JP2011134781A - Method of manufacturing semiconductor device, and substrate processing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a semiconductor device and a substrate processing device that shorten a cleaning time to improve productivity. <P>SOLUTION: After a process of forming a thin film on a substrate is repeated in which a first gas capable of depositing a film alone and a second gas incapable of depositing a film alone are supplied into a processing container respectively through a first nozzle portion and a second nozzle portion raised from a lower part to an upper part in the processing container to make the gases flow downward, and exhausted from an exhaust port provided to the lower part of the processing container, a gas obtained by adding at least part of the second gas to a halogen-based gas is supplied into the processing container through a third nozzle portion provided to a ceiling wall of the processing container, and the halogen-based gas is supplied into the processing container through the first nozzle portion to make those gases flow downward therein, and exhausted from the exhaust port to remove deposits sticking in the processing container and the first nozzle portion. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  As a process of manufacturing a semiconductor device (device), there is a process of forming a thin film on a substrate. In this step, for example, a first gas such as dichlorosilane gas is supplied into the processing container through the first nozzle portion that rises from the lower part to the upper part in the processing container, and is flowed downwardly to the lower part of the processing container. A second gas such as ammonia gas or hydrocarbon gas is supplied into the processing vessel through a step of exhausting from the provided exhaust port and a second nozzle portion rising from the lower part to the upper part in the processing vessel. A process of forming a thin film such as a silicon nitride film or a silicon carbonitride film on the substrate is performed by simultaneously or alternately performing a process of flowing toward and exhausting from an exhaust port provided at a lower portion of the processing container.

  In this case, deposits containing silicon nitride, silicon carbonitride, or the like adhere to the processing container, deposits containing silicon or the like adhere to the first nozzle portion, and the thickness of these deposits is a predetermined thickness. If the thickness is exceeded, cracks and peeling may occur in the deposit, and particles may be generated. Therefore, before the thickness of the deposit reaches a critical thickness at which the deposit is cracked or peeled off, the cleaning gas is supplied into the first nozzle part or the processing container and flows downwardly, and the lower part of the processing container A cleaning process is performed to remove deposits exhausted from the exhaust port provided in the processing chamber and adhered to the inside of the processing container and the first nozzle portion.

  However, in this case, the cleaning gas flows from the nozzle portion downward in the processing container in the processing container, so that the cleaning gas does not easily reach the upper part of the processing container that does not follow the flow, that is, the ceiling. For this reason, the ceiling portion may not be sufficiently cleaned. Therefore, when cleaning the inside of the processing container, a method of performing cleaning cyclically by repeating a process of supplying and containing a cleaning gas in the processing container and a process of evacuating the inside of the processing container alternately (hereinafter referred to as “cleaning”) (Referred to as Patent Document 1).

JP 2004-6620 A

  According to the above-mentioned cyclic cleaning, the ceiling portion in the processing container can be sufficiently cleaned. However, since the cyclic cleaning is a method of alternately repeating cleaning gas containment and evacuation, cleaning takes time. Further, the cyclic cleaning cannot sufficiently clean the first nozzle portion. For this reason, when this method is used, it is necessary to separately perform cleaning in the first nozzle portion and cyclic cleaning in the processing container. For example, it is necessary to first clean the inside of the first nozzle part, and after completing the cleaning inside the first nozzle part, it is necessary to separately perform cyclic cleaning inside the processing container. For this reason, the cleaning time becomes longer, the down time of the substrate processing apparatus becomes longer, and this may lead to a decrease in productivity.

  An object of the present invention is to provide a semiconductor device manufacturing method and a substrate processing apparatus that can shorten the cleaning time and improve the productivity.

According to one aspect of the present invention, a film can be deposited by itself through the step of carrying the substrate into the processing container and the first nozzle portion rising from the lower part to the upper part in the processing container. 1 gas (DCS or the like) was supplied into the processing vessel and flowed downward, and exhausted from an exhaust port provided at the lower portion of the processing vessel, and the gas flowed from the lower portion to the upper portion of the processing vessel. Via the second nozzle part, a second gas (C ₃ H ₆ , NH _3, etc.) that cannot deposit a film alone is supplied into the processing vessel and flows downward, and the exhaust port A step of performing a process of forming a thin film on the substrate by simultaneously or alternately performing a step of exhausting, a step of carrying out the processed substrate from the inside of the processing container, and a ceiling wall of the processing container. Through the third nozzle At least a portion of said second gas to a halogen-based gas (F ₂₎ Te (NH ₃₎ adding said halogen-containing gas through the first nozzle portion with the gas supplied into the processing vessel (F ₂₎ Is supplied to the processing container and flows downward, and exhausted from the exhaust port to remove deposits attached to the processing container and the first nozzle part. A method is provided.

According to another aspect of the present invention, a first gas capable of depositing a film alone through a processing container that accommodates a substrate and a first nozzle portion that rises from a lower part to an upper part in the processing container. A film cannot be deposited by itself through a first gas supply system for supplying (DCS or the like) into the processing container and a second nozzle portion rising from the lower part to the upper part in the processing container. A halogen-based gas (F ₂ ) is supplied via a second gas supply system for supplying a gas (C ₃ H ₆ , NH _3, etc.) into the processing container and a third nozzle portion provided on the ceiling wall in the processing container. ) And at least a part of the second gas (NH ₃ ) is supplied into the processing container and the halogen-based gas (F ₂ ) is supplied into the processing container through the first nozzle portion. Cleaning gas supply system An exhaust system that exhausts the inside of the processing container through an exhaust port provided at a lower portion of the processing container, and the first gas is supplied into the processing container through the first nozzle portion and directed downwardly. The exhaust gas is exhausted from the exhaust port, the second gas is supplied into the processing container through the second nozzle portion, and the second gas is flowed downward from the exhaust port and exhausted from the exhaust port, which is performed simultaneously or alternately. As a result, a process for forming a thin film on the substrate is performed, and at least one of the second gases is added to the halogen-based gas (F ₂ ) through the third nozzle portion in the processing container after the processed substrate is carried out. Supplying the gas added with the part (NH ₃ ), supplying the halogen-based gas (F ₂ ) through the first nozzle part, flowing downward, and exhausting from the exhaust port, In the processing vessel and the first nozzle Provided is a substrate processing apparatus having a control unit for controlling the first gas supply system, the second gas supply system, the cleaning gas supply system, and the exhaust system so as to remove deposits adhering to the inside of the tank part. Is done.

  According to the present invention, it is possible to provide a semiconductor device manufacturing method and a substrate processing apparatus that can shorten the cleaning time and improve the productivity.

It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus used suitably by this embodiment, and is a figure which shows a processing furnace part with a vertical cross section. It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus used suitably by this embodiment, and is a figure which shows a processing furnace part by the AA 'line sectional drawing of FIG. It is a figure which shows the timing of the gas supply in the film-forming sequence of this embodiment. It is a figure which shows the timing of the gas supply in the cleaning sequence of this embodiment.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in an embodiment of the present invention, and shows a processing furnace 202 portion in a vertical sectional view. FIG. 2 is a cross-sectional view of the processing furnace shown in FIG. The present invention is not limited to the substrate processing apparatus according to the present embodiment, and can be suitably applied to a substrate processing apparatus having a single wafer type, hot wall type, or cold wall type processing furnace.

  As shown in FIG. 1, the processing furnace 202 includes a heater 207 as a heating means (heating mechanism). The heater 207 has a cylindrical shape and is vertically installed by being supported by a heater base (not shown) as a holding plate.

