JP2008277785A - Method of manufacturing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a semiconductor device capable of performing a selective growth at a low temperature. <P>SOLUTION: The manufacturing method of a semiconductor device for placing in a processing chamber a substrate having at least a silicon surface and an insulating film surface on a surface; and allowing an epitaxial film to selectively grow only on the silicon surface by using a substrate processing apparatus for heating an atmosphere in the processing chamber and the substrate, using a heating means disposed outside of the processing chamber, includes a substrate carrying-in step of carrying in the substrate into the processing chamber; a pre-processing step of supplying dichlorsilane gas and hydrogen gas into the processing chamber while maintaining a temperature of the substrate and in the substrate processing chamber to a prescribed temperature of 700°C or less, and removing a natural oxide film or impurities formed on the silicon surface; and a substrate carrying-out step of carrying out the substrate to outside of the processing chamber. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method of manufacturing a semiconductor device for forming a film such as silicon or silicon germanium on a silicon substrate.

In general, a silicon substrate is used as a semiconductor substrate, and a technique for selectively growing an epitaxial film only on the silicon surface in a substrate having an insulating film such as a silicon surface and a silicon nitride film has been studied. Note that the selective growth refers to a technique for selectively growing a film only on the surface of silicon.
For example, miniaturization and high performance of MOSFET (Metal-Oxide-Semiconductor-Field-Effect-Transistor) are progressing, but as a problem when forming the source / drain of MOSFET, there is a reduction in contact resistance. As one method for solving this problem, an attempt has been made to selectively grow a silicon epitaxial film on the source / drain.
In addition, by recess-etching the source / drain and selectively growing a silicon epitaxial film doped with C (carbon) or the like having a different lattice constant in the dug source / drain portion, the channel is distorted to increase the transistor. In recent years, technology for improving the performance has attracted attention.

By the way, when a single crystal such as silicon or silicon germanium is selectively grown, it is necessary to remove a natural oxide film and impurities on the substrate before the selective growth process. As such a treatment method, a hydrogen reduction method using H ₂ gas as a reducing gas is used.
However, in order to obtain a sufficient effect by the hydrogen reduction method, it is necessary to perform a reduction treatment at a high temperature of 800 ° C. or higher, and there is a problem that the problem of thermal damage of the substrate element and increase of the thermal budget becomes serious. Further, in the conventional method, it is necessary to perform pre-cleaning with dilute hydrofluoric acid or the like before the reduction treatment, and there is a problem that this takes time.
Accordingly, an object of the present invention is to provide a method for manufacturing a semiconductor device capable of selective growth at a low temperature.

  In order to achieve the above-mentioned object, the present invention places a substrate having at least a silicon surface and an insulating film surface on the inside of a processing chamber, and the atmosphere in the processing chamber by the heating means disposed outside the processing chamber and the A method of manufacturing a semiconductor device in which an epitaxial film is selectively grown only on the silicon surface using a substrate processing apparatus for heating a substrate, the substrate carrying-in step for carrying the substrate into the processing chamber, and the substrate A pretreatment for removing a natural oxide film and impurities formed on the silicon surface by supplying dichlorosilane gas and hydrogen gas into the processing chamber while maintaining the temperature in the substrate processing chamber at a predetermined temperature of 700 ° C. or lower. There is provided a method for manufacturing a semiconductor device including a step and a substrate unloading step of unloading the substrate out of the processing chamber.

According to the present invention, an epitaxial growth film or a growth layer can be formed only on the silicon surface of a substrate having at least a silicon surface and an insulating film surface. Also, the interface between the epitaxial growth film or growth layer and the silicon surface can be cleaned to achieve high quality. Further, since the processing temperature during the cleaning and epitaxial growth of the interface between the silicon surface and the epitaxial growth film or growth layer can be set to 800 ° C. or less, the risk of thermal damage to the substrate element and thermal budget is greatly reduced. . Furthermore, since the etching as the pretreatment before the selective growth can be eliminated, cost reduction is achieved. Further, when a natural oxide film or impurities on the silicon surface is removed by reduction using a silicon-based gas, particularly SiH ₂ Cl ₂ (dichlorosilane gas), a silicon film is formed on the insulating film of the substrate when the processing temperature is high. However, in order to grow an epitaxial film only on the silicon surface of the substrate, it is necessary to prevent the formation of a silicon film or silicon nucleus on the insulating film. However, since the processing temperature when removing the natural oxide film and impurities on the silicon surface can be set to 800 ° C. or lower, it is possible to prevent the formation of the silicon film and the silicon nucleus on the insulating film, and thereafter It is possible to prevent adverse effects of selection and blurring in selective growth.

  In the best mode for carrying out the present invention, as an example, the substrate processing apparatus is configured as a semiconductor manufacturing apparatus that performs processing steps in a method of manufacturing a semiconductor device (IC). In the following description, a case where a vertical apparatus (hereinafter simply referred to as a processing apparatus) that performs oxidation, diffusion processing, CVD processing, or the like is applied to the substrate as the substrate processing apparatus will be described.

FIG. 1 is a perspective view of a substrate processing apparatus applied to the present invention.
As shown in FIG. 1, a substrate processing apparatus 101 of the present invention in which a cassette 110 as a wafer carrier storing a substrate (hereinafter referred to as a wafer) 200 made of silicon or the like is used includes a casing 111. . Below the front wall 111a of the housing 111, a front maintenance port 103 serving as an opening provided for maintenance is opened, and a front maintenance door 104 for opening and closing the front maintenance port 103 is installed. A cassette loading / unloading port (substrate container loading / unloading port) 112 is opened on the front maintenance door 104 so as to communicate between the inside and outside of the casing 111. The cassette loading / unloading port 112 is a front shutter (substrate container loading / unloading port). The opening / closing mechanism 113 is opened and closed. A cassette stage (substrate container delivery table) 114 is installed inside the casing 111 of the cassette loading / unloading port 112. The cassette 110 is carried onto the cassette stage 114 by an in-process carrying device (not shown), and is also carried out from the cassette stage 114. The cassette stage 114 is configured so that the wafer 200 in the cassette 110 is placed in a vertical posture and the wafer loading / unloading port of the cassette 110 faces upward by the in-process transfer device.

