JP5718031B2 - Substrate processing apparatus and semiconductor device manufacturing method - Google Patents

Description

  The present invention relates to a substrate processing apparatus and a semiconductor device manufacturing method, and more particularly to a substrate processing apparatus and a semiconductor device manufacturing method for processing a substrate using plasma.

  As one of semiconductor device manufacturing processes, there is a film forming process for depositing a predetermined thin film on a substrate using a CVD (Chemical Vapor Deposition) method using plasma or an ALD (Atomic Layer Deposition) method (see Patent Document 1). ). The CVD method is a method of depositing a thin film having an element contained in a source gas molecule as a constituent element on a substrate to be processed by utilizing a gas phase and a reaction at the surface of a gaseous source. In the CVD method, a plurality of types of source gases including a plurality of elements constituting a film to be formed are simultaneously supplied onto a substrate to be processed. In the case of the ALD method, a plurality of types of source gases containing a plurality of elements constituting a film to be formed are alternately supplied onto the substrate to be processed. Processing can be performed by lowering the temperature of the substrate to be processed with respect to the CVD method. In the ALD method, thin film deposition is controlled at the atomic layer level. The plasma is used for accelerating the chemical reaction of the thin film deposited by the CVD method, removing impurities from the thin film, or assisting the chemical reaction of the deposited film forming material by the ALD method. .

JP 2003-297818 A

  However, with the recent miniaturization of semiconductor devices, it is required to form a film at a low substrate temperature. However, when a film is formed on a metal film at a low temperature using plasma, the metal film and the film are formed. The adhesion of the formed film is deteriorated, and a phenomenon that the formed film is peeled off occurs.

  The main object of the present invention is to improve the adhesion between the metal film and the formed film when the film is formed on the metal film at a low temperature using plasma, and the formed film is peeled off. An object of the present invention is to provide a substrate processing apparatus and a method for manufacturing a semiconductor device that can be prevented or suppressed.

According to one aspect of the invention,
A processing chamber for processing the substrate;
One or more buffer chambers partitioned from the processing chamber and having a gas supply port that opens to the processing chamber;
A first processing gas supply system for supplying a first processing gas into the processing chamber,
A second processing gas supply system for supplying to the processing chamber a second process gas through the one or more buffer chamber,
A plasma source for generating plasma inside the buffer chamber and for exciting the second process gas inside the buffer chamber ;
In the processing chamber, the substrate on which the metal film or GST film formed on its surface, the process supplies a process for supplying the first processing gas, the second process gas in the state that has not been plasma-excited And performing the pretreatment for forming the first film on the metal film or the GST film by performing a cycle of alternately performing at least one time, and then performing the pretreatment on the substrate after the pretreatment , On the first film, a cycle of alternately performing a process of supplying the first process gas and a process of supplying the second process gas in a plasma-excited state is performed at least once. so as to form a second layer, the first process gas supply system, and a control unit configured to control the second process gas supply system and said plasma source,
A substrate processing apparatus is provided.

According to another aspect of the invention,
A processing chamber for processing the substrate;
One or more buffer chambers partitioned from the processing chamber and having a gas supply port that opens to the processing chamber;
A first processing gas supply system for supplying a first processing gas into the processing chamber,
A second processing gas supply system for supplying to the processing chamber a second process gas through the one or more buffer chamber,
A plasma source for generating plasma inside the buffer chamber and for exciting the second process gas inside the buffer chamber ;
In the processing chamber, the first processing gas is supplied to the substrate on which the metal film or the GST film is formed without supplying the second processing gas to the metal film or the GST film. Then, after the pretreatment is performed, a process for supplying the first process gas to a substrate after the pretreatment and a process for supplying the second process gas in a plasma-excited state are alternately performed. by performing at least once the cycle to be performed, so as to form a film on the metal film or the GST layer the pretreatment is performed, the first process gas supply system, the second process gas Control means configured to control the supply system and the plasma source ;
A substrate processing apparatus is provided.

According to yet another aspect of the invention,
The substrate having the metal film or GST film formed on a surface, and supplying the first processing gas, the cycle for performing the step of supplying a second processing gas in the state that has not been plasma-excited, the alternating Performing a pretreatment for forming a first film on the metal film or the GST film by performing at least once ;
With respect to the substrate after the pretreatment is carried out wherein the step of supplying the first processing gas, at least once a cycle of performing the steps, are alternately supplying the second processing gas while being plasma-excited A step of forming a second film on the first film ;
A method of manufacturing a semiconductor device having the above is provided.

According to yet another aspect of the invention,
Supplying a first process gas to a substrate having a metal film or a GST film on the surface without supplying a second process gas, and pre-treating the metal film or the GST film; ,
A cycle in which the step of supplying the first processing gas and the step of supplying the second processing gas in a plasma-excited state are alternately applied to the substrate after the pretreatment at least once. A step of forming a film on the pretreated metal film or the GST film,
A method of manufacturing a semiconductor device having the above is provided.

  According to the present invention, when a film is formed on a metal film at a low temperature using plasma, the adhesion between the metal film and the formed film is improved, and the formed film is prevented from peeling off or A substrate processing apparatus and a method for manufacturing a semiconductor device that can be suppressed are provided.

FIG. 1 is a schematic perspective view for explaining the configuration of a substrate processing apparatus suitably used in a preferred embodiment of the present invention. FIG. 2 is a schematic configuration diagram for explaining an example of a processing furnace suitably used in the first to third preferred embodiments of the present invention and members associated therewith, and a schematic longitudinal section of the processing furnace part. It is a figure shown by and is a BB line schematic longitudinal cross-section of FIG. 3 is a schematic cross-sectional view taken along line AA of the processing furnace shown in FIG. FIG. 4 is a block diagram for explaining a controller suitably used in the substrate processing apparatus according to the first to seventh embodiments of the present invention and each member controlled by the controller. FIG. 5 is a flowchart for explaining a silicon nitride film manufacturing process according to the first preferred embodiment of the present invention. FIG. 6 is a timing chart for explaining the manufacturing process of the silicon nitride film according to the first preferred embodiment of the present invention. FIG. 7 is a diagram showing the relationship between the input high frequency power and the number of generated particles. FIG. 8 is a diagram showing a typical particle distribution in the surface of the wafer 200. FIG. 9 is a flow chart for explaining a silicon nitride film manufacturing process according to the second preferred embodiment of the present invention. FIG. 10 is a timing chart for explaining the pretreatment in the manufacturing process of the silicon nitride film according to the second preferred embodiment of the present invention. FIG. 11 is a flow chart for explaining a silicon nitride film manufacturing process according to the third preferred embodiment of the present invention. FIG. 12 is a schematic cross-sectional view for explaining a modification of the preferred first to third embodiments of the present invention. FIG. 13 is a schematic cross-sectional view for explaining a modification of the preferred first to third embodiments of the present invention. FIG. 14 is a schematic cross-sectional view for explaining a modification of the preferred first to third embodiments of the present invention. FIG. 15 is a schematic cross-sectional view for explaining preferred fourth and fifth embodiments of the present invention. FIG. 16 is a schematic configuration diagram for explaining an example of a processing furnace suitably used in the preferred sixth and seventh embodiments of the present invention and members accompanying the processing furnace, and a schematic longitudinal section of the processing furnace part. It is a figure shown by and is the EE line schematic longitudinal cross-section of FIG. FIG. 17 is a schematic cross-sectional view taken along the line DD of the processing furnace shown in FIG. FIG. 18 is a schematic cross-sectional view for explaining a preferred seventh embodiment of the present invention.

  First, the background of the preferred embodiment of the present invention will be described.

For example, an amorphous silicon nitride film is formed on a substrate by an ALD method using DCS (dichlorosilane) and plasma excited NH ₃ (ammonia) at a substrate temperature of 650 ° C. or lower. The formation of the amorphous silicon nitride film on the substrate by the ALD method includes a DCS supply step on the substrate, a residual gas removal step such as DCS, a plasma excited NH ₃ supply step, and a residual gas removal step such as NH _3. These four steps are repeated (cycle processing). In the ALD method, the film thickness can be controlled by the number of cycle treatments.

  With the recent miniaturization of devices, attempts have been made to form an amorphous silicon nitride film by the ALD method using plasma as described above on a metal film formed on the substrate surface at a temperature of about 300 ° C. However, when the amorphous silicon nitride film is formed at such a low temperature, there is a problem that the adhesion between the metal film and the amorphous silicon nitride film is poor and the amorphous silicon nitride film peels off.

  When the present inventors formed an amorphous silicon nitride film by an ALD method using plasma, particles were generated. When the number of particles was large, the adhesion between the metal film and the amorphous silicon nitride film was poor, and the amorphous silicon nitride film was I found it easy to peel.

  The present inventors have also found that when the substrate temperature is as high as 400 ° C. or higher, DCS is likely to be chemisorbed. However, when the substrate temperature is lower than 400 ° C., DCS is mainly subject to physical adsorption rather than chemical adsorption. We thought that it became difficult to form a bond with the metal film formed on the surface, and the adhesiveness deteriorated.

  The preferred embodiments of the present invention described below are based on such knowledge and considerations, and are particularly generated when an amorphous silicon nitride film is formed by an ALD method using plasma at a low temperature (350 ° C. or lower). The number of particles to be reduced was reduced to improve the adhesion, or the pretreatment was performed before the amorphous silicon nitride film was formed by the ALD method using plasma to improve the adhesion.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

  First, the substrate processing apparatus suitably used in each preferred embodiment of the present invention will be described. This substrate processing apparatus is configured as an example of a semiconductor manufacturing apparatus used for manufacturing a semiconductor device.

  In the following description, as an example of the substrate processing apparatus, a case will be described in which a vertical apparatus that performs a film forming process or the like on a substrate is used. However, the present invention is not based on the use of a vertical apparatus, and for example, a single wafer apparatus may be used.

  Referring to FIG. 1, a substrate processing apparatus 101 uses a cassette 110 that contains a wafer 200 as an example of a substrate, and the wafer 200 is made of a material such as semiconductor silicon. The substrate processing apparatus 101 includes a housing 111, and a cassette stage 114 is installed inside the housing 111. The cassette 110 is carried on the cassette stage 114 by an in-process transfer device (not shown) or unloaded from the cassette stage 114.

  The cassette 110 is placed on the cassette stage 114 by an in-process transfer device (not shown) so that the wafer 200 in the cassette 110 maintains a vertical posture and the wafer loading / unloading port of the cassette 110 faces upward. The The cassette stage 114 rotates the cassette 110 clockwise 90 degrees rearward of the casing 111 so that the wafer 200 in the cassette 110 is in a horizontal posture, and the wafer loading / unloading port of the cassette 110 faces the rear of the casing 111. It is configured to be operable.

  A cassette shelf 105 is installed in front of the substantially central portion of the casing 111 in the front-rear direction, and the cassette shelf 105 is configured to store a plurality of cassettes 110 in a plurality of rows and a plurality of rows. The cassette shelf 105 is provided with a transfer shelf 123 in which the cassette 110 to be transferred by the wafer transfer mechanism 125 is stored.

  A reserve cassette shelf 107 is provided above the cassette stage 114, and is configured to store the cassette 110 in a preliminary manner.

  A cassette carrying device 118 is installed between the cassette stage 114 and the cassette shelf 105. The cassette carrying device 118 includes a cassette elevator 118a that can move up and down while holding the cassette 110, and a cassette carrying mechanism 118b as a carrying mechanism. The cassette carrying device 118 is configured to carry the cassette 110 among the cassette stage 114, the cassette shelf 105, and the spare cassette shelf 107 by an interlocking operation of the cassette elevator 118a and the cassette carrying mechanism 118b.

  A wafer transfer mechanism 125 is installed behind the cassette shelf 105. The wafer transfer mechanism 125 includes a wafer transfer device 125a capable of rotating or linearly moving the wafer 200 in the horizontal direction, and a wafer transfer device elevator 125b for moving the wafer transfer device 125a up and down. The wafer transfer device 125 a is provided with a tweezer 125 c for picking up the wafer 200. The wafer transfer device 125 loads (charges) the wafer 200 to the boat 217 using the tweezers 125c as the placement portion of the wafer 200 by the interlocking operation of the wafer transfer device 125a and the wafer transfer device elevator 125b. The boat 217 is configured to be detached (discharged).

  A processing furnace 202 for heat-treating the wafer 200 is provided above the rear portion of the casing 111, and a lower end portion of the processing furnace 202 is configured to be opened and closed by a furnace port shutter 147.