Inside the heater 207, a process tube 203 as a reaction tube is disposed concentrically with the heater 207. The process tube 203 is made of a heat resistant material such as quartz (SiO ₂ ) or silicon carbide (SiC), and is formed in a cylindrical shape with the upper end closed and the lower end opened. A process chamber 201 is formed in a cylindrical hollow portion of the process tube 203 so that wafers 200 as substrates can be accommodated by a boat 217, which will be described later, in a horizontal posture and aligned in multiple stages in the vertical direction. A reaction vessel (processing vessel) is formed by the process tube 203.

  Below the process tube 203 are a first nozzle 233a as a first gas introduction part, a second nozzle 233b as a second gas introduction part, and a third nozzle 233c as a third gas introduction part. 203 is provided so as to penetrate the lower side wall. A first gas supply pipe 232a, a second gas supply pipe 232b, and a third gas supply pipe 232c are connected to the first nozzle 233a, the second nozzle 233b, and the third nozzle 233c, respectively. Further, a fourth nozzle 233d as a fourth gas introduction part is provided on the ceiling part of the process tube 203, that is, the ceiling wall. A fourth gas supply pipe 232d is connected to the fourth nozzle 233d. As described above, four gas supply pipes are provided in the processing chamber 201 as gas supply paths for supplying a plurality of types, here, four types of processing gases. The first nozzle 233a constitutes a first nozzle part, the second nozzle 233b and the third nozzle 233c constitute a second nozzle part, and the fourth nozzle 233d constitutes a third nozzle part.

  The first gas supply pipe 232a is provided with a mass flow controller 241a as a flow rate controller (flow rate control means) and a valve 243a as an on-off valve in order from the upstream direction. A first inert gas supply pipe 234a that supplies an inert gas is connected to the downstream side of the valve 243a of the first gas supply pipe 232a. The first inert gas supply pipe 234a is provided with a mass flow controller 241c that is a flow rate controller (flow rate control means) and a valve 243c that is an on-off valve in order from the upstream direction. The first nozzle 233a is connected to the tip of the first gas supply pipe 232a. The first nozzle 233a is placed in an arcuate space between the inner wall of the process tube 203 constituting the processing chamber 201 and the wafer 200 along the upper direction from the lower part of the inner wall of the process tube 203, in the loading direction of the wafer 200. It is provided to rise upward. A gas supply hole 248a that is a supply hole for supplying a gas is provided on a side surface of the first nozzle 233a. The gas supply holes 248a have the same opening area from the lower part to the upper part, and are provided at the same opening pitch. A first gas supply system is mainly configured by the first gas supply pipe 232a, the mass flow controller 241a, the valve 243a, and the first nozzle 233a, and mainly by the first inert gas supply pipe 234a, the mass flow controller 241c, and the valve 243c. A first inert gas supply system is configured.

  The second gas supply pipe 232b is provided with a mass flow controller 241b as a flow rate controller (flow rate control means) and a valve 243b as an on-off valve in order from the upstream direction. A second inert gas supply pipe 234b that supplies an inert gas is connected to the downstream side of the valve 243b of the second gas supply pipe 232b. The second inert gas supply pipe 234b is provided with a mass flow controller 241d as a flow rate controller (flow rate control means) and a valve 243d as an on-off valve in order from the upstream direction. The second nozzle 233b is connected to the tip of the second gas supply pipe 232b. The second nozzle 233b is placed in an arc-shaped space between the inner wall of the process tube 203 constituting the processing chamber 201 and the wafer 200, along the upper portion from the lower portion of the inner wall of the process tube 203, in the loading direction of the wafer 200. It is provided to rise upward. A gas supply hole 248b, which is a supply hole for supplying gas, is provided on the side surface of the second nozzle 233b. The gas supply holes 248b have the same opening area from the lower part to the upper part, and are provided at the same opening pitch. A second gas supply system is mainly configured by the second gas supply pipe 232b, the mass flow controller 241b, the valve 243b, and the second nozzle 233b, and mainly by the second inert gas supply pipe 234b, the mass flow controller 241d, and the valve 243d. A second inert gas supply system is configured.

  The third gas supply pipe 232c is provided with a mass flow controller 241e as a flow rate controller (flow rate control means) and a valve 243e as an on-off valve in order from the upstream direction. The third gas supply pipe 232c branches downstream of the mass flow controller 241e and upstream of the valve 243e, and the branched portion is connected to a fourth gas supply pipe 232d described later. A valve 300 which is an on-off valve is provided at a branched portion of the third gas supply pipe 232c. Further, a third inert gas supply pipe 234c for supplying an inert gas is connected to the downstream side of the valve 243e of the third gas supply pipe 232c. The third inert gas supply pipe 234c is provided with a mass flow controller 241f as a flow rate controller (flow rate control means) and a valve 243f as an on-off valve in order from the upstream direction. The third nozzle 233c described above is connected to the tip of the third gas supply pipe 232c. The third nozzle 233c is placed in the arc-shaped space between the inner wall of the process tube 203 constituting the processing chamber 201 and the wafer 200, along the upper portion from the lower portion of the inner wall of the process tube 203, in the loading direction of the wafer 200. It is provided to rise upward. A gas supply hole 248c, which is a supply hole for supplying gas, is provided on the side surface of the third nozzle 233c. The gas supply holes 248c have the same opening area from the lower part to the upper part, and are provided at the same opening pitch. A third gas supply system is mainly configured by the third gas supply pipe 232c, the mass flow controller 241e, the valve 243e, and the third nozzle 233c, and is mainly configured by the third inert gas supply pipe 234c, the mass flow controller 241f, and the valve 243f. A third inert gas supply system is configured.

  The fourth gas supply pipe 232d is provided with a mass flow controller 241g as a flow rate controller (flow rate control means) and a valve 243g as an on-off valve in order from the upstream direction. Further, a fourth inert gas supply pipe 234d that supplies an inert gas is connected to the downstream side of the valve 243g of the fourth gas supply pipe 232d. The fourth inert gas supply pipe 234d is provided with a mass flow controller 241h as a flow rate controller (flow rate control means) and a valve 243h as an on-off valve in order from the upstream direction. The fourth nozzle 233d is connected to the tip of the fourth gas supply pipe 232d. The fourth nozzle 233d is provided along the top from the lower part of the outer wall of the process tube 203, and communicates with the inside of the processing chamber 201 at the top. A gas supply hole 248d, which is a supply hole for supplying gas, is provided at the tip of the fourth nozzle 233d. The gas supply hole 248 d is open downward in the stacking direction of the wafer 200 in the processing chamber 201. A fourth gas supply system is mainly configured by the fourth gas supply pipe 232d, the mass flow controller 241g, the valve 243g, and the fourth nozzle 233d, and is mainly configured by the fourth inert gas supply pipe 234d, the mass flow controller 241h, and the valve 243h. A fourth inert gas supply system is configured.

  A fifth gas supply pipe 232e is connected to the downstream side of the valve 243a of the first gas supply pipe 232a. The fifth gas supply pipe 232e is provided with a mass flow controller 241i as a flow rate controller (flow rate control means) and a valve 243i as an on-off valve in order from the upstream direction. A fifth gas supply system is mainly configured by the fifth gas supply pipe 232e, the mass flow controller 241i, and the valve 243i.

From the first gas supply pipe 232a, for example, dichlorosilane (SiH ₂ Cl ₂ , abbreviated as DCS) gas is supplied as a source gas, that is, a gas containing silicon (silicon-containing gas), a mass flow controller 241a, a valve 243a, and a first nozzle. It is supplied into the processing chamber 201 through 233a. That is, the first gas supply system is configured as a source gas supply system (silicon-containing gas supply system). At the same time, the inert gas may be supplied from the first inert gas supply pipe 234a into the first gas supply pipe 232a via the mass flow controller 241c and the valve 243c.