A cassette shelf (substrate container mounting shelf) 105 is installed at a substantially lower center in the front-rear direction in the casing 111, and the cassette shelf 105 stores a plurality of cassettes 110 in a plurality of rows and a plurality of rows. The wafers 200 in the cassette 110 are arranged so that they can be taken in and out. The cassette shelf 105 is installed on a slide stage (horizontal movement mechanism) 106 so as to be capable of traversing.
In addition, a buffer shelf (substrate container storage shelf) 107 is installed above the cassette shelf 105 and configured to store the cassette 110.
A cassette carrying device (substrate container carrying device) 118 is installed between the cassette stage 114 and the cassette shelf 105. The cassette transport device 118 includes a cassette elevator (substrate container lifting mechanism) 118a that can be moved up and down while holding the cassette 110, and a cassette transport mechanism (substrate container transport mechanism) 118b as a transport mechanism. The cassette 110 is transported between the cassette stage 114, the cassette shelf 105, and the buffer shelf 107 by continuous operation of the cassette 118a and the cassette transport mechanism 118b.

A wafer transfer mechanism (substrate transfer mechanism) 125 is installed behind the cassette shelf 105. The wafer transfer mechanism 125 is a wafer 2 that can rotate or linearly move the wafer 200 in the horizontal direction.
00 transfer device (substrate transfer device) 125a and wafer transfer device elevator (substrate transfer device lifting mechanism) 125b for moving the wafer transfer device 125a up and down.
As schematically shown in FIG. 1, the wafer transfer device elevator 125 b is installed at the left end of the pressure-resistant housing 111. By the continuous operation of the wafer transfer device elevator 125b and the wafer transfer device 125a, the tweezer (substrate holding body) 125c of the wafer transfer device 125a is used as a mounting portion for the wafer 200 with respect to the boat (substrate holding tool) 217. The wafer 200 is loaded (charged) and unloaded (discharged).

  As shown in FIG. 1, a clean unit 134a composed of a supply fan and a dustproof filter is provided behind the buffer shelf 107 so as to supply clean air that is a cleaned atmosphere. It is configured to circulate inside the body 111. In addition, a clean unit (not shown) composed of a supply fan and a dustproof filter for supplying clean air is installed at the right end opposite to the wafer transfer device elevator 125b side, and blown out from the clean unit. The clean air is circulated through the wafer transfer device 125 a and then sucked into an exhaust device (not shown) and exhausted to the outside of the casing 111.

On the rear side of the wafer transfer device (substrate transfer device) 125a, a case (hereinafter referred to as a pressure-resistant case) 140 having a confidential performance capable of maintaining a pressure lower than atmospheric pressure (hereinafter referred to as negative pressure) is provided. Is installed, and a load lock chamber 141 that is a load lock type standby chamber having a capacity capable of accommodating the boat 217 is formed by the pressure-resistant housing 140.
A wafer loading / unloading port (substrate loading / unloading port) 142 is opened on the front wall 140a of the pressure-resistant housing 140, and the wafer loading / unloading port 142 is opened and closed by a gate valve (substrate loading / unloading port opening / closing mechanism) 143. It has become. A gas supply pipe 144 for supplying an inert gas such as nitrogen gas to the load lock chamber 141 and a gas exhaust pipe (for exhausting the load lock chamber 141 to a negative pressure) on a pair of side walls of the pressure-resistant housing 140 (Not shown) are connected to each other.

A processing furnace 202 is provided above the load lock chamber 141. The lower end portion of the processing furnace 202 is configured to be opened and closed by a furnace port gate valve (furnace port opening / closing mechanism) 147.
As schematically shown in FIG. 1, a boat elevator (substrate holder lifting mechanism) 115 for lifting the boat 217 is installed in the load lock chamber 141. A seal cap 219 as a lid is horizontally installed on an arm (not shown) as a connecting tool connected to the boat elevator 115, and the seal cap 219 supports the boat 217 vertically, and the lower end of the processing furnace 202 is attached to the lower end of the processing furnace 202. It is configured to be occluded.
The boat 217 includes a plurality of holding members so that a plurality of (for example, about 50 to 150) wafers 200 are horizontally held in a state where their centers are aligned in the vertical direction. It is configured.

Next, the operation of the processing apparatus of the present invention will be described.
As shown in FIG. 1, the cassette loading / unloading port 112 is opened by the front shutter 113 before the cassette 110 is supplied to the cassette stage 114. Thereafter, the cassette 110 is loaded from the cassette loading / unloading port 112 and is placed on the cassette stage 114 so that the wafer 200 is in a vertical posture and the wafer loading / unloading port of the cassette 110 faces upward.
Next, the cassette 110 is scooped up from the cassette stage 114 by the cassette carrying device 118, 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 housing. It is rotated 90 ° clockwise around the right.
Subsequently, the cassette 110 is transferred to the cassette shelf 105 by the cassette transfer device 118.
Alternatively, after being automatically transferred to the designated shelf position of the buffer shelf 107 and transferred and temporarily stored, it is transferred to the cassette shelf 105 by the cassette conveyor 118 or directly, It is conveyed to.

The slide stage 106 moves the cassette shelf 105 horizontally and positions the cassette 110 to be transferred so as to face the wafer transfer device 125a.
When the wafer loading / unloading port 142 of the load lock chamber 141 whose interior is previously set to the atmospheric pressure state is opened by the operation of the gate valve 143, the wafer 200 is transferred from the cassette 110 to the wafer loading / unloading port by the tweezer 125c of the wafer transfer device 125a. And is loaded into the load lock chamber 141 through the wafer loading / unloading port 142, transferred to the boat 217, and loaded (wafer charging). The wafer transfer device 125 a that has delivered the wafer 200 to the boat 217 returns to the cassette 110 and loads the next wafer 200 into the boat 217.

  When a predetermined number of wafers 200 are loaded into the boat 217, the wafer loading / unloading port 142 is closed by the gate valve 143, and the load lock chamber 141 is evacuated from the exhaust pipe to be decompressed. When the load lock chamber 141 is reduced to the same pressure as that in the processing furnace 202, the lower end portion of the processing furnace 202 is opened by the furnace port gate valve 147. Subsequently, the seal cap 219 is raised by the boat elevator 115, and the boat 217 supported by the seal cap 219 is loaded into the processing furnace 202.

After loading, arbitrary processing is performed on the wafer 200 in the processing furnace 202.
After the processing, the boat 217 is pulled out by the boat elevator 115, and the gate valve 143 is opened after the inside of the load lock chamber 141 is returned to atmospheric pressure. Thereafter, the wafer 200 and the cassette 110 are discharged to the outside of the casing 111 in the reverse order of the above-described procedure.

