JP2011023576A - Method of manufacturing semiconductor device, and device for treating substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To lower a film formation temperature, and to increase a film formation speed. <P>SOLUTION: The method of manufacturing a semiconductor device includes: a silicon-containing and boron-containing film formation step of supplying a silicon-containing gas and a boron-containing gas into a treatment chamber with a substrate stored therein to form a silicon-containing and boron-containing film on the substrate; and a silicon-containing and boron-containing film-reforming step of supplying an oxygen-containing gas and a hydrogen-containing gas into the treatment chamber with pressure set below atmospheric pressure to reform the silicon-containing and boron-containing film formed on the substrate to a boron-containing and silicon-containing oxide film. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a semiconductor device manufacturing method and a substrate processing apparatus.

  Conventionally, a substrate processing step of forming a silicon oxide film on a substrate using an ALD (Atomic Layer Deposition) method is sometimes performed as a step of manufacturing a semiconductor device such as a DRAM (Dynamic Random Access Memory). In the substrate processing step using the ALD method, a silicon-containing gas supply step for supplying a silicon-containing gas into a processing chamber containing a substrate, an oxidation-reduction gas supply step for supplying an oxygen-containing gas and a hydrogen-containing gas into the processing chamber, By performing this cycle once or more as a cycle, a silicon oxide film having a desired film thickness is formed on the substrate. By using the ALD method, the step coverage characteristics of the silicon oxide film and the in-plane uniformity of the film quality and film thickness can be improved (see, for example, Patent Document 1).

JP 2006-66587 A

  However, in the substrate processing step using the conventional ALD method, the temperature of the substrate at the time of film formation (film formation temperature, also referred to as processing temperature) may have to be increased to, for example, 1000 ° C. In such a case, for example, impurities implanted into the source or drain region on the substrate may be diffused, so that the performance of the semiconductor device may be deteriorated or the production yield may be deteriorated. Further, in the conventional substrate processing process using the ALD method, when the film forming temperature is lowered, the film forming speed is decreased, and the productivity of the substrate processing may be decreased.

  In order to solve the above-described problems, an object of the present invention is to provide a method for manufacturing a semiconductor device and a substrate processing apparatus capable of reducing a film formation temperature and increasing a film formation rate.

  According to one aspect of the present invention, a silicon-containing and boron-containing film forming step of forming a silicon-containing and boron-containing film on the substrate by supplying a silicon-containing gas and a boron-containing gas into a processing chamber containing the substrate; The silicon-containing and boron-containing films formed on the substrate are reformed into boron-containing and silicon-containing oxide films by supplying an oxygen-containing gas and a hydrogen-containing gas into the processing chamber set to a pressure lower than atmospheric pressure. A silicon-containing and boron-containing film modifying step, wherein the silicon-containing and boron-containing film forming step and the silicon-containing and boron-containing film modifying step are performed as one cycle, and the semiconductor is performed one or more times. A method of manufacturing a device is provided.

  According to another aspect of the present invention, a silicon-containing film forming step of forming a silicon-containing film on the substrate by supplying a silicon-containing gas into a processing chamber containing the substrate, and the pressure set to a pressure less than atmospheric pressure. A silicon-containing film modifying step of supplying a boron-containing gas, an oxygen-containing gas, and a hydrogen-containing gas into the processing chamber to reform the silicon-containing film on the substrate into a boron-containing and silicon-containing oxide film. A method of manufacturing a semiconductor device is provided in which the silicon-containing film forming step and the silicon-containing film modifying step are set as one cycle, and the cycle is performed once or more.

  According to still another aspect of the present invention, a processing chamber containing a substrate, a silicon-containing gas supply system that supplies a silicon-containing gas into the processing chamber, and a boron-containing gas supply that supplies a boron-containing gas into the processing chamber. A system, an oxygen-containing gas supply system that supplies an oxygen-containing gas into the processing chamber, a hydrogen-containing gas supply system that supplies a hydrogen-containing gas into the processing chamber, and a pressure adjustment unit that adjusts the pressure in the processing chamber; A control unit that controls the silicon-containing gas supply system, the boron-containing gas supply system, the oxygen-containing gas supply system, the hydrogen-containing gas supply system, and the pressure adjustment unit, and the control unit includes the processing chamber. Supplying the silicon-containing gas from the silicon-containing gas supply system and the boron-containing gas from the boron-containing gas supply system to the silicon-containing and boron-containing substrates on the substrate. After forming the film, the oxygen-containing gas from the oxygen-containing gas supply system and the hydrogen-containing gas from the hydrogen-containing gas supply system are supplied into the processing chamber set to less than atmospheric pressure by the pressure adjusting unit. The silicon-containing and boron-containing film on the substrate is modified to a boron-containing and silicon-containing oxide film, and this is performed as one cycle or more, or the cycle is performed once or more from the silicon-containing gas supply system into the processing chamber. After forming the silicon-containing film on the substrate by supplying the silicon-containing gas, the boron-containing gas from the boron-containing gas supply system in the processing chamber set to less than atmospheric pressure by the pressure adjustment unit, and Supplying the oxygen-containing gas from the oxygen-containing gas supply system and the hydrogen-containing gas from the hydrogen-containing gas supply system to form the silicon-containing film on the substrate; Modified Ron-containing and silicon-containing oxide film, the cycle substrate processing apparatus for performing one or more times is provided so as one cycle.

  According to the method for manufacturing a semiconductor device and the substrate processing apparatus according to the present invention, the film formation temperature can be lowered and the film formation rate can be increased.

It is a longitudinal cross-sectional view of the processing furnace of the substrate processing apparatus used suitably in the 1st Embodiment of this invention. It is the sectional view on the AA line of the processing furnace of FIG. It is a film-forming flowchart in the substrate processing process of 1st Embodiment. It is a gas supply timing diagram in the substrate processing process of the first embodiment. A deposition model diagram in the substrate processing step of the first embodiment, (a) is supplied to the Si ₂ H ₆ gas and the B ₂ H ₆ gas to form a silicon-containing and boron-containing film on the wafer into the processing chamber (B) shows a state in which O ₂ gas and H ₂ gas are supplied into the processing chamber to generate oxidized species in the processing chamber, and (c) shows that the silicon-containing and boron-containing film is boron-doped silicon by the oxidizing species. Each of them is shown as being modified into an oxide film. FIG. 10 is a gas supply timing chart of a substrate processing process having an inert gas replacement process according to a modification of the first embodiment. It is the film-forming flowchart in the substrate processing process of the 2nd Embodiment of this invention. It is a gas supply timing diagram in the substrate processing process of the second embodiment. A deposition model diagram in the substrate processing step of the second embodiment, (a) is a state of forming a silicon-containing film on the wafer by supplying a Si ₂ H ₆ gas into the process chamber, (b) the processing chamber silicon to generate a O ₂ gas and H ₂ gas oxidizing species to the supply to the processing chamber and a state supplied into the processing chamber to B ₂ H ₆ gas, by (c) is oxidized species and B ₂ H ₆ gas Each of them shows how the contained film is modified to a boron-doped silicon oxide film. FIG. 10 is a gas supply timing chart of a substrate processing process having an inert gas replacement process according to a modification of the second embodiment. It is a longitudinal cross-sectional view of the processing furnace of the substrate processing apparatus used suitably in the 3rd Embodiment of this invention. It is a gas supply timing chart at the time of silicon oxide film formation by the conventional thermal CVD method.

<First Embodiment of the Present Invention>
The first embodiment of the present invention will be described below.

(1) Configuration of Substrate Processing Apparatus FIG. 1 is a longitudinal sectional view of a processing furnace 202 of a substrate processing apparatus suitably used in an embodiment of the present invention, and FIG. 2 is an AA view of the processing furnace 202 of FIG. It is line sectional drawing.

  As shown in FIGS. 1 and 2, the processing furnace 202 includes a processing chamber 201 containing a wafer 200 as a substrate, and a silicon-containing gas, a boron-containing gas, an oxygen-containing gas, a hydrogen-containing gas, etc. in the processing chamber 201. It mainly comprises a gas supply system for supplying a processing gas, a pressure adjustment unit for adjusting the pressure in the processing chamber 201, and a controller 240 as a control unit for controlling at least the gas supply system and the pressure adjustment unit. Has been.

(Processing room)
The processing chamber 201 is provided in a process tube 203 as a reaction tube. The process tube 203 is made of a heat resistant material such as quartz (SiO ₂ ) or silicon carbide (SiC). The process tube 203 is formed in a cylindrical shape having an open lower end. A processing chamber 201 is formed in the hollow cylindrical portion of the process tube 203. The processing chamber 201 is configured to be able to accommodate the wafers 200 in a state where the wafers 200 are aligned in a vertical direction in a horizontal posture by a boat 217 described later.

A manifold 209 is disposed below the process tube 203 concentrically with the process tube 203. The manifold 209 is made of, for example, stainless steel. The manifold 209 is formed in a cylindrical shape with an upper end and a lower end opened. The manifold 209 is provided so as to engage with and support the process tubes 203. An O-ring 220a as a seal member is provided between the manifold 209 and the process tube 203.
Since the manifold 209 is supported by a heater base (not shown), the process tube 203 is installed vertically. A reaction vessel is formed by the process tube 203 and the manifold 209.

  Below the manifold 209, a seal cap 219 is provided as a furnace port lid that can airtightly close the lower end opening of the manifold 209. The seal cap 219 is brought into contact with the lower end of the manifold 209 from the lower side in the vertical direction. The seal cap 219 is made of a metal such as stainless steel. The seal cap 219 is formed in a disc shape. On the upper surface of the seal cap 219, an O-ring 220b is provided as a seal member that comes into contact with the lower end of the manifold 209. The seal cap 219 is configured to hermetically close the lower end of the process tube 203 via the manifold 209 and the O-ring 220b when a boat 217 (to be described later) is carried into the processing chamber 201 by the boat elevator 115. Yes.

  A rotation mechanism 254 that rotates the boat 217 is installed near the lower center of the seal cap 219. A rotation shaft 254 a of the rotation mechanism 254 passes through the seal cap 219 and is connected to the boat 217. The rotation mechanism 254 is electrically connected to a controller 240 described later.

The boat 217 holds a plurality of wafers 200 as a substrate holder and can be stored in the processing chamber 201. The boat 217 is made of a heat resistant material such as quartz or silicon carbide (SiC). The boat 217 holds a plurality of wafers 200 aligned in a horizontal posture with their centers aligned. The boat 217 can be rotated while holding a plurality of wafers 200 by being rotated by a rotation mechanism 254.

  A heat insulating member 218 is provided at the lower part of the boat 217. The heat insulating member 218 is made of a heat resistant material such as quartz or silicon carbide. The heat insulating member 218 makes it difficult for heat from the heater 206 to be 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.

  The lower peripheral edge of the seal cap 219 is connected to the arm of the boat elevator 115 which is a lifting mechanism. The boat elevator 115 is vertically installed outside the process tube 203. The boat elevator 115 is configured to raise and lower the seal cap 219 in the vertical direction. That is, the boat elevator 115 can carry the boat 217 into and out of the processing chamber 201. The boat elevator 115 is electrically connected to a controller 240 described later.

  Outside the process tube 203, a heater 206 as a heating unit that uniformly heats the entire processing chamber 201 is provided concentrically so as to surround the process tube 203. The heater 206 is formed in a cylindrical shape. The heater 206 is vertically installed by being supported by a heater base (not shown) as a holding plate.

  In the process tube 203, a temperature sensor 263 (see FIG. 2) as a temperature detector is installed. The temperature of the heater 206 is controlled based on the temperature information of the temperature sensor 263. The heater 206 and the temperature sensor 263 are electrically connected to a controller 240 described later.

(Exhaust system)
A gas exhaust pipe 231 is connected to the lower side wall of the manifold 209. In the gas exhaust pipe 231, a pressure sensor 245, a pressure control device 242 configured as an APC (Auto Pressure Controller) valve as a pressure adjusting unit, and an exhaust device 246 configured as a vacuum pump are provided in order from the upstream side. . By adjusting the valve opening degree of the pressure control device 242 based on the pressure information detected by the pressure sensor 245 while exhausting the processing chamber 201 by the exhaust device 246, the processing chamber 201 can be adjusted to a predetermined pressure. It is configured. The pressure sensor 245, the pressure control device 242, and the exhaust device 246 are electrically connected to a controller 240 described later.

(Gas supply system)
Nozzles 233 </ b> A to 233 </ b> D as gas introduction portions are connected to the manifold 209 so as to penetrate the side walls. The nozzles 233 </ b> A to 233 </ b> D are arranged 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 part from the lower part of the inner wall of the process tube 203 and the wafer 200. It is provided along the loading direction. The nozzles 233A to 233D are configured as porous nozzles in which gas supply holes 234a to 234d for supplying gas to the side surfaces are formed. The gas supply holes 234a to 234c have, for example, the same opening area from the lower part to the upper part, and are provided at the same opening pitch.

The downstream end of the Si ₂ H ₆ (disilane) gas supply pipe 301 is connected to the upstream end of the nozzle 233A. The Si ₂ H ₆ gas supply pipe 301 includes, in order from the upstream direction, a Si ₂ H ₆ gas supply source (not shown), a valve 301 _b that is an upstream on-off valve, and a mass flow controller that is a flow controller (flow control means). 301c and valve | bulb 301d which is a downstream on-off valve are provided. _Si 2 _{H 6} gas as the silicon-containing gas supplied from the Si ₂ H ₆ gas supply source flows through the mass flow controller 301c by an opening operation of the valve 301b, by the mass flow controller 301c is adjusted to a predetermined flow rate, the valve 301d Through the opening operation, the gas flows through the Si ₂ H ₆ gas supply pipe 301, is introduced into the nozzle 233A, and is supplied into the processing chamber 201 from the gas supply hole 234a.

The downstream end of the B ₂ H ₆ (diborane) gas supply pipe 302 is connected to the upstream end of the nozzle 233B. The B ₂ H ₆ gas supply pipe 302 includes, in order from the upstream direction, a B ₂ H ₆ gas supply source (not shown), a valve 302b that is an upstream on-off valve, and a mass flow controller that is a flow controller (flow control means). 302c and a valve 302d which is a downstream opening / closing valve are provided. _B 2 _{H 6} gas as the boron-containing gas supplied from the B ₂ H ₆ gas supply source flows through the mass flow controller 302c by an opening operation of the valve 302b, by the mass flow controller 302c is adjusted to a predetermined flow rate, the valve 302d Through the opening operation, the gas flows through the B ₂ H ₆ gas supply pipe 302, is introduced into the nozzle 233B, and is supplied into the processing chamber 201 from the gas supply hole 234b.

The downstream end of the O ₂ (oxygen) gas supply pipe 303 is connected to the upstream end of the nozzle 233C. The O ₂ gas supply pipe 303 includes, in order from the upstream direction, an O ₂ gas supply source (not shown), a valve 303b that is an upstream side open / close valve, a mass flow controller 303c that is a flow rate controller (flow rate control means), and a downstream side. A valve 303d, which is a side opening / closing valve, is provided. O _{2 O 2} gas as an oxygen-containing gas supplied from the gas supply source flows through the mass flow controller 303c by an opening operation of the valve 303b by the mass flow controller 303c is adjusted to a predetermined flow rate, by an opening operation of the valve 303d The gas flows through the O ₂ gas supply pipe 303, is introduced into the nozzle 233C, and is supplied into the processing chamber 201 through the gas supply hole 234c.

The downstream end of the H ₂ (hydrogen) gas supply pipe 304 is connected to the upstream end of the nozzle 233D. The H ₂ gas supply pipe 304 includes, in order from the upstream direction, an H ₂ gas supply source (not shown), a valve 304b that is an upstream on-off valve, a mass flow controller 304c that is a flow controller (flow control means), and a downstream A valve 304d which is a side opening / closing valve is provided. _{H 2} gas as a hydrogen-containing gas supplied from the H ₂ gas supply source flows through the mass flow controller 304c by an opening operation of the valve 304b by the mass flow controller 304c is adjusted to a predetermined flow rate, by an opening operation of the valve 304d The gas flows through the H ₂ gas supply pipe 304, is introduced into the nozzle 233D, and is supplied into the processing chamber 201 through the gas supply hole 234d.

The downstream side of the valve 301d of the Si ₂ H ₆ gas supply pipe 301, the downstream side of the valve 302d of the B ₂ H ₆ gas supply pipe 302, the downstream side of the valve 303d of the O ₂ gas supply pipe 303, and the H ₂ gas supply pipe 304 Connected to the downstream side of the valve 304d are downstream ends of N ₂ gas supply pipes 305, 306, 307, and 308 that supply, for example, N ₂ gas as an inert gas used for purge gas or carrier gas. The N ₂ gas supply pipes 305, 306, 307, and 308 include an N ₂ gas supply source (not shown), mass flow controllers 305c, 305e, 305g, and 305i, a valve 305d, a valve 305f, a valve 305h, and a valve 305j, respectively. They are provided in order from the upstream side.

N ₂ gas supply source _{N 2} gas supplied from the (not shown) by an opening operation of the valve 305d, while being adjusted to a predetermined flow rate by the mass flow controller 305c, and flows in the _Si 2 _{H 6} gas supply pipe 301 The gas is supplied into the processing chamber 201 through the gas supply hole 234a of the nozzle 233A. Further, the N ₂ gas flows through the B ₂ H ₆ gas supply pipe 302 while being adjusted to a predetermined flow rate by the mass flow controller 305e by opening the valve 305f, and passes through the gas supply hole 234b of the nozzle 233B. It is supplied into the processing chamber 201. Further, the N ₂ gas flows through the O ₂ gas supply pipe 303 while being adjusted to a predetermined flow rate by the mass flow controller 305g by opening the valve 305h, and passes through the gas supply hole 234c of the nozzle 233C. 201 is supplied to the inside. Further, the N ₂ gas flows through the H ₂ gas supply pipe 304 while being adjusted to a predetermined flow rate by the mass flow controller 305i by opening the valve 305j, and passes through the gas supply hole 234d of the nozzle 233D. 201 is supplied to the inside. Note that the purge gas and the carrier gas are not limited to N ₂ gas, but may be a rare gas such as Ar gas or He gas.

Mainly, Si ₂ H ₆ gas supply source (not shown), valve 301b, mass flow controller 301c, valve 301d, Si ₂ H ₆ gas supply pipe 301, N ₂ gas supply pipe 305, N ₂ gas supply source (not shown) The mass flow controller 305c, the valve 305d, the nozzle 233A, and the gas supply hole 234a constitute the Si ₂ H ₆ gas supply system according to this embodiment.

In addition, mainly a B ₂ H ₆ gas supply source (not shown), a valve 302b, a mass flow controller 302c, a valve 302d, a B ₂ H ₆ gas supply pipe 302, an N ₂ gas supply pipe 305, an N ₂ gas supply source ( The B ₂ H ₆ gas supply system according to the present embodiment is configured by the mass flow controller 305e, the valve 305f, the nozzle 233B, and the gas supply hole 234b.

Also, mainly an O ₂ gas supply source (not shown), a valve 303b, a mass flow controller 303c, a valve 303d, an O ₂ gas supply pipe 303, an N ₂ gas supply pipe 305, an N ₂ gas supply source (not shown). The mass flow controller 305g, the valve 305h, the nozzle 233C, and the gas supply hole 234c constitute an O ₂ gas supply system according to this embodiment.

Further, mainly, an H ₂ gas supply source (not shown), a valve 304b, a mass flow controller 304c, a valve 304d, an H ₂ gas supply pipe 304, an N ₂ gas supply pipe 305, and an N ₂ gas supply source (not shown). The mass flow controller 305i, the valve 305j, the nozzle 233D, and the gas supply hole 234d constitute an H ₂ gas supply system according to this embodiment.

Then, mainly, _Si 2 _{H 6} gas supply _system, B 2 _{H 6} gas supply system, _{O 2} gas supply system, the _{H 2} gas supply system, gas supply system according to this embodiment is constructed.

  The mass flow controllers 301c to 305c, 305e, 305g, and 305i, and the valves 301b to 304b, 301d to 305d, 305f, 305h, and 305j are electrically connected to the controller 240 described later.

(Control part)
As described above, the controller 240 as the control unit includes the rotation mechanism 254, the boat elevator 115, the heater 206, the temperature sensor 263, the pressure sensor 245, the pressure control device 242, the exhaust device 246, the mass flow controllers 301c to 305c, 305e, 305g, 305i and valves 301b to 304b, 301d to 305d, 305f, 305h, and 305j are electrically connected to control the operation of each part of the substrate processing apparatus.

Specifically, the controller 240 rotates the rotating shaft 254a of the rotating mechanism 254 at a predetermined timing. The controller 240 is configured to raise and lower the boat elevator 115 at a predetermined timing. Further, the controller 240 adjusts the valve opening degree of the pressure control device 242 based on the pressure information detected by the pressure sensor 245 so that the inside of the processing chamber 201 becomes a predetermined pressure at a predetermined timing. In addition, the controller 240 adjusts the power supply to the heater 206 based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 and the surface of the wafer 200 reach a predetermined temperature at a predetermined timing. . In addition, the controller 240 controls the flow of the mass flow controllers 301c to 305c, 305e, 305g, and 305i, and controls the opening and closing of the valves 301b to 304b, 301d to 305d, 305f, 305h, and 305j, respectively. Gas supply at a predetermined flow rate is started or stopped at a predetermined timing.

In the present embodiment, Si ₂ H ₆ gas as a silicon-containing gas and B ₂ H ₆ gas as a boron-containing gas are supplied into the processing chamber 201 containing the wafer 200 to contain silicon on the wafer 200. A silicon-containing and boron-containing film forming step for forming a boron-containing film, an O ₂ gas as an oxygen-containing gas, and an H ₂ gas as a hydrogen-containing gas in the processing chamber 201 set to a pressure lower than atmospheric pressure. The silicon-containing and boron-containing film modifying step of modifying the silicon-containing and boron-containing film formed on the wafer 200 to be a boron-doped silicon oxide film is performed as one cycle, and the cycle is performed one or more times. It is configured.

(2) Substrate Processing Step Next, a substrate processing step of forming a boron-doped silicon oxide film on the wafer 200 as one step of the semiconductor device manufacturing process using the processing furnace 202 having the above configuration will be described. FIG. 3 shows a film formation flow chart in the substrate processing step of the present embodiment, FIG. 4 shows a gas supply timing chart in the substrate processing step of the present embodiment, and FIG. 5 shows a deposition model diagram in the substrate processing step of the present embodiment. . In the following description, the operation of each part constituting the substrate processing apparatus is mainly controlled by the controller 240.

(Import process)
First, a plurality of wafers 200 are loaded into the boat 217 (wafer charge) (step S1). Next, the boat elevator 115 is driven based on the control of the controller 240 to raise the boat 217. As a result, as shown in FIG. 1, the boat 217 holding a plurality of wafers 200 is loaded into the processing chamber 201 (boat loading) (step S2). At this time, the seal cap 219 closes the lower end of the process tube 203 via the O-ring 220b. Thereby, the processing chamber 201 is hermetically sealed.

Until the loading of the boat 217 into the processing chamber 201 is completed, it is preferable to flow N ₂ gas into the processing chamber 201 as a purge gas. Specifically, while adjusting the flow rate by the mass flow controllers 305c, 305e, 305h, and 305i, the valves 305d, 305f, 305h, and 305j are opened, and N is supplied into the processing chamber 201 from the gas supply holes 234a to 234d of the nozzles 233A to 233D. _Two gases are preferably introduced. Thereby, it is possible to suppress intrusion of particles into the processing chamber 201 when the boat 217 is transported.

(Pressure adjustment process and temperature rise process)
When the loading of the boat 217 into the processing chamber 201 is completed, the atmosphere in the processing chamber 201 is exhausted so that the inside of the processing chamber 201 becomes a predetermined pressure (for example, 40 to 60 Pa) (step S3). Specifically, while exhausting by the exhaust device 246, feedback control of the valve opening degree of the pressure control device 242 is performed based on pressure information detected by the pressure sensor 245, and the inside of the processing chamber 201 is set to a predetermined pressure.

Further, heating is performed by the heater 206 so that the inside of the processing chamber 201 becomes a predetermined temperature (film formation temperature) (step S4). Specifically, the degree of energization to the heater 206 is controlled based on the temperature information detected by the temperature sensor 263, and the film formation temperature (for example, 300 to 600 ° C., particularly Si ₂ as a silicon-containing gas) is set in the processing chamber 201. In the present embodiment using H ₆ gas, the temperature is 300 to 400 ° C.).

  Then, the rotation mechanism 254 is activated to start the rotation of the wafer 200 carried into the processing chamber 201. The rotation of the wafer 200 is repeated by repeating this cycle a predetermined number of times, with a silicon-containing and boron-containing film forming step (step S5) described later and a silicon-containing and boron-containing film modifying step (step S6) as one cycle. Continue until the process (step S7) ends.

(Silicon-containing and boron-containing film forming process)
Subsequently, Si ₂ H ₆ gas as a silicon-containing gas and B ₂ H ₆ gas as a boron-containing gas are simultaneously supplied into the processing chamber 201 to form silicon-containing and boron-containing films on the wafer 200. A containing and boron-containing film forming step (step S5) is performed.

Specifically, the valve 301b is opened, and the valve 301d is opened while the mass flow controller 301c adjusts the flow rate to be within a range of, for example, 0.1 to 10 slm, and the gas flows through the Si ₂ H ₆ gas supply pipe 301. The Si ₂ H ₆ gas thus supplied is supplied into the processing chamber 201 from the gas supply hole 234a of the nozzle 233A.

In parallel with the supply of the Si ₂ H ₆ gas, B ₂ H ₆ gas is supplied into the processing chamber 201. Specifically, the valve 302b is opened, and the mass flow controller 302c is adjusted so that the flow rate is within a range of, for example, 0.1 to 50 slm, while the valve 302d is opened, and the B ₂ H ₆ gas supply pipe 302 is circulated. The B ₂ H ₆ gas thus supplied is supplied into the processing chamber 201 from the gas supply hole 234b of the nozzle 233B.

The gas flow rate when SiH ₄ gas is used instead of Si ₂ H ₆ gas as the silicon-containing gas is preferably in the range of 0.1 to 10 slm, for example, and B ₂ H ₆ gas is used as the boron-containing gas. The gas flow rate when using BCl ₃ gas is preferably in the range of 0.1 to 50 slm, for example.

As shown in FIG. 5A, the Si ₂ H ₆ gas and the B ₂ H ₆ gas supplied into the processing chamber 201 are adsorbed on the surface of the wafer 200 and thermally decomposed, and 1 on the surface of the wafer 200. Silicon-containing and boron-containing films of less than atomic layers to several atomic layers are formed. Si ₂ H ₆ gas and B ₂ H ₆ gas that have not contributed to the generation of the silicon-containing and boron-containing films flow through the processing chamber 201 and are exhausted from the gas exhaust pipe 231. As described above, the temperature of the heater 206 is maintained at a temperature in the range of 300 to 400 ° C., for example, and the pressure in the processing chamber 201 is maintained at a pressure in the range of 40 to 60 Pa, for example.

When a predetermined time (for example, 1 to 120 seconds) elapses, the valves 301b and 301d are closed to stop the supply of Si ₂ H ₆ gas, and the valves 302b and 302d are closed to stop the supply of B ₂ H ₆ gas.
Then, the valve of the pressure control device 242 is opened or the opening degree is increased, the inside of the processing chamber 201 is evacuated by the exhaust device 246, and the remaining Si ₂ H ₆ gas, B ₂ H ₆ gas, reaction generation Objects and the like are discharged from the processing chamber 201.

In the silicon-containing and boron-containing film forming step (step S5), the flow rate is adjusted by the mass flow controllers 305c, 305e, 305h, and 305i, and the valves 305d, 305f, 305h, and 305j are opened, and the gases of the nozzles 233A to 233D are opened. By introducing N ₂ gas into the processing chamber 201 from the supply holes 234a to 234d, the diffusion of Si ₂ H ₆ gas and B ₂ H ₆ gas in the processing chamber 201 is promoted, and the nozzles 233C and 233D enter the processing chamber 201. the Si ₂ H ₆ gas and _B 2 _{H 6} gas penetration may be suppressed.

(Silicon-containing and boron-containing film modification process)
Subsequently, the inside of the processing chamber 201 is set to a pressure lower than atmospheric pressure, and O ₂ gas as an oxygen-containing gas and H ₂ gas as a hydrogen-containing gas are supplied into the processing chamber 201 to generate an oxidizing species. A silicon-containing and boron-containing film modifying step (step S6) is performed to modify the silicon-containing and boron-containing films into, for example, a boron-doped silicon oxide film as a boron-containing and silicon-containing oxide film.

  Specifically, the valve of the pressure control device 242 is closed or the opening degree is reduced, and the pressure in the processing chamber 201 is less than atmospheric pressure, for example, within a range of 13.3 to 13332 Pa (0.1 to 100 Torr). Maintain pressure.

Then, the valve 303b is opened, and the flow rate is adjusted within the range of, for example, 0.1 to 10 slm by the mass flow controller 303c, while the valve 303d is opened and the O ₂ gas flowing through the O ₂ gas supply pipe 301 is removed. Then, the gas is supplied into the processing chamber 201 from the gas supply hole 234c of the nozzle 233C.

In parallel with the supply of O ₂ gas, H ₂ gas is supplied into the processing chamber 201. Specifically, the valve 304b is opened and the mass flow controller 304c is adjusted so that the flow rate is within a range of 0.1 to 100 slm, for example, while the valve 304d is opened and the H ₂ gas flowing through the H ₂ gas supply pipe 304 is adjusted. Gas is supplied into the processing chamber 201 from the gas supply hole 234c of the nozzle 233D.

As shown in FIG. 5B, the O ₂ gas and the H ₂ gas supplied into the processing chamber 201 are activated and reacted with non-plasma in a heated reduced pressure atmosphere, whereby atomic oxygen is reacted. Oxidized species including O and the like are generated. Then, mainly with this oxidizing species, the silicon-containing and boron-containing film formed on the wafer 200 in the silicon-containing and boron-containing film forming step (step S5) is oxidized. Then, as shown in FIG. 5C, the silicon-containing and boron-containing films are modified into boron-doped silicon oxide films by this oxidation treatment. O ₂ gas, H ₂ gas, intermediate products, and the like that have not contributed to the formation of the boron-doped silicon oxide film flow through the processing chamber 201 and are exhausted from the gas exhaust pipe 231. Note that the temperature of the heater 206 is maintained at the same temperature within the range of 300 to 400 ° C. as that in the silicon-containing and boron-containing film forming step (step S5) described above.

When a predetermined time (for example, 1 to 120 seconds) elapses, the valves 303b and 303d are closed to stop the supply of O ₂ gas, and the valves 304b and 304d are closed to stop the supply of H ₂ gas. Then, the valve of the pressure control device 242 is opened or the opening degree is increased, the inside of the processing chamber 201 is evacuated by the exhaust device 246, and the remaining O ₂ gas, H ₂ gas, reaction products, etc. are removed from the processing chamber 201. Drain from inside.

In the silicon-containing and boron-containing film forming step (step S6), the flow rate is adjusted by the mass flow controllers 305c, 305e, 305h, and 305i, the valves 305d, 305f, 305h, and 305j are opened and the gases of the nozzles 233A to 233D are opened. By introducing N ₂ gas into the processing chamber 201 from the supply holes 234a to 234d, the diffusion of O ₂ gas and H ₂ gas in the processing chamber 201 is promoted, and the O ₂ gas into the nozzles 233C and 233D and it may be suppressed penetration of H ₂ gas.

(Repeated process)
The above-described silicon-containing and boron-containing film forming step (step S5) and silicon-containing and boron-containing film modifying step (step S6) are defined as one cycle, and this cycle is performed a predetermined number of times (one or more times) (step S7). .

(Purge process)
When the boron-doped silicon oxide film having a predetermined thickness is formed, the purge process (step S8) is performed. Specifically, the valves 305d, 305f, 305h, and 305j are opened or the opening degree is increased, and the inside of the processing chamber 201 is replaced with a gas atmosphere of N ₂ gas.

(Atmospheric pressure recovery process and cooling process)
When the purge process (step S8) is completed after a predetermined time (for example, 20 to 500 seconds) has elapsed, the rotation of the boat 217 is stopped and the rotation of the wafer 200 is stopped. Then, the temperature of the wafer 200 is lowered while returning the pressure in the processing chamber 201 to atmospheric pressure. Specifically, the valves 305 d, 305 f, 305 h, and 305 j are kept open, and N ₂ gas is supplied into the processing chamber 201, and the valve of the exhaust device 246 is controlled based on the pressure information detected by the pressure sensor 245. The opening degree is feedback-controlled, and the pressure in the processing chamber 201 is increased to atmospheric pressure (step S9). Then, the energization amount to the heater 206 is controlled to lower the temperature of the wafer 200.

(Unloading process)
Thereafter, the boat 217 holding the processed wafers 200 is unloaded from the processing chamber 201 (boat unloading) by reversing the above loading process (step S10). Thereafter, the processed wafer 200 is taken out from the boat 217 (wafer discharge) (step S11). Then, the substrate processing process according to this embodiment is completed.

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

(A) According to the present embodiment, Si ₂ H ₆ gas (silicon-containing gas) and B ₂ H ₆ gas (boron-containing gas) are supplied into the processing chamber 201 to contain silicon and boron on the surface of the wafer 200. A silicon-containing and boron-containing film forming step for forming a film (step S5), and an O ₂ gas (oxygen-containing gas) gas and an H ₂ gas (hydrogen-containing gas) in the processing chamber 201 set to a pressure lower than atmospheric pressure. The silicon-containing and boron-containing film modifying step (step S6) for modifying the silicon-containing and boron-containing film formed on the surface of the wafer 200 to a boron-doped silicon oxide film is defined as one cycle. More than once, a boron-doped silicon oxide film is formed. Thus, a boron-doped silicon oxide film is formed by supplying Si ₂ H ₆ gas and B ₂ H ₆ gas together into the processing chamber 201 in the silicon-containing and boron-containing film forming step (step S5). It is possible to reduce the film formation temperature (processing temperature) during the process. And the performance fall of a semiconductor device and the production yield fall can be suppressed. For example, when a heat-sensitive film exists on the surface of the wafer 200, it is effective to prevent the film from being thermally deteriorated.

(B) According to the present embodiment, in the silicon-containing and boron-containing film forming step (step S5), the Si ₂ H ₆ gas (silicon-containing gas) and the B ₂ H ₆ gas (boron-containing gas) are contained in the processing chamber 201. Are supplied at the same time. Thus, by supplying not only Si ₂ H ₆ gas but also B ₂ H ₆ gas into the processing chamber 201, decomposition of Si ₂ H ₆ gas supplied into the processing chamber 201 can be promoted. It becomes possible. Then, the deposition rate of the boron-doped silicon oxide film can be improved, and the substrate processing productivity can be increased.

(C) According to the present embodiment, in the silicon-containing and boron-containing film forming step (step S5), O ₂ gas (oxygen-containing gas) and H ₂ gas (in the processing chamber 201 set to a pressure lower than atmospheric pressure) Hydrogen-containing gas). Then, in a heated reduced pressure atmosphere, O ₂ gas and H ₂ gas are activated and reacted with non-plasma, thereby generating an oxidizing species containing O such as atomic oxygen. Then, the silicon-containing and boron-containing films are modified into boron-doped silicon oxide films by this oxidizing species. Thus, O by ₂ adding gas to H ₂ gas, than when supplying O ₂ gas alone into the processing chamber 201 can be performed to generate oxidizing species at low temperatures, yet low deposition temperature It becomes possible to make it. In addition, deterioration of the boron-doped silicon oxide film can be reduced.

(D) According to this embodiment, the inside of the processing chamber 201 is inert gas between the silicon-containing and boron-containing film forming step (step S5) and the silicon-containing and boron-containing film modifying step (step S6). There is no inert gas replacement step for replacing the atmosphere. In addition, the inside of the processing chamber 201 is also filled with an inert gas between the silicon-containing and boron-containing film modifying step (step S6) and the silicon-containing and boron-containing film forming step (step S5) performed in the next cycle. There is no inert gas replacement step for replacing the atmosphere. By simplifying the process in this way, it becomes possible to improve the productivity of substrate processing.

(E) According to this embodiment, Si ₂ H ₆ gas (silicon-containing gas) and B ₂ H ₆ gas (boron-containing gas) are simultaneously supplied into the processing chamber 201. Therefore, B can be positively doped in the silicon-containing film. Further, the B concentration in the boron-doped silicon oxide film can be positively controlled by controlling the gas flow rate and supply time of the B ₂ H ₆ gas into the processing chamber 201.

  For reference, a problem of a conventional silicon oxide film forming process will be described.

As a conventional process for forming a silicon oxide film, a silicon-containing gas such as TEOS (tetraethoxysilane, Si (OC ₂ H ₅ ) ₄ gas or SiH ₄ gas and an oxygen-containing gas such as O ₂ gas are placed in the processing chamber. At the same time, the CVD method, 3DMAS (trisdimethylaminosilane, Si (N (CH ₃ ) ₂ )) ₃ H) or other organic silicon-containing gas, and O ₃ gas or other oxygen-containing gas are alternately supplied into the processing chamber. The ALD method was used to repeat the cycle.

  FIG. 12 is a diagram showing gas supply timing by the conventional CVD method. In the conventional CVD method shown in FIG. 12, before supplying the silicon-containing gas into the processing chamber, the oxygen-containing gas is first supplied as a purge gas, and then the silicon-containing gas and the oxygen-containing gas are supplied into the processing chamber. The interior of the chamber is increased to a predetermined pressure to form a film, and then the supply of the silicon-containing gas is stopped first, the oxygen-containing gas is continuously supplied as a purge gas for a predetermined time, and then the supply of the oxygen-containing gas is stopped. The substrate processing is finished.

  However, in the conventional silicon oxide film formation process, it is necessary to increase the film formation temperature to, for example, 1000 ° C. As a result, for example, impurities implanted into the source or drain region on the substrate may be diffused, and the performance of the semiconductor device may be deteriorated or the production yield may be deteriorated. Further, in order to raise the film formation temperature, the power consumption increases, and TCOO (Total Cost Of Ownership) may increase.

Further, in the conventional silicon oxide film formation process, the film formation speed is determined by the film formation temperature and the film formation pressure. Therefore, in order to reduce the film formation temperature while avoiding the decrease in the film formation rate, it is necessary to increase the film formation pressure. However, when the film forming pressure is increased, the gas density in the processing chamber increases, the mean free process of gas molecules decreases, and the step coverage of the silicon oxide film may deteriorate. If the mean free path of gas molecules is reduced, the uniformity of the silicon oxide film thickness, film quality, etc. may be reduced (loading effect) between the upstream and downstream sides of the gas flow in the processing chamber. .

  In the conventional silicon oxide film formation process, when the film formation temperature is lowered, atoms other than silicon and oxygen (for example, carbon, hydrogen, nitrogen, etc.) contained in the processing gas are oxidized as unintended impurities. There was a tendency to remain in the film. These unintentional impurities can cause unexpected device malfunctions. According to this embodiment, these problems in the conventional silicon oxide film forming process can be solved.

<Modification of First Embodiment>
In this modification, the inside of the processing chamber 201 is replaced with an inert gas atmosphere between the silicon-containing and boron-containing film forming step (step S5) and the silicon-containing and boron-containing film modifying step (step S6). An inert gas replacement step is provided. In addition, between the silicon-containing and boron-containing film reforming step (step S6) and the silicon-containing and boron-containing film forming step (step S5) performed in the next cycle, the inside of the processing chamber 201 is filled with an inert gas. An inert gas replacement step for replacing the atmosphere is provided. Other configurations are the same as those of the first embodiment.

FIG. 6 is a gas supply timing chart of the substrate processing process provided with the inert gas replacement process.
6 shows the timing of supplying N ₂ gas as an inert gas used in the inert gas replacement step.

In this modification, after the silicon-containing and boron-containing film forming step (step S5) is finished, the supply of Si ₂ H ₆ gas and B ₂ H ₆ gas is stopped, and N ₂ gas is supplied to fill the inside of the processing chamber 201. Replace with N ₂ gas atmosphere. When a predetermined time (for example, 1 to 120 seconds) elapses, O ₂ gas and H ₂ gas are supplied into the processing chamber 201 to perform a silicon-containing and boron-containing film reforming step (step S6).

Then, after the silicon-containing and boron-containing film modification step (step S6) is finished, the supply of O ₂ gas and H ₂ gas is stopped, and N ₂ gas is supplied to bring the inside of the processing chamber 201 into an atmosphere of N ₂ gas. Replace again. When a predetermined time (for example, 1 to 120 seconds) elapses, the silicon-containing and boron-containing film forming step (step S5) in the next cycle is performed again.

According to this modification, after the silicon-containing and boron-containing film forming step (step S5) is finished, the supply of Si ₂ H ₆ gas and B ₂ H ₆ gas is stopped and the inside of the processing chamber 201 is filled with an atmosphere of N ₂ gas. Therefore, Si ₂ H ₆ gas, B ₂ H ₆ gas, intermediate products, etc. that have not contributed to the generation of the silicon-containing and boron-containing films are prevented from remaining in the processing chamber 201. it can. Thereby, in the silicon-containing and boron-containing film modification step (step S6) to be performed next, the generation of oxidized species due to the reaction of O ₂ gas and H ₂ gas is hindered by the residue, It can be avoided that the oxidation of the boron-containing film is hindered by the residue. Then, the oxidation of the silicon-containing and boron-containing films can be promoted, and the modification to the boron-doped silicon oxide film can be promoted. Moreover, it can avoid that the supply of the oxidation seed | species to the wafer 200 surface is prevented by the residue, and can improve the step coverage characteristic of a silicon oxide film.

Further, according to this modification, after the silicon-containing and boron-containing film modification step (step S6) is completed, the supply of O ₂ gas and H ₂ gas is stopped and the inside of the processing chamber 201 is replaced with an atmosphere of N ₂ gas. Therefore, O ₂ gas, H ₂ gas, intermediate products, etc. that have not contributed to the formation of the boron-doped silicon oxide film can be prevented from remaining in the processing chamber 201. Thereby, in the silicon-containing and boron-containing film forming step (step S5) performed in the next cycle, the adsorption of Si ₂ H ₆ gas and B ₂ H ₆ gas on the surface of the wafer 200 is hindered by the residue. The formation of silicon-containing and boron-containing films can be promoted, and the step coverage characteristics of the silicon oxide film can be improved.

<Second Embodiment>
In the present embodiment, a Si ₂ H ₆ gas as a silicon-containing gas is supplied into the processing chamber 201 to form a silicon-containing film on the wafer 200, and the pressure is set to a pressure lower than atmospheric pressure. A B ₂ H ₆ gas as a boron-containing gas, an O ₂ gas as an oxygen-containing gas, and an H ₂ gas as a hydrogen-containing gas are supplied into the processing chamber 201 so that the silicon-containing film on the wafer 200 contains silicon and boron. The silicon-containing film modifying step for modifying the boron-doped silicon oxide film as the containing film is one cycle, and the cycle is performed once or more. That is, in this embodiment, the supply of the boron-containing gas into the processing chamber 201 is performed not in the silicon-containing film forming step (step S21) but in the silicon-containing film modifying step (step S22). Is different from the first embodiment. The configuration of the processing furnace 202 is the same as that in the first embodiment.

  FIG. 7 is a diagram showing a film forming flow in the substrate processing step of the second embodiment of the present invention, FIG. 8 is a gas supply timing diagram in the substrate processing step of the second embodiment, and FIG. It is a deposition model figure in the substrate processing process of the embodiment.

(1) Substrate Processing Step First, the same wafer charge (step S1) to temperature adjustment (step S4) as in the first embodiment is performed.

(Silicon-containing film formation process)
Subsequently, a Si ₂ H ₆ gas as a silicon-containing gas is supplied into the processing chamber 201, and a silicon-containing film forming step (step S21) for forming a silicon-containing film on the wafer 200 is performed.

Specifically, the valve 301b is opened, and the valve 301d is opened while the mass flow controller 301c adjusts the flow rate to be within a range of, for example, 0.1 to 10 slm, and the gas flows through the Si ₂ H ₆ gas supply pipe 301. The Si ₂ H ₆ gas thus supplied is supplied into the processing chamber 201 from the gas supply hole 234a of the nozzle 233A.

As shown in FIG. 9A, the Si ₂ H ₆ gas supplied into the processing chamber 201 is adsorbed on the surface of the wafer 200 and thermally decomposes, and the surface of the wafer 200 is less than one atomic layer to several atomic layers. The silicon-containing film is formed. Si ₂ H ₆ gas that has not contributed to the generation of the silicon-containing film flows through the processing chamber 201 and is exhausted from the gas exhaust pipe 231. The temperature of the heater 206 is maintained at a temperature in the range of 300 to 400 ° C., for example, and the pressure in the processing chamber 201 is maintained at a pressure in the range of 40 to 60 Pa, for example.

When a predetermined time (for example, 1 to 120 seconds) elapses, the valves 301b and 301d are closed and the supply of Si ₂ H ₆ gas is stopped. Then, the valve of the pressure control device 242 is opened or the opening degree is increased, the inside of the processing chamber 201 is evacuated by the exhaust device 246, and the remaining Si ₂ H ₆ gas, reaction products, etc. are removed from the processing chamber 201. Discharge.

In the silicon-containing film formation step (step S21), the flow rate is adjusted by the mass flow controllers 305c, 305e, 305h, and 305i, and the valves 305d and 3
05f, 305h, and 305j are opened, and N ₂ gas is introduced into the processing chamber 201 from the gas supply holes 234a to 234d of the nozzles 233A to 233D, thereby accelerating the diffusion of the Si ₂ H ₆ gas in the processing chamber 201. At the same time, the intrusion of Si ₂ H ₆ gas into the nozzles 233C and 233D may be suppressed.

(Silicon-containing film modification process)
Subsequently, the inside of the processing chamber 201 is set to a pressure lower than atmospheric pressure, and B ₂ H ₆ gas as a boron-containing gas, O ₂ gas as an oxygen-containing gas, and H ₂ gas as a hydrogen-containing gas are put into the processing chamber 201. Then, a silicon-containing film modification step (step S22) is performed to modify the silicon-containing film on the wafer 200 into a boron-doped silicon oxide film.

  Specifically, the valve of the pressure control device 242 is closed or the opening degree is reduced, and the pressure in the processing chamber 201 is less than atmospheric pressure, for example, within a range of 13.3 to 13332 Pa (0.1 to 100 Torr). Maintain pressure.

Then, B ₂ H ₆ gas is supplied into the processing chamber 201. Specifically, the valve 302b is opened, and the mass flow controller 302c is adjusted so that the flow rate is within a range of, for example, 0.1 to 50 slm, while the valve 302d is opened, and the B ₂ H ₆ gas supply pipe 302 is circulated. The B ₂ H ₆ gas thus supplied is supplied into the processing chamber 201 from the gas supply hole 234b of the nozzle 233B.

In parallel with the supply of the B ₂ H ₆ gas, the valve 303b is opened, and the valve 303d is opened while the flow rate is adjusted within the range of 0.1 to 10 slm by the mass flow controller 303c, and the O ₂ gas is supplied. The O ₂ gas flowing through the pipe 301 is supplied into the processing chamber 201 from the gas supply hole 234c of the nozzle 233C.

_In parallel with the supply of the B 2 _{H 6} gas and _{O 2} gas, an _{H 2} gas is supplied into the process chamber 201. Specifically, the valve 304b is opened and the mass flow controller 304c is adjusted so that the flow rate is within a range of 0.1 to 100 slm, for example, while the valve 304d is opened and the H ₂ gas flowing through the H ₂ gas supply pipe 304 is adjusted. Gas is supplied into the processing chamber 201 from the gas supply hole 234c of the nozzle 233D.

As shown in FIG. 9B, the B ₂ H ₆ gas supplied into the processing chamber 201 is adsorbed on the silicon-containing film formed on the surface of the wafer 200 and thermally decomposed. At the same time, the O ₂ gas and the H ₂ gas supplied into the processing chamber 201 are activated and reacted with non-plasma in a heated reduced-pressure atmosphere, thereby generating oxidized species including atomic oxygen O and the like. The Then, as shown in FIG. 9C, the silicon-containing and boron-containing films are formed by the B ₂ H ₆ gas thermally decomposed on the surface of the silicon-containing film, while the silicon-containing and boron-containing films are formed by the generated oxidizing species. The contained film is oxidized to be modified into a boron-doped silicon oxide film. B ₂ H ₆ gas, O ₂ gas, H ₂ gas, intermediate products, etc. that have not contributed to the formation of the boron-doped silicon oxide film flow through the processing chamber 201 and are exhausted from the gas exhaust pipe 231. Note that the temperature of the heater 206 is maintained at the same temperature within the range of, for example, 300 to 400 ° C. as in the above-described silicon-containing film modification step (step S22).

When a predetermined time (for example, 1 to 120 seconds) elapses, the supply of B ₂ H ₆ gas, O ₂ gas, and H ₂ gas is stopped, the inside of the processing chamber 201 is evacuated, and the remaining B ₂ H ₆ gas, O _Two gases, H ₂ gas, and reaction products are discharged from the processing chamber 201.

In the silicon-containing film modification step (step S22), the flow rate is adjusted by the mass flow controllers 305c, 305e, 305h, and 305i, and the valves 305d and 3
05f, 305h, and 305j are opened, and N ₂ gas is introduced into the processing chamber 201 from the gas supply holes 234a to 234d of the nozzles 233A to 233D, whereby B ₂ H ₆ gas and O ₂ gas in the processing chamber 201 are introduced. , The diffusion of H ₂ gas may be promoted, and the penetration of B ₂ H ₆ gas, O ₂ gas, and H ₂ gas into the nozzles 233C and 233D may be suppressed.

(Repeated process)
The above-described silicon-containing film formation step (step S21) and silicon-containing film modification step (step S22) are set as one cycle, and this cycle is performed a predetermined number of times (one or more times) (step S23).

  Thereafter, the same purge (step S8) to wafer discharge (step S11) as in the first embodiment are performed, and the substrate processing step according to the present embodiment is completed.

(2) Effects According to the Present Embodiment According to the present embodiment, in addition to the one or more effects described in the first embodiment, the following one or more effects are achieved.

(A) According to the present embodiment, a silicon-containing film forming step (step S21) of forming a silicon-containing film on the wafer 200 by supplying Si ₂ H ₆ gas (silicon-containing gas) into the processing chamber 201. Then, B ₂ H ₆ gas (boron-containing gas), O ₂ gas (oxygen-containing gas), and H ₂ gas (hydrogen-containing gas) are supplied into the processing chamber 201 set to a pressure lower than atmospheric pressure, and the wafer 200 is supplied. The silicon-containing film modifying step (step S22) for modifying the upper silicon-containing film into a boron-doped silicon oxide film is performed as one cycle, and the cycle is performed once or more to form a boron-doped silicon oxide film. Yes. As described above, in the silicon-containing film modification step (step S22), the B ₂ H ₆ gas is also supplied into the processing chamber 201 to thereby form a deposition temperature (processing chamber) when forming the boron-doped silicon oxide film. It is possible to reduce the temperature in 201). And the performance fall of a semiconductor device and the production yield fall can be suppressed.

(B) According to the present embodiment, B ₂ H ₆ gas, O ₂ gas, and H ₂ gas are simultaneously supplied into the processing chamber 201 in the silicon-containing film modification step (step S22). As described above, by supplying the B ₂ H ₆ gas together into the processing chamber 201, it becomes possible to promote the decomposition of the Si ₂ H ₆ gas adsorbed on the wafer 200. Then, the deposition rate of the boron-doped silicon oxide film can be improved, and the substrate processing productivity can be increased.

(C) According to the present embodiment, the B ₂ H ₆ gas is also supplied into the processing chamber 201 in the silicon-containing film modification step (step S22). Therefore, B can be positively doped in the silicon-containing film. Further, the B concentration in the boron-doped silicon oxide film can be positively controlled by controlling the gas flow rate and supply time of the B ₂ H ₆ gas into the processing chamber 201.

<Modification of Second Embodiment>
In this modification, an inert gas replacement step of replacing the inside of the processing chamber 201 with an inert gas atmosphere between the silicon-containing film formation step (step S21) and the silicon-containing film modification step (step S22). Is provided. Moreover, the inertness which replaces the inside of the process chamber 201 with the atmosphere of an inert gas also between a silicon-containing film modification process (step S22) and the silicon-containing film formation process (step S21) implemented in the next cycle. A gas replacement step is provided. Other configurations are the same as those of the second embodiment.

FIG. 10 is a gas supply timing chart of the substrate processing step provided with an inert gas replacement step showing a modification of the second embodiment. At the bottom of FIG. 10, the timing of supplying N ₂ gas as an inert gas used in the inert gas replacement step is shown.

In this modification, after the silicon-containing film forming step (step S21) is completed, the supply of Si ₂ H ₆ gas is stopped, and N ₂ gas is supplied to replace the inside of the processing chamber 201 with an atmosphere of N ₂ gas. When a predetermined time (for example, 1 to 120 seconds) elapses, B ₂ H ₆ gas, O ₂ gas, and H ₂ gas are supplied into the processing chamber 201 to perform the silicon-containing film modification step (step S22).

After completion of the silicon-containing Makuaratame quality step (step _S22), B 2 _{H 6} gas, the supply of _{O 2} gas and _{H 2} gas is stopped, _{N 2} gas _{N 2} gas supplied to the processing chamber 201 Replace again with the atmosphere. When a predetermined time (for example, 1 to 120 seconds) elapses, the silicon-containing film forming step (step S21) of the next cycle is performed again.

According to this modification, after the silicon-containing film forming step (step S21) is completed, the supply of Si ₂ H ₆ gas is stopped and the inside of the processing chamber 201 is replaced with an N ₂ gas atmosphere. It is possible to suppress Si ₂ H ₆ gas, intermediate products, and the like that have not contributed to the film formation from remaining in the processing chamber 201. Thereby, in the silicon-containing film modification process (step S22) performed next, it can be avoided that the adsorption of B ₂ H ₆ gas to the silicon-containing film formed on the wafer 200 is hindered by the residue, Formation of silicon-containing and boron-containing films (boron doping into silicon-containing films) can be promoted. In addition, it is possible to prevent the generation of oxidizing species due to the reaction of O ₂ gas and H ₂ gas from being hindered by the residue, and the oxidation of the silicon-containing and boron-containing film by the oxidizing species from being hindered by the residue. Then, the oxidation of the silicon-containing and boron-containing films can be promoted, and the modification to the boron-doped silicon oxide film can be promoted. In addition, it can be avoided that the supply of B ₂ H ₆ gas and oxidizing species to the silicon-containing film formed on the wafer 200 is hindered by the residue, and the step coverage characteristics of the silicon oxide film can be improved.

Further, according to this modification, after the silicon-containing film modification step (step S22) is completed, the supply of B ₂ H ₆ gas, O ₂ gas, and H ₂ gas is stopped and the inside of the processing chamber 201 is filled with N ₂ gas. Since the atmosphere is replaced, B ₂ H ₆ gas, O ₂ gas, H ₂ gas, intermediate products, etc. that have not contributed to the formation of the boron-doped silicon oxide film remain in the processing chamber 201 as residues. This can be suppressed. Thereby, in the silicon-containing film forming step (step S21) to be performed in the next cycle, it is possible to avoid that the adsorption of Si ₂ H ₆ gas to the surface of the wafer 200 is hindered by the residue, and the formation of the silicon-containing film. And step coverage characteristics of the silicon oxide film can be improved.

<Third Embodiment>
In this embodiment, the point from which the process tube 203 as a reaction tube is comprised as a double tube structure provided with the inner tube 204 and the outer tube 205 differs from the above-mentioned embodiment. And the nozzles 233A-233D with which a gas supply system is provided are comprised short, and the point from which the gas supply system is comprised so that gas may be supplied from the downward direction in the inner tube 204 differs from the above-mentioned embodiment. The configurations other than the process tube 203 and the gas supply system nozzles 233A to 233D are the same as those in the first embodiment.

  FIG. 11 is a longitudinal sectional view of the processing furnace 202 of the substrate processing apparatus used in the third embodiment of the present invention.

As shown in FIG. 11, the process tube 203 according to the present embodiment includes an inner tube 204 as an internal reaction tube and an outer tube 205 as an external reaction tube provided outside the inner tube 204. . The inner tube 204 is formed in a cylindrical shape with an upper end and a lower end opened. A processing chamber 201 is formed in the cylindrical hollow portion of the inner tube 204. The outer tube 205 has an inner diameter larger than the outer diameter of the inner tube 204, is formed in a cylindrical shape with the upper end closed and the lower end opened. The outer tube 205 is provided concentrically with the inner tube 204. The inner tube 204 and the outer tube 205 are made of a heat resistant material such as quartz or silicon carbide. The inner tube 204 may have a gas exhaust hole on the opposite side of the gas supply system. In this case, the gas exhaust holes may have the same opening area from the lower part to the upper part, for example, and may be provided at the same opening pitch.

  The manifold 209 is configured to engage with the inner tube 204 and the outer tube 205 and support them from below. An O-ring 220a as a seal member is provided between the manifold 209 and the outer tube 205. The heater 206 is vertically installed by being supported by a heater base 251 as a holding plate. In addition, a plurality of heat insulating plates 216 are arranged in a multi-stage in a horizontal posture instead of the heat insulating member 218 at the lower portion of the boat 217. The heat insulating plate 216 is made of a heat resistant material such as quartz or silicon carbide. The heat insulating plate 216 is formed in a disc shape. The heat insulating plate 216 makes it difficult to transfer the heat from the heater 206 to the lower end side of the manifold 209. The gas exhaust pipe 231 is disposed at the lower end portion of the cylindrical space formed by the gap between the inner tube 204 and the outer tube 205, and communicates with the cylindrical space.

Nozzles 230 </ b> A to 230 </ b> D as gas introduction portions are connected to the seal cap 219 so as to communicate with the inside of the processing chamber 201. A Si ₂ H ₆ gas supply pipe 301 is connected to the upstream end of the nozzle 230A. Further, a B ₂ H ₆ gas supply pipe 302 is connected to the nozzle 230B. Further, an O ₂ gas supply pipe 303 is connected to the nozzle 230C. Further, an H ₂ gas supply pipe 304 is connected to the nozzle 230D. The downstream ends of the nozzles 230 </ b> A to 230 </ b> D are configured to supply gas into the inner tube 204 from the lower side of the inner tube 204. The nozzles 230A to 230D may be configured as the porous nozzle described in the first embodiment.

  Various gases supplied into the processing chamber 201 from the nozzles 230 </ b> A to 230 </ b> D flow from the lower stage (the gas upstream side) to the upper stage (the gas upstream side) of the boat 217 and are supplied to the surface of the wafer 200 held by the boat 217. . Gases and intermediate products that have not contributed to the film formation flow from the upper end opening of the inner tube 204 to the outer tube 205, flow through the outer tube 205, and are exhausted from the gas exhaust pipe 231.

  According to this embodiment, the process tube 203 as a reaction tube is configured by a double tube structure of an inner tube 204 and an outer tube 205. Thereby, the gas concentration supplied into the processing chamber 201 can be increased.

  Further, according to the present embodiment, in the silicon-containing and boron-containing film modifying step (S6), the pressure in the processing chamber 201 is less than atmospheric pressure, for example, in the range of 13.3 to 13332 Pa (0.1 to 100 Torr). It is easy to maintain the pressure at a low pressure. Therefore, the silicon-containing and boron-containing film forming step (S5) and the silicon-containing and boron-containing film modifying step (S6) can be performed efficiently.

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

For example, as a silicon-containing gas, in addition to Si ₂ H ₆ gas, inorganic gas such as SiH ₄ gas, Si ₃ H ₈ gas, SiH ₂ Cl ₂ gas, SiHCl ₃ gas, SiCl ₄ gas, and aminosilane-based gas can be used. 4DMAS (tetrakisdimethylaminosilane, Si (N (CH ₃ ) ₂ )) ₄ ), 3DMAS (trisdimethylaminosilane, Si (N (CH ₃ ) ₂ )) ₃ H), 2DEAS (bisdiethylaminosilane, Si (N (C Organic gases such as ₂ H ₅ ) ₂ ) ₂ H ₂ ), BTBAS (Bisturary butylaminosilane, SiH ₂ (NH (C ₄ H ₉ )) ₂ ) may be used. In particular, when SiH ₄ gas or Si ₂ H ₆ gas is used, processing can be performed at a lower cost than when effective HCD (hexachlorodisilane) gas is used.

As the boron-containing gas, BCl ₃ gas may be used in addition to B ₂ H ₆ gas.

Further, in the silicon-containing and boron-containing film forming step (step S5) according to the first embodiment, a Ge (germane) -containing gas may be further supplied into the processing chamber 201. Further, in the silicon-containing film modifying step (step S22) according to the second embodiment, a Ge (germane) -containing gas may be further supplied into the processing chamber 201. Thus, by further supplying the Ge-containing gas, the decomposition of the silicon-containing gas supplied into the processing chamber 201 can be further promoted. As the Ge-containing gas, for example, GeH ₄ gas or Ge ₂ H ₆ gas can be used.

As the oxygen-containing gas, O ₃ gas, H ₂ O gas, NO gas, N ₂ O gas, NO _x gas, CO gas, CH ₃ COOH gas, or the like may be used in addition to O ₂ gas. By using NO gas, N ₂ O gas, NO _x gas, or the like as the oxygen-containing gas, the boron-doped silicon oxide film can be doped with nitrogen (N), and the gas enters the processing chamber 201. By controlling the supply flow rate and supply time of N, the N concentration in the boron-doped silicon oxide film can be positively controlled. Further, by using CO gas, CH ₃ COOH gas, or the like as the oxygen-containing gas, carbon (C) can be doped into the boron-doped silicon oxide film, and supply of such gas into the processing chamber 201 is possible. By controlling the flow rate and the supply time, the C concentration in the boron-doped silicon oxide film can be positively controlled. By controlling the concentration of impurities such as N and C in the boron-doped silicon oxide film, the charge trap density in the semiconductor device can be improved.

Further, as the hydrogen-containing gas, in addition to H ₂ gas, may be used NH ₃ gas is a nitrogen-containing gas. Thereby, nitrogen (N) can be doped in the boron-doped silicon oxide film. Further, by controlling the gas flow rate and supply time of NH ₃ gas into the processing chamber 201, the N concentration in the boron-doped silicon oxide film can be controlled.

In the above-described embodiment, the silicon oxide film is formed. However, the present invention is not limited to such a form, and can be suitably applied to the case of forming a silicon nitride film. That is, instead of the oxygen-containing gas and the hydrogen-containing gas, for example, NH ₃ gas or the like is supplied as a nitrogen-containing gas into the processing chamber 201, and the silicon-containing and boron-containing films are nitrided to form a SiBN film having a high dielectric constant. be able to. In such a case, the SiGeN film can be formed by using a germane-containing gas instead of the boron-containing gas.

  Moreover, an SiON film, a SiCN film, or the like can be formed by using an organic silicon-containing gas as the silicon-containing gas and using a nitrogen-containing gas, a carbon-containing gas, or a mixed gas thereof instead of the boron-containing gas. That is, a good ternary insulating film such as a SiON film, a SiCN film, a SiBN film, or a SiGeN film can be formed. Furthermore, by controlling the gas flow rate and supply time of the gas, a low-temperature insulating film in which the N concentration, C concentration, Ge concentration, and B concentration in the film are controlled can be formed.

  Further, the present invention is not limited to the substrate processing apparatus provided with the vertical processing furnace according to the present embodiment, but can be suitably applied to a substrate processing apparatus having a single wafer type, a Hot Wall type, or a Cold Wall type processing furnace. it can.

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

According to one aspect of the invention,
A silicon-containing and boron-containing film forming step of forming a silicon-containing and boron-containing film on the substrate by supplying a silicon-containing gas and a boron-containing gas into a processing chamber containing the substrate;
Silicon for reforming the silicon-containing and boron-containing films formed on the substrate by supplying an oxygen-containing gas and a hydrogen-containing gas into the processing chamber set to a pressure lower than atmospheric pressure into a boron-containing and silicon-containing oxide film Containing and boron containing film modifying step;
Have
A method of manufacturing a semiconductor device is provided in which the silicon-containing and boron-containing film forming step and the silicon-containing and boron-containing film modifying step are set as one cycle, and the cycle is performed once or more.

  Preferably, in the silicon-containing and boron-containing film reforming step, an oxygen-containing oxidizing species is obtained by reacting the oxygen-containing gas and the hydrogen-containing gas in the processing chamber under a pressure atmosphere lower than atmospheric pressure. The silicon-containing and boron-containing film formed and formed on the substrate by the oxidizing species is modified.

More preferably, the silicon-containing gas is SiH ₄ gas, Si ₂ H ₆ gas, or Si ₂ Cl ₆ gas.

  More preferably, the silicon-containing and boron-containing film forming step and the silicon-containing and boron-containing film modifying step are performed while maintaining the processing chamber at a constant temperature.

  More preferably, after completion of the silicon-containing and boron-containing film forming step, the supply of the silicon-containing gas and the boron-containing gas is stopped, an inert gas is supplied into the processing chamber, and the processing chamber is inerted. It further has an inert gas replacement step of replacing with a gas atmosphere.

  More preferably, after completion of the silicon-containing and boron-containing film reforming step, the supply of the oxygen-containing gas and the hydrogen-containing gas is stopped, an inert gas is supplied into the processing chamber, and the processing chamber is filled with the inert gas. It further has an inert gas replacement step of replacing the atmosphere with an active gas.

More preferably, the hydrogen-containing gas is H ₂ gas or NH ₃ gas.

More preferably, the oxidation-containing gas is O ₂ gas, O ₃ gas, NO gas, N ₂ O gas, NO _x gas, CO gas, H ₂ O gas, or CH ₃ COOH gas.

More preferably, the boron-containing gas is B ₂ H ₆ gas or BCl ₃ gas.

  More preferably, the silicon-containing and boron-containing film forming step and the silicon-containing and boron-containing film reforming step are provided in an inner tube that forms the processing chamber and an outer side of the inner tube in a gas exhaust part. It is performed by a processing furnace having a double tube structure with an outer tube to be connected.

  More preferably, the silicon-containing and boron-containing film forming step, the silicon-containing and boron-containing film modifying step, and the inert gas replacement step include an inner tube that forms the processing chamber, and the inner tube It is carried out by a processing furnace having a double tube structure with an outer tube provided outside and connected to the gas exhaust part.

According to another aspect of the invention,
A silicon-containing film forming step of forming a silicon-containing film on the substrate by supplying a silicon-containing gas into a processing chamber containing the substrate;
A silicon-containing film for reforming the silicon-containing film on the substrate into a boron-containing and silicon-containing oxide film by supplying a boron-containing gas, an oxygen-containing gas, and a hydrogen-containing gas into the processing chamber set to a pressure lower than atmospheric pressure. Membrane reforming process;
Have
A method for manufacturing a semiconductor device is provided in which the silicon-containing film forming step and the silicon-containing film modifying step are set as one cycle, and the cycle is performed once or more.

  Preferably, the silicon-containing film modification step generates an oxidized species containing oxygen by reacting the oxygen-containing gas and the hydrogen-containing gas in the processing chamber under a pressure atmosphere lower than atmospheric pressure, The silicon-containing film formed on the substrate by the oxidizing species is modified into a boron-containing and silicon-containing oxide film.

More preferably, the silicon-containing gas is SiH ₄ gas, Si ₂ H ₆ gas, or Si ₂ Cl ₆ gas.

  More preferably, the silicon-containing film forming step and the silicon-containing film modifying step are performed while maintaining the processing chamber at a constant temperature.

  More preferably, after completion of the silicon-containing film forming step, the supply of the silicon-containing gas is stopped, an inert gas is supplied into the processing chamber, and the processing chamber is replaced with an inert gas atmosphere. It further has a gas replacement process.

  More preferably, after completion of the silicon-containing film modification step, the supply of the boron-containing gas, the oxygen-containing gas, and the hydrogen-containing gas is stopped, and an inert gas is supplied into the processing chamber to supply the inside of the processing chamber. It further has an inert gas replacement step of replacing with the inert gas atmosphere.

More preferably, the hydrogen-containing gas is H ₂ gas or NH ₃ gas.

More preferably, the oxidation-containing gas is O ₂ gas, O ₃ gas, NO gas, N ₂ O gas, NO _x gas, CO gas, H ₂ O gas, or CH ₃ COOH gas.

More preferably, the boron-containing gas is B ₂ H ₆ gas or BCl ₃ gas.

  More preferably, the silicon-containing film forming step and the silicon-containing film modifying step include an inner tube that forms the processing chamber, and an outer tube that is provided outside the inner tube and connected to a gas exhaust unit. It is performed by a processing furnace having a double tube structure.

More preferably, the silicon-containing film forming step, the silicon-containing film modifying step, and the inert gas replacement step are provided with an inner tube that forms the processing chamber, and an exhaust gas that is provided outside the inner tube. It is performed by a processing furnace having a double tube structure with an outer tube connected to the part.

According to yet another aspect of the invention,
A processing chamber containing a substrate;
A silicon-containing gas supply system for supplying a silicon-containing gas into the processing chamber;
A boron-containing gas supply system for supplying a boron-containing gas into the processing chamber;
An oxygen-containing gas supply system for supplying an oxygen-containing gas into the processing chamber;
A hydrogen-containing gas supply system for supplying a hydrogen-containing gas into the processing chamber;
A pressure adjusting unit for adjusting the pressure in the processing chamber;
A control unit that controls the silicon-containing gas supply system, the boron-containing gas supply system, the oxygen-containing gas supply system, the hydrogen-containing gas supply system, and the pressure adjustment unit,
The controller is
After forming the silicon-containing and boron-containing film on the substrate by supplying the silicon-containing gas from the silicon-containing gas supply system and the boron-containing gas from the boron-containing gas supply system into the processing chamber, The silicon on the substrate is supplied by supplying the oxygen-containing gas from the oxygen-containing gas supply system and the hydrogen-containing gas from the hydrogen-containing gas supply system into the processing chamber set to less than atmospheric pressure by a pressure adjusting unit. The boron-containing and boron-containing film is modified to a boron-containing and silicon-containing oxide film, and this cycle is performed one or more times, or
After supplying the silicon-containing gas from the silicon-containing gas supply system into the processing chamber to form a silicon-containing film on the substrate, the boron containing is contained in the processing chamber set to less than atmospheric pressure by the pressure adjusting unit. Boron is contained in the silicon-containing film on the substrate by supplying a boron-containing gas from a gas supply system, the oxygen-containing gas from the oxygen-containing gas supply system, and the hydrogen-containing gas from the hydrogen-containing gas supply system. There is provided a substrate processing apparatus which is modified to contain and silicon-containing oxide film and performs this cycle one or more times.

  Preferably, there is provided a processing furnace having a double tube structure of an inner tube forming the processing chamber and an outer tube provided outside the inner tube and connected to a gas exhaust part.

According to yet another aspect of the invention,
A silicon-containing and germane-containing film forming step of forming a silicon-containing and germane-containing film on the substrate by supplying a silicon-containing gas and a germane-containing gas into a processing chamber containing the substrate;
Silicon for reforming the silicon-containing and germane-containing films formed on the substrate by supplying an oxygen-containing gas and a hydrogen-containing gas into the processing chamber set to a pressure lower than atmospheric pressure to a germane-containing and silicon-containing oxide film Containing and germane containing film modification step;
Have
A method for manufacturing a semiconductor device is provided in which the silicon-containing and germane-containing film forming step and the silicon-containing and germane-containing film modifying step are set as one cycle, and the cycle is performed once or more.

  Preferably, in the silicon-containing and germane-containing film modification step, the oxygen-containing oxidizing species is obtained by reacting the oxygen-containing gas and the hydrogen-containing gas in the processing chamber under a pressure atmosphere less than atmospheric pressure. The silicon-containing and germane-containing films generated and formed on the substrate by the oxidizing species are modified.

More preferably, the silicon-containing gas is SiH ₄ gas, Si ₂ H ₆ gas, or Si ₂ Cl ₆ gas.

  More preferably, the silicon-containing and germane-containing film forming step and the silicon-containing and germane-containing film modifying step are performed while maintaining the processing chamber at a constant temperature.

  More preferably, after completion of the silicon-containing and germane-containing film forming step, the supply of the silicon-containing gas and the germane-containing gas is stopped, an inert gas is supplied into the processing chamber, and the inertness in the processing chamber is established. It further has an inert gas replacement step of replacing with a gas atmosphere.

  More preferably, after completion of the silicon-containing and germane-containing film reforming step, the supply of the oxygen-containing gas and the hydrogen-containing gas is stopped, an inert gas is supplied into the processing chamber, and the processing chamber is filled with the inert gas. It further has an inert gas replacement step of replacing the atmosphere with an active gas.

More preferably, the hydrogen-containing gas is H ₂ gas or NH ₃ gas.

More preferably, the oxidation-containing gas is O ₂ gas, O ₃ gas, NO gas, N ₂ O gas, NO _x gas, CO gas, H ₂ O gas, or CH ₃ COOH gas.

More preferably, the germane-containing gas is GeH ₄ gas or Ge ₂ H ₆ gas.

  More preferably, the silicon-containing and germane-containing film forming step, and the silicon-containing and germane-containing film modifying step are provided in an inner tube that forms the processing chamber and an outer side of the inner tube in a gas exhaust part. It is performed by a processing furnace having a double tube structure with an outer tube to be connected.

  More preferably, the silicon-containing and germane-containing film forming step, the silicon-containing and germane-containing film modifying step, and the inert gas replacement step include an inner tube that forms the processing chamber, and the inner tube It is carried out by a processing furnace having a double tube structure with an outer tube provided outside and connected to the gas exhaust part.

According to another aspect of the invention,
A silicon-containing film forming step of forming a silicon-containing film on the substrate by supplying a silicon-containing gas into a processing chamber containing the substrate;
A silicon-containing gas that reforms the silicon-containing film on the substrate into a germane-containing and silicon-containing oxide film by supplying a germane-containing gas, an oxygen-containing gas, and a hydrogen-containing gas into the processing chamber set to a pressure lower than atmospheric pressure. Membrane reforming process;
Have
There is provided a method of manufacturing a semiconductor device in which the silicon-containing film forming step and the silicon-containing film modifying step are set as one cycle and the cycle is performed once or more.

  Preferably, the silicon-containing film modification step generates an oxidized species containing oxygen by reacting the oxygen-containing gas and the hydrogen-containing gas in the processing chamber under a pressure atmosphere lower than atmospheric pressure, The silicon-containing film formed on the substrate by the oxidizing species is modified into germane-containing and silicon-containing oxide films.

More preferably, the silicon-containing gas is SiH ₄ gas, Si ₂ H ₆ gas, or Si ₂ Cl ₆ gas.

  More preferably, the silicon-containing film forming step and the silicon-containing film modifying step are performed while maintaining the processing chamber at a constant temperature.

  More preferably, after completion of the silicon-containing film forming step, the supply of the silicon-containing gas is stopped, an inert gas is supplied into the processing chamber, and the processing chamber is replaced with an inert gas atmosphere. It further has a gas replacement process.

  More preferably, after completion of the silicon-containing film modification step, the supply of the germane-containing gas, the oxygen-containing gas, and the hydrogen-containing gas is stopped, and an inert gas is supplied into the processing chamber to supply the inside of the processing chamber. It further has an inert gas replacement step of replacing with the inert gas atmosphere.

More preferably, the hydrogen-containing gas is H ₂ gas or NH ₃ gas.

More preferably, the oxidation-containing gas is O ₂ gas, O ₃ gas, NO gas, N ₂ O gas, NO _x gas, CO gas, H ₂ O gas, or CH ₃ COOH gas.

More preferably, the germane-containing gas is GeH ₄ gas or Ge ₂ H ₆ gas.

  More preferably, the silicon-containing film forming step and the silicon-containing film modifying step include an inner tube that forms the processing chamber, and an outer tube that is provided outside the inner tube and connected to a gas exhaust unit. It is performed by a processing furnace having a double tube structure.

  More preferably, the silicon-containing film forming step, the silicon-containing film modifying step, and the inert gas replacement step are provided with an inner tube that forms the processing chamber, and an exhaust gas that is provided outside the inner tube. It is performed by a processing furnace having a double tube structure with an outer tube connected to the part.

According to yet another aspect of the invention,
A processing chamber containing a substrate;
A silicon-containing gas supply system for supplying a silicon-containing gas into the processing chamber;
A germane-containing gas supply system for supplying a germane-containing gas into the processing chamber;
An oxygen-containing gas supply system for supplying an oxygen-containing gas into the processing chamber;
A hydrogen-containing gas supply system for supplying a hydrogen-containing gas into the processing chamber;
A pressure adjusting unit for adjusting the pressure in the processing chamber;
A control unit that controls the silicon-containing gas supply system, the germane-containing gas supply system, the oxygen-containing gas supply system, the hydrogen-containing gas supply system, and the pressure adjustment unit,
The controller is
After forming the silicon-containing and germane-containing films on the substrate by supplying the silicon-containing gas from the silicon-containing gas supply system and the germane-containing gas from the germane-containing gas supply system into the processing chamber, The silicon on the substrate is supplied by supplying the oxygen-containing gas from the oxygen-containing gas supply system and the hydrogen-containing gas from the hydrogen-containing gas supply system into the processing chamber set to less than atmospheric pressure by a pressure adjusting unit. The containing and germane-containing films are modified into germane-containing and silicon-containing oxide films, and this cycle is performed one or more times, or
The silicon-containing gas from the silicon-containing gas supply system is supplied into the processing chamber to form a silicon-containing film on the substrate, and then the germane is contained in the processing chamber set to less than atmospheric pressure by the pressure adjusting unit. A germane-containing gas from a gas supply system, the oxygen-containing gas from the oxygen-containing gas supply system, and the hydrogen-containing gas from the hydrogen-containing gas supply system are supplied to the germanium-containing film on the substrate. There is provided a substrate processing apparatus which is modified to contain and silicon-containing oxide film and performs this cycle one or more times.

  Preferably, there is provided a processing furnace having a double tube structure of an inner tube forming the processing chamber and an outer tube provided outside the inner tube and connected to a gas exhaust part.

According to yet another aspect of the invention,
Forming a silicon-containing and germane-containing / boron-containing film by supplying a silicon-containing gas, a germane-containing gas, and a boron-containing gas into a processing chamber containing the substrate to form a silicon-containing and germane-containing / boron-containing film on the substrate Process,
Supplying oxygen-containing gas and hydrogen-containing gas into the processing chamber set to a pressure lower than atmospheric pressure, the silicon-containing and germane-containing / boron-containing films formed on the substrate are silicon-containing and germane-containing / boron-containing. A silicon-containing and germane-containing / boron-containing film modifying step for modifying the oxide film,
There is provided a semiconductor device manufacturing method in which the silicon-containing and germane-containing / boron-containing film forming step and the silicon-containing and germane-containing / boron-containing film modifying step are performed as one cycle, and the cycle is performed once or more.

  Preferably, the silicon-containing and germane-containing / boron-containing film reforming step includes oxygen by reacting the oxygen-containing gas and the hydrogen-containing gas in the processing chamber under a pressure atmosphere less than atmospheric pressure. Oxidizing species are generated, and the silicon-containing and germane-containing / boron-containing films formed on the substrate are modified by the oxidizing species.

More preferably, the silicon-containing gas is SiH ₄ gas, Si ₂ H ₆ gas, or Si ₂ Cl ₆ gas.

  More preferably, the silicon-containing and germane-containing / boron-containing film forming step and the silicon-containing and germane-containing / boron-containing film modifying step are performed while maintaining the processing chamber at a constant temperature.

  More preferably, after completion of the silicon-containing and germane-containing / boron-containing film forming step, the supply of the silicon-containing gas, the germane-containing gas, and the boron-containing gas is stopped, and an inert gas is supplied into the processing chamber. The process chamber further includes an inert gas replacement step of replacing the processing chamber with the inert gas atmosphere.

  More preferably, after completion of the silicon-containing and germane-containing / boron-containing film reforming step, the supply of the oxygen-containing gas and the hydrogen-containing gas is stopped, and an inert gas is supplied into the processing chamber. And an inert gas replacement step of replacing the atmosphere with the inert gas atmosphere.

More preferably, the hydrogen-containing gas is H ₂ gas or NH ₃ gas.

More preferably, the oxidation-containing gas is O ₂ gas, O ₃ gas, NO gas, N ₂ O gas, NO _x gas, CO gas, H ₂ O gas, or CH ₃ COOH gas.

More preferably, the germane-containing gas is GeH ₄ gas or Ge ₂ H ₆ gas.

More preferably, the boron-containing gas is B ₂ H ₆ gas or BCl ₃ gas.

  More preferably, the silicon-containing and germane-containing / boron-containing film forming step, and the silicon-containing and germane-containing / boron-containing film modifying step include an inner tube that forms the processing chamber, and an outer side of the inner tube. It is performed by a processing furnace having a double tube structure with an outer tube that is provided and connected to the gas exhaust part.

  More preferably, the silicon-containing and germane-containing / boron-containing film forming step, the silicon-containing and germane-containing / boron-containing film modifying step, and the inert gas replacement step are inner tubes that form the processing chamber. And a processing furnace having a double tube structure with an outer tube provided outside the inner tube and connected to a gas exhaust part.

According to another aspect of the invention,
A silicon-containing film forming step of forming a silicon-containing film on the substrate by supplying a silicon-containing gas into a processing chamber containing the substrate;
A germane-containing gas, a boron-containing gas, an oxygen-containing gas, and a hydrogen-containing gas are supplied into the processing chamber set to a pressure lower than atmospheric pressure, and the silicon-containing film on the substrate is silicon-containing and germane-containing / boron-containing oxidized. A silicon-containing film modification step for modifying the film;
Have
There is provided a method of manufacturing a semiconductor device in which the silicon-containing film forming step and the silicon-containing film modifying step are set as one cycle and the cycle is performed once or more.

  Preferably, the silicon-containing film modification step generates an oxidized species containing oxygen by reacting the oxygen-containing gas and the hydrogen-containing gas in the processing chamber under a pressure atmosphere lower than atmospheric pressure, The silicon-containing film formed on the substrate by the oxidizing species is modified into a silicon-containing and germane-containing / boron-containing oxide film.

More preferably, the silicon-containing gas is SiH ₄ gas, Si ₂ H ₆ gas, or Si ₂ Cl ₆ gas.

  More preferably, the silicon-containing film forming step and the silicon-containing film modifying step are performed while maintaining the processing chamber at a constant temperature.

  More preferably, after completion of the silicon-containing film forming step, the supply of the silicon-containing gas is stopped, an inert gas is supplied into the processing chamber, and the processing chamber is replaced with an inert gas atmosphere. It further has a gas replacement process.

  More preferably, after the silicon-containing film modification step, the supply of the germane-containing gas, the boron-containing gas, the oxygen-containing gas, and the hydrogen-containing gas is stopped, and an inert gas is supplied into the processing chamber. And an inert gas replacement step of replacing the processing chamber with the inert gas atmosphere.

More preferably, the hydrogen-containing gas is H ₂ gas or NH ₃ gas.

More preferably, the oxidation-containing gas is O ₂ gas, O ₃ gas, NO gas, N ₂ O gas, NO _x gas, CO gas, H ₂ O gas, or CH ₃ COOH gas.

More preferably, the germane-containing gas is GeH ₄ gas or Ge ₂ H ₆ gas.

More preferably, the boron-containing gas is B ₂ H ₆ gas or BCl ₃ gas.

  More preferably, the silicon-containing film forming step and the silicon-containing film modifying step include an inner tube that forms the processing chamber, and an outer tube that is provided outside the inner tube and connected to a gas exhaust unit. It is performed by a processing furnace having a double tube structure.

  More preferably, the silicon-containing film forming step, the silicon-containing film modifying step, and the inert gas replacement step are provided with an inner tube that forms the processing chamber, and an exhaust gas that is provided outside the inner tube. It is performed by a processing furnace having a double tube structure with an outer tube connected to the part.

According to yet another aspect of the invention,
A processing chamber containing a substrate;
A silicon-containing gas supply system for supplying a silicon-containing gas into the processing chamber;
A germane-containing gas supply system for supplying a germane-containing gas into the processing chamber;
A boron-containing gas supply system for supplying a boron-containing gas into the processing chamber;
An oxygen-containing gas supply system for supplying an oxygen-containing gas into the processing chamber;
A hydrogen-containing gas supply system for supplying a hydrogen-containing gas into the processing chamber;
A pressure adjusting unit for adjusting the pressure in the processing chamber;
A control unit for controlling the silicon-containing gas supply system, the germane-containing gas supply system, the boron-containing gas supply system, the oxygen-containing gas supply system, the hydrogen-containing gas supply system, and the pressure adjustment unit,
The controller is
Supplying the silicon-containing gas from the silicon-containing gas supply system, the germane-containing gas from the germane-containing gas supply system, and the boron-containing gas from the boron-containing gas supply system into the processing chamber; After the silicon-containing and germane-containing / boron-containing films are formed on the substrate, the oxygen-containing gas and the hydrogen-containing gas are supplied from the oxygen-containing gas supply system into the processing chamber set to less than atmospheric pressure by the pressure adjusting unit. The hydrogen-containing gas from the system is supplied to modify the silicon-containing and germane-containing / boron-containing film on the substrate into a silicon-containing and germane-containing / boron-containing oxide film. Do it more than once,
The silicon-containing gas from the silicon-containing gas supply system is supplied into the processing chamber to form a silicon-containing film on the substrate, and then the germane is contained in the processing chamber set to less than atmospheric pressure by the pressure adjustment unit. A germane-containing gas from a gas supply system, a boron-containing gas from the boron-containing gas supply system, the oxygen-containing gas from the oxygen-containing gas supply system, and the hydrogen-containing gas from the hydrogen-containing gas supply system. There is provided a substrate processing apparatus for supplying and modifying the silicon-containing film on the substrate into a silicon-containing and germane-containing / boron-containing oxide film, and taking this as one cycle, and performing the cycle one or more times.

  Preferably, there is provided a processing furnace having a double tube structure of an inner tube forming the processing chamber and an outer tube provided outside the inner tube and connected to a gas exhaust part.

200 wafer (substrate)
201 treatment room

Claims (3)

A silicon-containing and boron-containing film forming step of forming a silicon-containing and boron-containing film on the substrate by supplying a silicon-containing gas and a boron-containing gas into a processing chamber containing the substrate;
Silicon for reforming the silicon-containing and boron-containing films formed on the substrate by supplying an oxygen-containing gas and a hydrogen-containing gas into the processing chamber set to a pressure lower than atmospheric pressure into a boron-containing and silicon-containing oxide film Containing and boron containing film modifying step;
Have
The silicon-containing and boron-containing film forming step and the silicon-containing and boron-containing film reforming step are set as one cycle, and the cycle is performed once or more.
A method for manufacturing a semiconductor device. A silicon-containing film forming step of forming a silicon-containing film on the substrate by supplying a silicon-containing gas into a processing chamber containing the substrate;
A silicon-containing film for reforming the silicon-containing film on the substrate into a boron-containing and silicon-containing oxide film by supplying a boron-containing gas, an oxygen-containing gas, and a hydrogen-containing gas into the processing chamber set to a pressure lower than atmospheric pressure. Membrane reforming process;
Have
The method of manufacturing a semiconductor device, wherein the cycle is performed at least once, with the silicon-containing film forming step and the silicon-containing film modifying step as one cycle. A processing chamber containing a substrate;
A silicon-containing gas supply system for supplying a silicon-containing gas into the processing chamber;
A boron-containing gas supply system for supplying a boron-containing gas into the processing chamber;
An oxygen-containing gas supply system for supplying an oxygen-containing gas into the processing chamber;
A hydrogen-containing gas supply system for supplying a hydrogen-containing gas into the processing chamber;
A pressure adjusting unit for adjusting the pressure in the processing chamber;
A control unit that controls the silicon-containing gas supply system, the boron-containing gas supply system, the oxygen-containing gas supply system, the hydrogen-containing gas supply system, and the pressure adjustment unit,
The controller is
After forming the silicon-containing and boron-containing film on the substrate by supplying the silicon-containing gas from the silicon-containing gas supply system and the boron-containing gas from the boron-containing gas supply system into the processing chamber, The silicon on the substrate is supplied by supplying the oxygen-containing gas from the oxygen-containing gas supply system and the hydrogen-containing gas from the hydrogen-containing gas supply system into the processing chamber set to less than atmospheric pressure by a pressure adjusting unit. The boron-containing and boron-containing film is modified to a boron-containing and silicon-containing oxide film, and this cycle is performed one or more times, or
After supplying the silicon-containing gas from the silicon-containing gas supply system into the processing chamber to form a silicon-containing film on the substrate, the boron containing is contained in the processing chamber set to less than atmospheric pressure by the pressure adjusting unit. Boron is contained in the silicon-containing film on the substrate by supplying a boron-containing gas from a gas supply system, the oxygen-containing gas from the oxygen-containing gas supply system, and the hydrogen-containing gas from the hydrogen-containing gas supply system. Containing and modifying the silicon-containing oxide film, this is defined as one cycle, and the cycle is performed once or more.
A substrate processing apparatus.

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