Further, from the second gas supply pipe 232b, as a gas containing carbon (carbon-containing gas), for example, propylene (C ₃ H ₆ ) gas, which is a hydrocarbon gas, passes through the mass flow controller 241b, the valve 243b, and the second nozzle 233b. Is supplied into the processing chamber 201. That is, the second gas supply system is configured as a carbon-containing gas supply system. At the same time, the inert gas may be supplied from the second inert gas supply pipe 234b into the second gas supply pipe 232b via the mass flow controller 241d and the valve 243d.

Further, from the third gas supply pipe 232c, for example, ammonia (NH ₃ ) gas as nitrogen-containing gas (nitrogen-containing gas) enters the processing chamber 201 via the mass flow controller 241e, the valve 243e, and the third nozzle 233c. Supplied. That is, the third gas supply system is configured as a nitrogen-containing gas supply system. At the same time, the inert gas may be supplied from the third inert gas supply pipe 234c into the third gas supply pipe 232c via the mass flow controller 241f and the valve 243f.

Further, from the fourth gas supply pipe 232d, as a cleaning gas (etching gas), for example, fluorine (F ₂ ) gas, which is a halogen-based gas, passes through the mass flow controller 241g, the valve 243g, and the fourth nozzle 233d, and the processing chamber 201. Supplied in. At the same time, for example, ammonia (NH ₃ ) gas is supplied from the third gas supply pipe 232c as nitrogen-containing gas (nitrogen-containing gas) through the mass flow controller 241e, the valve 300, the fourth gas supply pipe 232d, and the fourth nozzle 233d. Is supplied into the processing chamber 201. Also from the fifth gas supply pipe 232e, as a cleaning gas (etching gas), for example, an F ₂ gas which is a halogen-based gas is passed through the mass flow controller 241i, the valve 243i, the first gas supply pipe 232a, and the first nozzle 233a. It is supplied into the processing chamber 201. That is, the fourth gas supply system, the fifth gas supply system, and a part of the third gas supply system are configured as a cleaning gas supply system. At the same time, the inert gas may be supplied from the fourth inert gas supply pipe 234d into the fourth gas supply pipe 232d via the mass flow controller 241h and the valve 243h. Further, the inert gas may be supplied from the first inert gas supply pipe 234a into the first gas supply pipe 232a via the mass flow controller 241c and the valve 243c.

In this embodiment, DCS gas, C ₃ H ₆ gas, and NH ₃ gas are supplied into the processing chamber 201 from separate nozzles, respectively. For example, C ₃ H ₆ gas and NH ₃ gas are used. May be supplied into the processing chamber 201 from the same nozzle. Further, DCS gas and C ₃ H ₆ gas may be supplied into the processing chamber 201 from the same nozzle. As described above, if the nozzles are shared by a plurality of types of gases, the number of nozzles can be reduced, the apparatus cost can be reduced, and maintenance can be facilitated.

  A gas exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201 is provided below the process tube 203. An exhaust port is formed at the connection between the process tube 203 and the gas exhaust pipe 231. A vacuum pump 246 as an evacuation device is connected to the gas exhaust pipe 231 via a pressure sensor 245 as a pressure detector and an APC (Auto Pressure Controller) valve 242 as a pressure regulator (pressure regulator). Yes. The APC valve 242 is an open / close valve configured to open / close the valve to stop evacuation / evacuation in the processing chamber 201 and to adjust the pressure by adjusting the valve opening. By adjusting the opening degree of the APC valve 242 based on the pressure detected by the pressure sensor 245 while operating the vacuum pump 246, the pressure in the processing chamber 201 becomes a predetermined pressure (degree of vacuum). It is configured to be evacuated. An exhaust system is mainly configured by the gas exhaust pipe 231, the pressure sensor 245, the APC valve 242, and the vacuum pump 246.

  Below the process tube 203, a seal cap 219 is provided as a furnace port lid capable of airtightly closing the lower end opening of the process tube 203. The seal cap 219 is configured to contact the lower end of the process tube 203 from the lower side in the vertical direction. The seal cap 219 is made of a metal such as stainless steel and has a disk shape. An O-ring 220 b is provided on the upper surface of the seal cap 219 as a seal member that comes into contact with the lower end of the process tube 203. On the opposite side of the seal cap 219 from the processing chamber 201, a rotation mechanism 267 for rotating a boat 217 as a substrate holder described later is installed. A rotation shaft 255 of the rotation mechanism 267 passes through the seal cap 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be lifted and lowered in the vertical direction by a boat elevator 115 as a lifting mechanism that is vertically installed outside the process tube 203. The boat elevator 115 is configured such that the boat 217 can be carried into and out of the processing chamber 201 by moving the seal cap 219 up and down.

  A boat 217 as a substrate holder is made of a heat-resistant material such as quartz or silicon carbide, and holds a plurality of wafers 200 in a horizontal posture and in a state where the centers are aligned with each other and held in multiple stages. It is configured. A heat insulating member 218 made of a heat resistant material such as quartz or silicon carbide is provided at the lower part of the boat 217 so that heat from the heater 207 is not easily transmitted to the seal cap 219 side. . The heat insulating member 218 may be constituted by a plurality of heat insulating plates made of a heat resistant material such as quartz or silicon carbide, and a heat insulating plate holder that supports the heat insulating plates in a horizontal posture in multiple stages.

  A temperature sensor 263 as a temperature detector is installed in the process tube 203, and the temperature in the processing chamber 201 is adjusted by adjusting the degree of energization to the heater 207 based on the temperature information detected by the temperature sensor 263. Is configured to have a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the process tube 203, similarly to the first nozzle 233a, the second nozzle 233b, and the third nozzle 233c.

  The controller 280 serving as a control unit (control means) includes mass flow controllers 241a, 241b, 241c, 241d, 241e, 241f, 241g, 241h, 241i, valves 243a, 243b, 243c, 243d, 243e, 243f, 243g, 243h, 243i. 300, a pressure sensor 245, an APC valve 242, a heater 207, a temperature sensor 263, a vacuum pump 246, a rotating mechanism 267, a boat elevator 115, and the like. The controller 280 adjusts the gas flow rate by the mass flow controllers 241a, 241b, 241c, 241d, 241e, 241f, 241g, 241h, 241i, and opens / closes the valves 243a, 243b, 243c, 243d, 243e, 243f, 243g, 243h, 243i, 300 Operation, opening / closing operation of APC valve 242 and pressure adjustment operation based on pressure sensor 245, temperature adjustment of heater 207 based on temperature sensor 263, start / stop of vacuum pump 246, rotation speed adjustment of rotating mechanism 267, boat by boat elevator 115 Control such as lifting / lowering operation 217 is performed.

  Next, as a process of manufacturing a semiconductor device (device) using the processing furnace of the above-described substrate processing apparatus, a method of forming a silicon carbonitride film (SiCN film) on the substrate, and a processing container An example of a method for simultaneously cleaning the inside of the first nozzle portion will be described. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 280.