  FIG. 2 is a schematic configuration diagram of the processing furnace 202 and the periphery of the processing furnace 202 of the substrate processing apparatus 101, and is shown as a longitudinal sectional view.

As shown in FIG. 2, the processing furnace 202 has a heater 206 as a heating mechanism.
The heater 206 has a cylindrical shape, is composed of a heater wire and a heat insulating member provided around the heater wire, and is vertically installed by being supported by a holding body (not shown).

Inside the heater 206, an outer tube 205 as a reaction tube is disposed concentrically with the heater 206. The outer tube 205 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 processing chamber 201 is formed in a cylindrical hollow portion inside the outer tube 205, and is configured so that wafers 200 as substrates can be accommodated by the boat 217 in a horizontal posture and aligned in multiple stages in the vertical direction. .

  A manifold 209 is disposed below the outer tube 205 concentrically with the outer tube 205. The manifold 209 is made of, for example, stainless steel and has a cylindrical shape with an upper end and a lower end opened. The manifold 209 is provided to support the outer tube 205. An O-ring 309 as a seal member is provided between the manifold 209 and the outer tube 205. Since the manifold 209 is supported by a holding body (not shown), the outer tube 205 is installed vertically. In this way, a reaction vessel is formed by the outer tube 205 and the manifold 209.

The manifold 209 is provided with a gas exhaust pipe 231 and a gas supply pipe 232 that passes therethrough. The gas supply pipe 232 is divided into three on the upstream side, and the first gas supply source 180 and the second gas supply are provided via valves 177, 178 and 179 and MFCs 183, 184 and 185 as gas flow rate control devices. A source 181 and a third gas supply source 182 are connected to each other. A gas flow rate control unit 235 is electrically connected to the MFCs 183, 184, 185 and the valves 177, 178, 179 so that the flow rate of the supplied gas is controlled at a desired timing. It is configured.
A vacuum exhaust device 246 such as a vacuum pump is connected to the downstream side of the gas exhaust pipe 231 via a pressure sensor (not shown) as a pressure detector and an APC valve 242 as a pressure regulator.
A pressure control unit 236 is electrically connected to the pressure sensor and the APC valve 242, and the pressure control unit 236 adjusts the opening degree of the APC valve 242 based on the pressure detected by the pressure sensor. Control is performed at a desired timing so that the pressure in the processing chamber 201 becomes a desired pressure.

Below the manifold 209, the seal cap 219 is provided as a furnace port lid for hermetically closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal such as stainless steel and has a disk shape. On the upper surface of the seal cap 219, an O-ring 301 is provided as a seal member that contacts the lower end of the manifold 209.
The seal cap 219 is provided with a rotation mechanism 254.
A rotation shaft 255 of the rotation mechanism 254 passes through the seal cap 219 and is connected to the boat 217, and is configured to rotate the wafer 200 by rotating the boat 217.
The seal cap 219 is configured to be moved up and down in a vertical direction by a lifting motor 248 described later as a lifting mechanism provided on the outside of the processing furnace 202, and thereby the boat 217 is carried into and out of the processing chamber 201. It is possible.
A drive control unit 237 is electrically connected to the rotation mechanism 254 and the lift motor 248, and is configured to control at a desired timing so as to perform a desired operation.

  The boat 217 as a substrate holder is made of a heat-resistant material such as quartz or silicon carbide, and is configured to hold a plurality of wafers 200 in a multi-stage by aligning them in a horizontal posture with their centers aligned. ing. In addition, a plurality of heat insulating plates 216 as a disk-shaped heat insulating member made of a heat resistant material such as quartz or silicon carbide are arranged in a plurality of stages in a horizontal posture at the lower part of the boat 217, Heat is configured not to be transmitted to the manifold 209 side.

In the vicinity of the heater 206, a temperature sensor (not shown) is provided as a temperature detector for detecting the temperature in the processing chamber 201.
A temperature controller 238 is electrically connected to the heater 206 and the temperature sensor, and the temperature in the processing chamber 201 is adjusted by adjusting the power supply to the heater 206 based on the temperature information detected by the temperature sensor. It is configured to control at a desired timing so that the temperature distribution is as follows.

In the configuration of the processing furnace 202, the first processing gas is supplied from the first gas supply source 180, the flow rate thereof is adjusted by the MFC 183, and then the processing chamber 201 is connected to the processing chamber 201 by the gas supply pipe 232 through the valve 177. Introduced in.
The second processing gas is supplied from the second gas supply source 181, the flow rate of which is adjusted by the MFC 184, and then introduced into the processing chamber 201 through the valve 178 through the gas supply pipe 232.
The third processing gas is supplied from the third gas supply source 182, the flow rate of which is adjusted by the MFC 185, and then introduced into the processing chamber 201 from the gas supply pipe 232 through the valve 179.
The gas in the processing chamber 201 is exhausted from the processing chamber 201 by a vacuum pump as the vacuum exhaust device 246 connected to the gas exhaust pipe 231.

  Next, the configuration around the processing furnace 202 of the substrate processing apparatus 101 used in the present invention will be specifically described.

A lower substrate 245 is provided on the outer surface of the load lock chamber 141 as a spare chamber.
The lower substrate 245 is provided with a guide shaft 264 that fits with the lifting platform 249 and a ball screw 244 that screws with the lifting platform 249. The upper substrate 247 is provided on the upper ends of the guide shaft 264 and the ball screw 244 that are erected on the lower substrate 245.
The ball screw 244 is rotated by an elevating motor 248 provided on the upper substrate 247. The lifting platform 249 is configured to move up and down as the ball screw 244 rotates.

A hollow elevating shaft 250 is vertically suspended from the elevating table 249, and a connecting portion between the elevating table 249 and the elevating shaft 250 is airtight. The elevating shaft 250 moves up and down together with the elevating table 249. The elevating shaft 250 penetrates the top plate 251 of the load lock chamber 141. The through hole of the top plate 251 through which the elevating shaft 250 penetrates has a sufficient margin so as not to contact the elevating shaft 250.
A bellows 265 as a hollow elastic body having elasticity is provided between the load lock chamber 141 and the lifting platform 249 so as to cover the periphery of the lifting shaft 250 in order to keep the load lock chamber 141 airtight.
The bellows 265 has a sufficient amount of expansion / contraction that can accommodate the amount of elevation of the lifting platform 249, and the inner diameter of the bellows 265 is sufficiently larger than the outer shape of the lifting / lowering shaft 250 to prevent contact with the expansion / contraction of the bellows 265. Yes.

