appendices 1 to 11, preferably,
The predetermined element includes a silicon element.

(Appendix 14)
According to yet another aspect of the invention,
Performing a step of supplying a source gas containing a predetermined element to a substrate in a processing chamber and a step of supplying a nitriding gas to the substrate in the processing chamber; Forming a first layer containing nitrogen;
The step of supplying a source gas containing the predetermined element to the substrate in the processing chamber and the step of supplying an oxidizing gas to the substrate in the processing chamber are performed on the first layer. And forming a second layer containing the predetermined element and oxygen,
By performing the above, there is provided a substrate processing method for forming a thin film containing the predetermined element, nitrogen and oxygen on the substrate.

(Appendix 15)
According to yet another aspect of the invention,
Supplying a source gas containing a predetermined element to a substrate in the processing chamber;
Supplying a nitriding gas to the substrate in the processing chamber;
A substrate processing apparatus for forming a thin film containing the predetermined element, nitrogen and oxygen on the substrate by performing a cycle including a step of supplying an oxidizing gas to the substrate in the processing chamber a predetermined number of times. Is done.

(Appendix 16)
According to yet another aspect of the invention,
Supplying a source gas containing a predetermined element to a substrate in the processing chamber;
Supplying a nitriding gas to the substrate in the processing chamber;
Supplying a source gas containing the predetermined element to the substrate in the processing chamber;
A substrate processing apparatus for forming a thin film containing the predetermined element, nitrogen and oxygen on the substrate by performing a cycle including a step of supplying an oxidizing gas to the substrate in the processing chamber a predetermined number of times. Is done.

(Appendix 17)
According to yet another aspect of the invention,
A processing chamber for processing the substrate;
A raw material gas supply system for supplying a raw material gas containing a predetermined element into the processing chamber;
A nitriding gas supply system for supplying a nitriding gas into the processing chamber;
An oxidizing gas supply system for supplying an oxidizing gas into the processing chamber,
By performing the process of supplying the source gas containing the predetermined element to the substrate in the processing chamber and the process of supplying the nitriding gas to the substrate in the processing chamber, Forming a first layer containing a predetermined element and nitrogen;
The first layer is obtained by performing a process of supplying a source gas containing the predetermined element to the substrate in the process chamber and a process of supplying the oxidizing gas to the substrate in the process chamber. A process for forming a second layer containing the predetermined element and oxygen;
A control unit that controls the source gas supply system, the nitriding gas supply system, and the oxidizing gas supply system so as to form a thin film containing the predetermined element, nitrogen, and oxygen on the substrate. A substrate processing apparatus is provided.

(Appendix 18)
According to yet another aspect of the invention,
A processing chamber for processing the substrate;
A raw material gas supply system for supplying a raw material gas containing a predetermined element into the processing chamber;
A nitriding gas supply system for supplying a nitriding gas into the processing chamber;
An oxidizing gas supply system for supplying an oxidizing gas into the processing chamber,
A process for supplying a source gas containing the predetermined element to a substrate in the processing chamber; a process for supplying a nitriding gas to the substrate in the processing chamber; and an oxidizing gas for the substrate in the processing chamber. And supplying the raw material gas supply system, the nitriding gas supply system, and the oxidation so as to form a thin film containing the predetermined element, nitrogen and oxygen on the substrate by performing a cycle including the supply process a predetermined number of times. A substrate processing apparatus having a controller for controlling a gas supply system is provided.

(Appendix 19)
According to yet another aspect of the invention,
A processing chamber for processing the substrate;
A raw material gas supply system for supplying a raw material gas containing a predetermined element into the processing chamber;
A nitriding gas supply system for supplying a nitriding gas into the processing chamber;
An oxidizing gas supply system for supplying an oxidizing gas into the processing chamber,
A process for supplying a source gas containing the predetermined element to a substrate in the processing chamber; a process for supplying a nitriding gas to the substrate in the processing chamber; and the predetermined element for the substrate in the processing chamber A predetermined number of cycles including a process of supplying a source gas containing oxygen and a process of supplying an oxidizing gas to the substrate in the processing chamber, whereby the predetermined element, nitrogen, and oxygen are added to the substrate. There is provided a substrate processing apparatus having a control unit for controlling the source gas supply system, the nitriding gas supply system, and the oxidizing gas supply system so as to form a thin film including the thin film.

(Appendix 20)
According to yet another aspect of the invention,
By performing a procedure for supplying a source gas containing a predetermined element to a substrate in a processing chamber of the substrate processing apparatus and a procedure for supplying a nitriding gas to the substrate in the processing chamber, on the substrate, Forming a first layer containing the predetermined element and nitrogen;
By performing a procedure for supplying a source gas containing the predetermined element to the substrate in the processing chamber and a procedure for supplying an oxidizing gas to the substrate in the processing chamber, And forming a second layer containing the predetermined element and oxygen,
By performing the above, a program for causing a computer to execute a procedure for forming a thin film containing the predetermined element, nitrogen and oxygen on the substrate is provided.

(Appendix 21)
According to yet another aspect of the invention,
A procedure for supplying a source gas containing a predetermined element to a substrate in a processing chamber of the substrate processing apparatus;
Supplying a nitriding gas to the substrate in the processing chamber;
And a step of forming a thin film containing the predetermined element, nitrogen and oxygen on the substrate by performing a cycle including a step of supplying an oxidizing gas to the substrate in the processing chamber a predetermined number of times. A program is provided.

(Appendix 22)
According to yet another aspect of the invention,
A procedure for supplying a source gas containing a predetermined element to a substrate in a processing chamber;
Supplying a nitriding gas to the substrate in the processing chamber;
Supplying a source gas containing the predetermined element to the substrate in the processing chamber;
A step of forming a thin film containing the predetermined element, nitrogen and oxygen on the substrate by executing a cycle including a step of supplying an oxidizing gas to the substrate in the processing chamber a predetermined number of times. A program is provided.

(Appendix 23)
According to yet another aspect of the invention,
By performing a procedure for supplying a source gas containing a predetermined element to a substrate in a processing chamber of the substrate processing apparatus and a procedure for supplying a nitriding gas to the substrate in the processing chamber, on the substrate, Forming a first layer containing the predetermined element and nitrogen;
By performing a procedure for supplying a source gas containing the predetermined element to the substrate in the processing chamber and a procedure for supplying an oxidizing gas to the substrate in the processing chamber, And forming a second layer containing the predetermined element and oxygen,
By performing the above, a computer-readable recording medium recording a program for causing a computer to execute a procedure for forming a thin film containing the predetermined element, nitrogen and oxygen on the substrate is provided.

(Appendix 24)
According to yet another aspect of the invention,
A procedure for supplying a source gas containing a predetermined element to a substrate in a processing chamber of the substrate processing apparatus;
Supplying a nitriding gas to the substrate in the processing chamber;
And a step of forming a thin film containing the predetermined element, nitrogen and oxygen on the substrate by performing a cycle including a step of supplying an oxidizing gas to the substrate in the processing chamber a predetermined number of times. A computer-readable recording medium on which a program to be recorded is recorded is provided.

(Appendix 25)
According to yet another aspect of the invention,
A procedure for supplying a source gas containing a predetermined element to a substrate in a processing chamber;
Supplying a nitriding gas to the substrate in the processing chamber;
Supplying a source gas containing the predetermined element to the substrate in the processing chamber;
A step of forming a thin film containing the predetermined element, nitrogen and oxygen on the substrate by executing a cycle including a step of supplying an oxidizing gas to the substrate in the processing chamber a predetermined number of times. A computer-readable recording medium on which a program to be recorded is recorded is provided.

200 wafer (substrate)
201 processing chamber 280 controller (control unit)
301 Source gas supply system 302 Nitridation gas supply system 303 Oxidation gas supply system 501 First inert gas supply system 502 Second inert gas supply system 503 Third inert gas supply system

Claims (5)

Supplying the substrate with the resist pattern formed on the surface thereof at a predetermined temperature of 200 ° C. or lower while supplying a first source gas containing a predetermined element to the substrate, and nitriding the substrate; Forming a first layer containing the predetermined element and nitrogen to a thickness of 0.5 nm to 5 nm on the substrate by performing a process of supplying and exhausting a gas a plurality of times;
Supplying a second source gas containing the predetermined element to the substrate and exhausting the substrate while maintaining the substrate at a predetermined temperature of 200 ° C. or less; and supplying the nitriding gas to the substrate A second layer containing the predetermined element, nitrogen, and oxygen is formed on the first layer by performing a process of exhausting and a process of supplying and exhausting an oxidizing gas to the substrate a plurality of times. Forming, and
A method for manufacturing a semiconductor device. The method of manufacturing a semiconductor device according to claim 1, wherein the nitriding gas and the oxidizing gas are supplied to the substrate while being activated by plasma excitation. The method for manufacturing a semiconductor device according to claim 1, wherein the first source gas and the second source gas are different gases. A processing chamber for accommodating the substrate;
A first source gas supply system for supplying a first source gas containing a predetermined element into the processing chamber;
A second source gas supply system for supplying a second source gas containing a predetermined element into the processing chamber;
A nitriding gas supply system for supplying a nitriding gas into the processing chamber;
An oxidizing gas supply system for supplying an oxidizing gas into the processing chamber;
A heating system for heating the substrate;
An exhaust system for exhausting the processing chamber;
A process of supplying and exhausting a first source gas containing a predetermined element into the processing chamber while maintaining a substrate having a resist pattern formed on the surface accommodated in the processing chamber at a predetermined temperature of 200 ° C. or lower; A process of supplying and exhausting a nitriding gas into the processing chamber is performed a plurality of times so that the first layer containing the predetermined element and nitrogen has a thickness of 0.5 nm to 5 nm on the substrate. a process of forming, one protein maintains the substrate at a predetermined temperature of 200 ° C. or less, a process of exhausting and supplying a second source gas containing the specific element into the processing chamber, the nitride to the substrate By performing a process of supplying and exhausting a gas and a process of supplying and exhausting an oxidizing gas into the processing chamber a plurality of times, a first layer containing the predetermined element , nitrogen, and oxygen is formed on the first layer. The process of forming the two layers, and so on The first raw material gas supply system, and the second source gas supply system, the nitriding gas supply system, the oxidizing gas supply system, a heating system, and a control unit to control the exhaust system,
A substrate processing apparatus. A substrate having a resist pattern formed on a surface accommodated in a processing chamber of a substrate processing apparatus is maintained at a predetermined temperature of 200 ° C. or lower, and a first source gas containing a predetermined element is supplied to the substrate and exhausted. And a step of supplying and exhausting a nitriding gas to the substrate a plurality of times to form a first layer containing the predetermined element and nitrogen on the substrate with a thickness of 0.5 nm to 5 nm. A procedure for forming a film thickness;
While maintaining the substrate at a predetermined temperature of 200 ° C. or lower, supplying a second source gas containing the predetermined element to the substrate and exhausting the substrate, and supplying the nitriding gas to the substrate A second layer containing the predetermined element , nitrogen, and oxygen is formed on the first layer by performing a procedure for exhausting and a procedure for supplying and exhausting an oxidizing gas to the substrate a plurality of times. And a program for causing a computer to control the substrate processing apparatus for performing the forming process .

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