[Film formation process]
FIG. 3 shows a gas supply timing chart in the film forming sequence according to the present embodiment. In the film forming sequence of the present embodiment, a process of forming a silicon-containing layer (raw material adsorption layer or silicon layer) on a substrate by supplying a source gas containing silicon into a processing container containing the substrate, and a process A step of forming a carbon-containing layer (carbon-containing gas adsorption layer or carbon layer) on the silicon-containing layer formed on the substrate by supplying a carbon-containing gas into the vessel, and a nitrogen-containing gas in the processing vessel , By nitriding the silicon-containing layer and the carbon-containing layer formed on the substrate to form a silicon carbonitride layer, this cycle is repeated a plurality of times as one cycle. A silicon carbonitride film having a predetermined thickness is formed. Here, the raw material adsorption layer (chemical adsorption layer) includes a continuous raw material adsorption layer as well as a discontinuous adsorption layer. The silicon layer includes a continuous layer composed of silicon (Si), a discontinuous layer, and a silicon thin film formed by overlapping these layers. A continuous layer made of silicon may be referred to as a silicon thin film. The carbon-containing gas adsorption layer (chemical adsorption layer) includes a discontinuous layer of carbon-containing gas, and the carbon layer includes a discontinuous layer composed of carbon (C).

  The step of forming a silicon-containing layer (raw material adsorption layer or silicon layer) on the substrate is performed under conditions that cause a CVD (Chemical Vapor Deposition) reaction. A silicon-containing layer is formed. In addition, the layer less than 1 atomic layer means the atomic layer formed discontinuously.

  The step of forming a carbon-containing layer (carbon-containing gas adsorption layer or carbon layer) is performed in a non-plasma atmosphere, and at this time, a carbon-containing layer of less than one atomic layer is adsorbed on the silicon-containing layer. That is, a discontinuous atomic layer of the carbon-containing layer is formed on the silicon-containing layer. In this state, a part of the silicon-containing layer is exposed on the outermost surface of the substrate. Further, the step of forming the silicon carbonitride layer is performed in a non-plasma atmosphere. At this time, the silicon-containing layer of less than one atomic layer to several atomic layers and less than one atomic layer adsorbed on the silicon-containing layer are formed. The carbon-containing layer is nitrided to modify it into a silicon carbonitride layer.

This will be specifically described below. In this embodiment, DCS gas, which is a source gas containing silicon, is used as a source gas, C ₃ H ₆ gas is used as a carbon-containing gas, NH ₃ gas is used as a nitrogen-containing gas, and N ₂ gas is used as an inert gas. An example of forming a silicon carbonitride film (SiCN film) on the substrate by the sequence of FIG. 3 will be described.

  When a plurality of wafers 200 are loaded into the boat 217 (wafer charge), as shown in FIG. 1, the boat 217 holding the plurality of wafers 200 is lifted by the boat elevator 115 and processed in the processing chamber 201. It is carried in (boat loading). In this state, the seal cap 219 seals the lower end of the process tube 203 via the O-ring 220b.

  The processing chamber 201 is evacuated by a vacuum pump 246 so that a desired pressure (degree of vacuum) is obtained. At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 242 is feedback-controlled based on the measured pressure (pressure adjustment step). Further, the processing chamber 201 is heated by the heater 207 so as to have a desired temperature. At this time, the power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution (temperature adjustment step). Subsequently, the wafer 200 is rotated by rotating the boat 217 by the rotation mechanism 267. Thereafter, the following six steps are sequentially executed.

[Step 1]
The valve 243a of the first gas supply pipe 232a and the valve 243c of the first inert gas supply pipe 234a are opened, and DCS gas is passed through the first gas supply pipe 232a and N ₂ gas is passed through the first inert gas supply pipe 234a. N ₂ gas flows from the first inert gas supply pipe 234a and the flow rate is adjusted by the mass flow controller 241c. The DCS gas flows from the first gas supply pipe 232a, and the flow rate is adjusted by the mass flow controller 241a. The flow-adjusted DCS gas is mixed with the flow-adjusted N ₂ gas in the first gas supply pipe 232a, and is heated from the gas supply hole 248a of the first nozzle 233a into the heated processing chamber 201 in a reduced pressure state. While being supplied, the gas is exhausted from the gas exhaust pipe 231 (DCS gas supply process).

  At this time, the APC valve 242 is appropriately adjusted to maintain the pressure in the processing chamber 201 at a pressure lower than atmospheric pressure, for example, in a range of 10 to 1000 Pa. The supply flow rate of the DCS gas controlled by the mass flow controller 241a is, for example, a flow rate in the range of 10 to 1000 sccm. The time for exposing the wafer 200 to the DCS gas is, for example, a time within a range of 1 to 180 seconds. The temperature of the heater 207 is set so that the CVD reaction occurs in the processing chamber 201. That is, the temperature of the heater 207 is set so that the temperature of the wafer 200 becomes a temperature within a range of 300 to 650 ° C., for example. Note that when the temperature of the wafer 200 is less than 300 ° C., DCS is hardly adsorbed on the wafer 200. Further, when the temperature of the wafer 200 exceeds 650 ° C., the CVD reaction becomes strong, and the uniformity tends to deteriorate. Therefore, the temperature of the wafer 200 is preferably 300 to 650 ° C.

  By supplying DCS gas into the processing chamber 201 under the above-described conditions, a silicon-containing layer (DCS adsorption layer or silicon layer) of less than one atomic layer to several atomic layers is formed on the wafer 200 (surface underlayer film). It is formed. Note that DCS is adsorbed on the surface of the wafer 200 and a DCS adsorption layer is formed under a relatively low temperature condition in which the DCS does not self-decompose. Under relatively high temperature conditions where the DCS self-decomposes, silicon molecules are deposited on the wafer 200 to form a silicon layer. When the thickness of the silicon-containing layer formed on the wafer 200 exceeds several atomic layers, the nitriding action in step 5 described later does not reach the entire silicon-containing layer. The minimum value of the silicon-containing layer that can be formed on the wafer 200 is less than one atomic layer. Therefore, the thickness of the silicon-containing layer is preferably less than one atomic layer to several atomic layers.

In addition to DCS, raw materials containing Si include not only inorganic materials such as HCD (hexachlorodisilane, Si ₂ Cl ₆ ), TCS (tetrachlorosilane, SiCl ₄ ), SiH ₄ (monosilane), but also aminosilane-based 4DMAS (tetrakis). Dimethylaminosilane, Si (N (CH ₃ ) ₂ )) ₄ ), 3DMAS (Trisdimethylaminosilane, Si (N (CH ₃ ) ₂ )) ₃ H), 2DEAS (bisdiethylaminosilane, Si (N (C ₂ H ₅₎ ) ₂ ) ₂ H ₂ ), BTBAS (Bicterary butylaminosilane, SiH ₂ (NH (C ₄ H ₉ )) ₂ ) or the like may be used. As the inert gas, a rare gas such as Ar, He, Ne, or Xe may be used in addition to the N ₂ gas.

[Step 2]
After the silicon-containing layer is formed on the wafer 200, the valve 243a of the first gas supply pipe 232a is closed, and the supply of DCS gas is stopped. At this time, the APC valve 242 of the gas exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the remaining DCS gas is removed from the processing chamber 201. At this time, if N ₂ gas is supplied into the processing chamber 201, the effect of removing the remaining DCS gas is further enhanced (residual gas removing step). At this time, the temperature of the heater 207 is set so that the temperature of the wafer 200 is in the range of 300 to 650 ° C. as in the case of supplying the HCD gas.