  A lifting substrate 252 is fixed horizontally to the lower end of the lifting shaft 250. A drive unit cover 253 is airtightly attached to the lower surface of the elevating substrate 252 via a seal member such as an O-ring. The elevating board 252 and the drive unit cover 253 constitute a drive unit storage case 256. With this configuration, the inside of the drive unit storage case 256 is isolated from the atmosphere in the load lock chamber 141.

  A rotation mechanism 254 of the boat 217 is provided inside the drive unit storage case 256, and the periphery of the rotation mechanism 254 is cooled by the cooling mechanism 257.

  The power supply cable 258 is led from the upper end of the lifting shaft 250 through the hollow portion of the lifting shaft 250 to the rotating mechanism 254 and connected thereto. The cooling mechanism 257 and the seal cap 219 are provided with a cooling flow path 259, and a cooling water pipe 260 for supplying cooling water is connected to the cooling flow path 259. It passes through the hollow part.

  As the elevating motor 248 is driven and the ball screw 244 rotates, the drive unit storage case 256 moves up and down via the elevating platform 249 and the elevating shaft 250.

As the drive unit storage case 256 rises, the seal cap 219 provided in an airtight manner on the elevating substrate 252 closes the furnace port 161, which is an opening of the process furnace 202, so that wafer processing is possible. When the drive unit storage case 256 is lowered, the seal cap 219 is moved.
At the same time, the boat 217 is lowered and the wafer 200 can be unloaded.

  The gas flow rate control unit 235, the pressure control unit 236, the drive control unit 237, and the temperature control unit 238 also constitute an operation unit and an input / output unit, and are electrically connected to a main control unit 239 that controls the entire substrate processing apparatus 101. Has been. These gas flow rate control unit 235, pressure control unit 236, drive control unit 237, temperature control unit 238, and main control unit 239 are configured as a controller 240.

Next, a method for forming a film on a substrate such as the wafer 200 as one step of a semiconductor device manufacturing process using the processing furnace 202 having the above configuration will be described.
In the following description, the operation of each unit constituting the substrate processing apparatus 101 is controlled by the controller 240.

  When a plurality of wafers 200 are loaded into the boat 217, as shown in FIG. 2, the boat 217 holding the plurality of wafers 200 is processed by a lifting operation of the lifting platform 249 and the lifting shaft 250 by the lifting motor 248. It is carried into the chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring.

  The processing chamber 201 is evacuated by a vacuum evacuation device 246 so that a desired pressure (degree of vacuum) is obtained. At this time, the pressure in the processing chamber 201 is measured by a pressure sensor, and the APC valve 242 as a pressure regulator is feedback-controlled based on the measured pressure. Further, the processing chamber 201 is heated by the heater 206 so as to have a desired temperature. At this time, the power supply to the heater 206 is feedback-controlled based on the temperature information detected by the temperature sensor so that the inside of the processing chamber 201 has a desired temperature distribution. Subsequently, the wafer 200 is rotated by rotating the boat 217 by the rotation mechanism 254.

For example, the first gas supply source 180, the second gas supply source 181, and the third gas supply source 182 contain SiH ₄ or Si ₂ H ₆ , GeH ₄ , and H ₂ as processing gases, respectively. Then, each processing gas is supplied from these processing gas supply sources. After the openings of the MFCs 183, 184, and 185 are adjusted so as to obtain a desired flow rate, the valves 176, 177, and 178 are opened, and the respective processing gases flow through the gas supply pipe 232, and the upper portion of the processing chamber 201 is opened. Are introduced into the processing chamber 201. The introduced gas passes through the processing chamber 201 and is exhausted from the gas exhaust pipe 231.
The processing gas contacts the wafer 200 when passing through the processing chamber 201, and an Epi-SiGe film is deposited (deposited) on the surface of the wafer 200.
When the Si single crystal film is deposited or epitaxially grown on the silicon surface of the silicon substrate instead of the Epi-SiGe film, any of the first gas supply source 180, the second gas supply source 181 and the third gas supply source 182 is used. SiH ₂ Cl ₂ (dichlorosilane) is enclosed.
The gas inlet of the gas supply pipe 232 is opened vertically downward from the position near the ceiling of the processing chamber 201 toward the lower portion of the processing chamber 201. It should be noted that the gas supply pipe 232 extends toward the gas inlet and extends to the lower part of the processing chamber 201 and closes the tip, so that the processing gas is introduced between the upper and lower wafers 200 adjacent to each other in the vertical direction. A plurality of gas inlets may be provided in the extended portion of the gas supply pipe 232. Further, in this case, the opening area or the opening diameter of the gas supply pipe is adjusted based on the pressure loss of the gas supply pipe 232 so that the flow rate of the processing gas introduced from each gas inlet to the wafer 200 is the same. May be.

  When a preset time elapses, an inert gas is supplied as a purge gas from an inert gas supply source (not shown), the inside of the processing chamber 201 is replaced with the inert gas, and the pressure in the processing chamber 201 is returned to normal pressure. Will be restored.

  Thereafter, the seal cap 219 is lowered by the rotation of the elevating motor 248, the lower end of the manifold 209 is opened, and the processed wafer 200 is held by the boat 217 from the lower end of the manifold 209 to the outside of the outer tube 205. Unloaded (boat unloading). Thereafter, the processed wafer 200 is taken out from the boat 217 (wafer removal).

  FIG. 3 shows an example of a process sequence when a semiconductor device is manufactured by epitaxial growth according to the present invention using the substrate processing apparatus 101.

In the process sequence, a wafer loading process for inserting the wafer 200 into the processing chamber 201 in a state where the wafer 200 is mounted on the boat 217, a pretreatment process for removing a natural oxide film and impurities from the silicon surface of the wafer 200, and a wafer after the pretreatment are performed. An epitaxial growth step of selectively growing an epitaxial film of a Si single crystal on the silicon surface of 200, a purge step of exhausting the gas in the processing chamber 201 with an inert gas, and a wafer for removing the processed wafer 200 from the processing chamber 201 The unload process is performed in this order. Note that the epitaxial growth step may be performed in one step or stepwise.
Hereinafter, each step will be described.

<Wafer loading process>
In the wafer loading step, the wafer (silicon substrate) 200 is charged to the holding member of the boat 217 described above, and the boat 217 is carried into the processing chamber 201 as the boat elevator 115 rises. When the loading of the boat 217 is completed and the furnace port 161 is closed by the seal cap 219, the atmosphere in the processing chamber 201 is then exhausted by a vacuum pump as a vacuum exhaust device 246 connected to the gas exhaust pipe 231. The pressure is set to 300 Pa or less suitable for pretreatment. When the pressure is maintained at 300 Pa or less, the wafer loading process is terminated.

<Temperature setting process>
In the temperature setting step, the atmosphere in the processing chamber 201 and the temperature of the wafer 200 are heated to a pretreatment temperature of 600 to 700 ° C. by heating of a heater 206 as a heating unit. When the temperature is stabilized, this process is terminated.

<Wafer pretreatment process (removal process of natural oxide film and impurities on silicon surface)>
In the pretreatment process, a reducing gas and a dilution gas are introduced to remove a natural oxide film and impurities on the silicon surface of the wafer 200.
SiH ₂ Cl ₂ (dichlorosilane gas) is used as the reducing gas, and H ₂ gas is used as the dilution gas.
The flow rate of SiH ₂ Cl ₂ (dichlorosilane gas) is 1 to 300 sccm, and the flow rate of H ₂ gas (hydrogen gas) is 10 to 50000 sccm.
Further, the pressure in the processing chamber 201 is set to 300 pa or less, the temperatures of the processing chamber 201 and the wafer 200 are maintained at 600 to 700 ° C., and the reduction time with the SiH ₂ Cl ₂ gas is empirically set to 5 to 120 minutes. .
When SiH ₂ Cl ₂ gas and H ₂ gas are introduced into the processing chamber 201, H and C of SiH ₂ Cl ₂ are thermally decomposed.
The natural oxide film (SiO ₂ ) and impurities on the silicon surface react with the thermally decomposed elements to become a hydrogen compound and a carbon compound and are exhausted from the gas exhaust pipe 231. In this case, the H ₂ gas does not work for the reduction reaction because the temperature of the processing chamber 201 and the wafer 200 is as low as 600 to 700 ° C.
In the pre-processing step of the wafer 200, when the temperature, pressure, and flow rate condition values are out of the range of the respective condition values, the reduction action of SiH ₂ Cl ₂ is reduced, and the natural oxide film (SiO ₂ or the like) or impurities The removal ability decreases.

<SiH ₂ Cl ₂ gas introduction (initial selective growth process)>
The first epitaxial growth process (processing process) is shown below.
In this step, SiH ₂ Cl ₂ gas (dichlorocyan gas) is introduced into the processing chamber 201 as a raw material gas for epitaxial growth and H ₂ gas (hydrogen gas) is introduced as a dilution gas while the wafer 200 is installed in the processing chamber 201. .
At this time, the pressure in the processing chamber 201 is 300 Pa or less, the flow rate of SiH ₂ Cl ₂ (dichlorosilane gas) is 1 to 300 sccm, the flow rate of H ₂ gas (hydrogen gas) is 10 to 50000 sccm, Same conditions. The temperature of the processing chamber 201 and the wafer 200 is heated to a temperature in the range of 680 to 720 ° C. by a heater.
The treatment time varies depending on the film thickness or layer thickness to be epitaxially grown, but is 5 to 120 minutes.
If the temperature, pressure, and flow rate condition values are out of the range of the condition values, the epitaxial growth using SiH ₂ Cl ₂ deteriorates.
When SiH ₂ Cl ₂ gas is introduced into the processing chamber 201 under the above-mentioned epitaxial growth conditions, the SiH ₂ Cl ₂ gas is thermally decomposed on the surface of the wafer 200 cleaned in the pretreatment process, and only Si silicon is formed on the silicon surface of the wafer 200. The crystal film is selectively epitaxially grown.
In this initial selective growth step, epitaxial growth may be performed up to a desired film thickness. However, when the growth rate is further increased, the next growth step may be further performed.
Further, as the epitaxial growth process, the initial selective growth may not be performed, and the epitaxial growth may be performed up to a desired film thickness only by the next growth process.

<Predetermined gas introduction process (selective growth process)>
The second epitaxial growth process (processing process) is shown below.
The epitaxial growth conditions in this step may be the same as those in the initial selective growth step, but the pressure in the processing chamber 201, the flow rate of SiH ₂ Cl ₂ (dichlorosilane gas), and the flow rate of H ₂ gas (hydrogen gas) are the same as described above. This is the same as the pretreatment process and the initial selective growth process.
And processing temperature shall be the temperature of the range of 720-800 degreeC, for example. Here, it is set to 760 ° C. as an example. Further, if the temperature is increased to increase the epitaxial growth rate, selective growth cannot be performed only with SiH ₂ Cl ₂ gas and H ₂ gas (hydrogen gas). In this case, for example, HCl is used as a chlorine-based gas. Add as appropriate. In this case, a preferable flow rate of the chlorine-based gas, for example, HCl gas is 1 to 300 sccm.
Thereby, the Si single crystal can be grown on the Si single crystal epitaxially grown in the initial selective growth process at a speed higher than that in the initial selective growth process.
If GeH ₄ gas is used under the same conditions as in the selective growth step instead of dichlorosilane gas, a silicon germanium single crystal film or layer can be grown.
Further, the treatment time in this step is in the range of 5 to 120 minutes, although it varies depending on the film thickness (layer thickness).

<Purge process>
In the purge process, an inert gas is introduced into the processing chamber 201 from an inert gas supply source (not shown), and the residual gas in the processing chamber 201 is pushed out to the gas exhaust pipe 231 by the pressure of the inert gas. When the residual gas in the processing chamber 201 is replaced with an inert gas, the pressure in the processing chamber 201 returns to normal pressure.

<Wafer unload process>
In the wafer unload process, the boat elevator 115 is lowered and the wafer 200 after epitaxial growth is delivered from the boat 217.

  Next, an embodiment of a semiconductor device manufacturing method according to the present invention will be described.

<Example>
First, the atmospheric temperature of the processing chamber 201 and the temperature of the wafer 200 are 620 ° C., the pressure of the processing chamber 201 is 30 Pa, the flow rate of SiH ₂ Cl ₂ (dichlorosilane) gas as a reducing gas is 200 sccm, and H ₂ gas as a diluent gas ( Hydrogen gas) was flowed at 1000 sccm, and a wafer 200 having a silicon surface and an insulating film surface on its surface was used as a test sample, and pretreatment was performed for 60 minutes.
Next, while maintaining the temperature of the processing chamber 201 and the wafer 200 at 700 ° C. and maintaining the pressure in the processing chamber 201 at 30 Pa, the processing chamber 201 is diluted with SiH ₂ Cl ₂ (dichlorosilane gas) as an epitaxial growth material. A gas such as H ₂ gas (hydrogen gas) was introduced to perform epitaxial growth on the silicon surface.
At this time, the flow rate of SiH ₂ Cl ₂ (dichlorosilane gas) was 200 sccm, and the flow rate of H ₂ gas was 1000 sccm. The processing time was 60 minutes.

<Comparative example>
For comparison, the wafer 200 of the same lot as the wafer 200 of the example is used, the atmospheric temperature of the processing chamber 201 and the temperature of the wafer 200 are set to 300 ° C., the pressure of the processing chamber 201 is set to 50 Pa, and SiH ₄ (monosilane) is used as the reducing gas. The wafer 200 was pretreated with a gas of 50 sccm and H ₂ gas (hydrogen gas) of 3500 sccm, and then epitaxial growth was performed under the same epitaxial growth conditions as in the example.
At this time, the reduction treatment time was 30 minutes and the epitaxial growth time was 60 minutes.
In addition, when removing the natural oxide film and impurities of the wafer 200 with SiH ₄ (monosilane) gas and H ₂ gas, the temperature of the processing chamber 201 and the wafer 200 is set to 200 to 400 ° C., and the flow rate of SiH ₄ (monosilane) gas. 1 to 150 sccm, the flow rate of H ₂ gas (hydrogen gas) is preferably 10 to 5000 sccm, the pressure in the processing chamber 201 is 300 Pa or less, and the processing time is preferably 5 to 120 minutes.

Next, the cleanliness of the interface was evaluated by SIMS (Secondary Ionization Mass Spectrometer) based on the interfacial oxygen concentration of the wafers 200 of the example and the comparative example. The interface oxygen concentration of the example was 3.4E12 atoms / cm ² , and the comparative example was 1.8E13 atoms / cm ² . From this result, it was found that SiH ₂ Cl ₂ gas (dichlorosilane gas) is superior as a reducing gas compared to SiH ₄ (monosilane) gas.
Conventionally, in order to remove the natural oxide film and impurities on the silicon surface BR of the wafer 200 after the etching process, the temperature in the processing chamber 201 and the wafer 200 is set to 800 ° C. or more, and H ₂ gas is used as a reducing gas. However, in the method for manufacturing a semiconductor device according to the present invention, by using SiH ₂ Cl ₂ gas and H ₂ gas as a dilution gas, the natural surface of the silicon surface of the wafer 200 can be formed at a low temperature of 600 to 700 ° C. The oxide film and impurities could be removed.

[Effect of this embodiment]
(1) In the method of manufacturing a semiconductor device from the cleaning of the silicon surface of the substrate to the end of the epitaxial growth of the silicon surface, the temperature of the substrate can be set to 800 ° C. or lower. The risk of increase is greatly reduced.
(2) Further, when a natural oxide film or impurities are removed by reduction using a silane-based gas, particularly SiH ₂ Cl ₂ (dichlorosilane gas), a silicon film or a silicon nucleus is formed on the insulating film of the wafer. In the subsequent selective growth, there is a possibility that adverse effects such as selection and blurring may occur. However, in the semiconductor device manufacturing method according to the present embodiment, such a concern does not occur.
(3) Further, according to the substrate processing method according to the present embodiment and the present example, etching before selective growth is unnecessary, and an epitaxial film is selectively applied only to the silicon surface of the wafer in a state where the interface oxygen concentration is low. Can grow into.
(4) Furthermore, since the processes from the cleaning of the silicon surface of the substrate to the end of the epitaxial growth of the silicon surface are performed in the same processing chamber, contamination can be prevented.

[Appendix]
Below, the preferable aspect which concerns on this embodiment is appended.

[Appendix 1]
Using a substrate processing apparatus that mounts a substrate having at least a silicon surface and an insulating film surface in a processing chamber, and heats the atmosphere in the processing chamber and the substrate by a heating unit disposed outside the processing chamber A method of manufacturing a semiconductor device in which an epitaxial film is selectively grown only on the silicon surface, a substrate carrying-in step for carrying the substrate into the processing chamber, and a temperature of the substrate and the substrate processing chamber being 700 ° C. or lower. A dichlorosilane gas and a hydrogen gas are supplied into the processing chamber while maintaining the predetermined temperature, and a pretreatment process for removing a natural oxide film and impurities formed on the silicon surface, and the substrate is carried out of the processing chamber. And a substrate carrying-out process.

[Appendix 2]
The semiconductor device manufacturing method according to appendix 1, wherein the predetermined temperature is a first temperature between 600 ° C. and 700 ° C.

[Appendix 3]
Using a substrate processing apparatus that mounts a substrate having at least a silicon surface and an insulating film surface in a processing chamber, and heats the atmosphere in the processing chamber and the substrate by a heating unit disposed outside the processing chamber A method of manufacturing a semiconductor device in which an epitaxial film is selectively grown only on the silicon surface, the substrate carrying-in step for carrying the substrate into the processing chamber, and the temperature of the substrate and the substrate processing chamber being set to a predetermined temperature. A pretreatment process for supplying dichlorosilane gas and hydrogen gas into the treatment chamber while removing the natural oxide film and impurities formed on the silicon surface, and the same as the pretreatment process after the pretreatment process. An epitaxial growth step of growing an epitaxial film only on the silicon surface by supplying dichlorosilane gas and hydrogen gas to the processing chamber under flow rate conditions; A substrate unloading step of unloading the substrate out of the processing chamber, wherein the pretreatment step and the substrate and the substrate processing chamber are maintained at a predetermined temperature of 800 ° C. or less. A method of manufacturing a semiconductor device that performs an epitaxial growth process is provided.

[Appendix 4]
The semiconductor device manufacturing method according to attachment 3, wherein the pretreatment step is performed while maintaining the temperature of the substrate and the substrate processing chamber at a first temperature between 600 ° C. and 700 ° C., and the epitaxial growth step is performed on the substrate. And a method of manufacturing a semiconductor device, which is performed while maintaining the temperature of the substrate processing chamber at a second temperature between 680 ° C. and 800 ° C.

[Appendix 5]
The semiconductor device manufacturing method according to attachment 3, wherein the pretreatment step is performed while maintaining a temperature in the substrate and the substrate processing chamber at a first temperature between 600 ° C. and 700 ° C., and in the epitaxial growth step, the substrate The substrate processing chamber is maintained at a second temperature between 680 ° C. and 720 ° C., and only dichlorosilane gas and hydrogen gas are supplied to the processing chamber to grow an epitaxial film only on the silicon surface. A method for manufacturing a semiconductor device is provided.

[Appendix 6]
The semiconductor device manufacturing method according to attachment 3, wherein the pretreatment step is performed while maintaining a temperature in the substrate and the substrate processing chamber at a first temperature between 600 ° C. and 700 ° C., and in the epitaxial growth step, the substrate And the substrate processing chamber at a second temperature between 720 ° C. and 800 ° C., and further supplying a chlorine-based gas to the processing chamber to grow an epitaxial film only on the silicon surface The manufacturing method of this is provided.

[Appendix 7]
Using a substrate processing apparatus that mounts a substrate having at least a silicon surface and an insulating film surface in a processing chamber, and heats the atmosphere in the processing chamber and the substrate by a heating unit disposed outside the processing chamber A method of manufacturing a semiconductor device in which an epitaxial film is selectively grown only on the silicon surface, the substrate carrying-in step for carrying the substrate into the processing chamber, and the temperature of the substrate and the substrate processing chamber being set to a predetermined temperature. A dichlorosilane gas and a hydrogen gas are supplied into the processing chamber while maintaining the pretreatment step for removing a natural oxide film and impurities formed on the silicon surface, and the dichlorosilane gas is used under the same flow conditions as the processing step. Supplying a hydrogen gas to the processing chamber to grow an epitaxial film only on the silicon surface; and the pretreatment step A dichlorosilane gas, a chlorine-based gas, and a hydrogen gas are supplied to the processing chamber under the same flow rate conditions as in the second epitaxial growth step for growing an epitaxial film only on the silicon surface, and the substrate is carried out of the processing chamber. A method of manufacturing a semiconductor device including a substrate unloading step, wherein the pretreatment step and each of the epitaxial growths are performed while maintaining the temperature of the substrate and the substrate processing chamber at a predetermined temperature of 800 ° C. or lower. A method is provided.

[Appendix 8]
The semiconductor device manufacturing method according to appendix 7, wherein the pretreatment step is performed while maintaining the substrate and the substrate processing chamber at a first temperature of 600 ° C. to 700 ° C., and the first epitaxial growth step is performed on the substrate and the substrate. The temperature in the substrate processing chamber is kept at a second temperature between 680 ° C. and 800 ° C., and the second epitaxial growth step is performed at a third temperature of 720 ° C. to 800 ° C. in the substrate and the substrate processing chamber. 8. A method of manufacturing a semiconductor device according to claim 7, which is performed while maintaining the temperature.

[Appendix 9]
Using a substrate processing apparatus, wherein a substrate having at least a silicon surface and an insulating film surface is placed in a processing chamber, and the atmosphere in the processing chamber and the substrate are heated by heating means disposed outside the processing chamber. A pre-treatment method of a selective epitaxial film growth method for selectively growing an epitaxial film only on the silicon surface, wherein a temperature in the substrate and the substrate processing chamber is kept at a predetermined temperature of 700 ° C. or lower while the substrate is in the processing chamber. The present invention provides a pretreatment method for removing a natural oxide film and impurities formed on the silicon surface by supplying chlorosilane gas and hydrogen gas.

[Appendix 10]
The pretreatment method of the selective epitaxial film growth method according to appendix 9, wherein the predetermined temperature is a first temperature between 600 ° C. and 700 ° C. between the substrate and the substrate processing chamber. A pre-processing method is provided.

[Appendix 11]
A processing chamber for accommodating a substrate having at least a silicon surface and an insulating film surface on the surface; a heating unit disposed outside the processing chamber for heating the atmosphere in the processing chamber and the substrate; A gas supply unit that supplies a gas; a pressure control unit that controls the pressure in the processing chamber to a desired pressure; an exhaust unit that exhausts the atmosphere in the processing chamber; the heating unit; the gas supply unit; and the pressure control. A substrate processing apparatus for selectively growing an epitaxial film only on the silicon surface, wherein the control unit is configured to keep the substrate and the processing chamber at 700 ° C. The silicon unit is controlled by controlling the heating unit and the gas supply unit so as to supply dichlorosilane gas and hydrogen gas while maintaining the following predetermined temperature. There is provided a substrate processing apparatus for removing the natural oxide film and impurities formed on the surface.

[Appendix 12]
The substrate processing apparatus according to appendix 11, wherein the control unit supplies the dichlorosilane gas and the hydrogen gas while maintaining the substrate and the processing chamber at a predetermined temperature between 600 ° C. and 700 ° C. A substrate processing apparatus for removing a natural oxide film and impurities formed on the silicon surface by controlling a gas supply unit is provided.

[Appendix 13]
The substrate processing apparatus according to appendix 11, wherein the control unit includes a pretreatment process for removing a natural oxide film and impurities formed on the silicon surface and an epitaxial growth process for selectively growing an epitaxial film only on the silicon surface. There is provided a substrate processing apparatus for controlling the heating unit and the gas supply unit so as to supply a dichlorosilane gas and a hydrogen gas to the processing chamber while keeping the temperature of the substrate and the processing chamber at 800 ° C. or lower.

[Appendix 14]
The substrate processing apparatus according to appendix 13, wherein the control unit controls the heating unit so as to maintain the temperature of the substrate and the processing chamber at a first temperature between 600 ° C. and 700 ° C. in the preprocessing step. In the epitaxial growth step, there is provided a substrate processing apparatus for controlling the heating unit so as to maintain a second temperature between 680 ° C. and 800 ° C. between the substrate and the processing chamber.