  Below the processing furnace 202, a boat elevator 115 that raises and lowers the boat 217 with respect to the processing furnace 202 is provided. An arm 128 is connected to the lifting platform of the boat elevator 115, and a seal cap 219 is horizontally installed on the arm 128. The seal cap 219 is configured to support the boat 217 vertically and to close the lower end portion of the processing furnace 202.

  The boat 217 includes a plurality of holding members, and is configured to hold a plurality of (for example, about 50 to 150) wafers 200 horizontally with the centers thereof aligned in the vertical direction. Yes.

  Above the cassette shelf 105, a clean unit 134a for supplying clean air that is a cleaned atmosphere is installed. The clean unit 134 a includes a supply fan (not shown) and a dustproof filter (not shown), and is configured to distribute clean air inside the casing 111.

  A clean unit 134 b that supplies clean air is installed at the left end of the housing 111. The clean unit 134b also includes a supply fan (not shown) and a dustproof filter (not shown), and is configured to circulate clean air in the vicinity of the wafer transfer device 125a, the boat 217, and the like. The clean air is exhausted to the outside of the casing 111 after circulating in the vicinity of the wafer transfer device 125a, the boat 217, and the like.

  Next, main operations of the substrate processing apparatus 101 will be described.

  When the cassette 110 is loaded onto the cassette stage 114 by an in-process transfer device (not shown), the cassette 110 holds the wafer 200 in a vertical position on the cassette stage 114 and the wafer loading / unloading port of the cassette 110 is directed upward. It is placed on the cassette stage 114 so as to face. Thereafter, the cassette 110 is placed in a clockwise direction 90 in the clockwise direction behind the housing 111 so that the wafer 200 in the cassette 110 is placed in a horizontal posture by the cassette stage 114 and the wafer loading / unloading port of the cassette 110 faces the rear of the housing 111. ° Rotated.

  Thereafter, the cassette 110 is automatically transported and delivered by the cassette transport device 118 to the designated shelf position of the cassette shelf 105 or the spare cassette shelf 107 and temporarily stored, and then the cassette shelf 105 or the spare cassette shelf. It is transferred from 107 to the transfer shelf 123 by the cassette transfer device 118 or directly transferred to the transfer shelf 123.

  When the cassette 110 is transferred to the transfer shelf 123, the wafers 200 are picked up from the cassette 110 by the tweezers 125c of the wafer transfer device 125a through the wafer loading / unloading port of the cassette 110 and loaded (charged) into the boat 217. The wafer transfer device 125 a that has delivered the wafer 200 to the boat 217 returns to the cassette 110 and loads the subsequent wafer 200 into the boat 217.

  When a predetermined number of wafers 200 are loaded into the boat 217, the furnace port shutter 147 that has closed the lower end of the processing furnace 202 is opened, and the lower end of the processing furnace 202 is opened. Thereafter, the boat 217 holding the wafer group 200 is loaded into the processing furnace 202 by the ascending operation of the boat elevator 115, and the lower part of the processing furnace 202 is closed by the seal cap 219.

  After loading, arbitrary processing is performed on the wafer 200 in the processing furnace 202. After the processing, the wafer 200 and the cassette 110 are carried out of the casing 111 in the reverse procedure described above.

(First embodiment)
Next, the processing furnace 202 of the first embodiment used in the substrate processing apparatus 101 described above will be described with reference to FIGS.

  2 and 3, the processing furnace 202 is provided with a heater 207 which is 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. Inside the heater 207, a quartz reaction tube 203 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 port lid capable of airtightly closing the lower end opening of the reaction tube 203. The seal cap 219 is brought 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 airtight member (hereinafter referred to as an O-ring) 220 is disposed between an annular flange provided at the lower opening end of the reaction tube 203 and the upper surface of the seal cap 219, and the space between them is hermetically sealed. 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, and functions as a heat insulating portion and is a support that supports the boat. The boat 217 is erected on the boat support 218. The boat 217 is made of a heat resistant material such as quartz or silicon carbide. The boat 217 includes a bottom plate 210 fixed to the boat support 218 and a top plate 211 disposed above the bottom plate 210, and a plurality of support columns 212 are constructed between the bottom plate 210 and the top plate 211. (See FIG. 1). A plurality of wafers 200 are held on the boat 217. The plurality of wafers 200 are loaded in multiple stages in the tube axis direction of the reaction tube 203 in a state where the horizontal posture is maintained while keeping the center of each other while keeping a certain distance from each other, and are supported by the columns 212 of the boat 217.

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

  The seal cap 219 is raised and lowered in the vertical direction by a boat elevator 115 as an elevating mechanism provided outside the reaction tube 203, so that the boat 217 can be carried 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 on the boat 217 in multiple stages, the boat 217 is inserted into the processing chamber 201 while being supported by the boat support 218, and the heater 207 is The wafer 200 inserted into the processing chamber 201 is heated to a predetermined temperature.

  Referring to FIGS. 2 and 3, three gas supply pipes 310, 320, and 330 for supplying source gas are connected.

  In the processing chamber 201, nozzles 410, 420, and 430 are provided. The nozzles 410, 420, and 430 are provided through the lower part of the reaction tube 203. A gas supply pipe 310 is connected to the nozzle 410, a gas supply pipe 320 is connected to the nozzle 420, and a gas supply pipe 330 is connected to the nozzle 430.

  The gas supply pipe 310 is provided with, in order from the upstream side, a mass flow controller 312 that is a flow rate control device, a valve 314 that is an on-off valve, a gas reservoir 315, and a valve 313 that is an on-off valve.

  The downstream end of the gas supply pipe 310 is connected to the end of the nozzle 410. The nozzle 410 is an arc-shaped space between the inner wall of the reaction tube 203 and the wafer 200, and is provided so as to rise upward from the lower portion of the inner wall of the reaction tube 203 in the stacking direction of the wafer 200. . The nozzle 410 is configured as an L-shaped long nozzle. A large number of gas supply holes 411 for supplying a raw material 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.

  A gas reservoir 315 for accumulating gas supplied from the gas supply pipe 310 is provided in the middle of the gas supply pipe 310. The gas reservoir 315 is constituted by, 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 stored in the gas reservoir 315, or the gas stored in the gas reservoir 315 is stored in the processing chamber 201. It can be supplied.

  Further, the gas supply pipe 310 is provided with a vent line 610 and a valve 612 connected to an exhaust pipe 232 described later between the valve 314 and the mass flow controller 312.

  A gas supply system 301 is mainly constituted by the gas supply pipe 310, the mass flow controller 312, the valve 314, the gas reservoir 315, the valve 313, the nozzle 410, the vent line 610, and the valve 612.

  A carrier gas supply pipe 510 for supplying a carrier gas (inert gas) is connected to the gas supply pipe 310 on the downstream side of the valve 313. The carrier gas supply pipe 510 is provided with a mass flow controller 512 and a valve 513. A carrier gas supply system (inert gas supply system) 501 is mainly configured by the carrier gas supply pipe 510, the mass flow controller 512, and the valve 513.

  In the gas supply pipe 310, with the valve 313 closed and the valve 314 opened, the flow rate of the gas source gas is adjusted by the mass flow controller 312, supplied to the gas reservoir 315, and stored in the gas reservoir 315. When a predetermined amount is accumulated in the gas reservoir 315, the valve 314 is closed.

  While the source gas is not supplied to the gas reservoir 315, the valve 314 is closed, the valve 612 is opened, and the source gas is allowed to flow to the vent line 610 through the valve 612.

  When supplying the source gas to the processing chamber 201, the valve 313 is opened with the valves 314 and 513 closed, and the source gas is supplied to the processing chamber 201 via the gas supply pipe 310 downstream of the valve 313. To supply at once.

  The gas supply pipe 320 is provided with a mass flow controller 322 as a flow rate control device and a valve 323 as an on-off valve in order from the upstream side.

  The downstream end of the gas supply pipe 320 is connected to the 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. The nozzle 420, the electrode protection tube 451, and the electrode protection tube 452 are arranged in this order in the buffer chamber 423.

  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 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 the present embodiment, by adjusting the opening area and the opening pitch of the gas supply holes 421 of the nozzle 420 from the upstream side to the downstream side as described above, first, the flow velocity from each of the gas supply holes 421 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 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.

  Further, the gas supply pipe 320 is provided with a vent line 620 and a valve 622 connected to an exhaust pipe 232 described later between the valve 323 and the mass flow controller 322.

  A gas supply system 302 is mainly configured by a gas supply pipe 320, a mass flow controller 322, a valve 323, a nozzle 420, a buffer chamber 423, a vent line 620, and a valve 622.

  Further, a carrier gas supply pipe 520 for supplying a carrier gas (inert gas) is connected to the gas supply pipe 320 on the downstream side of the valve 323. The carrier gas supply pipe 520 is provided with a mass flow controller 522 and a valve 523. A carrier gas supply system (inert gas supply system) 502 is mainly configured by the carrier gas supply pipe 520, the mass flow controller 522, and the valve 523.

  In the gas supply pipe 320, the gas source gas is supplied with the flow rate adjusted by the mass flow controller 322.

  While the source gas is not supplied to the processing chamber 201, the valve 323 is closed, the valve 622 is opened, and the source gas is allowed to flow to the vent line 620 via the valve 622.

  When supplying the source gas to the processing chamber 201, the valve 622 is closed, the valve 323 is opened, and the source gas is supplied to the gas supply pipe 320 downstream of the valve 323. On the other hand, the flow rate of the carrier gas is adjusted by the mass flow controller 522 and supplied from the carrier gas supply pipe 520 via the valve 523, and the raw material gas merges with this carrier gas on the downstream side of the valve 323, and the nozzle 420 and the buffer chamber 423 are passed through. And supplied to the processing chamber 201.

  The gas supply pipe 330 is provided with a mass flow controller 332 that is a flow rate control device and a valve 333 that is an on-off valve in order from the upstream side.

  The downstream end of the gas supply pipe 330 is connected to the 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. The nozzle 430, the electrode protection tube 461, and the electrode protection tube 462 are arranged in this order in the buffer chamber 433.

  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 in a 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 the gas supply holes 431 of the nozzle 430 from the upstream side to the downstream side as described above, first, the flow velocity from each of the gas supply holes 431 is adjusted. Although there is a difference, the gas with the same flow rate is ejected. Then, the gas ejected from each of the gas supply holes 431 is once introduced into the buffer chamber 433, and the flow velocity difference of the gas 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.

  Further, the gas supply pipe 330 is provided with a vent line 630 and a valve 632 connected to an exhaust pipe 232 described later between the valve 333 and the mass flow controller 332.

  A gas supply system 303 is mainly configured by the gas supply pipe 330, the mass flow controller 332, the valve 333, the nozzle 430, the buffer chamber 433, the vent line 630, and the valve 632.

  A carrier gas supply pipe 530 for supplying a carrier gas (inert gas) is connected to the gas supply pipe 330 on the downstream side of the valve 333. The carrier gas supply pipe 530 is provided with a mass flow controller 532 and a valve 533. A carrier gas supply system (inert gas supply system) 503 is mainly configured by the carrier gas supply pipe 530, the mass flow controller 532, and the valve 533.

  In the gas supply pipe 330, the gas source gas is supplied with its flow rate adjusted by the mass flow controller 332.

  While the source gas is not supplied to the processing chamber 201, the valve 333 is closed, the valve 632 is opened, and the source gas is allowed to flow to the vent line 630 through the valve 632.

  When supplying the source gas to the processing chamber 201, the valve 632 is closed, the valve 333 is opened, and the source gas is supplied to the gas supply pipe 330 downstream of the valve 333. On the other hand, the flow rate of the carrier gas is adjusted by the mass flow controller 532 and supplied from the carrier gas supply pipe 530 via the valve 533, and the raw material gas merges with this carrier gas on the downstream side of the valve 333, and passes through the nozzle 430 and the buffer chamber 433. And supplied to the processing chamber 201.

  In the buffer chamber 423, a rod-shaped electrode 471 and a rod-shaped electrode 472 having an elongated structure are disposed along the stacking direction of the wafers 200 from the bottom to the top 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 electrodes 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. As a result, 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, the buffer chamber 423, and the gas supply hole 425. The rod-shaped electrode 471, the rod-shaped electrode 472, the electrode protection tube 451, the electrode protection tube 452, the matching unit 271, and the high-frequency power source 270 constitute a first plasma source as a plasma generator (plasma generation unit). 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, rod-shaped electrodes 481 and rod-shaped 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. Each of the rod-shaped electrode 481 and the rod-shaped electrode 482 is 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. 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. As a result, plasma is generated in the plasma generation region between the rod-shaped electrode 481 and the rod-shaped electrode 482. A 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, the buffer chamber 433, and the gas supply hole 435. A second plasma source as a plasma generator (plasma generator) is mainly configured by the rod-shaped electrode 481, the rod-shaped electrode 482, the electrode protection tube 461, the electrode protection tube 462, the matching unit 271, and the high-frequency power source 270. 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 tube 451 and the electrode protection tube 452 are inserted into the buffer chamber 423 through a through hole (not shown) provided in the reaction tube 203 at a height near the lower portion of the boat support 218. ing. The electrode protection tube 461 and the electrode protection tube 462 are inserted into the buffer chamber 433 through a through hole (not shown) provided in the reaction tube 203 at a position near the lower portion of the boat support 218. ing.