[Step 3]
After the residual gas in the processing chamber 201 is removed, the valve 243b of the second gas supply pipe 232b and the valve 243d of the second inert gas supply pipe 234b are opened, and the C ₃ H ₆ gas, the second gas is supplied to the second gas supply pipe 232b. flowing _{N 2} gas to the second inert gas supply pipe 234b. The N ₂ gas flows from the second inert gas supply pipe 234b and the flow rate is adjusted by the mass flow controller 241d. The C ₃ H ₆ gas flows from the second gas supply pipe 232b, and the flow rate is adjusted by the mass flow controller 241b. The flow-adjusted C ₃ H ₆ gas is mixed with the flow-adjusted N ₂ gas in the second gas supply pipe 232b, and is heated from the gas supply hole 248b of the second nozzle 233b to be heated in a decompressed processing chamber. The gas is exhausted from the gas exhaust pipe 231 while being supplied into the 201 (C ₃ H ₆ gas supply process). Note that the C ₃ H ₆ gas is supplied into the processing chamber 201 without being activated by plasma.

At this time, the APC valve 242 is appropriately adjusted to maintain the pressure in the processing chamber 201 at a pressure lower than atmospheric pressure, for example, in a range of 50 to 3000 Pa. The supply flow rate of the C ₃ H ₆ gas controlled by the mass flow controller 241b is set to a flow rate in the range of 100 to 10,000 sccm, for example. The time for exposing the wafer 200 to the C ₃ H ₆ gas is, for example, a time within a range of 1 to 180 seconds. The temperature of the heater 207 is set so that the temperature of the wafer 200 becomes a temperature within a range of 300 to 650 ° C., for example. In consideration of the throughput, the temperature in the processing chamber 201 is maintained at the same temperature in Step 1 and Step 3 so that the temperature of the wafer 200 becomes the same as that at the time of supplying the DCS gas in Step 1. It is preferable to set the temperature of the heater 207 so that it does. In this case, in step 1 and step 3, the temperature of the heater 207 is set so that the temperature of the wafer 200, that is, the temperature in the processing chamber 201 becomes a constant temperature in the range of 300 to 650 ° C. Furthermore, it is more preferable to set the temperature of the heater 207 so as to keep the temperature in the processing chamber 201 at the same temperature from step 1 to step 6 (described later). In this case, the temperature of the heater 207 is set so that the temperature in the processing chamber 201 becomes a constant temperature in the range of 300 to 650 ° C. from Step 1 to Step 6 (described later).

By supplying C ₃ H ₆ gas into the processing chamber 201 under the above-described conditions, a carbon-containing layer of less than one atomic layer is formed on the silicon-containing layer of less than one atomic layer to several atomic layers formed on the wafer 200. (Adsorption layer of carbon-containing gas or carbon layer) is formed. That is, a carbon-containing layer of less than one atomic layer is adsorbed on the silicon-containing layer, and a discontinuous atomic layer of the carbon-containing layer is formed on the silicon-containing layer. In this state, a part of the silicon-containing layer is exposed on the outermost surface of the substrate.

As the carbon-containing gas, in addition to propylene (C ₃ H ₆ ) gas, hydrocarbon gas such as ethylene (C ₂ H ₄ ) gas, acetylene (C ₂ H ₂ ) gas may be used.

[Step 4]
After the carbon-containing layer is formed on the silicon-containing layer, the valve 243b of the second gas supply pipe 232b is closed, and the supply of C ₃ H ₆ gas is stopped. At this time, the APC valve 242 of the gas exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the remaining C ₃ H ₆ gas is removed from the processing chamber 201. At this time, if N ₂ gas is supplied into the processing chamber 201, the effect of removing the remaining C ₃ H ₆ gas is further enhanced (residual gas removing step). The temperature of the heater 207 at this time is set to such a temperature that the temperature of the wafer 200 becomes a temperature within the range of 300 to 650 ° C. as in the supply of the C ₃ H ₆ gas.

[Step 5]
After the residual gas in the processing chamber 201 is removed, the valve 243e of the third gas supply pipe 232c and the valve 243f of the third inert gas supply pipe 234c are opened, and the NH ₃ gas and the third inert gas are supplied to the third gas supply pipe 232c. N ₂ gas is allowed to flow through the active gas supply pipe 234c. N ₂ gas flows from the third inert gas supply pipe 234c, and the flow rate is adjusted by the mass flow controller 241f. The NH ₃ gas flows from the third gas supply pipe 232c and the flow rate is adjusted by the mass flow controller 241e. The NH ₃ gas whose flow rate has been adjusted is mixed with the N ₂ gas whose flow rate has been adjusted in the third gas supply pipe 232c, and is heated from the gas supply hole 248c of the third nozzle 233c into the heated processing chamber 201 in a reduced pressure state. Are exhausted from the gas exhaust pipe 231 (NH ₃ gas supply step). Note that the NH ₃ gas is supplied into the processing chamber 201 without being activated by plasma.

At this time, the APC valve 242 is appropriately adjusted to maintain the pressure in the processing chamber 201 at a pressure lower than atmospheric pressure, for example, in a range of 50 to 3000 Pa. The supply flow rate of NH ₃ gas controlled by the mass flow controller 241e is, for example, a flow rate in the range of 100 to 10,000 sccm. The time for which the wafer 200 is exposed to the NH ₃ gas is set to a time within a range of 1 to 180 seconds, for example. The temperature of the heater 207 is set so that the temperature of the wafer 200 becomes a temperature within a range of 300 to 650 ° C., for example. Note that, when the NH ₃ gas is activated by heat without being activated by plasma and supplied to the wafer 200, a soft reaction can be caused and nitridation described later can be performed softly.

By supplying NH ₃ gas into the processing chamber 201 under the above-described conditions, a silicon-containing layer of less than one atomic layer to several atomic layers formed on the wafer 200 and one atom formed on the silicon-containing layer are formed. A silicon carbonitride layer (SiCN layer) is formed by nitriding and modifying the carbon-containing layer less than the layer.

As the nitrogen-containing gas, in addition to ammonia (NH ₃ ) gas, hydrazine (N ₂ H ₄ ) gas or the like may be used.

[Step 6]
After the silicon carbonitride layer is formed on the wafer 200, the valve 243e of the third gas supply pipe 232c is closed, and the supply of NH ₃ gas is stopped. At this time, the APC valve 242 of the gas exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the remaining NH ₃ gas is removed from the processing chamber 201. At this time, if N ₂ gas is supplied into the processing chamber 201, the effect of removing the remaining NH ₃ gas is further enhanced (residual gas removing step). The temperature of the heater 207 at this time is set to such a temperature that the temperature of the wafer 200 is in the range of 300 to 650 ° C. as in the case of supplying the NH ₃ gas.

  By repeating steps 1 to 6 described above as one cycle and repeating this cycle a plurality of times, a silicon carbonitride film (SiCN film) having a predetermined thickness can be formed on the wafer 200 (film formation step). Note that a silicon carbonitride film (SiCN film) having a predetermined thickness can be formed on the wafer 200 by simultaneously performing the above-described steps 1, 3, and 5. However, the film forming process is preferably performed cyclically as in the above-described embodiment because the film thickness control, film quality control, and composition control can be performed strictly and accurately.

When forming the silicon carbonitride film having a predetermined thickness, N ₂ gas inside the processing chamber 201 by being evacuated while being supplied into the processing chamber 201 is purged with N ₂ gas (purge process). Thereafter, the atmosphere in the processing chamber 201 is replaced with N ₂ gas, and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure return step).

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

[Cleaning process]
When the film formation is repeated, a deposit containing silicon carbonitride (SiCN) adheres to the inner wall of the process tube 203 as a processing container. Further, a deposit containing silicon (Si) adheres to the inner wall or the like of the first nozzle 233a which is the first nozzle portion. When the thickness of these deposits exceeds a predetermined thickness, the deposits are cracked or peeled, and particles are generated. Therefore, when the thickness of the deposit reaches a predetermined thickness before reaching the critical thickness at which the deposit is cracked or peeled off, cleaning in the process tube 203 and the first nozzle 233a is performed. This will be specifically described below.