[Appendix 15]
The substrate processing apparatus according to appendix 14, wherein, in the epitaxial growth step, the control unit supplies only the dichlorosilane gas and hydrogen gas while maintaining the temperature of the substrate and the processing chamber at a predetermined temperature between 680 ° C. and 720 ° C. The present invention provides a substrate processing apparatus for controlling the heating unit and the gas supply unit so as to be supplied to a processing chamber.

[Appendix 16]
The substrate processing apparatus according to appendix 14, wherein, in the epitaxial growth step, the controller further supplies a chlorine-based gas while maintaining the temperature of the substrate and the processing chamber at a predetermined temperature between 720 ° C. and 800 ° C. Thus, a substrate processing apparatus for controlling the heating unit and the gas supply unit is provided.

[Appendix 17]
The substrate processing apparatus according to appendix 11, wherein the control unit is configured to supply dichlorosilane gas and hydrogen gas to the processing chamber in a preprocessing step of removing a natural oxide film and impurities formed on the silicon surface. In a first epitaxial growth step of controlling a gas supply unit and selectively growing an epitaxial film only on the silicon surface, the gas supply unit is controlled to supply dichlorosilane gas and hydrogen gas to the processing chamber, In a second epitaxial growth step of selectively growing an epitaxial film only on the silicon surface, the gas supply unit is controlled so as to supply dichlorosilane gas, chlorine gas and hydrogen gas to the processing chamber, and In the processing step, the first epitaxial growth step, and the second epitaxial growth step There is provided a substrate processing apparatus for controlling the heating unit so as to maintain the temperature of the processing chamber and the substrate to a predetermined temperature of 800 ° C. or less.

[Appendix 18]
The substrate processing apparatus according to appendix 17, wherein the control unit controls the heating unit so as to maintain the temperature of the substrate and the processing chamber at a first temperature between 600 ° C. and 700 ° C. in the preprocessing step. In the first epitaxial growth step, the heating unit is controlled so as to keep the temperature of the substrate and the processing chamber at a second temperature between 680 ° C. and 720 ° C., and in the second epitaxial growth step, the substrate and the processing are controlled. The present invention provides a substrate processing apparatus for controlling the heating unit so as to keep the indoor temperature at a third temperature between 720 ° C. and 800 ° C.

[Appendix 19]
Using a substrate processing apparatus that mounts a substrate having at least a silicon surface and an insulating film surface in a processing chamber, and heats the atmosphere in the processing chamber and the substrate by a heating unit disposed outside the processing chamber Then, dichlorosilane gas is supplied to the processing chamber within a flow rate range of 1 to 300 sccm and hydrogen gas is within a range of 10 to 50000 sccm, and the process chamber is selectively epitaxially applied only to the silicon surface under the condition of 300 Pa or less. A method of manufacturing a semiconductor device for growing a film, the step of carrying the substrate into the processing chamber, and dichlorosilane gas and hydrogen gas in the processing chamber while heating the substrate and the substrate processing chamber to 600 to 700 ° C. And a pretreatment process for removing a natural oxide film and impurities formed on the silicon surface, and a temperature in the substrate and the substrate processing chamber A semiconductor device including an epitaxial growth step of growing an epitaxial film only on the silicon surface by supplying dichlorosilane gas and hydrogen gas to the processing chamber under the same flow rate conditions as in the pretreatment step while heating to 680 to 800 ° C. The manufacturing method of this is provided.

[Appendix 20]
A substrate having at least a silicon surface and an insulating film surface is placed in a processing chamber, and the atmosphere in the processing chamber and the substrate are heated to a temperature of 600 to 800 ° C. by heating means disposed outside the processing chamber. Using a substrate processing apparatus to
An epitaxial film is selectively formed only on the silicon surface under the condition that the pressure of the processing chamber is 300 Pa or less, by supplying dichlorosilane gas to the processing chamber within a flow range of 1 to 300 sccm and hydrogen gas from 10 to 50000 sccm. A method of manufacturing a semiconductor device, the step of carrying the substrate into the processing chamber, the step of heating the substrate and the substrate processing chamber to 600 to 700 ° C., and the dichlorosilane gas and hydrogen in the processing chamber. The same as the pretreatment step while supplying a gas to remove the natural oxide film and impurities formed on the silicon surface, and heating the temperature of the substrate and the substrate processing chamber to 680 to 720 ° C. A dichlorosilane gas and a hydrogen gas are supplied to the processing chamber under a flow rate condition, and a first process for growing an epitaxial film only on the silicon surface is performed. Dichlorosilane gas and hydrogen gas are introduced into the processing chamber under the same flow conditions as in the pretreatment step while heating the substrate and the substrate processing chamber at a temperature of 720 to 800 ° C., preferably 760 ° C. And a second epitaxial growth step of growing an epitaxial film only on the silicon surface by supplying chlorine gas and providing a semiconductor device manufacturing method.

  In the above embodiment, the vertical CVD apparatus is used as the substrate processing apparatus. However, the present invention is not limited to this, and the substrate processing apparatus in general, for example, a single wafer hot-wall type single wafer substrate. A processing apparatus or a cold wall type single substrate processing apparatus may be used. The film or layer to be deposited is not limited to an epitaxially grown film or layer, and can be applied to all techniques for depositing a film using a chemical reaction on the substrate surface, such as a polysilicon film.

It is a perspective view of the substrate processing apparatus applied to this invention. 1 is a schematic configuration diagram of a processing furnace and a periphery of a processing furnace of a substrate processing apparatus according to an embodiment of the present invention. It is a figure which shows an example of the process sequence in the case of manufacturing the semiconductor device which concerns on one embodiment of this invention using a substrate processing apparatus.

Explanation of symbols

200 Substrate 201 Processing chamber 206 Heater (heating means)

Claims (1)

Using a substrate processing apparatus that mounts a substrate having at least a silicon surface and an insulating film surface in a processing chamber, and heats the atmosphere in the processing chamber and the substrate by a heating unit disposed outside the processing chamber A method of manufacturing a semiconductor device in which an epitaxial film is selectively grown only on the silicon surface,
A substrate carrying-in step for carrying the substrate into the processing chamber;
A dichlorosilane gas and a hydrogen gas are supplied into the processing chamber while keeping the substrate and the substrate processing chamber at a predetermined temperature of 700 ° C. or less to remove a natural oxide film and impurities formed on the silicon surface. A pre-processing step to perform,
A substrate unloading step of unloading the substrate out of the processing chamber;
A method of manufacturing a semiconductor device including:

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