  The electrode protection tube 451 and the electrode protection tube 452 have a structure in which the rod-shaped electrode 471 and the rod-shaped electrode 472 can be inserted into the buffer chamber 423 while being isolated from the atmosphere of the buffer chamber 423, respectively. The electrode protection tube 461 and the electrode protection tube 462 have a structure in which the rod-shaped electrode 481 and the rod-shaped electrode 482 can be inserted into the buffer chamber 433 while being isolated from the atmosphere of the buffer chamber 433, respectively. When the inside of the electrode protection tubes 451, 452, 461, 462 is the same atmosphere as the outside air (atmosphere), the rod-shaped electrodes 471, 472, 481, 482 inserted into the electrode protection tubes 451, 452, 461, 462, respectively, are heaters. It is oxidized by the heat of 207. Therefore, the inside of the electrode protection tubes 451, 452, 461, 462 is filled or purged with an inert gas such as nitrogen to keep the oxygen concentration sufficiently low to prevent oxidation of the rod-shaped electrodes 471, 472, 481, 482. An inert gas purge mechanism (not shown) is provided.

  Note that 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. However, the structure is such that it does not easily 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 easily reach the surface of the wafer 200 without being deactivated.

  2 and 3, an exhaust port 230 is provided in the lower part of the reaction tube. The exhaust port 230 is connected to the exhaust pipe 231. The gas supply hole 411 and the exhaust port 230 of the nozzle 410 are provided at positions facing each other across the wafer 200 (on the opposite side by 180 degrees). In this way, the source gas supplied from the gas supply hole 411 flows across the main surface of the wafer 200 toward the exhaust pipe 231, and the source gas is supplied uniformly over the entire surface of the wafer 200. This makes it easier to form a more uniform film on the wafer 200.

  In the present embodiment, a first plasma source mainly composed of a rod-shaped electrode 471, a rod-shaped electrode 472, an electrode protection tube 451, an electrode protection tube 452, a matching unit 271, and a high-frequency power source 270, and mainly a rod-shaped electrode 481, a rod-shaped electrode 482, an electrode protection tube 461, an electrode protection tube 462, a matching unit 271, and a second plasma source including a high-frequency power source 270. In the case of one plasma source, the input high frequency power density per unit volume is large and many particles are generated. In this embodiment, two plasma sources such as a first plasma source and a second plasma source are used. Since it is provided, the high frequency power supplied to each plasma source can be reduced (halved) and the number of generated particles can be reduced as compared with the case where there is one plasma source.

  The first plasma generation structure 429 mainly composed of the rod-shaped electrode 471, the rod-shaped electrode 472, the electrode protection tube 451, the electrode protection tube 452, the buffer chamber 423, and the gas supply hole 425, and mainly the rod-shaped electrode 481. The second plasma generation structure 439 including the rod-shaped electrode 482, the electrode protection tube 461, the electrode protection tube 462, the buffer chamber 433, and the gas supply hole 435 is a line passing through the center of the wafer 200 (center of the reaction tube 203). Therefore, the plasma is easily supplied uniformly from the two plasma generation structures to the entire surface of the wafer 200, and a uniform film can be formed on the wafer 200.

  Further, since the exhaust port 230 is also provided on a line passing through the center of the wafer 200 (the center of the reaction tube 203), the plasma is easily supplied uniformly over the entire surface of the wafer 200, and a uniform film is formed on the wafer 200. Can be formed. Further, since the gas supply hole 411 of the nozzle 410 is also provided on a line passing through the center of the wafer 200 (the center of the reaction tube 203), the source gas is easily supplied uniformly over the entire surface of the wafer 200. A more uniform film on 200 can be formed.

  Further, the distance between the gas supply hole 411 of the nozzle 410 and the gas supply hole 425 of the buffer chamber 423 and the distance between the gas supply hole 411 of the nozzle 410 and the gas supply hole 435 of the buffer chamber 433 are equal. Since the gas supply hole 411, the gas supply hole 425, and the gas supply hole 435 are disposed, a more uniform film can be formed on the wafer 200.

  Referring to FIGS. 2 and 3 again, an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201 is connected to the exhaust port 230 at the bottom of the reaction tube. The exhaust pipe 231 is evacuated via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 243 as a pressure regulator (pressure adjustment unit). A vacuum pump 246 serving as an exhaust device is connected, and the processing chamber 201 can be evacuated so that the pressure in the processing chamber 201 becomes a predetermined pressure (degree of vacuum). An exhaust pipe 232 on the downstream side of the vacuum pump 246 is connected to a waste gas treatment device (not shown) or the like. The APC valve 243 can open and close the valve to evacuate / stop the evacuation in the processing chamber 201, and further adjust the valve opening to adjust the conductance to adjust the pressure in the processing chamber 201. It is an open / close valve. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 243, the vacuum pump 246, and the pressure sensor 245.

  A temperature sensor 263 as a temperature detector is installed in the reaction tube 203. By adjusting the power supplied to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature in the processing chamber 201 can be adjusted. It is configured to have a desired temperature distribution. The temperature sensor 263 is configured in an L shape, is introduced through the manifold 209, and is provided along the inner wall of the reaction tube 203.

  A boat 217 is provided at the center in the reaction tube 203. The boat 217 can be moved up and down (in and out) with respect to the reaction tube 203 by the boat elevator 115. When the boat 217 is introduced into the reaction tube 203, the lower end portion of the reaction tube 203 is hermetically sealed with the seal cap 219 via the O-ring 220. The boat 217 is supported on a boat support 218. In order to improve the uniformity of processing, the boat rotation mechanism 267 is driven to rotate the boat 217 supported by the boat support 218.

  Referring to FIG. 4, the controller 280 includes a display 288 that displays an operation menu and the like, and an operation input unit 290 that includes a plurality of keys and inputs various information and operation instructions. . The controller 280 stores a CPU 281 that controls the overall operation of the substrate processing apparatus 101, a ROM 282 that stores various programs including a control program in advance, a RAM 283 that temporarily stores various data, and various data. An HDD 284 to be held, a display driver 287 that controls display of various types of information on the display 288 and receives operation information from the display 288, an operation input detection unit 289 that detects an operation state of the operation input unit 290, and a temperature described later Control unit 291, pressure control unit 294 described later, vacuum pump 246, boat rotation mechanism 267, boat elevator 115, mass flow controllers 312, 322, 332, 512, 522, 532, valve control unit 299 described later, cassette stage 114, Tsu DOO transfer device 118, and a communication interface (I / F) unit 285 for transmitting and receiving the respective members and various kinds of information such as the wafer transfer device 125, a.

  The CPU 281, ROM 282, RAM 283, HDD 284, display driver 287, operation input detection unit 289, and communication I / F unit 285 are connected to each other via a system bus BUS 286. Therefore, the CPU 281 can access the ROM 282, RAM 283, and HDD 284, control display of various information on the display 288 via the display driver 287, grasp operation information from the display 288, communication I / F It is possible to control transmission / reception of various information to / from each member via the unit 285. Further, the CPU 281 can grasp the operation state of the user with respect to the operation input unit 290 via the operation input detection unit 289.

  The temperature control unit 291 is a communication I / F unit 293 that transmits and receives various information such as set temperature information between the heater 207, the heating power source 250 that supplies power to the heater 207, the temperature sensor 263, and the controller 280. And a heater control unit 292 that controls the power supplied from the heating power source 250 to the heater 207 based on the received set temperature information, temperature information from the temperature sensor 263, and the like. The heater control unit 292 is also realized by a computer. The communication I / F unit 293 of the temperature control unit 291 and the communication I / F unit 285 of the controller 280 are connected by a cable 751.

  The pressure control unit 294 includes a communication I / F unit 296 that transmits and receives various types of information such as set pressure information and APC valve 243 opening / closing information between the APC valve 243, the pressure sensor 245, and the controller 280, and the received setting. An APC valve control unit 295 that controls the opening and closing and the opening degree of the APC valve 243 based on the pressure information, the opening and closing information of the APC valve 243, the pressure information from the pressure sensor 245, and the like. The APC valve control unit 295 is also realized by a computer. The communication I / F unit 296 of the pressure control unit 294 and the communication I / F unit 285 of the controller 280 are connected by a cable 752.

  Communication between vacuum pump 246, boat rotation mechanism 267, boat elevator 115, mass flow controllers 312, 322, 332, 512, 522, 532, high frequency power supply 270, cassette stage 114, cassette transfer device 118, wafer transfer device 125 and controller 280 The I / F unit 285 is connected by cables 753, 754, 755, 756, 757, 758, 759, 760, 761, 762, 781, 782, and 783, respectively.

  The valve control unit 299 includes valves 313, 314, 323, 333, 513, 523, 533, 612, 622, 632 and valves 313, 314, 323, 333, 513, 523, 533, 612, 622, which are air valves. And an electromagnetic valve group 298 that controls the supply of air to 632. The electromagnetic valve group 298 includes electromagnetic valves 297 corresponding to the valves 313, 314, 323, 333, 513, 523, 533, 612, 622, and 632, respectively. The electromagnetic valve group 298 and the communication I / F unit 285 of the controller 280 are connected by a cable 763.

  As described above, the mass flow controllers 312, 322, 332, 512, 522, 532, the valves 313, 314, 323, 333, 513, 523, 533, 612, 622, 632, the APC valve 243, the heating power source 250, Each member such as the temperature sensor 263, the pressure sensor 245, the vacuum pump 246, the boat rotation mechanism 267, the boat elevator 115, and the high frequency power source 270 is connected to the controller 280. The controller 280 controls the orientation of the cassette 110 by the cassette stage 114, controls the transfer operation of the cassette 110 by the cassette transfer device 118, controls the transfer operation of the wafer 200 by the wafer transfer device 125, mass flow controllers 312, 322, 332, 512, 522, 532 flow rate control, valves 313, 314, 323, 333, 513, 523, 533, 612, 622, 632 open / close operation control, APC valve 243 open / close control, and opening based on pressure information from pressure sensor 245 Pressure control via the adjustment operation, temperature control via the power supply amount adjustment operation from the heating power source 250 to the heater 207 based on temperature information from the temperature sensor 263, control of the high frequency power supplied from the high frequency power source 270, vacuum Start / stop control of pump 246, baud Rotation speed adjustment control of the rotation mechanism 267, which is elevating operation control and the like of the boat elevator 115 to carry out respectively.

  Next, an example of a manufacturing process of a semiconductor device (device) that manufactures a large scale integrated circuit (LSI) using the above-described substrate processing apparatus will be described. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 280.

  An LSI is manufactured through an assembly process, a test process, and a reliability test process after performing a wafer process for processing on a silicon wafer. The wafer process is divided into a substrate process in which processing such as oxidation and diffusion is performed on a silicon wafer and a wiring process in which wiring is formed on the surface. In the wiring process, cleaning, heat treatment, film formation, etc. are performed mainly in the lithography process. Repeatedly. In the lithography process, a resist pattern is formed, and the lower layer of the pattern is processed by etching using the pattern as a mask.

Next, an example in which an amorphous silicon nitride film is formed on a GST (GeSbTe) film formed on the surface of the wafer 200 in the substrate process or the wiring process using the substrate processing apparatus 101 will be described.

  In a conventional CVD method or ALD method, for example, in the case of a CVD method, a plurality of types of gases including a plurality of elements constituting a film to be formed are supplied simultaneously, and in the case of an ALD method, a film to be formed is formed. A plurality of types of gases containing a plurality of elements are supplied alternately. Then, a silicon oxide film (SiO film) or a silicon nitride film (SiN film) is formed by controlling processing conditions such as supply flow rate, supply time, and plasma power during supply. In these techniques, for example, when a SiO film is formed, the composition ratio of the film is O / Si≈2 which is a stoichiometric composition, and when a SiN film is formed, for example, the composition ratio of the film is the stoichiometric amount. The supply conditions are controlled for the purpose of satisfying the theoretical composition N / Si≈1.33.

  On the other hand, it is possible to control the supply conditions for the purpose of setting the composition ratio of the film to be formed to a predetermined composition ratio different from the stoichiometric composition. That is, the supply conditions are controlled for the purpose of making at least one element out of the plurality of elements constituting the film to be formed more excessive than the other elements with respect to the stoichiometric composition. It is also possible to perform film formation while controlling the ratio of a plurality of elements constituting the film to be formed as described above, that is, the composition ratio of the film. Hereinafter, a sequence example in which a silicon oxide film having a stoichiometric composition is formed by alternately supplying a plurality of types of gases containing different types of elements by the ALD method will be described.

Here, silicon (Si) is used as the first element, nitrogen (N) is used as the second element, DCS (dichlorosilane), which is a silicon-containing raw material, is used as a raw material containing the first element, and a reaction containing the second element is performed. An example in which an amorphous silicon nitride film is formed on a GST (GeSbTe) film formed on the wafer 200 using NH 3 (ammonia), which is a nitrogen-containing gas, will be described with reference to FIGS. FIG. 5 is a flowchart for explaining the manufacturing process of the amorphous silicon nitride film. FIG. 6 is a timing chart for explaining the manufacturing process of the amorphous silicon nitride film.

  First, the heating power supply 250 for supplying power to the heater 207 is controlled to cause the inside of the processing chamber 201 to have a temperature of 400 ° C. or lower, more preferably 350 ° C. or lower, which is the DCS self-decomposition temperature, for example, 300 ° C. Keep at such a temperature.

  Thereafter, a plurality of (100) wafers 200 on which the GST film is formed are loaded into the boat 217 (wafer charge) (step S201). The wafer 200 having a diameter of 300 mm was used.

  Thereafter, the vacuum pump 246 is started. Further, the furnace port shutter 147 (see FIG. 1) is opened. 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) (step S202). In this state, the seal cap 219 seals the lower end of the reaction tube 203 via the O-ring 220. Thereafter, the boat 217 is rotated by the boat driving mechanism 267 to rotate the wafer 200.

  Thereafter, the APC valve 243 is opened, and the vacuum pump 246 is evacuated so that the inside of the processing chamber 201 has a desired pressure (degree of vacuum). When the temperature of the wafer 200 reaches 300 ° C. and the temperature is stabilized (step S203). ), The next steps are sequentially executed while the temperature in the processing chamber 201 is kept at 300 ° C.

  At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the opening degree of the APC valve 244 is feedback-controlled based on the measured pressure (pressure adjustment). Further, the processing chamber 201 is heated by the heater 207 so as to have a desired temperature. At this time, the power supply from the heating power supply 250 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 (temperature adjustment).

(Preprocessing)
Next, as a pretreatment, N ₂ that is not activated by plasma is supplied, and then the residual gas is removed.

(N ₂ supply not activated by plasma: step S211)
In step S204, N ₂ is supplied from the carrier gas supply pipes 501, 502, and 503. The valve 313 is closed, the valve 513 is opened, and N ₂ is supplied from the carrier gas supply pipe 510. The flow rate of N ₂ is adjusted by the mass flow controller 512. The valve 323 is closed, the valve 523 is opened, and N ₂ is supplied from the carrier gas supply pipe 520. The flow rate of N ₂ is adjusted by the mass flow controller 522. The valve 333 is closed, the valve 533 is opened, and N ₂ is supplied from the carrier gas supply pipe 530. The flow rate of N ₂ is adjusted by the mass flow controller 532. Note that high-frequency power is not applied from the high-frequency power source 270 between the rod-shaped electrode 471 and the rod-shaped electrode 472 and between the rod-shaped electrode 481 and the rod-shaped electrode 482, so that N ₂ is supplied in a state where it is not activated by plasma.

(Residual gas removal: Step S213)
In step S213, residual N ₂ is removed from the processing chamber 201. The valve 513 of the carrier gas supply pipe 510 is closed, the valve 523 of the carrier gas supply pipe 520 is closed, the valve 533 of the carrier gas supply pipe 530 is closed, and the supply of N ₂ to the processing chamber 201 is stopped. At this time, the APC valve 243 of the exhaust pipe 231 is fully opened, and the inside of the processing chamber 201 is exhausted to 20 Pa or less by the vacuum pump 246, and residual N ₂ remaining in the processing chamber 201 is removed from the processing chamber 201.

(Amorphous silicon nitride film formation)

Next, a silicon nitride film forming step for forming an amorphous silicon nitride film by supplying DCS gas and NH ₃ gas into the processing chamber 201 is performed. In the silicon nitride film forming process, the following four steps (S231 to S237) are sequentially repeated. In this embodiment mode, a silicon nitride film is formed using an ALD method.

(DCS supply: Step S231)
In step S <b> 231, DCS is supplied into the processing chamber 201 from the gas supply pipe 310 and the nozzle 410 of the gas supply system 301.

With the valve 313 closed and the valve 314 opened, the flow rate of DCS is adjusted by the mass flow controller 312 and supplied to the gas reservoir 315 and stored in the gas reservoir 315. When a predetermined amount is stored in the gas reservoir 315, the valve 314 is closed and the DCS is confined in the gas reservoir 315. In the gas reservoir 315, DCS is accumulated so that the pressure is 10 times or more of the pressure in the processing chamber 201, for example, 13000 Pa or more. In addition, the apparatus is configured so that the conductance between the gas reservoir 315 and the processing chamber 201 is 1.5 × 10 ⁻³ m ³ / s or more. Considering the ratio between the volume of the processing chamber 201 and the volume of the required gas reservoir 315, the volume of the gas reservoir 315 is preferably 100 to 300 cc when the volume of the processing chamber 201 is 100 l. The volume ratio of the gas reservoir 315 is preferably 1/1000 to 3/1000 times the volume of the processing chamber 201. In the present embodiment, the volume of the gas reservoir 315 is 180 cc. The process of storing the DCS in the gas reservoir 315 can be initially performed during the residual gas removal process (step S213) described above, and the NH ₃ supply process (step S235) described later is performed after the second cycle. Can be done.

  When the above-described residual gas removal step (step S213) is completed, the APC valve 243 is closed and the exhaust of the processing chamber 201 is stopped. Thereafter, the valve 313 on the downstream side of the gas reservoir 315 is opened. As a result, the DCS stored in the gas reservoir 315 is supplied into the processing chamber 201 at once. At this time, since the APC valve 243 of the exhaust pipe 231 is closed, the pressure in the processing chamber 201 is rapidly increased to about 400 to 500 Pa. The time for supplying DCS was set to 2 to 4 seconds, and then the time for exposure to the increased pressure atmosphere was set to 2 to 4 seconds, for a total of 6 seconds. Further, the heating power source 250 that supplies power to the heater 207 is controlled to keep the inside of the processing chamber 201 at 300 ° C. When the supply of DCS to the processing chamber 201 is completed, the valve 313 is closed, the valve 314 is opened, and the supply of DCS to the gas reservoir 315 is started.

At this time, the gas flowing into the processing chamber 201 is only DCS, and NH ₃ does not exist. Therefore, DCS does not cause a gas phase reaction, and reacts with the surface of the GST film on wafer 200 (chemical adsorption) to form an adsorption layer or Si layer (hereinafter referred to as Si-containing layer) of raw material (DCS). To do. The chemical adsorption layer of DCS includes a discontinuous chemical adsorption layer as well as a continuous adsorption layer of DCS molecules. The Si layer includes a continuous layer composed of Si and a Si thin film formed by overlapping these layers. In addition, the continuous layer comprised by Si may be called Si thin film.

At the same time, when the valve 523 is opened from the carrier gas supply pipe 520 connected to the gas supply pipe 320 and N ₂ (inert gas) flows, the NH ₃ side nozzle 420, the buffer chamber 423, and the gas supply pipe 320 are supplied. It is possible to prevent the DCS from wrapping around. Similarly, when the valve 533 is opened and N ₂ (inert gas) is allowed to flow from the carrier gas supply pipe 530 connected to the gas supply pipe 330 at the same time, the NH ₃ side nozzle 430, the buffer chamber 433 and the gas supply are supplied. It is possible to prevent DCS from entering the tube 330. Note that the flow rate of N ₂ (inert gas) controlled by the mass flow controllers 522 and 532 may be small in order to prevent the DCS from wrapping around.

  In the ALD apparatus, the gas is adsorbed on the surface of the base film. The amount of gas adsorption is proportional to the gas pressure and the gas exposure time. Therefore, in order to adsorb a desired amount of gas in a short time, it is necessary to increase the gas pressure in a short time. In this respect, in this embodiment, since the DCS accumulated in the gas reservoir 315 is instantaneously supplied after the APC valve 243 is closed, the DCS pressure in the processing chamber 201 can be rapidly increased. It is possible to instantaneously adsorb a desired amount of gas.

(Residual gas removal: Step S233)
In step S233, residual gas such as residual DCS is removed from the processing chamber 201. The valve 313 of the gas supply pipe 310 is closed, and the supply of DCS to the processing chamber 201 is stopped. At this time, the APC valve 243 of the exhaust pipe 231 is fully opened and the inside of the processing chamber 201 is exhausted to 20 Pa or less by the vacuum pump 246, and residual gas such as residual DCS remaining in the processing chamber 201 is removed from the processing chamber 201. To do. At this time, when an inert gas such as N _{2 is} supplied from the gas supply pipes 320 and 330 into the processing chamber 201, the effect of removing residual gas such as residual DCS is further enhanced. The residual gas removal step (step S233) is 9 seconds.

(Supply of NH ₃ activated by plasma: step S235)
In step S235, NH ₃ is supplied from the gas supply pipe 320 of the gas supply system 302 into the buffer chamber 423 through the gas supply hole 421 of the nozzle 420, and NH ₃ is supplied from the gas supply pipe 330 of the gas supply system 303 to the nozzle 430. The gas is supplied into the buffer chamber 433 through the gas supply hole 431. At this time, NH ₃ gas supplied into the buffer chamber 423 is plasma-excited 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, and gas is used as active species. The gas is exhausted from the gas exhaust pipe 231 while being supplied into the processing chamber 201 from the supply hole 425. Further, by applying high frequency power from the high frequency power source 270 via the matching unit 271 between the rod electrode 481 and the rod electrode 482, the NH ₃ gas supplied into the buffer chamber 433 is plasma-excited and supplied as active species. The gas is exhausted from the gas exhaust pipe 231 while being supplied into the processing chamber 201 from the hole 435.

The flow rate of NH ₃ is adjusted by the mass flow controller 322 and supplied into the buffer chamber 423 from the gas supply pipe 320, and the flow rate of the NH ₃ is adjusted by the mass flow controller 332 and supplied from the gas supply pipe 330 into the buffer chamber 433. Before supplying NH ₃ to the buffer chamber 423, the valve 323 is closed, the valve 622 is opened, and the NH ₃ is allowed to flow through the valve 622 to the vent line 620. Before being supplied to the buffer chamber 433, the valve 333 is closed. Then, the valve 632 is opened and allowed to flow through the valve 632 to the vent line 630. When supplying NH ₃ to the buffer chamber 423, the valve 622 is closed, the valve 323 is opened, NH ₃ is supplied to the gas supply pipe 320 downstream of the valve 323, and the valve 523 is opened to open the carrier. Gas (N ₂ ) is supplied from the carrier gas supply pipe 520. The flow rate of the carrier gas (N ₂ ) is adjusted by the mass flow controller 522. NH ₃ is mixed and mixed with the carrier gas (N ₂ ) on the downstream side of the valve 323 and supplied to the buffer chamber 423 through the nozzle 420. When NH ₃ is supplied to the buffer chamber 433, the valve 632 is closed and the valve 333 is opened to supply NH ₃ to the gas supply pipe 330 downstream of the valve 333 and the valve 533 is opened to Gas (N ₂ ) is supplied from the carrier gas supply pipe 530. The flow rate of the carrier gas (N ₂ ) is adjusted by the mass flow controller 532. NH ₃ is mixed and mixed with the carrier gas (N ₂ ) on the downstream side of the valve 333 and supplied to the buffer chamber 433 through the nozzle 430.

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, 40 to 100 Pa. The supply flow rate of NH ₃ gas controlled by the mass flow controller 322 is, for example, 3000 sccm. The supply flow rate of NH ₃ gas controlled by the mass flow controller 332 is, for example, 3000 sccm. The time during which the wafer 200 is exposed to the active species obtained by exciting the NH ₃ gas with plasma, that is, the gas supply time is set to 23 seconds, for example. The high-frequency power applied between the rod-shaped electrode 471 and the rod-shaped electrode 472 from the high-frequency power source 270 is set to 50 W, for example, and the high-frequency power applied from the high-frequency power source 270 to the rod-shaped electrode 481 and the rod-shaped electrode 482 is, for example, 50 W. Set to be In addition, the inside of the processing chamber 201 is kept at 300 ° C. by controlling the heating power supply 250 that supplies power to the heater 207.

Incidentally, when the flow NH ₃ gas as the active species by plasma excitation, if, when a state of stopping the evacuation and closing the APC valve 243 provided in the exhaust pipe 231, by plasma-exciting the NH ₃ gas Since the activated active species is deactivated before reaching the wafer 200, and as a result, there is a problem that the reaction with the surface of the wafer 200 does not occur. Therefore, NH ₃ gas is caused to flow as active species by plasma excitation. In this case, the APC valve 243 is opened and the reaction furnace 20 is exhausted.

At this time, the gas flowing in the processing chamber 201 is activated species (NH ₃ plasma) obtained by plasma exciting NH ₃ gas, and no DCS gas is flowing in the processing chamber 201. Therefore, NH ₃ gas does not cause a gas phase reaction became active species, or activated NH ₃ gas, as a first layer formed on the GST layer on the wafer 200 in step S231 Reacts with the silicon-containing layer. As a result, the silicon-containing layer is nitrided and modified into a second layer containing silicon (first element) and nitrogen (second element), that is, a silicon nitride film layer.

At the same time, when the valve 513 is opened from the carrier gas supply pipe 510 connected to the gas supply pipe 310 and N ₂ (inert gas) flows, NH ₃ flows into the nozzle 410 on the DCS side and the gas supply pipe 310. Can be prevented. Note that the flow rate of N ₂ (inert gas) controlled by the mass flow controller 512 may be small in order to prevent the NH ₃ from entering.

When NH ₃ is supplied as an active species by plasma excitation, the upstream valve 314 of the gas reservoir 315 is opened, the downstream valve 313 is closed, and DCS is accumulated in the gas reservoir 315. When a predetermined pressure and a predetermined amount of DCS accumulate in the gas reservoir 315, the upstream valve 314 is also closed, and the DCS is confined in the gas reservoir 315.

(Residual gas removal: Step S237)
In step S237, residual gas such as residual NH ₃ that has not reacted or contributed to oxidation is removed from the processing chamber 201. The valve 323 of the gas supply pipe 320 is closed to stop the supply of NH ₃ to the processing chamber 201, the valve 622 is opened to flow NH ₃ to the vent line 620, and the valve 333 of the gas supply pipe 330 is closed to close the processing chamber 201. to stop the supply of the NH ₃ to flow the NH ₃ to the vent line 630 by opening the valve 632. At this time, the APC valve 243 of the exhaust pipe 231 is fully opened, and the inside of the processing chamber 201 is exhausted to 20 Pa or less by the vacuum pump 246, and residual gas such as residual NH ₃ remaining in the processing chamber 201 is discharged from the processing chamber 201. Exclude. At this time, if an inert gas such as N ₂ is supplied into the processing chamber 201 from the gas supply pipes 320 and 330 that are NH ₃ supply lines, the effect of eliminating residual gas such as residual NH _{3 is} further enhanced. The residual gas removing step (step S237) is 5 seconds.

In this embodiment, while DCS is stored in the gas reservoir 315, NH ₃ gas, which is a necessary step in the ALD method, is supplied as active species by plasma excitation (step S235), and the residual gas Since the removal (step S237) is performed, a special step for accumulating DCS is not required.

  The above steps S231 to S237 are set as one cycle, and at least once (step S239), a silicon nitride film having a predetermined thickness is formed on the GST film on the wafer 200 by using the ALD method. In this embodiment, 500 cycles were performed to form a 350-nm silicon nitride film.

When a film forming process for forming a silicon nitride film having a predetermined thickness is performed, the inside of the processing chamber 201 is purged with an inert gas by exhausting while supplying an inert gas such as N ₂ into the processing chamber 201 ( Gas purge: Step S241). The gas purge is performed by removing the residual gas, closing the APC valve 243 and opening the valves 513, 523, and 533, and supplying the inert gas such as N ₂ into the processing chamber 201, and then the valves 513, It is preferable to close 523 and 533 to stop supplying the inert gas such as N ₂ into the processing chamber 201 and to repeatedly perform evacuation in the processing chamber 201 by opening the APC valve 243.

Thereafter, the boat rotation mechanism 267 is stopped and the rotation of the boat 217 is stopped. Thereafter, the valves 513, 523, and 533 are opened to replace the atmosphere in the processing chamber 201 with an inert gas such as N ₂ (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure). Return: Step S243). Thereafter, the boat cap 115 lowers the seal cap 219 to open the lower end of the reaction tube 203, and the processed wafer 200 is unloaded from the lower end of the reaction tube 203 to the outside of the processing chamber 201 while being supported by the boat 217. (Boat unloading: Step S245). Thereafter, the lower end of the reaction tube 203 is closed by the furnace port shutter 147. Thereafter, the vacuum pump 246 is stopped. Thereafter, the processed wafer 200 is taken out from the boat 217 (wafer discharge: step S247). This completes one film formation process (batch process).

  In this embodiment, a plasma generation structure 429 and a plasma generation structure 439 are provided, and high-frequency power is distributed to the two plasma generation structures and supplied by 50 W each. On the other hand, when the number of plasma generation structures is one, for example, when the plasma generation structure 439 is not provided and only the plasma generation structure 429 is provided, 100 W is supplied to the plasma generation structure 429. FIG. 7 is a diagram showing the relationship between the input high frequency power (W) and the number of generated particles. When only one plasma generation structure is provided, the power supplied to the one plasma generation structure is equal to the input high frequency power (W). However, when two plasma generation structures are provided, The power supplied to each plasma generation structure is half of the input high frequency power (W). Referring to FIG. 7, it can be seen that when two plasma generation structures are provided, the number of particles generated is significantly reduced as compared with the case where only one plasma generation structure is provided. Therefore, by providing two plasma generation structures, the number of generated particles can be greatly reduced, and peeling of the silicon nitride film formed on the GST film can be suppressed or prevented. FIG. 8 shows a typical particle distribution in the surface of the wafer 200 when there is only one plasma generation structure, for example, when the plasma generation structure 439 is not provided and only the plasma generation structure 429 is provided. It can be seen that the particles are biased toward the periphery of the wafer, and are generated from the direction of the plasma generation structure 429 disposed in the vicinity of the periphery of the wafer 200, considering that the wafer 200 is rotated and processed. On the other hand, when the plasma generation structure 429 and the plasma generation structure 439 are provided and high frequency power is distributed and supplied to the two plasma generation structures, particles are not generated.

  When the processing temperature is low, there is a market demand to increase the input amount of high-frequency power from the viewpoint of maintaining the film quality of the formed film. On the other hand, as shown in FIG. 7, the input amount of high-frequency power is increased. There is a problem that many particles are generated. However, as in this embodiment, a plurality of plasma generation structures are provided, and high frequency power is distributed and supplied to a plurality of plasma generation structures. The input power density per volume can be reduced, and as a result, the number of generated particles can be reduced and the adhesion can be improved.

(Second Embodiment)
Next, a second embodiment will be described with reference to FIGS.
In the first embodiment, as pre-processing, N ₂ that has not been activated by plasma is supplied (step S211), and then the residual gas is removed (step S213). In the present embodiment, as pre-processing, The first point is that each step of supplying DCS (step S221), removing residual gas (step 223), supplying NH ₃ not excited by plasma (step S225), and removing residual gas (step 227) is performed at least one cycle. However, the other points are the same. The substrate processing apparatus 101 to be used is the same, and the silicon nitride film forming process is also the same.

The supply of DCS (step S221) is the same as the supply of DCS (step S231) of the first embodiment, and the residual gas removal (step 223) is the residual gas removal (step 223) of the first embodiment. The residual gas removal (step 227) is the same as the step 233), and the residual gas removal (step 237) of the first embodiment is the same. In the NH ₃ supply excited by plasma of the first embodiment (step S235), high frequency power is applied from the high frequency power source 270 between the rod-shaped electrode 471 and the rod-shaped electrode 472, and the rod-shaped electrode 481 and the rod-shaped electrode 482 are connected. The high frequency power is applied from the high frequency power source 270, but the NH ₃ supply (step S225) which is not excited by the plasma of this embodiment is performed between the rod electrode 471 and the rod electrode 472 and between the rod electrode 481 and the rod electrode 482. The point that high frequency power is not applied from the power source 270 is different from the NH ₃ supply (step S235) excited by the plasma of the first embodiment, but the other points are the same.

(Third embodiment)
Next, a third embodiment will be described with reference to FIG.
In the first embodiment, as pre-processing, N ₂ that has not been activated by plasma is supplied (step S211), and then the residual gas is removed (step S213). In the present embodiment, as pre-processing, The point that DCS that is not activated by plasma is supplied (step S215) and then the residual gas is removed (step S217) is different from the first embodiment, but the other points are the same. The substrate processing apparatus 101 to be used is the same, and the silicon nitride film forming process is also the same.

Next, a modification of the first to third embodiments will be described with reference to FIG.
In the first to third embodiments, the first plasma generation mainly including the rod-shaped electrode 471, the rod-shaped electrode 472, the electrode protection tube 451, the electrode protection tube 452, the buffer chamber 423, and the gas supply hole 425 is generated. The structure 429 and the second plasma generation structure 439 mainly composed of the rod-shaped electrode 481, the rod-shaped electrode 482, the electrode protection tube 461, the electrode protection tube 462, the buffer chamber 433 and the gas supply hole 435 are the center of the wafer 200. The exhaust port 230 is also provided on a line passing through the center of the wafer 200 (center of the reaction tube 203), and the gas from the nozzle 410 is provided. The supply hole 411 is also provided on a line passing through the center of the wafer 200 (the center of the reaction tube 203), and the first plasma generation structure 429 and the second plasma are provided. Although the raw structure 439 is provided in the vicinity of the exhaust port 230, in the present modification, the first plasma generation structure 429 and the second plasma generation structure 439 are opposed to each other with the wafer 200 interposed therebetween (180 degrees opposite side). The nozzle 410 is provided point-symmetrically with respect to the center of the wafer 200 and the center of the reaction tube 203, and the nozzle 410 is provided between the exhaust port 230 and the second plasma generation structure 439. Although different from the first embodiment, the other points are the same.

  Also in this modification, a first plasma source mainly composed of a rod-shaped electrode 471, a rod-shaped electrode 472, an electrode protection tube 451, an electrode protection tube 452, a matching unit 271, and a high-frequency power source 270, and mainly a rod-shaped electrode 481. , A rod-shaped electrode 482, an electrode protection tube 461, an electrode protection tube 462, a matching unit 271, and a second plasma source constituted by a high-frequency power source 270. Can be distributed to multiple plasma sources to reduce the input power density per unit volume of high-frequency power, thereby reducing the number of particles generated and improving adhesion. Can do.

  The first plasma generation structure 429 mainly composed of the rod-shaped electrode 471, the rod-shaped electrode 472, the electrode protection tube 451, the electrode protection tube 452, the buffer chamber 423, and the gas supply hole 425, and mainly the rod-shaped electrode 481. The second plasma generation structure 439 configured by the rod-shaped electrode 482, the electrode protection tube 461, the electrode protection tube 462, the buffer chamber 433, and the gas supply hole 435 is opposed to the wafer 200 (180 degrees opposite side). Are provided symmetrically with respect to the center of the wafer 200 and the center of the reaction tube 203, so that the plasma can be more easily supplied from both plasma generation structures to the entire surface of the wafer 200, and more uniformly on the wafer 200. A simple film can be formed.

Next, another modification of the present embodiment will be described with reference to FIG.
In the first embodiment, the gas supply hole 411 of the nozzle 410 is mainly configured by the rod-shaped electrode 471, the rod-shaped electrode 472, the electrode protection tube 451, the electrode protection tube 452, the buffer chamber 423, and the gas supply hole 425. The first plasma generation structure 429, and the second plasma generation structure 439 mainly composed of the rod-shaped electrode 481, the rod-shaped electrode 482, the electrode protection tube 461, the electrode protection tube 462, the buffer chamber 433, and the gas supply hole 435. Are provided symmetrically with respect to a line passing through the center of the wafer 200 (center of the reaction tube 203), and the gas supply hole 411 of the nozzle 410 is also on a line passing through the center of the wafer 200 (center of the reaction tube 203). However, in the present modification, the first plasma generation structure 429 and the second plasma generation structure 439 are arranged at the center (on the opposite side) of the wafer 200. The gas supply hole 411 of the nozzle 410 is not provided on a line passing through the center of the wafer 200 (center of the reaction tube 203). Although different from the first embodiment, the other points are the same.

  Also in this modification, a first plasma source mainly composed of a rod-shaped electrode 471, a rod-shaped electrode 472, an electrode protection tube 451, an electrode protection tube 452, a matching unit 271, and a high-frequency power source 270, and mainly a rod-shaped electrode 481. , A rod-shaped electrode 482, an electrode protection tube 461, an electrode protection tube 462, a matching unit 271, and a second plasma source constituted by a high-frequency power source 270. Can be distributed to multiple plasma sources to reduce the input power density per unit volume of high-frequency power, thereby reducing the number of particles generated and improving adhesion. Can do.

  The first plasma generation structure mainly composed of the rod-shaped electrode 471, the rod-shaped electrode 472, the electrode protection tube 451, the electrode protection tube 452, the buffer chamber 423, and the gas supply hole 425 and mainly the rod-shaped electrode 481, the rod-shaped electrode The second plasma generation structure constituted by the electrode 482, the electrode protection tube 461, the electrode protection tube 462, the buffer chamber 433, and the gas supply hole 435 is relative to a line passing through the center of the wafer 200 (center of the reaction tube 203). Since they are provided in line symmetry, the plasma is easily supplied uniformly from the two plasma generation structures to the entire surface of the wafer 200, and a uniform film can be formed on the wafer 200.

Next, still another modification of the present embodiment will be described with reference to FIG.
In the present modification, the rod-shaped electrode 481 ′, the rod-shaped electrode 482 ′, the electrode protection tube 461 ′, the electrode protection tube 462 ′, the buffer chamber 433 ′, and the gas supply are mainly compared to the other modification shown in FIG. The second plasma generation structure 439 which is configured by the hole 435 ′ and mainly includes the rod-shaped electrode 481, the rod-shaped electrode 482, the electrode protection tube 461, the electrode protection tube 462, the buffer chamber 433, and the gas supply hole 435. The third plasma generation structure 439 ′ is added, and the third plasma generation structure 439 ′ is mainly added to 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 first plasma generation structure 429 configured by the gas supply holes 425 and the center of the wafer 200 and the center of the reaction tube 203 are provided point-symmetrically.

  In this modification, a first plasma source mainly composed of a rod-shaped electrode 471, a rod-shaped electrode 472, an electrode protection tube 451, an electrode protection tube 452, a matching unit 271, and a high-frequency power source 270, and mainly a rod-shaped electrode 481. , A rod-shaped electrode 482, an electrode protection tube 461, an electrode protection tube 462, a matching device 271, a second plasma source constituted by a high-frequency power source 270, and a rod-shaped electrode 481 ′, a rod-shaped electrode 482 ′, Since a third plasma source constituted by the tube 461 ′, the electrode protection tube 462 ′, the matching unit 271 and the high frequency power source 270 is added, the high frequency power is supplied to a plurality of plasma sources as compared with the case of two plasma sources. The power density per unit volume of high-frequency power can be further reduced, and as a result, the number of generated particles can be reduced. Can be reduced, it is possible to further improve the adhesion.

(Fourth embodiment)
Referring to FIG. 15, in the second embodiment, a plasma generation structure 429 including a rod-shaped electrode 471, a rod-shaped electrode 472, an electrode protection tube 451, an electrode protection tube 452, a buffer chamber 423, and a gas supply hole 425, , A rod-shaped electrode 481, a rod-shaped electrode 482, an electrode protection tube 461, an electrode protection tube 462, a buffer chamber 433, and a plasma generation structure 439 including a gas supply hole 435, and the gas supply system includes a gas supply tube 310. In contrast to the gas supply system 301, the gas supply system 302 including the gas supply pipe 320, and the gas supply system 303 including the gas supply pipe 330, the present embodiment does not include the plasma generation structure 439, and has a rod shape. Electrode 471, rod-shaped electrode 472, electrode protection tube 451, electrode protection tube 452, buffer chamber 423 and gas supply hole 425 The second point is that only a plasma generation structure 429 configured by the above is provided, the gas supply system 303 is not provided, the gas supply system 301 including the gas supply pipe 310 and the gas supply system 302 including the gas supply pipe 320 are provided. However, the other points are the same.

In the second embodiment and the present embodiment (fourth embodiment) described above, as pre-processing, DCS supply (step S221), residual gas removal (step 223), and NH not excited by plasma are used. By performing at least one cycle of the _three supply (step S225) and residual gas removal (step 227) steps, the number of generated particles can be reduced, and the adhesion can be improved. As in the second embodiment, it is more effective to reduce the number of generated particles and improve the adhesion by providing two plasma generation structures, but this embodiment includes one plasma generation structure. Even in this case, the number of generated particles can be reduced and the adhesion can be improved.

The principle of pretreatment using NH3 that is not activated by DCS and plasma is considered as follows. When DCS is supplied to a substrate on which GST or a metal film is exposed, a reaction intermediate of metal and Si is formed thinly on the substrate. However, in that case, it is considered that Cl contained in DCS is also adsorbed to the substrate at the same time. When NH 3 is supplied thereto, ammonia chloride is formed and Cl is removed from the film while reacting with Si adsorbed on the substrate to form silicide. At low temperature, NH3 does not form a silicon nitride film unless it is excited by plasma, so that the above effect can be obtained by using NH3 that is not activated by plasma.

(Fifth embodiment)
Referring to FIG. 15, in the third embodiment, a plasma generating structure 429 including a rod-shaped electrode 471, a rod-shaped electrode 472, an electrode protection tube 451, an electrode protection tube 452, a buffer chamber 423, and a gas supply hole 425, , A rod-shaped electrode 481, a rod-shaped electrode 482, an electrode protection tube 461, an electrode protection tube 462, a buffer chamber 433, and a plasma generation structure 439 including a gas supply hole 435, and the gas supply system includes a gas supply tube 310. In contrast to the gas supply system 301, the gas supply system 302 including the gas supply pipe 320, and the gas supply system 303 including the gas supply pipe 330, the present embodiment does not include the plasma generation structure 439, and has a rod shape. Electrode 471, rod-shaped electrode 472, electrode protection tube 451, electrode protection tube 452, buffer chamber 423 and gas supply hole 425 The second point is that only a plasma generation structure 429 configured by the above is provided, the gas supply system 303 is not provided, the gas supply system 301 including the gas supply pipe 310 and the gas supply system 302 including the gas supply pipe 320 are provided. However, the other points are the same.

In the third embodiment and the present embodiment (fifth embodiment) described above, DCS that has not been activated by plasma is supplied as a pretreatment (step S215), and then the residual gas is removed (step S215). By step S217), the number of generated particles can be reduced, and the adhesion can be improved. As in the third embodiment, it is more effective to reduce the number of generated particles and improve the adhesion by providing two plasma generation structures, but this embodiment includes one plasma generation structure. Even in this case, the number of generated particles can be reduced and the adhesion can be improved.
(Sixth embodiment)
The present embodiment will be described with reference to FIGS.
In the first to third embodiments described above, the first plasma mainly composed of the rod-shaped electrode 471, the rod-shaped electrode 472, the electrode protection tube 451, the electrode protection tube 452, the buffer chamber 423, and the gas supply hole 425 is used. The generation structure 429 and the second plasma generation structure 439 mainly composed of the rod-shaped electrode 481, the rod-shaped electrode 482, the electrode protection tube 461, the electrode protection tube 462, the buffer chamber 433, and the gas supply hole 435 include the reaction tube 203. However, in the present embodiment, the plasma generating structure is provided so as to protrude outside the reaction tube 203, but is different from the first to third embodiments, but the other points are the same.

  An elongated rectangular opening 822 is provided on the side wall of the reaction tube 203 from the bottom to the top of the reaction tube, and a plasma forming chamber wall 428 is provided on the outer wall of the reaction tube 203 so as to cover the opening 822. The plasma forming chamber wall 428 has a U-shaped cross section and is formed to be elongated vertically. The plasma forming chamber wall 428 is made of, for example, quartz. A plasma forming chamber 821 is formed in the plasma forming chamber wall 428. The plasma formation chamber 821 communicates with the inside of the reaction tube 203 through the opening 822. The opening 822 is formed to be elongated vertically from the lower side to the upper side of the lowermost part of the plurality of wafers 200 stacked and mounted on the boat 217.

  A nozzle 426 is erected in the inner part of the plasma forming chamber 821 (the part farthest from the center of the reaction tube 203). The lower portion of the nozzle 426 is bent to the inside of the reaction tube 203 at one end, and then protrudes from the tube wall of the reaction tube 203 below the plasma forming chamber wall 428 to the outside of the reaction tube 203, and its end is a gas supply tube. 320 is connected.

  The nozzle 426 is provided so as to rise upward from the lower portion of the inner wall of the reaction tube 203 in the stacking direction of the wafer 200. The upper end of the nozzle 426 is closed. A gas supply hole 427 for supplying gas is provided on the side surface of the nozzle 426 in the stacking direction of the wafer 200 from the lower side to the upper side of the lowermost part of the plurality of wafers 200 stacked and mounted on the boat 217. A plurality are provided along. The gas supply hole 427 opens toward the center of the reaction tube 203. The plurality of gas supply holes 427 have the same opening area and are provided at the same pitch.

  A pair of elongated plasma forming electrodes 473 and 474 are provided on the outer surfaces of both side walls 428a and 428b of the plasma forming chamber wall 428 so as to face each other in the vertical direction. Electrode covers 475 and 476 are provided so as to cover the plasma forming electrodes 473 and 474, respectively. An inert gas purge mechanism is provided in the electrode covers 475 and 476 for filling or purging an inert gas such as nitrogen to keep the oxygen concentration sufficiently low to prevent oxidation of the plasma forming electrodes 473 and 474. .

  The plasma forming electrode 473 is connected to the high frequency power source 270 via the matching unit 271, and the plasma forming electrode 474 is connected to the ground 272 that is a reference potential. The first plasma generation structure 820 is mainly configured by the plasma forming electrodes 473 and 474, the plasma forming chamber wall 428, the plasma forming chamber 821, the opening 822, the nozzle 426, and the gas supply hole 427. The plasma forming electrodes 473 and 474, the matching unit 271 and the high-frequency power source 270 mainly constitute a first plasma source as a plasma generator (plasma generator).

  As a result of the configuration described above, gas is supplied between the plasma forming electrodes 473 and 474 from the gas supply hole 427 of the nozzle 426 provided in the inner part of the plasma forming chamber 821, and between the plasma forming electrodes 473 and 474. Plasma is generated in the plasma generation region and flows while diffusing toward the center of the reaction tube 203 through the opening 822.

  On the side wall of the reaction tube 203, an elongated rectangular opening 832 extending from the bottom to the top of the reaction tube is provided, and a plasma forming chamber wall 438 is provided on the outer wall of the reaction tube 203 so as to cover the opening 832. The plasma forming chamber wall 438 has a U-shaped cross section and is elongated vertically. The plasma forming chamber wall 438 is made of, for example, quartz. A plasma forming chamber 831 is formed in the plasma forming chamber wall 438. The plasma forming chamber 831 communicates with the inside of the reaction tube 203 through the opening 832. The opening 832 is formed to be elongated vertically from the lower side to the upper side of the lowermost part of the plurality of wafers 200 stacked and mounted on the boat 217.

  A nozzle 436 is erected in the inner part of the plasma forming chamber 831 (the part farthest from the center of the reaction tube 203). The lower part of the nozzle 436 is bent to the inside of the reaction tube 203 at one end, and then protrudes from the tube wall of the reaction tube 203 below the plasma forming chamber wall 438 to the outside of the reaction tube 203, and its end is a gas supply tube. 330 is connected.

  The nozzle 436 is provided so as to rise upward from the lower portion of the inner wall of the reaction tube 203 in the stacking direction of the wafer 200. The upper end of the nozzle 436 is closed. A gas supply hole 437 for supplying gas is provided on the side surface of the nozzle 436 in the stacking direction of the wafers 200 from the lower side to the upper side of the lowermost part of the plurality of wafers 200 stacked and mounted on the boat 217. A plurality are provided along. The gas supply hole 437 opens toward the center of the reaction tube 203. The plurality of gas supply holes 437 have the same opening area and are provided at the same pitch.

  A pair of elongated plasma forming electrodes 483 and 484 are provided on the outer surfaces of both side walls 438a and 438b of the plasma forming chamber wall 438 so as to face each other in the vertical direction. Electrode covers 485 and 486 are provided to cover the plasma forming electrodes 483 and 484, respectively. An inert gas purge mechanism is provided in the inside of the electrode covers 485 and 486 for filling or purging with an inert gas such as nitrogen to keep the oxygen concentration sufficiently low to prevent oxidation of the plasma forming electrodes 483 and 484. .

  The plasma forming electrode 483 is connected to the high frequency power source 270 via the matching unit 271, and the plasma forming electrode 484 is connected to the ground 272 that is a reference potential. The second plasma generation structure 830 is mainly configured by the plasma forming electrodes 483 and 484, the plasma forming chamber wall 438, the plasma forming chamber 831, the opening 832, the nozzle 436 and the gas supply hole 437. The plasma forming electrodes 483 and 484, the matching unit 271 and the high frequency power source 270 mainly constitute a second plasma source as a plasma generator (plasma generating unit).

  As a result of the above configuration, gas is supplied between the plasma forming electrodes 483 and 484 from the gas supply hole 437 of the nozzle 436 provided in the inner part of the plasma forming chamber 831, and between the plasma forming electrodes 483 and 484. Plasma is generated in the plasma generation region and flows while diffusing toward the center of the reaction tube 203 through the opening 832.

  Remote plasma is also generated by the plasma generation structures 820 and 830 having the above-described configuration. That is, radicals generated in the plasma generation structures 820 and 830 are not deactivated until they reach the entire surface of the wafer 200 in the processing chamber 201, and ions generated in the plasma generation structures 820 and 830 are applied to the wafer 200 in the processing chamber. Not reachable to do damage.

  When the plasma generation structures 820 and 830 are provided to protrude outside the reaction tube 203 as in the present embodiment, the buffer chambers 423 and 433 are provided inside the reaction tube 203 as in the first embodiment. Compared to the case, the distance between the outer periphery of the wafer 200 and the inner peripheral surface of the reaction tube 203 can be made closer.

  In the present embodiment, the first plasma source mainly composed of the plasma forming electrodes 473 and 474, the matching unit 271 and the high frequency power source 270, and mainly the plasma forming electrodes 483 and 484, the matching unit 271 and the high frequency power source. Since the second plasma source configured by 270 is provided, a sufficient amount of plasma can be generated even when the high-frequency power supplied to each plasma source is small as compared with the case of one plasma source. . Therefore, when the wafer 200 is processed using plasma, damage to the wafer 200 and a film to be formed can be reduced, and the processing temperature of the wafer 200 can be lowered.

  Further, the first plasma generation structure 820 mainly composed of the plasma forming electrodes 473 and 474, the plasma forming chamber wall 428, the plasma forming chamber 821, the opening 822, the nozzle 426 and the gas supply hole 427, and mainly the plasma The second plasma generation structure 830 including the formation electrodes 483 and 484, the plasma formation chamber wall 438, the plasma formation chamber 831, the opening 832, the nozzle 436 and the gas supply hole 437 is formed at the center of the wafer 200 (the center of the reaction tube 203 ) Is provided symmetrically with respect to the line passing through (), it becomes easy to supply plasma uniformly from the two plasma generation structures to the entire surface of the wafer 200, and a uniform film can be formed on the wafer 200.

  Further, since the exhaust port 230 is also provided on a line passing through the center of the wafer 200 (the center of the reaction tube 203), the plasma is easily supplied uniformly over the entire surface of the wafer 200, and a uniform film is formed on the wafer 200. Can be formed. Further, since the gas supply hole 411 of the nozzle 410 is also provided on a line passing through the center of the wafer 200 (the center of the reaction tube 203), the source gas is easily supplied uniformly over the entire surface of the wafer 200. A more uniform film on 200 can be formed.

Also in the substrate processing apparatus having the structure of the present embodiment, as a pretreatment described with reference to FIG. 5, N ₂ that is not activated by plasma is supplied (step S211), and then the residual gas is removed ( Step S213), and thereafter, a silicon nitride film is formed (Steps S231 to S237), and DCS supply (Step S221) and residual gas removal (Step 223) are performed as pre-processing described with reference to FIG. The NH ₃ supply (step S225) and residual gas removal (step 227) that are not excited by plasma are performed at least one cycle, and then a silicon nitride film is formed (steps S231 to S237). As a pretreatment described with reference to FIG. 11, DCS that has not been activated by plasma is supplied (step S215). , Then, to remove the residual gas (step S217), then, a silicon nitride film (step S231～S237) processing methods can be applied, to reduce the number of particles generated can be improved adhesion.

(Seventh embodiment)
Referring to FIG. 18, in the sixth embodiment, a plasma generation structure 820 including an electrode 473, an electrode 474, an electrode cover 475, an electrode cover 476, a plasma formation chamber 821 and an opening 822, an electrode 483, and an electrode 484, an electrode cover 485, an electrode cover 486, a plasma generation chamber 831 and a plasma generation structure 830 including an opening 832, and a gas supply system includes a gas supply system 301 including a gas supply pipe 310, and a gas supply pipe 320. In contrast to the gas supply system 303 provided with the gas supply system 302 and the gas supply pipe 330 provided in this embodiment, the present embodiment does not include the plasma generation structure 820, and includes the electrode 483, the electrode 484, the electrode cover 485, and the electrode. A plasma generating structure constituted by a cover 486, a plasma forming chamber 831 and an opening 832. Although only 830 is provided, the gas supply system 303 is not provided, the gas supply system 301 is provided with the gas supply pipe 310, and only the gas supply system 302 is provided with the gas supply pipe 320 is different from the sixth embodiment. The other points are the same.

In the substrate processing apparatus having the structure of the present embodiment, as preprocessing described with reference to FIG. 9, DCS supply (step S221), residual gas removal (step 223), and NH ₃ that is not excited by plasma. Each process of supply (step S225) and residual gas removal (step 227) is performed for at least one cycle, and then a silicon nitride film is formed (steps S231 to S237). The processing method described above with reference to FIG. As a process, DCS that is not activated by plasma is supplied (step S215), and then the residual gas is removed (step S217), and then a silicon nitride film is formed (steps S231 to S237), and a processing method can be applied. The number of generated particles can be reduced and the adhesion can be improved.

  In each of the above embodiments, the case where the ALD method is used has been described as an example. However, even when the CVD method is used, by providing a plurality of plasma sources, high-frequency power can be distributed, and one plasma source is provided. Compared to the case, the high-frequency power supplied to each plasma source can be reduced, and the generation of particles can be suppressed when forming a film on the metal film on the wafer 200 using plasma, improving the adhesion of the formed film. it can.

In each of the above embodiments, an example in which an amorphous silicon nitride film is formed on a GST film has been described . However, even when an amorphous silicon nitride film is formed on a metal film that is a film other than the GST film, The embodiment can be applied. Examples of metal films that can be suitably applied include Ti, TiN, TiSi, W, WN, WSi, Co, CoSi, Al, AlSi, Cu, and alloys thereof.

  In each of the above embodiments, a CCP (Capacitively Coupled Plasma) type high frequency power supply is used. However, the same effect can be obtained even if an ICP (Inductively Coupled Plasma) type high frequency power supply is used.

(Preferred embodiment of the present invention)
Hereinafter, preferred embodiments of the present invention will be additionally described.

(Appendix 1)
According to a preferred aspect of the present invention,
A processing chamber for processing the substrate;
One or more buffer chambers partitioned from the processing chamber and having a gas supply port that opens to the processing chamber;
A first processing gas supply system for supplying a first processing gas to the processing chamber;
A second processing gas supply system capable of supplying a second processing gas to the one or more buffer chambers;
A power supply that outputs high-frequency power;
An electrode for plasma generation that activates the second processing gas inside the buffer chamber by applying high-frequency power from the power source;
A substrate having a metal film formed on the surface is exposed to the first processing gas and the second processing gas in a state where high-frequency power is not applied to the electrode, and the first film is formed on the metal film. After forming, the substrate on which the first film is formed is exposed to the first processing gas and the second processing gas activated by applying high-frequency power to the electrode, and the metal Control means for controlling the first process gas supply system, the power source and the second process gas supply system to form a second film on the film;
A substrate processing apparatus is provided.

(Appendix 2)
According to another preferred aspect of the invention,
A processing chamber for processing the substrate;
One or more buffer chambers partitioned from the processing chamber and having a gas supply port that opens to the processing chamber;
A first processing gas supply system for supplying a first processing gas to the processing chamber;
A second processing gas supply system capable of supplying a second processing gas to the one or more buffer chambers;
A power supply that outputs high-frequency power;
An electrode for plasma generation that activates the second processing gas inside the buffer chamber by applying high-frequency power from the power source;
After the substrate having a metal film formed on the surface is exposed to the first processing gas, the second processing is activated by applying high-frequency power to the first processing gas and the electrode. Control means for controlling the first processing gas supply system, the power source and the second processing gas supply system so as to be exposed to gas and form a film on the metal film;
A substrate processing apparatus is provided.

(Appendix 3)
The substrate processing apparatus of appendix 1 or 2, preferably further comprising an exhaust system for exhausting the processing chamber,
The control means supplies the first processing gas and the activated second processing gas alternately to the processing chamber so as not to mix with each other to form the film on the metal film. Control means for controlling the first processing gas supply system, the power source, and the second processing gas supply system.

(Appendix 4)
Be any of the substrate processing apparatus according to Supplementary Note 1-3, preferably, a surface of the substrate, the metal film or GST film is formed.

(Appendix 5)
The substrate processing apparatus according to appendix 4, preferably, the first processing gas is DCS, and the second processing gas is NH ₃ .

(Appendix 6)
The substrate processing apparatus according to any one of appendices 1 to 5, preferably including a plurality of the buffer chambers.

(Appendix 7)
The substrate processing apparatus according to appendix 5, preferably further comprising a heating system for heating the substrate,
A substrate having a metal film formed on the surface is heated to a temperature lower than the self-decomposition temperature of DCS and exposed to the first processing gas, and then heated to a temperature lower than the self-decomposition temperature of DCS to thereby form the first processing gas. The first processing gas supply system is controlled by the control means so as to be exposed to the second processing gas activated by applying high-frequency power to the electrode and to form a film on the metal film. , Controlling the power source, the second processing gas supply system, and the heating system.

(Appendix 8)
According to still another preferred aspect of the present invention,
Carrying a substrate having a metal film formed on the surface thereof into a processing chamber;
A preprocessing step of preprocessing the substrate by supplying a first processing gas and a second processing gas not activated by plasma excitation to the processing chamber from a plurality of processing gas supply systems independent of each other; ,
The first processing gas and the second processing gas activated by plasma excitation are supplied to the processing chamber from the plurality of processing gas supply systems, respectively, and a predetermined amount is applied onto the preprocessed substrate. A film forming step for forming a film;
Unloading the substrate on which the predetermined film is formed from the processing chamber;
A method of manufacturing a semiconductor device having the above is provided.

(Appendix 9)
According to still another preferred aspect of the present invention,
Carrying a substrate having a metal film formed on the surface thereof into a processing chamber;
A preprocessing step of preprocessing the substrate by supplying a first processing gas to the processing chamber from a plurality of processing gas supply systems independent of each other;
The first processing gas and the second processing gas activated by plasma excitation are supplied to the processing chamber from the plurality of processing gas supply systems, respectively, and a predetermined amount is applied onto the preprocessed substrate. A film forming step for forming a film;
Unloading the substrate on which the predetermined film is formed from the processing chamber;
A method of manufacturing a semiconductor device having the above is provided.

(Appendix 10)
The manufacturing method of a semiconductor device according to appendix 8 or 9, wherein, in the film forming step, the first processing gas and the activated second processing gas are mutually supplied from the plurality of processing gas supply systems. In this film forming process, a predetermined film is formed on the preprocessed substrate by alternately supplying the processing chambers without mixing.

(Appendix 11)
In the method of any one of Supplementary Notes 8 to 10, preferably, a surface of the substrate, the metal film or GST film is formed.

(Appendix 12)
The method for manufacturing a semiconductor device according to appendix 11, wherein the first processing gas is preferably DCS and the second processing gas is NH ₃ .

(Appendix 13)
The method for manufacturing a semiconductor device according to attachment 12, wherein the pretreatment step and the film formation step are preferably performed by heating to a temperature lower than the self-decomposition temperature of DCS.

(Appendix 14)
According to still another preferred aspect of the present invention,
A processing chamber for processing the substrate;
A plurality of buffer chambers that are partitioned from the processing chamber and each have a gas supply port that opens to the processing chamber;
A first processing gas supply system for supplying a first processing gas to the processing chamber;
A second processing gas supply system capable of supplying a second processing gas to each of the plurality of buffer chambers;
A power supply that outputs high-frequency power;
An electrode for generating plasma that activates the second processing gas inside each of the plurality of buffer chambers by applying high frequency power from the power source;
A heating system for heating the substrate;
A substrate having a metal film formed on the surface is activated inside the plurality of buffer chambers by applying high-frequency power to the first processing gas and the electrodes, and the processing is performed from the plurality of buffer chambers. The first processing gas supply is formed so as to form a film on the metal film while being exposed to the second processing gas supplied to the chamber and heating the substrate below the self-decomposition temperature of the first processing gas. Control means for controlling the system, the power source, the second process gas supply system and the heating system;
A substrate processing apparatus is provided.

(Appendix 15)
The substrate processing apparatus of appendix 14, preferably,
The control means supplies the first processing gas and the activated second processing gas alternately to the processing chamber so as not to mix with each other to form the film on the metal film. Control means for controlling the first processing gas supply system, the power source, the second processing gas supply system, and the heating system.

(Appendix 16)
The substrate processing apparatus of appendix 15, preferably further comprising an exhaust system for exhausting the processing chamber,
The control means supplies the first processing gas and the activated second processing gas alternately to the processing chamber so as not to mix with each other to form the film on the metal film. Control means for controlling the first processing gas supply system, the power source, the second processing gas supply system, the heating system, and the exhaust system.

(Appendix 17)
Be any of the substrate processing apparatus according to Supplementary Note 13 to 15, preferably, a surface of the substrate, the metal film or GST film is formed.

(Appendix 18)
The substrate processing apparatus according to appendix 16, wherein the first processing gas is preferably DCS and the second processing gas is NH ₃ .

(Appendix 19)
According to still another preferred aspect of the present invention,
Carrying a substrate having a metal film formed on the surface thereof into a processing chamber;
Exposing a substrate having a metal film formed on a surface to a first processing gas and a second processing gas activated by a plurality of plasma generation structures and supplied from the plurality of plasma generation structures to the processing chamber; Forming a film on the metal film while heating the substrate below the self-decomposition temperature of the first process gas;
Unloading the substrate on which the film is formed from the processing chamber;
A method for manufacturing a semiconductor device is provided.

(Appendix 20)
A method of manufacturing a semiconductor device according to Note 19, preferably, a surface of the substrate, the metal film or GST film is formed.

(Appendix 21)
The manufacturing method of a semiconductor device according to appendix 20, preferably, the first processing gas is DCS, and the second processing gas is NH ₃ .

(Appendix 22)
According to still another preferred aspect of the present invention, there is provided a semiconductor device formed by using any one of the semiconductor device manufacturing methods according to appendices 8 to 13 and 19 to 21.

(Appendix 23)
According to still another preferred aspect of the present invention,
A computer controls a plurality of processing gas supply systems and plasma excitation means independent from each other, and supplies a first processing gas and a second processing gas that is not activated by plasma excitation to the processing chamber, respectively. Then, the first processing gas and the second processing gas activated by plasma excitation are respectively supplied from the plurality of processing gas supply systems to the processing chamber to perform the preprocessing. There is provided a program that functions as control means for controlling to form a predetermined film on the substrate.

(Appendix 24)
According to still another preferred aspect of the present invention,
The computer controls a plurality of processing gas supply systems and plasma excitation means independent from each other, supplies a first processing gas to the processing chamber, pre-processes the substrate, and then from the plurality of processing gas supply systems. Supplying the first processing gas and the second processing gas activated by plasma excitation to a processing chamber, respectively, and controlling to form a predetermined film on the preprocessed substrate; A program that functions as a control means is provided.

(Appendix 25)
According to still another preferred aspect of the present invention,
The computer controls a plurality of processing gas supply systems independent of each other, a heating system for heating the substrate, and a plurality of plasma generation structures, so that the substrate having a metal film formed on the surface is converted into a first processing gas and a plurality of The metal is activated by the plasma generation structure, exposed to a second processing gas supplied from the plurality of plasma generation structures to the processing chamber, and the substrate is heated below the self-decomposition temperature of the first processing gas. A program is provided that functions as control means for controlling the formation of a film on the film.

(Appendix 26)
According to still another preferred aspect of the present invention, there is provided a computer-readable recording medium recording the program according to any one of appendices 23 to 25.

(Appendix 27)
According to still another preferred aspect of the present invention, a substrate processing apparatus including the recording medium according to attachment 26 is provided.

(Appendix 28)
According to still another preferred aspect of the present invention,
By reducing the input power density per unit area of the high-frequency power to be input, a substrate processing apparatus for forming an amorphous silicon nitride film on a metal film with good adhesion at a temperature of 350 ° C. or lower is provided.

(Appendix 29)
According to still another preferred aspect of the present invention,
In a processing chamber where two or more buffer chambers for applying high-frequency power are arranged,
By distributing and supplying high frequency power to be supplied to the two or more buffer chambers,
There is provided a substrate processing apparatus for forming an amorphous silicon nitride film on a metal film with good adhesion at a temperature of 350 ° C. or lower.

(Appendix 30)
According to still another preferred aspect of the present invention,
On the metal film at a temperature of 350 ° C or lower,
DCS irradiation and NH ₃ irradiation without application of high frequency power are repeated at least once or more,
Thereafter, a substrate processing apparatus for forming an amorphous silicon nitride film on a metal film with good adhesion is provided by repeating DCS irradiation and NH ₃ irradiation with application of high-frequency power at least once.

(Appendix 31)
According to still another preferred aspect of the present invention,
DCS irradiation is performed on the metal film at a temperature of 350 ° C. or lower,
Thereafter, by repeatedly performing DCS irradiation and NH ₃ irradiation with application of high-frequency power, a substrate processing apparatus for forming an amorphous silicon nitride film on a metal film with good adhesion is provided.

  While various typical embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Accordingly, the scope of the invention is limited only by the following claims.

101 Substrate processing apparatus 105 Cassette shelf 107 Preliminary cassette shelf 110 Cassette 111 Housing 114 Cassette stage 115 Boat elevator 118 Cassette transport device 118a Cassette elevator 118b Cassette transport mechanism 123 Transfer shelf 125 Wafer transfer mechanism 125a Wafer transfer device 125b Wafer transfer Loading device elevator 125 c Tweezer 128 Arm 134 a Clean unit 134 b Clean unit 147 Furnace port shutter 200 Wafer 201 Processing chamber 202 Processing furnace 203 Reaction tube 207 Heater 210 Bottom plate 211 Top plate 212 Column 217 Boat 218 Boat support 219 Seal cap 220 O-ring 230 Exhaust port 231 Exhaust pipe 232 Exhaust pipe 243 APC valve 245 Pressure sensor 246 Vacuum pump 250 Heating power supply 263 Temperature Capacitors 265 rotating shaft 267 boat rotating mechanism 270 high-frequency power source 271 matching device 272 ground 280 Controller 281 CPU
282 ROM
283 RAM
284 HDD
285, 293, 296 I / F unit 286 Bus 287 Display driver 288 Display 289 Operation input detection unit 290 Operation input unit 291 Temperature control unit 292 Heater control unit 294 Pressure control unit 295 APC valve control unit 297 Electromagnetic valve 298 Electromagnetic valve group 299 Valve control units 301, 302, 303 Gas supply systems 310, 320, 330, 330 ′ Gas supply pipes 312, 322, 332, 512, 522, 532 Mass flow controllers 313, 314, 323, 333, 513, 523, 533, 612 , 622, 632 Valve 315 Gas reservoir 410, 420, 430, 430 ′, 426, 436 Nozzle 411, 421, 431, 431 ′, 427, 437 Gas supply hole 423, 433, 433 ′ Buffer chamber 424, 434, 434 ′ Ba Walls 425, 435, 435 ′ Gas supply holes 428, 438 Plasma forming walls 429, 439, 439 ′ Plasma generating structures 428a, 428b, 438a, 438b Side walls 451, 452, 461, 462, 461 ′, 462 ′ Electrode protection Tubes 471, 472, 481, 482, 481 ′, 482 ′ Rod electrodes 473, 474, 483, 484 Electrodes 475, 476, 485, 486 Electrode covers 501, 502, 503 Carrier gas supply system (inert gas supply system)
510, 520, 530 Carrier gas supply pipes 610, 620, 630 Vent lines 820, 830 Plasma generation structures 821, 831 Plasma formation chambers 822, 832 Open

Claims (8)

A processing chamber for processing the substrate;
One or more buffer chambers partitioned from the processing chamber and having a gas supply port that opens to the processing chamber;
A first processing gas supply system for supplying a first processing gas into the processing chamber,
A second processing gas supply system for supplying to the processing chamber a second process gas through the one or more buffer chamber,
A plasma source for generating plasma inside the buffer chamber and for exciting the second process gas inside the buffer chamber ;
In the processing chamber, the substrate on which the metal film or GST film formed on its surface, the process supplies a process for supplying the first processing gas, the second process gas in the state that has not been plasma-excited And performing the pretreatment for forming the first film on the metal film or the GST film by performing a cycle of alternately performing at least one time, and then performing the pretreatment on the substrate after the pretreatment , On the first film, a cycle of alternately performing a process of supplying the first process gas and a process of supplying the second process gas in a plasma-excited state is performed at least once. so as to form a second layer, the first process gas supply system, and a control unit configured to control the second process gas supply system and said plasma source,
A substrate processing apparatus comprising: A processing chamber for processing the substrate;
One or more buffer chambers partitioned from the processing chamber and having a gas supply port that opens to the processing chamber;
A first processing gas supply system for supplying a first processing gas into the processing chamber,
A second processing gas supply system for supplying to the processing chamber a second process gas through the one or more buffer chamber,
A plasma source for generating plasma inside the buffer chamber and for exciting the second process gas inside the buffer chamber ;
In the processing chamber, the first processing gas is supplied to the substrate on which the metal film or the GST film is formed without supplying the second processing gas to the metal film or the GST film. Then, after the pretreatment is performed, a process for supplying the first process gas to a substrate after the pretreatment and a process for supplying the second process gas in a plasma-excited state are alternately performed. by performing at least once the cycle to be performed, so as to form a film on the metal film or the GST layer the pretreatment is performed, the first process gas supply system, the second process gas Control means configured to control the supply system and the plasma source ;
A substrate processing apparatus comprising: The substrate having the metal film or GST film formed on a surface, and supplying the first processing gas, the cycle for performing the step of supplying a second processing gas in the state that has not been plasma-excited, the alternating Performing a pretreatment for forming a first film on the metal film or the GST film by performing at least once ;
With respect to the substrate after the pretreatment is carried out wherein the step of supplying the first processing gas, at least once a cycle of performing the steps, are alternately supplying the second processing gas while being plasma-excited A step of forming a second film on the first film ;
A method for manufacturing a semiconductor device comprising: Supplying a first process gas to a substrate having a metal film or a GST film on the surface without supplying a second process gas, and pre-treating the metal film or the GST film; ,
A cycle in which the step of supplying the first processing gas and the step of supplying the second processing gas in a plasma-excited state are alternately applied to the substrate after the pretreatment at least once. A step of forming a film on the pretreated metal film or the GST film,
A method for manufacturing a semiconductor device comprising: 5. The method of manufacturing a semiconductor device according to claim 3, wherein, in the pretreatment step and the film formation step, the substrate is heated to a temperature equal to or lower than a self-decomposition temperature of the first processing gas. 6. The metal film according to claim 3, wherein the metal film includes at least one of Ti, TiN, TiSi, W, WN, WSi, Co, CoSi, Al, AlSi, Cu, and alloys thereof. Semiconductor device manufacturing method. A cycle in which a procedure for supplying a first process gas to a substrate having a metal film or a GST film formed on the surface and a procedure for supplying a second process gas that is not plasma-excited are alternately performed. Performing a pretreatment for forming a first film on the metal film or the GST film by performing at least once;
At least one cycle in which the procedure for supplying the first process gas and the procedure for supplying the second process gas in a plasma-excited state are alternately performed on the substrate after the pretreatment is performed. A procedure for forming a second film on the first film;
A program that causes a computer to execute. A procedure in which a first processing gas is supplied to a substrate having a metal film or a GST film formed on the surface without supplying a second processing gas to perform a pretreatment on the metal film or the GST film; ,
At least one cycle in which the procedure for supplying the first process gas and the procedure for supplying the second process gas in a plasma-excited state are alternately performed on the substrate after the pretreatment is performed. Thus, a procedure for forming a film on the metal film or the GST film on which the pretreatment has been performed,
A program that causes a computer to execute.