FIG. 4 shows a gas supply timing chart in the cleaning sequence according to the present embodiment. In this embodiment, fluorine (F ₂ ) gas, which is a halogen-based gas, is used as the cleaning gas for the first nozzle, and ammonia (NH ₃ ) is added to fluorine (F ₂ ) gas, which is a halogen-based gas, as the cleaning gas for the processing container. The gas added is N ₂ gas as an inert gas, and cleaning in the process tube 203 as a processing container and the inside of the first nozzle 233a as a first nozzle part (DCS nozzle) by the sequence of FIG. An example of simultaneously performing the cleaning will be described.

  An empty boat 217, that is, a boat 217 not loaded with a wafer 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the process tube 203 via the O-ring 220b.

  The processing chamber 201 is evacuated by a vacuum pump 246 so that a desired pressure (degree of vacuum) is obtained. At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 242 is feedback-controlled based on the measured pressure. Further, the processing chamber 201 is heated by the heater 207 so as to have a desired temperature. At this time, the current supply to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. Subsequently, the boat 217 is rotated by the rotation mechanism 254. The boat 217 may not be rotated.

Next, the valve 243g of the fourth gas supply pipe 232d and the valve 243h of the fourth inert gas supply pipe 234d are opened, and F ₂ gas is supplied to the fourth gas supply pipe 232d, and N ₂ gas is supplied to the fourth inert gas supply pipe 234d. Shed. At the same time, the valve 300 of the third gas supply pipe 232c is opened, and NH ₃ gas is caused to flow from the third gas supply pipe 232c into the fourth gas supply pipe 232d. That is, NH ₃ gas is added to the F ₂ gas flowing in the fourth gas supply pipe 232d. The N ₂ gas flows from the fourth inert gas supply pipe 234d and the flow rate is adjusted by the mass flow controller 241h. F ₂ gas flows from the fourth gas supply pipe 232d and the flow rate is adjusted by the mass flow controller 241g. The NH ₃ gas flows from the third gas supply pipe 232c, and the flow rate is adjusted by the mass flow controller 241e. The flow-adjusted F ₂ gas is mixed with the flow-adjusted NH ₃ gas and the flow-adjusted N ₂ gas in the fourth gas supply pipe 232d, and is heated from the gas supply hole 248d of the fourth nozzle 233d. Then, the gas is exhausted from the gas exhaust pipe 231 while being supplied into the processing chamber 201 in a reduced pressure state (F ₂ gas + NH ₃ gas supply step into the processing container). At this time, the valve 243e may be opened at the same time, and NH ₃ gas may be supplied from the third nozzle 233c. If the NH ₃ gas is also supplied from the third nozzle 233c, the NH ₃ gas can be more uniformly distributed throughout the processing chamber 201, and the processing chamber 201 can be more uniformly cleaned. become able to.

At the same time, the valve 243i of the fifth gas supply pipe 232e and the valve 243c of the first inert gas supply pipe 234a are opened, and F ₂ gas is supplied to the fifth gas supply pipe 232a and N ₂ gas is supplied to the first inert gas supply pipe 234a. Shed. N ₂ gas flows from the first inert gas supply pipe 234a and the flow rate is adjusted by the mass flow controller 241c. F ₂ gas flows from the fifth gas supply pipe 232e, and the flow rate is adjusted by the mass flow controller 241i. The flow-adjusted F ₂ gas is mixed with the flow-adjusted N ₂ gas in the first gas supply pipe 232a, and is heated from the gas supply hole 248a of the first nozzle 233a into the heated processing chamber 201 in a reduced pressure state. Is exhausted from the gas exhaust pipe 231 (F ₂ gas supply step into the first nozzle portion).

The F ₂ gas supplied from the first nozzle 233 a into the processing chamber 201 descends from the first nozzle 233 a in the processing chamber 201 and exhausts from the exhaust pipe 231 through the exhaust port in the lower part of the processing chamber 201. Is done. That is, a flow of F ₂ gas from the first nozzle 233a toward the lower part in the processing chamber 201 is generated in the processing chamber 201. At this time, it is difficult for F ₂ gas to reach the ceiling in the processing chamber 201 that is not along the flow. However, in the present embodiment, a nozzle (fourth nozzle 233d) is provided in the ceiling portion in the processing chamber 201, and a gas obtained by adding NH ₃ gas to F ₂ gas is allowed to flow from the ceiling portion. Then, the F ₂ gas and the NH ₃ gas supplied from the fourth nozzle 233d into the processing chamber 201 descend from the ceiling portion of the processing chamber 201 through the processing chamber 201 and pass through the exhaust port at the lower part of the processing chamber 201. The exhaust pipe 231 is exhausted. In other words, a flow of a mixed gas of F ₂ gas and NH ₃ gas is generated in the processing chamber 201 from the ceiling in the processing chamber 201 toward the lower portion in the processing chamber 201. Thereby, it is possible to simultaneously perform the cleaning in the first nozzle 233a and the cleaning in the processing chamber 201. When the F ₂ gas passes through the first nozzle 233a, it comes into contact with a deposit containing silicon (Si) attached to the inner wall of the first nozzle 233a, and the mixed gas of F ₂ gas and NH ₃ gas is in the processing chamber. When passing through 201, it comes into contact with deposits containing silicon carbonitride (SiCN) adhering to the inner wall of process tube 203 and boat 217, and at this time, each deposit is removed by a thermochemical reaction. The deposit containing Si adhering to the inner wall of the first nozzle 233a and the deposit containing SiCN adhering to the inner wall of the process tube 203 or the boat 217 have different etching rates, and the deposit containing SiCN is etched. Hateful. Further, the inner wall surface of the process tube 203 and the surface of the boat 217 have a larger area than the inner wall surface of the first nozzle 233a, and the amount of deposits attached is larger. Therefore, it takes much more time to remove the deposit containing SiCN attached to the inner wall of the process tube 203 or the boat 217 than to remove the deposit containing Si attached to the inner wall of the first nozzle 233a. . Therefore, in the present embodiment, the F ₂ gas is allowed to flow alone into the first nozzle 233a, while a gas obtained by adding NH ₃ gas to the F ₂ gas is allowed to flow into the processing chamber 201. By adding NH ₃ gas to the F ₂ gas, than if the flow F ₂ gas alone, it is possible to increase the etching rate, the deposit comprising SiCN adhered to the inner wall and the boat 217 of process tube 203 The time for removal can be shortened. As a result, the total cleaning time can be shortened.

When the preset cleaning time in the first nozzle 233a has elapsed, the supply of F ₂ gas into the first nozzle 233a is stopped, and the cleaning in the first nozzle 233a is completed. After the cleaning in the first nozzle 233a is completed, the supply of N ₂ gas into the first nozzle 233a is continued. When a preset cleaning time in the processing chamber 201 elapses, the supply of F ₂ gas and NH ₃ gas into the processing chamber 201 is stopped, and the cleaning in the processing chamber 201 is finished. After the cleaning of the processing chamber 201 is completed, the supply of N ₂ gas into the processing chamber 201 is continued to purge with the N ₂ gas in the processing chamber 201, and the processing chamber 201 is changed to N ₂ gas. Replaced.

4 shows an example in which the cleaning in the first nozzle 233a and the cleaning in the processing chamber 201 are started at the same time, and the cleaning in the first nozzle 233a is finished first. That is, the supply of F ₂ gas and NH ₃ gas into the processing chamber 201 is continued even after the cleaning in the first nozzle 233a is completed and the supply of F ₂ gas into the first nozzle 233a is stopped. Then, the inside of the processing chamber 201 is continuously cleaned. When the inside of the processing chamber 201 is continuously cleaned after the cleaning of the first nozzle 233a, the F ₂ gas and NH ₃ gas into the first nozzle 233a are purged in order to purge the inside of the first nozzle 233a after cleaning. In order to prevent overetching due to intrusion of N ₂ , N ₂ gas is continuously supplied into the first nozzle 233a. Also, during the cleaning step, the F ₂ gas from entering the F ₂ other nozzle does not flow gas (second nozzle 233b and the third nozzle 233 c) in the nozzle and continually supplying the N ₂ gas is prevented To do.

The cleaning conditions include, for example, cleaning temperature (processing chamber temperature): 300 to 600 ° C., cleaning pressure (processing chamber pressure): 13300 to 66500 Pa, F ₂ gas supply flow rate (total flow rate): 0.5 to 5 slm, NH ₃ Gas supply flow rate: 0.05 to 1 slm, N ₂ gas supply flow rate (total flow rate): 0.5 to 20 slm are exemplified, and cleaning is performed by keeping each cleaning condition constant at a certain value within each range. Is made. Note that the processing chamber temperature at the time of cleaning can be set to the same temperature as the processing chamber temperature at the time of film formation.

As the cleaning gas, a halogen-based gas (fluorine-based gas) such as nitrogen trifluoride (NF ₃ ) gas or chlorine trifluoride (ClF ₃ ) gas may be used in addition to the F ₂ gas. Further, as a gas to be added to the halogen-based gas such as F ₂ gas, NF ₃ gas, and ClF ₃ gas, hydrogen (H ₂ ) gas or hydrogen fluoride (HF) gas is used in addition to NH ₃ gas. Also good. That is, the cleaning gas for the first nozzle, _{F 2} gas, NF ₃ gas, may be used halogen-based gas such as ClF ₃ gas as cleaning gas for the processing vessel, _{F 2} gas, NF ₃ gas A gas obtained by adding a hydrogen-containing gas such as NH ₃ gas, H ₂ gas, or HF gas to a halogen-based gas such as ClF ₃ gas can be used. In the present embodiment, since the NH ₃ gas used in the film forming process is used as the additive gas added to the halogen-based gas, it is not necessary to separately install (add) a gas line for the additive gas. On the other hand, when H ₂ gas or HF gas is used as the additive gas, it is necessary to separately install a gas line for H ₂ gas or HF gas, which may increase the cost.

After purging with N ₂ gas in the processing chamber 201 and replacing the processing chamber 201 with N ₂ gas, the pressure in the processing chamber 201 is returned to normal pressure. If necessary, before the inside of the processing chamber 201 is replaced with N ₂ gas, the inside of the processing chamber 201 may be purged with NH ₃ in order to remove halogen species remaining in the processing chamber 201 (NH 3 ₃ purge step). In this case, the NH ₃ gas is supplied from the fourth nozzle 233d, but may be supplied from the third nozzle 233c at the same time. Further, if necessary, precoating for depositing the same thin film as the thin film formed in the film forming process, that is, a SiCN film, on the inner wall of the process tube 203 or the boat 217 may be performed (precoat process). Note that the NH ₃ purge step can be performed under the same processing conditions as the cleaning step and the film forming step. The precoat process can be performed under the same processing conditions and sequence as the film forming process.

  Thereafter, the seal cap 219 is lowered by the boat elevator 115, the lower end of the process tube 203 is opened, and the boat 217 is unloaded from the lower end of the process tube 203 to the outside of the process tube 203 (boat unloading). Thereafter, the film forming process is resumed.

According to the present embodiment, when cleaning the inside of the processing chamber 201, the exhaust pipe is supplied while supplying a gas obtained by adding NH ₃ gas to F ₂ gas from the fourth nozzle 233 d provided on the ceiling portion in the processing chamber 201. Since the exhaust gas is exhausted from H.231, the flow of F ₂ gas and NH ₃ gas from the ceiling portion in the processing chamber 201 toward the lower portion in the processing chamber 201 can be formed, and the ceiling portion in the processing chamber 201 can be sufficiently cleaned. It can be carried out. Thereby, there is no need to perform cyclic cleaning, and the cleaning time in the processing chamber 201 can be shortened. In addition, since the cleaning in the first nozzle 233a and the cleaning in the processing chamber 201 can be performed simultaneously in parallel, the cleaning time can be further shortened. Furthermore, cleaning of the processing chamber 201, since the performed using a gas obtained by adding NH ₃ gas to the F ₂ gas, it is possible to increase the etching rate as compared with the case of using the F ₂ gas alone, treatment The cleaning time in the chamber 201 can be further shortened. Note that since the etching rate can be increased, the cleaning temperature can be lowered. Thus, according to the present embodiment, the cleaning time can be greatly shortened, and the productivity of the substrate processing apparatus can be greatly improved.

  Hereinafter, preferred embodiments of the present invention will be additionally described.

According to one aspect of the invention,
Carrying a substrate into a processing container;
A first gas (DCS or the like) capable of depositing a film by itself is supplied into the processing container through the first nozzle portion rising from the lower part to the upper part in the processing container and directed downwardly. The film cannot be deposited by itself through the step of evacuating and exhausting from the exhaust port provided in the lower part of the processing container and the second nozzle part rising from the lower part to the upper part in the processing container. A thin film is formed on the substrate by simultaneously or alternately performing a process of supplying gas (C ₃ H ₆ , NH _3, etc.) into the processing container, flowing it downward, and exhausting it from the exhaust port. A process of performing
Unloading the processed substrate from the processing container;
A gas obtained by adding at least a part of the second gas (NH ₃ ) to the halogen-based gas (F ₂ ) is supplied into the processing container through a third nozzle portion provided on the ceiling wall of the processing container. The halogen-based gas (F ₂ ) is supplied into the processing container through the first nozzle part and flows downward, and exhausted from the exhaust port into the processing container and the first nozzle part. Removing the deposited deposits;
A method of manufacturing a semiconductor device having the above is provided.

  Preferably, in the step of removing the deposit, the third nozzle can be removed even after the removal of the deposit adhering to the first nozzle portion is finished and the supply of the halogen-based gas into the first nozzle portion is stopped. The deposit adhered in the processing chamber is continuously removed by continuing to supply a gas obtained by adding at least a part of the second gas to the halogen-based gas from the section into the processing container. The inert gas is supplied into the first nozzle part.

  Preferably, in the step of removing the deposit, an inert gas is supplied into the second nozzle portion.

According to another aspect of the invention,
Carrying a substrate into a processing container;
A first gas (DCS) capable of depositing a film by itself is supplied into the processing container through the first nozzle rising from the lower part to the upper part in the processing container, and flows downward. A second gas (C that cannot deposit a film by itself through a step of exhausting from an exhaust port provided at a lower portion of the processing vessel and a second nozzle rising from the lower portion to the upper portion of the processing vessel by itself. ₃ H ₆ ) is supplied into the processing vessel and flows downward, and is exhausted from the exhaust port, and the third nozzle rising from the lower part to the upper part in the processing vessel is used alone. A process of supplying a third gas (NH ₃ ), which cannot deposit a film, into the processing vessel, flowing downwardly, and exhausting it from the exhaust port, is performed on the substrate simultaneously or alternately. Thin And performing a process for forming a
Unloading the processed substrate from the processing container;
A gas obtained by adding the third gas (NH ₃ ) to the halogen-based gas (F ₂ ) is supplied into the processing container through a fourth nozzle provided on the ceiling wall of the processing container, and the first nozzle is connected to the processing container. Through which the halogen-based gas (F ₂ ) is supplied into the processing vessel and flows downward, and exhausted from the exhaust port to remove deposits adhering to the processing vessel and the first nozzle. And a process of
A method of manufacturing a semiconductor device having the above is provided.

  Preferably, in the step of removing the deposit, the fourth nozzle is removed even after the removal of the deposit adhering to the first nozzle is finished and the supply of the halogen-based gas into the first nozzle is stopped. The deposit attached to the processing chamber is continuously removed by continuing to supply the gas obtained by adding the third gas to the halogen-based gas into the processing container. An inert gas is supplied into the interior.

  Preferably, in the step of removing the deposit, an inert gas is supplied into the second nozzle and the third nozzle.

According to yet another aspect of the invention,
A processing container for containing a substrate;
A first gas supply system for supplying a first gas (DCS) capable of depositing a film by itself through the first nozzle portion rising from the lower part to the upper part in the processing container;
A second gas (C ₃ H ₆ , NH _3, etc.) by which a film cannot be deposited alone is supplied into the processing container through the second nozzle portion rising from the lower part to the upper part in the processing container. A second gas supply system;
A gas obtained by adding at least a part of the second gas (NH ₃ ) to the halogen-based gas (F ₂ ) is supplied into the processing container through a third nozzle portion provided on the ceiling wall in the processing container. And a cleaning gas supply system for supplying the halogen-based gas (F ₂ ) into the processing container via the first nozzle portion,
A cleaning gas supply system for supplying a cleaning gas into the processing container via a third nozzle part and the first nozzle part provided on a ceiling wall in the processing container;
An exhaust system for exhausting the inside of the processing container through an exhaust port provided in a lower portion of the processing container;
The first gas is supplied into the processing container through the first nozzle part, flows downwardly and is exhausted from the exhaust port, and the second gas is supplied to the processing container through the second nozzle part. The inside of the processing container is supplied to the inside, exhausted from the exhaust port, exhausted through the exhaust port, and simultaneously or alternately to form a thin film on the substrate, and the processed substrate is unloaded. A gas obtained by adding at least a part of the second gas (NH ₃ ) to the halogen-based gas (F ₂ ) is supplied into the halogen-based gas (F ₂ ) through the third nozzle portion, and the halogen-based gas is supplied through the first nozzle portion. (F ₂ ) is supplied, flows downward, and exhausted from the exhaust port to remove deposits adhering to the inside of the processing vessel and the first nozzle part. System, second gas supply system A control unit for controlling the cleaning gas supply system and the exhaust system,
A substrate processing apparatus is provided.

According to yet another aspect of the invention,
A processing container for containing a substrate;
A first gas supply system for supplying a first gas (DCS) capable of depositing a film by itself into the processing container through a first nozzle rising from the lower part to the upper part in the processing container;
A second gas supply system that supplies a second gas (C ₃ H ₆ ) that cannot deposit a film by itself into the processing container through a second nozzle that rises from the lower part to the upper part in the processing container. When,
A third gas supply system that supplies a third gas (NH ₃ ) that cannot be deposited by itself through the third nozzle rising from the lower part to the upper part in the processing container;
A gas obtained by adding the third gas (NH ₃ ) to the halogen-based gas (F ₂ ) is supplied into the processing container through a fourth nozzle provided on the ceiling wall in the processing container, and the first nozzle A cleaning gas supply system for supplying the halogen-based gas (F ₂ ) into the processing container via
An exhaust system for exhausting the inside of the processing container through an exhaust port provided in a lower portion of the processing container;
The first gas is supplied into the processing container through the first nozzle, flows downwardly and is exhausted from the exhaust port, and the second gas is supplied into the processing container through the second nozzle. Supply, flow downward and exhaust from the exhaust port, supply the third gas into the processing vessel via the third nozzle, flow downward and exhaust from the exhaust port, Are simultaneously or alternately performed to form a thin film on the substrate, and the halogen-based gas (F ₂ ) is added to the halogen-based gas (F ₂ ) through the fourth nozzle in the processing container after the processed substrate is unloaded. 3 gas (NH ₃ ) added gas and the halogen-based gas (F ₂ ) is supplied through the first nozzle to flow downward, and exhausted from the exhaust port, In the processing vessel and the first nozzle To remove deposits adhering to the inner, and the first gas supply system, the second gas supply system, the third gas supply system, control unit for controlling the cleaning gas supply system and the exhaust system,
A substrate processing apparatus is provided.

200 Wafer 201 Processing chamber 202 Processing furnace 203 Process tube 207 Heater 231 Gas exhaust pipe 233a First nozzle 233b Second nozzle 233c Third nozzle 233d Fourth nozzle 280 Controller

Claims (2)

Carrying a substrate into a processing container;
A first gas capable of depositing a film by itself is supplied into the processing container through the first nozzle portion rising from the lower part to the upper part in the processing container, and flows downward in the processing container. Exhaust from an exhaust port provided in the lower part of the container, and the second gas that cannot deposit a film by itself through the second nozzle part rising from the lower part to the upper part in the process container. A process of forming a thin film on the substrate by simultaneously or alternately performing a process of supplying into the container and flowing downwards and exhausting from the exhaust port; and
Unloading the processed substrate from the processing container;
A gas obtained by adding at least a part of the second gas to the halogen-based gas is supplied into the processing vessel through a third nozzle portion provided on the ceiling wall of the processing vessel, and is supplied through the first nozzle portion. Supplying the halogen-based gas into the processing container and flowing it downward, exhausting from the exhaust port to remove deposits adhering to the inside of the processing container and the first nozzle part;
A method for manufacturing a semiconductor device, comprising: A processing container for containing a substrate;
A first gas supply system for supplying a first gas capable of depositing a film by itself into the processing container through a first nozzle portion rising from the lower part to the upper part in the processing container;
A second gas supply system for supplying a second gas, which cannot be deposited by itself, into the processing container via the second nozzle portion rising from the lower part to the upper part in the processing container;
A gas obtained by adding at least a part of the second gas to the halogen-based gas is supplied into the processing vessel through a third nozzle portion provided on a ceiling wall in the processing vessel, and is supplied through the first nozzle portion. Cleaning gas supply system for supplying the halogen-based gas into the processing container;
A cleaning gas supply system for supplying a cleaning gas into the processing container via a third nozzle part and the first nozzle part provided on a ceiling wall in the processing container;
An exhaust system for exhausting the inside of the processing container through an exhaust port provided in a lower portion of the processing container;
The first gas is supplied into the processing container through the first nozzle part, flows downwardly and is exhausted from the exhaust port, and the second gas is supplied to the processing container through the second nozzle part. The inside of the processing container is supplied to the inside, exhausted from the exhaust port, exhausted through the exhaust port, and simultaneously or alternately to form a thin film on the substrate, and the processed substrate is unloaded. A gas in which at least a part of the second gas is added to the halogen-based gas is supplied through the third nozzle portion, and the halogen-based gas is supplied through the first nozzle portion and directed downwardly. The first gas supply system, the second gas supply system, and the cleaning gas so as to remove deposits adhering to the inside of the processing container and the first nozzle portion by exhausting the gas from the exhaust port. Supply system A control unit for controlling the fine the exhaust system,
A substrate processing apparatus comprising: