JP2012015460A - Substrate treatment apparatus and method for manufacturing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate treatment apparatus which increases a concentration of active seed fed to a surface of a substrate, and improves efficiency and productivity in substrate treatment process, and a method for manufacturing a semiconductor device.SOLUTION: A substrate treatment apparatus comprises a treatment chamber for laminating and stocking a plurality of substrates at predetermined intervals in multiple stages; and a gas nozzle 270a in which a plurality of gas ejection ports for ejecting treatment gas to a surface of the substrate in the treatment chamber and which extends along a lamination direction of the substrate. Gas activation sections 22a, 22b, 22c, 22d for activating the treatment gas ejected from the gas ejection ports and feeding to the substrate is provided outside of the gas nozzle 270a with gaps allowing the treatment gas to pass therethrough so as to surround the gas ejection ports so that a flow of the treatment gas is perpendicular to the outer peripheral edge of the substrate.

Description

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

  As a process of manufacturing a semiconductor device such as a DRAM (Dynamic Random Access Memory), a process of carrying a plurality of substrates into a process chamber, and a process gas is ejected from a plurality of gas jets provided in a gas nozzle in the process chamber And a substrate processing step having a step of supplying the substrate. The substrate processing step is performed by a substrate processing apparatus having a processing chamber for storing a plurality of substrates stacked in multiple stages at predetermined intervals and a processing gas supply unit for supplying a processing gas for processing the substrate into the processing chamber. It has been. The processing gas supply unit is provided with a gas nozzle provided with a plurality of gas outlets for jetting the processing gas to the surface of the substrate and extending along the stacking direction of the substrates.

In the above-described substrate processing step, the processing gas supplied into the processing chamber is activated by heat, and this is supplied to the substrate surface, thereby performing a predetermined substrate processing. For example, when ozone (O ₃ ) gas is used as a processing gas, ozone is heated and decomposed by raising the temperature in the processing chamber to generate oxygen radicals, which are supplied to the substrate surface for oxidation treatment and the like. It was carried out.

  However, when the inside of the processing chamber is heated to a high temperature, the temperature in the gas nozzle also becomes high, which may reduce the concentration of active species supplied to the substrate surface. That is, for example, when ozone gas is used as the processing gas, the ozone gas is decomposed in the gas nozzle to generate oxygen radicals, and the generated oxygen radicals are repeatedly lost in collision with other ozone molecules in the gas nozzle. There was a life. As a result, the concentration of oxygen radicals supplied to the substrate surface is reduced, and a desired substrate processing speed cannot be obtained, and the efficiency and productivity of the substrate processing process may be reduced.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a substrate processing apparatus and a semiconductor device manufacturing method capable of increasing the concentration of active species supplied to the substrate surface and improving the efficiency and productivity of the substrate processing process. It is to be.

  One embodiment of the present invention includes a processing chamber that houses a plurality of substrates stacked in a multistage manner at a predetermined interval, and a processing gas supply unit that supplies a processing gas for processing the substrate into the processing chamber, The processing gas supply unit includes a gas nozzle provided with a plurality of gas jets for jetting the processing gas to the surface of the substrate, and extending along the stacking direction of the substrate, and the flow of the processing gas flows to the substrate. The process gas that is provided outside the gas nozzle so as to surround the gas jet port while leaving a gap through which the process gas can pass so as to be perpendicular to the outer peripheral edge and activates the process gas jetted from the gas jet port A substrate processing apparatus having a gas activation unit that supplies the substrate to the substrate.

According to another aspect of the present invention, there are provided a step of carrying a plurality of substrates into a processing chamber, and a plurality of gas jets for ejecting the processing gas for processing the substrate to the surface of the substrate. A step of supplying the gas into the processing chamber from a gas nozzle extending along the stacking direction, and a gap through which the processing gas can pass so that the flow of the processing gas is perpendicular to the outer peripheral edge of the substrate. A step of activating the processing gas ejected from the gas ejection port by a gas activation unit provided outside the gas nozzle so as to surround the gas ejection port, and supplying the processing gas to the substrate; And a step of unloading the semiconductor device.

  According to the substrate processing apparatus and the semiconductor device manufacturing method of the present invention, the concentration of active species supplied to the substrate surface can be increased, and the efficiency and productivity of the substrate processing process can be improved. .

1 is a perspective view of a substrate processing apparatus according to a first embodiment of the present invention. It is a block diagram of the processing furnace which concerns on 1st Embodiment of this invention, Comprising: It is a figure which shows a process chamber part with sectional drawing especially. It is a block diagram of the processing furnace which concerns on 1st Embodiment of this invention, Comprising: Especially a process chamber part is AA sectional drawing of FIG. It is a figure which shows the gas activation mechanism with which the processing furnace which concerns on 1st Embodiment of this invention is equipped, Comprising: (a) is a block diagram of a porous nozzle and a sheath heater assembly, (b) shows the internal structure of a sheath heater. It is a block diagram. It is a BB sectional view of Drawing 4 (a) showing a porous nozzle and a sheath heater aggregate with which a processing furnace concerning a 1st embodiment of the present invention is provided. It is a flowchart which illustrates the substrate processing process concerning a 1st embodiment of the present invention. It is a gas supply timing diagram of the ZrO film formation process in the substrate processing process concerning a 1st embodiment of the present invention. It is a figure which shows the gas activation mechanism with which the process furnace which concerns on 2nd Embodiment of this invention is equipped, Comprising: (a) is a block diagram of a porous nozzle and a sheath heater assembly, (b) shows the internal structure of a sheath heater. It is a block diagram. It is CC sectional drawing of Fig.8 (a) about the porous nozzle and sheath heater assembly with which the processing furnace concerning 2nd Embodiment of this invention is provided. It is a figure which shows the gas activation mechanism with which the processing furnace which concerns on 3rd Embodiment of this invention is equipped, Comprising: (a) is a block diagram of a porous nozzle and a sheath heater assembly, (b) shows the internal structure of a sheath heater. It is a block diagram.

[First Embodiment]
The configuration of the substrate processing apparatus according to the first embodiment of the present invention will be described below.

(1) Overall Configuration of Substrate Processing Apparatus FIG. 1 is a perspective view of a substrate processing apparatus 101 according to this embodiment. The surface with the cassette stage 114 is the front side of the substrate processing apparatus 101, the front side is the front side of the substrate processing apparatus 101, the side with the processing furnace 202 opposite to the front side is the rear side, and the right hand side is facing the front side of the substrate processing apparatus 101. Is on the right and the left hand side is on the left. The upper and lower sides of the substrate processing apparatus 101 are in the direction of gravity.

  As shown in FIG. 1, the substrate processing apparatus 101 according to the present embodiment includes a housing 111. In order to transport the wafer 200 as a substrate into and out of the casing 111, a cassette 110 as a wafer carrier (substrate storage container) that stores a plurality of wafers 200 is used. A cassette stage (substrate storage container delivery table) 114 is provided inside the casing 111 of a cassette loading / unloading port (substrate storage container loading / unloading port, not shown) that is an opening for transporting the cassette 110 into and out of the housing 111. ing. The cassette 110 is placed on the cassette stage 114 by an in-factory transport device (not shown), and is carried out of the casing 111 from the cassette stage 114.

  The cassette 110 is placed on the cassette stage 114 so that the wafer 200 in the cassette 110 is in a vertical posture and the wafer loading / unloading port of the cassette 110 faces upward by an in-factory transfer device. The cassette stage 114 rotates the cassette 110 90 degrees toward the rear of the casing 111 to bring the wafer 200 in the cassette 110 into a horizontal posture, and directs the wafer loading / unloading port of the cassette 110 toward the rear in the casing 111. Is configured to be possible.

  A cassette shelf (substrate storage container mounting shelf) 105 is installed in a substantially central portion of the housing 111 as viewed in the front-rear direction. The cassette shelf 105 is configured to store a plurality of cassettes 110 in a plurality of rows and a plurality of rows. The cassette shelf 105 is provided with a transfer shelf 123 in which a cassette 110 to be transferred by a wafer transfer mechanism 125 described later is stored. In addition, a spare cassette shelf 107 is provided above the cassette stage 114 and is configured to store the spare cassette 110.

  A cassette transfer device (substrate container transfer device) 118 is provided between the cassette stage 114 and the cassette shelf 105. The cassette transport device 118 includes a cassette elevator (substrate storage container lifting mechanism) 118a that can be moved up and down while holding the cassette 110, and a cassette transport mechanism (substrate storage container transport mechanism) as a transport mechanism that can move horizontally while holding the cassette 110. 118b. The cassette 110 is transported between the cassette stage 114, the cassette shelf 105, the spare cassette shelf 107, and the transfer shelf 123 by the continuous operation of the cassette elevator 118a and the cassette transport mechanism 118b.

  A wafer transfer mechanism (substrate transfer mechanism) 125 is provided behind the cassette shelf 105. The wafer transfer mechanism 125 includes a wafer transfer device (substrate transfer device) 125a that can rotate or linearly move the wafer 200 in the horizontal direction, and a wafer transfer device elevator (substrate transfer device) that moves the wafer transfer device 125a up and down. Elevating mechanism) 125b. The wafer transfer device 125a includes a tweezer (substrate holder) 125c that holds the wafer 200 in a horizontal posture. By continuous operation of the wafer transfer device 125a and the wafer transfer device elevator 125b, the wafer 200 is picked up from the cassette 110 on the transfer shelf 123 and loaded into a boat (substrate holder) 217 described later (wafer charge). The wafer 200 is removed from the boat 217 (wafer discharge) and stored in the cassette 110 on the transfer shelf 123.

  A processing furnace 202 is provided above the rear portion of the casing 111. An opening is provided at the lower end of the processing furnace 202, and the opening is configured to be opened and closed by a furnace port shutter (furnace port opening / closing mechanism) 147. The configuration of the processing furnace 202 will be described later.

  Below the processing furnace 202, a transfer chamber 124, which is a space for loading and unloading the wafers 200 into and from the boat (substrate holder) 217 from the cassette 110 on the transfer shelf 123, is provided. In the transfer chamber 124, a boat elevator (substrate holder lifting mechanism) 115 is provided as a lifting mechanism that lifts and lowers the boat 217 into and out of the processing furnace 202. The elevator 128 of the boat elevator 115 is provided with an arm 128 as a connecting tool. On the arm 128, a seal cap 219 is provided in a horizontal posture as a furnace port lid body that supports the boat 217 vertically and that hermetically closes the lower end of the processing furnace 202 when the boat 217 is raised by the boat elevator 115. It has been.

  The boat 217 includes a plurality of holding members, and a plurality of (for example, about 25 to 125) wafers 200 are aligned in the vertical direction in a horizontal posture and in a state where the centers thereof are aligned in multiple stages. Configured to hold.

  Above the cassette shelf 105, a clean unit 134a having a supply fan and a dustproof filter is provided. The clean unit 134a is configured to circulate clean air, which is a cleaned atmosphere, inside the casing 111.

  In addition, a clean unit (not shown) having a supply fan and a dustproof filter for supplying clean air is provided at the left end of the casing 111 on the opposite side of the wafer transfer device elevator 125b and the boat elevator 115 side. is set up. The clean air blown from the clean unit is configured to be sucked into an exhaust device (not shown) and exhausted to the outside of the casing 111 after passing through the wafer transfer device 125a and the boat 217.

(2) Operation of Substrate Processing Apparatus Next, the operation of the substrate processing apparatus 101 according to the present embodiment will be described.

  First, the cassette 110 is loaded from a cassette loading / unloading port (not shown) by the in-factory transfer device, the wafer 200 is placed in a vertical posture, and the wafer loading / unloading port of the cassette 110 faces upward. Placed. Thereafter, the cassette 110 is rotated 90 ° toward the rear of the casing 111 by the cassette stage 114. As a result, the wafer 200 in the cassette 110 assumes a horizontal posture, and the wafer loading / unloading port of the cassette 110 faces rearward in the housing 111.

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

  When the cassette 110 is transferred to the transfer shelf 123, the wafer 200 is picked up from the cassette 110 through the wafer loading / unloading port by the tweezer 125c of the wafer transfer device 125a, and the wafer transfer device 125a and the wafer transfer device elevator 125b are picked up. Are loaded (wafer charged) into the boat 217 behind the transfer chamber 124. The wafer transfer mechanism 125 that has transferred the wafer 200 to the boat 217 returns to the cassette 110 and loads the next wafer 200 into the boat 217.

  When a predetermined number of wafers 200 are loaded into the boat 217, the furnace port shutter 147 that has closed the lower end of the processing furnace 202 is opened. Subsequently, as the seal cap 219 is raised by the boat elevator 115, the boat 217 holding the wafer 200 group is loaded into the processing furnace 202 (boat loading). After loading, arbitrary processing is performed on the wafer 200 in the processing furnace 202. Such processing will be described later. After the processing, the wafer 200 and the cassette 110 are carried out of the casing 111 by a procedure reverse to the above procedure.

(3) Configuration of Processing Furnace Next, the configuration of the processing furnace 202 according to the present embodiment will be described with reference mainly to FIG. 2 and FIG. FIG. 2 is a configuration diagram of the processing furnace 202 of the substrate processing apparatus 101 shown in FIG. 1, and particularly shows a processing chamber 201 portion in a sectional view. Further, FIG. 3 shows the processing furnace 202 portion in the AA sectional view of FIG.

(Processing room)
The processing furnace 202 according to the present embodiment supplies a processing gas to the surface of the wafer 200 and performs CVD (
For example, it is configured as a vertical processing furnace so that a thin film such as ZrO (zirconium oxide) can be formed on the wafer 200 by a chemical vapor deposition (ALP) method or an ALD (Atomic Layer Deposition) method.

As shown in FIG. 2, the processing furnace 202 has a reaction tube 203 and a manifold 209. The reaction tube 203 is made of a heat-resistant non-metallic material such as quartz (SiO ₂ ) or silicon carbide (SiC), and has a cylindrical shape with the upper end closed and the lower end open. The manifold 209 is made of, for example, a metal material such as SUS, and has a cylindrical shape with an upper end portion and a lower end portion opened. The reaction tube 203 is supported vertically by the manifold 209 from the lower end side. An annular flange is provided at each of the lower end of the reaction tube 203 and the upper and lower opening ends of the manifold 209. A sealing member 220 such as an O-ring is provided between the lower end of the reaction tube 203 and the upper end of the manifold 209, and the gap between the two is hermetically sealed.

  Inside the reaction tube 203 and the manifold 209, a processing chamber 201 for storing a plurality of stacked wafers 200 as substrates is formed. The boat 217 as the substrate support mechanism is configured to be inserted into the processing chamber 201 from below by the boat elevator 115 as the lifting mechanism described above.

  The boat 217 is configured to hold a plurality of (for example, about 25 to 125) wafers 200 stacked in multiple stages with a predetermined gap (substrate pitch interval) in a substantially horizontal state. The maximum outer diameter of the boat 217 loaded with the wafers 200 is configured to be smaller than the inner diameters of the reaction tube 203 and the manifold 209. The boat 217 is mounted on the seal cap 219 via a boat support 218 as a holding body that holds the boat 217. 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 SUS and is formed in a disk shape. When the boat elevator 115 is lifted, the sealing member 220 provided between the flange at the lower end of the manifold 209 and the seal cap 219 seals between the two in an airtight manner. Since the space between the reaction tube 203 and the manifold 209 and the space between the manifold 209 and the seal cap 219 are hermetically sealed, the airtightness in the processing chamber 201 is maintained. Further, the boat 217 can be transported into and out of the processing chamber 201 by raising and lowering the seal cap 219 in the vertical direction by the boat elevator 115.

  A rotation mechanism 267 is provided below the seal cap 219. The rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the seal cap 219, and can rotate the boat 217 on which a plurality of wafers 200 are mounted while maintaining the airtightness in the processing chamber 201. It is configured to be able to. By rotating the boat 217, the processing uniformity of the wafers 200 can be improved.

  On the outer periphery of the reaction tube 203, a heater 207 as a substrate heating unit is provided in a cylindrical shape concentric with the reaction tube 203, and the wafer 200 inserted into the processing chamber 201 is heated to a predetermined temperature. The heater 207 is vertically installed by being supported by a heater base 210 as a holding plate. The heater base 210 fixes the manifold 209.

In addition, a temperature sensor 263 as a temperature detector is installed in the reaction tube 203, and the inside of the processing chamber 201 is adjusted by adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263. Are configured to have a desired temperature distribution. The temperature sensor 263 is configured in an L shape similarly to a porous nozzle 270a and a porous nozzle 270b described later, and is provided along the inner wall of the reaction tube 203. As shown in FIG. 3, the temperature sensor 263 is provided, for example, between the porous nozzle 270a and the porous nozzle 270b. However, in FIG. 2, in order to show the detailed structures of the porous nozzle 270a, the porous nozzle 270b, and the temperature sensor 263, for convenience, the temperature sensor 263 is shown at a position facing the porous nozzles 270a and 270b on the right side of the drawing.

  The processing chamber 201 is mainly configured by the reaction tube 203, the manifold 209, and the seal cap 219, and the processing furnace 202 is configured by the heater 207, the reaction tube 203, the manifold 209, and the seal cap 219.

(Porous nozzle)
The processing furnace 202 is provided with a porous nozzle 270a and a porous nozzle 270b as gas nozzles that are provided in the processing chamber 201 along the stacking direction of the wafers 200 and have a plurality of gas ejection ports 248a and 248b, respectively. The perforated nozzle 270a and the perforated nozzle 270b are each configured in an L shape having a vertical portion and a horizontal portion. The vertical portions of the porous nozzle 270 a and the porous nozzle 270 b are respectively arranged in the vertical direction along the inner wall of the reaction tube 203. The horizontal portion of the porous nozzle 270a is provided so as to penetrate the side wall of the manifold 209 via a collecting member 26 (see FIG. 4A) described later. The horizontal portion of the multi-hole nozzle 270b is provided so as to penetrate the side wall of the manifold 209 separately from the multi-hole nozzle 270a.

  A plurality of gas outlets 248a and 248b are respectively provided on the side surfaces of the vertical portions of the porous nozzle 270a and the porous nozzle 270b so as to be arranged in the vertical direction. The gas ejection ports 248a and 248b are configured to open between the stacked wafers 200, respectively. The gas outlets 248a and 248b are configured to face substantially the center in the processing chamber 201 (substantially the center of the wafer 200 loaded into the processing chamber 201), and are supplied from the gas outlets 248a and 248b. Each gas is configured to be ejected toward the substantial center in the processing chamber 201. The opening diameters of the gas outlets 248a and 248b may be the same from the lower part to the upper part, or may be gradually increased from the lower part to the upper part.

The porous nozzle 270a and the porous nozzle 270b supply, for example, an oxidizing agent or a raw material (vaporized gas) as a processing gas into the processing chamber 201 as described later. For example, O ₃ gas or the like can be used as the oxidizing agent, and TEMAZ (tetrakisethylmethylaminozirconium) gas or the like can be used as the raw material.

(Oxidant supply section)
The downstream end of a gas supply pipe 233a that supplies, for example, O ₃ (ozone) gas as an oxidant is connected to the upstream end (horizontal end) of the porous nozzle 270a. The gas supply pipe 233a is provided with an ozonizer 261a, a valve 252a as an on-off valve, a mass flow controller 241a as a flow control mechanism, and a valve 253a in order from the upstream side. The downstream end of a gas supply pipe 232a that supplies O ₂ gas is connected to the ozonizer 261a. The upstream end of the gas supply pipe 232a is, O ₂ gas supply source (not shown) for supplying a O ₂ gas is connected. The O ₂ gas supplied from the gas supply pipe 232a to the ozonizer 261a is at least partially converted to O ₃ gas by the ozonizer 261a. Then, by opening the valves 252a and 253a, the O ₃ gas generated by the ozonizer 261a can be supplied into the processing chamber 201 while controlling the flow rate by the mass flow controller 241a. Note that the O ₃ gas supplied into the processing chamber 201 includes residual O ₂ gas that has not been ozonized by the ozonizer 261a, and O ₂ gas or oxygen (O) generated again by decomposition of the O ₃ gas. ) Radicals are included.

The upstream end of the gas exhaust pipe 236a is connected to the upstream side of the valve 252a of the gas supply pipe 233a. A valve 256a is provided in the gas exhaust pipe 236a. The downstream end of the gas exhaust pipe 236a is connected to an exhaust pipe 231 described later. By opening the valve 256a, the O ₃ gas can be exhausted without passing through the processing chamber 201. O ₃ for gas to generate a stable manner requires a predetermined time, even while stopping supply of the O ₃ gas into the processing chamber 201, to continue the production of the O ₃ gas by the ozonizer 261a desirable. With the above-described configuration, the supply of O ₃ gas into the processing chamber 201 is started by performing the opening / closing switching operation of the valve 252a and the valve 256a while the generation of the O ₃ gas by the ozonizer 261a is continued. The supply can be stopped quickly.

A downstream end of an inert gas supply pipe 234a that supplies an inert gas is further connected to a downstream side of the valve 253a of the gas supply pipe 233a. The inert gas supply pipe 234a is provided with an inert gas supply source (not shown), a mass flow controller (not shown), and a valve 254a in order from the upstream side. By opening the valve 254a, the inert gas can be supplied from the inert gas supply source into the processing chamber 201 while the flow rate is controlled by the mass flow controller. By supplying the inert gas, for example, after the supply of the O ₃ gas is completed, the inert gas can be purged and O ₃ gas remaining in the processing chamber 201 can be removed.

Mainly, the O ₂ gas supply pipe 232a, the ozonizer 261a, the gas exhaust pipe 236a, the valve 256a, the gas supply pipe 233a, the mass flow controller 241a, the valves 252a, 253a, the perforated nozzle 270a, and the gas outlet 248a enter the processing chamber 201. An oxidant supply unit for supplying the oxidant is configured.

(Raw material supply department)
For example, TEMAZ gas as a raw material (vaporized gas) obtained by vaporizing TEMAZ (tetrakisethylmethylaminozirconium: Zr (NEtMe) ₄ ) as a liquid raw material is supplied to the upstream end (horizontal end) of the porous nozzle 270b. The downstream end of the gas supply pipe 233b is connected. Since TEMAZ is a liquid at normal temperature, in order to supply the TEMAZ gas into the processing chamber 201, a method of supplying TEMAZ after heating and vaporizing it, He (helium), Ne (neon), Ar serving as carrier gases There is a method (a bubbling method) in which an inert gas such as (argon) or N ₂ (nitrogen) is supplied into a TEMAZ liquid, and a gas obtained by vaporizing TEMAZ is supplied into the processing chamber 201 together with a carrier gas. . The following is a configuration in the case where TEMAZ gas vaporized by heating is supplied as an example.

The upstream end of the gas supply pipe 233b for supplying the TEMAZ gas is disposed above the liquid surface of the TEMAZ in the TEMAZ container 260b in which the TEMAZ liquid is stored. The gas supply pipe 233b is provided with a vaporizer 261b, a mass flow controller 241b, and a valve 253b as a vaporization unit that heats and vaporizes TEMAZ as a liquid raw material in order from the upstream side. The downstream end of the gas supply pipe 233b is connected to the upstream end of the porous nozzle 270b as described above. The gas supply pipe 233b from the vaporizer 261b to the manifold 209 is provided with a heater 281b, and the gas supply pipe 233b is maintained at 130 ° C., for example. In the TEMAZ liquid in the TEMAZ container 260b, the downstream end of the pressurized gas supply pipe 232b for supplying the pressurized gas is immersed. The pressure gas supply pipe 232b is provided with a pressure gas supply source and a valve 252b (not shown) in order from the upstream side. As the pressurized gas, for example, an inert gas such as N ₂ gas can be used. By opening the valve 252b, it is possible to supply pressurized gas from a pressurized gas supply source, and pressure-feed (supply) TEMAZ as a liquid raw material from the TEMAZ container 260b to the vaporizer 261b. The vaporizer 261b is configured to heat the pressure-fed TEMAZ and generate a vaporized TEMAZ gas.
The TEMAZ gas generated in the vaporizer 261b can be supplied into the processing chamber 201 by opening the valve 253b while controlling the flow rate with the mass flow controller 241b.

  The upstream end of the gas exhaust pipe 236b is connected to the upstream side of the valve 253b of the gas supply pipe 233b. A valve 256b is provided in the gas exhaust pipe 236b. The downstream end of the gas exhaust pipe 236b is connected to an exhaust pipe 231 described later. By opening the valve 256b, the TEMAZ gas can be exhausted without going through the processing chamber 201. Since it takes a predetermined time to stably generate the TEMAZ gas, the liquid raw material is continuously supplied to the vaporizer 261b even while the supply of the TEMAZ gas into the processing chamber 201 is stopped. It is desirable to continue. With the above-described configuration, the supply of TEMAZ gas into the processing chamber 201 is started by switching the opening and closing of the valve 253b and the valve 256b while continuing the generation of the TEMAZ gas in the vaporizer 261b. And supply can be stopped quickly.

  A downstream end of an inert gas supply pipe 234b for supplying an inert gas is further connected to the downstream side of the valve 253b of the gas supply pipe 233b. The inert gas supply pipe 234b is provided with an inert gas supply source (not shown), a mass flow controller (not shown), and a valve 254b in order from the upstream side. By opening the valve 254b, the inert gas can be supplied into the processing chamber 201 from the inert gas supply source while the flow rate is controlled by the mass flow controller. By supplying the inert gas, for example, after the supply of the TEMAZ gas is completed, the inert gas can be purged to remove the TEMAZ gas remaining in the processing chamber 201.

  Mainly by a pressure gas supply pipe 232b, a valve 252b, a TEMAZ container 260b, a gas exhaust pipe 236b, a valve 256b, a vaporizer 261b, a gas supply pipe 233b, a mass flow controller 241b, a valve 253b, a porous nozzle 270b, and a gas jet outlet 248b, A raw material supply unit that supplies the raw material into the processing chamber 201 is configured.

Also, mainly the raw material supply unit and the above-described oxidant supply unit (O ₂ gas supply pipe 232a, ozonizer 261a, gas exhaust pipe 236a, valve 256a, gas supply pipe 233a, mass flow controller 241a, valves 252a, 253a, porous nozzle 270a. The gas jet outlet 248a) constitutes a processing gas supply unit.

(Gas activation part)
The processing furnace 202 is provided with a sheath heater assembly 319 that is erected along the perforated nozzle 270a and includes a plurality of sheath heaters 22a, 22b, 22c, 22d, and the like. The sheath heater assembly 319 is configured in an L shape having a vertical portion and a horizontal portion. The vertical portion of the sheath heater assembly 319 is disposed in the vertical direction along the outer wall of the porous nozzle 270a. The horizontal portion of the sheath heater assembly 319 is provided so as to penetrate the side wall of the manifold 209.

  The configuration of the sheath heater assembly 319 standing along the perforated nozzle 270a is shown in FIG. In FIG. 4A, the right side of the drawing corresponds to the wafer 200 side. In order to show the internal structure and the like of each part, the porous nozzle 270a and the sheath heater assembly 319 are shown in a partially cut out form in the drawing. As shown in FIG. 4A, the sheath heater assembly 319 has a plurality of sheath heaters 22a, 22b, 22c, and 22d as gas activation units.

FIG. 4B is a configuration diagram illustrating the internal structure of the sheath heaters 22a, 22b, 22c, and 22d, in which the left side of the drawing is a perspective view, and the right side of the drawing is a cross-sectional view. The sheath heaters 22a, 22b, 22c, and 22d are, for example, heater main bodies 221a, 221b, 221c, and 221d made of resistance wires such as nichrome wires, and sheaths 223a, 223b, 223c that wrap the heater main bodies 221a, 221b, 221c, and 221d, 223d. The sheaths 223a, 223b, 223c, and 223d are formed in a tube shape whose upper end is closed, and are made of a metal material such as SUS, for example. Fillers 222a, 222b, 222c, and 222d made of insulating powder such as magnesia (MgO) are filled between the heater bodies 221a, 221b, 221c, and 221d and the sheaths 223a, 223b, 223c, and 223d. . The heater main bodies 221a, 221b, 221c, and 221d are heated by energization from a sheath heater power source 20 described later. That is, in the present embodiment, the sheath heaters 22a, 22b, 22c, and 22d as the gas activating unit particularly function as heating elements.

  The sheath heaters 22a, 22b, 22c, and 22d are respectively covered with heater protective tubes 21a, 21b, 21c, and 21d as protective tubes. The heater protection tubes 21a, 21b, 21c, and 21d are made of a dielectric material such as resin or ceramic, and are formed in a tube shape with the upper end closed. The inside of the heater protective tubes 21a, 21b, 21c, and 21d is, for example, an atmospheric pressure atmosphere. Thus, the sheath heaters 22a, 22b, 22c, and 22d are covered with the heater protective tubes 21a, 21b, 21c, and 21d, thereby protecting the sheath heaters 22a, 22b, 22c, and 22d from oxygen radicals and the like. Thereby, the lifetime of the sheath heaters 22a, 22b, 22c, and 22d is extended, and contamination of the processing chamber 201 and the wafer 200 can be reduced.

  Inside the heater protective tubes 21a, 21b, 21c, and 21d, thermocouples (not shown) are provided. Based on the temperature information detected by the thermocouple, the sheath heaters 22a, 22b, 22c, and 22d are desired by adjusting the power supply to the heater main bodies 221a, 221b, 221c, and 221d. It is comprised so that it may become the temperature of.

A vertical portion of the sheath heater assembly 319, more specifically, a vertical portion of the sheath heaters 22a, 22b, 22c, and 22d covered with the heater protection tubes 21a, 21b, 21c, and 21d is a gas outlet 248a provided in the porous nozzle 270a. Are arranged in the vertical direction along the outer wall of the multi-hole nozzle 270a. The respective arrangement of the sheath heaters 22a, 22b, 22c, and 22d is shown in FIG. FIG. 5 is a cross-sectional view of the porous nozzle 270a and the sheath heater assembly 319 taken along the line BB in FIG. 4 (a). In FIG. 5, the right side of the drawing corresponds to the wafer 200 side. As shown in FIG. 5, the sheath heaters 22a, 22b, 22c, and 22d are provided outside the porous nozzle 270a so as to surround the gas ejection port 248a. The sheath heaters 22 a, 22 b, 22 c, and 22 d have gaps through which O ₃ gas can pass so that the flow of O ₃ gas ejected from the gas ejection port 248 a is perpendicular to the outer peripheral edge of the wafer 200. . That is, the sheath heaters 22a and 22b are provided at predetermined intervals on both sides of the gas outlet 248a along the outer wall of the porous nozzle 270a. The sheath heaters 22c and 22d are provided at predetermined intervals on both sides of the gas outlet 248a with the sheath heaters 22a and 22b separated from the outer wall of the porous nozzle 270a. The O ₃ gas ejected from the gas ejection port 248a passes through the gap between the sheath heater 22a and the sheath heater 22b heated by energization from the sheath heater power source 20, and the gap between the sheath heater 22c and the sheath heater 22d, and is activated in the wafer. 200 surfaces. That is, the O ₃ gas is heated and decomposed by the sheath heaters 22a, 22b, 22c, and 22d, and oxygen (O) radicals are generated.

Horizontal portions of the heater protection tubes 21a, 21b, 21c, and 21d, and the above-described porous nozzle 270a
The horizontal portion is welded to a collecting member 26 made of, for example, quartz. As described above, the horizontal portion of the porous nozzle 270a and the horizontal portions of the heater protection tubes 21a, 21b, 21c, and 21d are bundled by the collecting member 26 and penetrate to the outside of the manifold 209 via the collecting member 26. . A sealing member 23 such as an O-ring is provided on the outer periphery of the collecting member 26, and the airtightness in the processing chamber 201 configured by the manifold 209 and the like is maintained.

  The sheath heaters 22a, 22b, 22c, and 22d inside the heater protection tubes 21a, 21b, 21c, and 21d penetrating the manifold 209, more specifically, the heater main bodies 221a, 221b, 221c, and 221d are sheath heater power supplies as gas heating units. 20 are connected to each other. When the heater body 221a, 221b, 221c, 221d is energized from the sheath heater power source 20, the heater bodies 221a, 221b, 221c, 221d composed of resistance wires such as nichrome wires are heated, and the sheath heaters 22a, 22b, 22c, 22d are passed through. Thus, the entire sheath heater assembly 319 is heated.

  Mainly, gas activation is performed by sheath heaters 22a, 22b, 22c, and 22d as gas activation units (heating bodies), heater protection tubes 21a, 21b, 21c, and 21d as protection tubes, and a sheath heater power source 20 as a gas heating unit. The mechanism is configured.

By providing such a gas activation mechanism, it is possible to sufficiently activate a processing gas such as O ₃ gas while keeping the inside of the processing chamber 201 and the porous nozzle 270a at a low temperature.

Note that by the porous nozzle 270a is kept at a low temperature, it is possible to prevent activation of the O ₃ gas in the porous nozzle 270a. As a result, it is possible to prevent the active species such as oxygen radicals from deactivating due to repeated collisions with other O ₃ molecules in the porous nozzle 270a, and the O ₃ gas is supplied to the wafer 200. In this case, a decrease in the concentration of active species in the O ₃ gas can be suppressed.

Further, since the sheath heaters 22a, 22b, 22c, and 22d as the gas activation units are provided in the vicinity of the wafer 200, oxygen radicals that are active species are efficiently supplied to the surface of the wafer 200. That is, the distance (time) from the activation of the O ₃ gas to the surface of the wafer 200 is short, and the active species collides with other molecules before reaching the wafer 200 and is deactivated. put away it can be suppressed in a state containing oxygen radicals at a high concentration, it is possible to supply the O ₃ gas to the wafer 200.

  Moreover, the gas activation part is provided in the immediate vicinity of the gas ejection port 248a of the porous nozzle 270a. That is, it is provided on the flow path that always passes when the processing gas is supplied into the processing chamber 201. Thereby, process gas can be heated and activated efficiently.

  Further, the gas activation unit rectifies the processing gas so that the flow of the processing gas is perpendicular to the outer peripheral edge of the wafer 200. Thereby, the processing gas, that is, the active species can be efficiently supplied to the central portion of the wafer 200.

(Exhaust part)
An exhaust pipe 231 is connected to the side wall of the manifold 209. In the exhaust pipe 231, a pressure sensor 245 as a pressure detector (pressure detection unit) that detects the pressure in the processing chamber 201, an APC (Auto Pressure Controller) valve 251 as a pressure regulator, and vacuum exhaust are sequentially provided from the upstream side. A vacuum pump 246 as an apparatus is provided. The APC valve 251 is an on-off valve that can be evacuated and stopped by opening and closing the valve and that can further adjust the opening of the valve. By adjusting the opening degree of the opening / closing valve of the APC valve 251 while operating the vacuum pump 246, the inside of the processing chamber 201 can be set to a desired pressure.

  The exhaust pipe 231, the pressure sensor 245, the APC valve 251, and the vacuum pump 246 mainly constitute an exhaust unit that exhausts the atmosphere in the processing chamber 201. Note that the exhaust section including the exhaust pipe 231 and the like is provided at a position close to, for example, the porous nozzles 270a and 270b as shown in FIG. However, in FIG. 2, in order to show the detailed structure of the exhaust part, it is shown at a position facing the porous nozzles 270a and 270b on the right side of the drawing.

(Control part)
The controller 280 as a control unit includes a mass flow controller 241a, 241b, an APC valve 251, a valve 252a, 253a, 254a, 256a, 252b, 253b, 254b, 256b, an ozonizer 261a, a sheath heater power supply 20, a heater 207, a pressure sensor 245, a temperature. The sensor 263, the vacuum pump 246, the rotation mechanism 267, the boat elevator 115, etc. are connected. The controller 280 adjusts the flow rate of the mass flow controllers 241a and 241b, opens and closes the APC valve 251, valves 252a, 253a, 254a, 256a, 252b, 253b, 254b, and 256b, and further adjusts the pressure of the APC valve 251 by the ozonizer 261a. O ₃ gas generation control, sheath heater power supply 20, temperature adjustment operation of heater 207, pressure detection operation of pressure sensor 245, temperature detection operation by temperature sensor 263, start / stop of vacuum pump 246, rotation speed adjustment of rotation mechanism 267, The lift operation of the boat elevator 115 is controlled.

(4) Substrate Processing Step Next, the substrate processing step according to this embodiment will be described. The substrate processing process according to the present embodiment is performed by the above-described processing furnace 202 using the CVD method or the ALD method as one process of manufacturing a semiconductor device such as a DRAM.

  In the conventional CVD method or ALD method, for example, in the case of the CVD method, a plurality of types of gases including a plurality of elements constituting the film to be formed are simultaneously supplied. A plurality of types of gas containing these elements are alternately supplied. Then, a ZrO (zirconium oxide) film or the like is formed by controlling the gas supply flow rate at the time of gas supply, the gas supply time, the temperature in the processing chamber 201, and in the case of the plasma method, the film formation conditions such as plasma power. For example, in forming a ZrO film, the film forming conditions are controlled so that the composition ratio of the film becomes O / Zr≈2 which is a stoichiometric composition. Alternatively, the film formation conditions can be controlled so that the composition ratio of the film to be formed becomes a predetermined composition ratio different from the stoichiometric composition. That is, the film formation conditions are controlled so that at least one element out of a plurality of elements constituting the film to be formed becomes excessive with respect to the stoichiometric composition than the other elements. As described above, film formation can be performed while controlling the ratio of a plurality of elements constituting the film to be formed, that is, the composition ratio of the film. Hereinafter, a sequence example in which a film having a stoichiometric composition is formed by alternately supplying a plurality of types of gases containing different types of elements by the ALD method will be described.

  The ALD method, which is a type of CVD method, uses a reactive gas containing two types (or more) of raw materials used for film formation alternately one by one under a certain film formation condition (temperature, time, etc.). This is a method of forming a film by utilizing surface reaction by supplying it onto the substrate and adsorbing it on the substrate in units of one atomic layer. When a ZrO film is formed on the wafer 200 by the ALD method, for example, a process of supplying a Zr (zirconium) -containing material and a process of supplying an oxidizing agent are set as one cycle, and this cycle is performed a predetermined number of times. In a single cycle, a discontinuous ZrO film of less than one atomic layer or several atomic layers is formed. Therefore, the film thickness of the ZrO film can be controlled by the number of cycle repetitions. For example, if the deposition rate is 1 cm / cycle, a 20 cm ZrO film can be formed by performing the cycle 20 times.

Hereinafter, a substrate processing process in the case where a desired insulating film, for example, a ZrO film, is formed on the wafer 200 using the TEMAZ gas as the Zr-containing raw material and the O ₃ gas as the oxidant by the processing furnace 202 described above. This will be described in detail mainly with reference to FIGS. FIG. 6 is a flowchart of a substrate processing process performed by the processing furnace 202. FIG. 7 is a sequence diagram as a timing chart illustrating the timing of supply / exhaust when the material supply and the oxidant supply according to this embodiment are alternately repeated. In the following description, the operation of each part constituting the processing furnace 202 according to FIG. 3 is controlled by the controller 280. Here, the ZrO film is a ZrO film having an arbitrary composition including ZrO ₂ . Alternatively, a base film such as a TiN film may be formed in advance on the wafer 200, and a ZrO film may be formed on the base film. A base film such as a TiN film may be formed by an apparatus different from the processing furnace 202, or a ZrO film may be continuously formed after the base film is formed in the processing furnace 202.

(Substrate carrying-in process S1)
First, a plurality of wafers 200 are loaded into the boat 217 (wafer charge). Then, the boat 217 holding the plurality of wafers 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the sealing member 220. In the substrate carrying-in process S1, it is preferable that the valves 254a and 254b are opened and an inert gas such as N ₂ gas as a purge gas is continuously supplied into the processing chamber 201.

(Decompression step S2, temperature rising step S3)
Subsequently, the valves 254 a and 254 b are closed, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246. Further, the temperature in the processing chamber 201 is controlled by the heater 207 so that the wafer 200 has a desired temperature, for example, 150 ° C. to 250 ° C. At this time, feedback control of the power supply to the heater 207 is performed based on the temperature information detected by the temperature sensor 263 so that the processing chamber 201 has a desired temperature distribution. Then, the boat 217 is rotated by the rotation mechanism 267, and the rotation of the wafer 200 is started.

(ZrO film forming step S4 to S8)
Subsequently, a ZrO film is formed on the wafer 200. That is, S4 to S7 in FIG. 6 are defined as one cycle, and this cycle is performed a predetermined number of times (S8), thereby forming a ZrO film having a predetermined thickness on the wafer 200. Below, ZrO film | membrane formation process S4-S8 is explained in full detail.

(Raw material supply process S4)
In the raw material supply step S <b> 4, TEMAZ gas as a raw material (vaporized gas) is flowed into the processing chamber 201 to adsorb TEMAZ molecules on the surface of the wafer 200. Specifically, a pressured gas is supplied in advance from a pressured gas supply source (not shown) into the TEMAZ container 260b, and TEMAZ as a liquid raw material is pressured (supplied) to the vaporizer 261b to stably generate the TEMAZ gas. deep. When supplying the TEMAZ gas into the processing chamber 201, the valve 256b of the gas exhaust pipe 236b is closed and the valve 253b of the gas supply pipe 233b is opened, so that the flow rate is controlled by the mass flow controller 241b and the vaporizer 261b. The generated TEMAZ gas is supplied into the processing chamber 201. At the same time, the valve 254 b of the inert gas supply pipe 234 b is opened to supply the inert gas into the processing chamber 201. At this time, the opening degree of the APC valve 251 is adjusted to maintain the pressure in the processing chamber 201 within a range of 50 Pa to 400 Pa. The amount of TEMAZ gas supplied is, for example, in the range of 0.1 g / min to 0.5 g / min. The supply time of the TEMAZ gas is, for example, in the range of 30 seconds to 240 seconds. When the predetermined time has elapsed, the valve 253b is closed, and the valve 256b and the APC valve 251 are opened.

In the raw material supply step S4, the gas flowing into the processing chamber 201 is mainly TEMAZ.
It is only inert gas such as gas and N ₂ gas, and there is no oxidant such as O ₃ gas. Therefore, the TEMAZ gas causes chemical adsorption (surface reaction) with the surface of the wafer 200 or the surface of the underlying film such as a TiN film formed on the wafer 200 without causing a gas phase reaction, and the adsorption layer of the TEMAZ molecule. Alternatively, a Zr layer is formed. The adsorption layer of TEMAZ molecules includes a discontinuous adsorption layer as well as a continuous adsorption layer of TEMAZ molecules. The Zr layer includes not only a continuous layer composed of Zr produced by decomposing TEMAZ molecules, but also a Zr thin film formed by overlapping these layers. In addition, all of these may be referred to as a Zr-containing layer.

(Evacuation process S5)
After opening the valve 256b and flowing the TEMAZ gas to the gas exhaust pipe 236b side, after closing the valve 253b and stopping the supply of the raw material into the processing chamber 201, the APC valve 251 is opened and the inside of the processing chamber 201 is evacuated. Then, the remaining vaporized TEMAZ gas and the decomposition products (exhaust gas) after the reaction are excluded. At this time, the valve 254b included in the inert gas supply pipe 234b is kept open, and the supply of the inert gas such as N ₂ into the processing chamber 201 is maintained. Thereby, the effect of removing the residual gas from the processing chamber 201 can be further enhanced.

(Oxidant supply step S6)
In the oxidant supply step S6, an O ₃ gas as an oxidant is flowed into the processing chamber 201 to form a ZrO film on the wafer. Specifically, advance, stably to generate O ₃ gas by supplying O ₂ gas from the O ₂ gas supply source (not shown) to the ozonizer 261a. When supplying the O ₃ gas into the processing chamber 201, the valve 256a of the gas exhaust pipe 236a is closed and the valves 252a and 253a of the gas supply pipe 233a are opened, so that the flow rate is controlled by the mass flow controller 241a. The O ₃ gas generated in 261a is supplied into the processing chamber 201. At the same time, the valve 254 a of the inert gas supply pipe 234 a is opened to supply the inert gas into the processing chamber 201. At this time, the opening degree of the APC valve 251 is adjusted to maintain the pressure in the processing chamber 201 within a range of 50 Pa to 400 Pa. The supply amount of the O ₃ gas is, for example, in the range of 10 slm to 20 slm. The supply time of the O ₃ gas is set within a range of 60 seconds to 300 seconds, for example. When a predetermined time elapses, the valves 252a and 253a are closed, and the valves 256a and the APC valve 251 are opened.

When supplying the O ₂ gas into the processing chamber 201, the sheath heater power source is set so that the sheath heaters 22a, 22b, 22c, and 22d included in the sheath heater assembly 319 have a predetermined temperature, for example, 300 ° C. to 400 ° C. Power is supplied from 20 to the heater main bodies 221a, 221b, 221c, and 221d of the sheath heaters 22a, 22b, 22c, and 22d. At this time, feedback of the power supply to the heater main bodies 221a, 221b, 221c, and 221d based on the temperature information detected by the thermocouple provided in the sheath heater assembly 319 is performed so that the sheath heaters 22a, 22b, 22c, and 22d have a desired temperature. Control. The O ₃ gas ejected from the gas ejection port 248a of the porous nozzle 270a is decomposed by heat to generate oxygen radicals when passing through the gap between the heated sheath heaters 22a and 22b and the gap between the sheath heaters 22c and 22d. O ₃ gas is supplied to the wafer 200 in a state of containing oxygen radicals at a high concentration and being activated.

In this way, the sheath heaters 22a, 22b, 22c, and 22d heat the O ₃ gas at a position near the wafer 200 near the gas outlet 248a, and the activated O ₃ gas passes through the gaps between the sheath heaters 22a, 22b, 22c, and 22d. From the outer periphery of the wafer 200 so as to be perpendicular to the outer periphery. As a result, the O ₃ gas containing a high concentration of active species can be efficiently supplied to the center of the wafer 200 while keeping the inside of the processing chamber 201 and the porous nozzle 248 a at a low temperature.

In the oxidant supply step S6, the gas flowing into the processing chamber 201 is mainly only O ₃ gas, and there is no raw material such as TEMAZ gas. Therefore, the O ₃ gas reacts with at least a part of the Zr-containing layer formed on the surface of the wafer 200 without causing a gas phase reaction. By supplying the O ₃ gas in this way, the Zr-containing layer adsorbed on the wafer 200 and the O ₃ gas, more specifically, oxygen (O) radicals contained in the O ₃ gas are chemically adsorbed (surface Reaction) occurs, and a ZrO thin film of less than one atomic layer to several atomic layers is formed on the wafer 200.

(Evacuation step S7)
After opening the valve 256a and allowing O ₃ gas to flow to the gas exhaust pipe 236a side, and closing the valves 252a and 253a and stopping the supply of O ₃ gas into the processing chamber 201, the APC valve 251 is opened to open the processing chamber. The inside of 201 is evacuated to remove remaining O ₃ gas, decomposition gas after reaction, and the like. At this time, the valve 254a included in the inert gas supply pipe 234a is kept open, and the supply of the inert gas such as N ₂ into the processing chamber 201 is maintained. Thereby, the effect of removing the residual gas from the processing chamber 201 can be further enhanced. In addition, energization of the heater bodies 221a, 221b, 221c, and 221d of the sheath heaters 22a, 22b, 22c, and 22d is stopped.

(Cycle step S8)
The above S4 to S7 are defined as one cycle, and this cycle is performed a predetermined number of times to form a ZrO film having a predetermined film thickness, for example, 30 to 100 mm on the wafer 200. FIG. 7 shows an example in which the above cycle is performed n times. In FIG. 7, the horizontal axis indicates the elapsed time, and the vertical axis indicates the supply timing of each gas.

(Temperature drop step and normal pressure return step S9)
When a predetermined cycle is repeated and a ZrO film having a desired film thickness is formed, power supply to the heater 207 is stopped, and the boat 217 and the wafer 200 are lowered to a predetermined temperature. While the temperature is lowered, the valves 254a and 254b are kept open, and the supply of the inert gas from the inert gas supply source (not shown) into the processing chamber 201 is continued. Thereby, the inside of the processing chamber 201 is replaced with the inert gas, and the pressure in the processing chamber 201 is returned to the normal pressure.

(Substrate unloading step S10)
When the wafer 200 is lowered to a predetermined temperature and the inside of the processing chamber 201 returns to normal pressure, the wafer 200 after film formation is unloaded from the processing chamber 201 by a procedure reverse to the above procedure. That is, the seal cap 219 is lowered by the boat elevator 115 to open the lower end of the manifold 209, and the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being held by the boat 217. Unload). Thereafter, the processed wafer 200 is taken out from the boat 217 (wafer discharge). Note that when the boat 217 is carried out, it is preferable that the valves 254 a and 254 b are opened and the purge gas is continuously supplied into the processing chamber 201. Thus, the substrate processing process by the processing furnace 202 is completed.

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

(A) sheath heater 22a as a gas activating unit according to the present embodiment, 22b, 22c, 22d is, the _{O 3} gas flow can pass is the _{O 3} gas so as to be perpendicular to the outer peripheral edge of the wafer 200 The O ₃ gas ejected from the gas ejection port 248a is activated and supplied to the wafer 200 so as to surround the gas ejection port 248a while leaving a gap. Accordingly, the O ₃ gas can be sufficiently activated while keeping the inside of the processing chamber 201 and the porous nozzle 270 a at a low temperature, and the concentration of oxygen radicals supplied to the surface of the wafer 200 can be increased.

For example, by the O ₃ gas as an oxidizing agent, in forming the ZrO film by oxidizing the Zr-containing layer as described above, oxygen radicals O ₃ gas is generated by decomposition oxidation reaction of the Zr-containing layer Contribute to. The decomposition of O ₃ gas in the gas phase is promoted with increasing temperature. In terms of the half-life of the O ₃ concentration in the gas phase, for example, the half-life at 20 ° C. is 2 hours to 20 hours, but at 200 ° C. it is several seconds and at 350 ° C. it is less than 1 second. Then, oxygen radicals are generated according to the decrease in the O ₃ concentration. Since 1 mol of oxygen radicals are generated when 1 mol of O ₃ is decomposed, the time until oxygen radicals corresponding to 50% of the original O ₃ concentration are generated (that is, 100 mol of O ₃ gas is initially present). In this case, the time until 50 mol of oxygen radicals are generated is shortened to 1/7200 to 1/72000 when the O ₃ gas temperature is increased from 20 ° C. to 350 ° C. In the present embodiment, the temperature of the sheath heaters 22a, 22b, 22c, and 22d is set to, for example, 300 ° C. to 400 ° C. The O ₃ gas passes through the gaps between the sheath heaters 22a and 22b and the sheath heaters 22c and 22d thus heated. When passing, a large amount of oxygen radicals are generated by the decomposition reaction. Thereby, O ₃ gas containing oxygen radicals at a high concentration can be supplied to the wafer 200.

(B) According to this embodiment, since the inside of the porous nozzle 270a is kept at a low temperature, activation of the O ₃ gas in the porous nozzle 270a can be prevented. Thus, in the multi-hole nozzle 270a, it is the oxygen radical is prevented from colliding with another O ₃ molecules like, when the O ₃ gas is supplied to the wafer 200, the density reduction of the oxygen radicals O ₃ gas Can be suppressed. Therefore, the processing speed of the wafer 200 is improved, and the efficiency and productivity of the substrate processing process can be improved.

(C) Further, since the gas activation unit according to the present embodiment is provided in the vicinity of the wafer 200, oxygen radicals are efficiently supplied to the wafer 200. That is, the distance (time) from the activation of the O ₃ gas to the surface of the wafer 200 is short, and the oxygen radicals collide with other molecules before reaching the wafer 200 and are deactivated. Can be suppressed. Thereby, the processing speed of the wafer 200 is improved.

In a conventional substrate processing apparatus, a processing gas such as O ₃ gas is supplied into the processing chamber while the temperature in the processing chamber is maintained at, for example, 150 ° C. to 250 ° C. Thereby, the O ₃ gas is heated and decomposed in the processing chamber to generate oxygen radicals. The oxygen radicals reached the surface of the wafer, and a ZrO film was formed by an oxidation reaction with the Zr-containing layer. However, in the conventional substrate processing apparatus, the decomposition reaction due to the heating of the O ₃ gas may be insufficient, and the O ₃ gas may reach the wafer surface in a state where the O ₃ gas is not sufficiently activated. In such a case, for example, if the temperature in the processing chamber is further increased, it is possible to promote the decomposition reaction by heating the O ₃ gas. However, when the temperature in the processing chamber is increased, the porous nozzle standing in the processing chamber is also heated, and for example, the decomposition reaction of O ₃ gas may occur in the porous nozzle. Usually, the lifetime of active species such as oxygen radicals is very short, and many of the oxygen radicals generated in the porous nozzle cannot reach the surface of the wafer. Further, the oxygen radicals repeatedly collide with the O ₃ gas or O ₂ gas generated by the decomposition of the O ₃ gas in the perforated nozzle, thereby reducing the concentration of the O ₃ gas ejected from the gas ejection port. This may result in a further decrease in the amount of oxygen radicals reaching the wafer.

However, according to the present embodiment, while the temperature in the processing chamber 201 is kept relatively low, for example, 150 ° C. to 250 ° C., the gas is ejected by the sheath heaters 22a, 22b, 22c, and 22d provided so as to surround the gas ejection port 248a. Immediately after jetting from the outlet 248a, the O ₃ gas is heated from 300 ° C. to 400 ° C., for example. Thus, while suppressing the decomposition reaction of the O ₃ gas in the porous nozzle 270a, in the process chamber 201, at a position closer to the wafer 200, it may be decomposed more reliably O ₃ gases, the substrate processing Speed can be improved.

(D) The gas activation unit according to the present embodiment is provided in the immediate vicinity of the gas ejection port 248a of the porous nozzle 270a. That is, the gas activation unit is provided on a flow path that always passes when the O ₃ gas is supplied into the processing chamber 201. Thus, it is possible to activate efficiently heated without omission O ₃ gas.

Gas activation unit according to (e) embodiment, the flow of O ₃ gas to rectify the O ₃ gas so as to be perpendicular to the outer peripheral edge of the wafer 200. Thereby, the processing gas, that is, the active species can be efficiently supplied to the central portion of the wafer 200. Therefore, in-plane uniformity of substrate processing is improved.

(F) The gas activation unit according to the present embodiment is covered with the heater protection tubes 21a, 21b, 21c, and 21d made of a dielectric, and the heater main bodies 221a, 221b, 221c, and 221d and the heater main bodies 221a, 221b, and 221c. The sheath heaters 22a, 22b, 22c, and 22d include sheaths 223a, 223b, 223c, and 223d that wrap the 221d. By covering the sheath heaters 22a, 22b, 22c, and 22d with the heater protection tubes 21a, 21b, 21c, and 21d, the sheath heaters 22a, 22b, 22c, and 22d can be protected from active species and the like. Therefore, the life of the sheath heaters 22a, 22b, 22c, and 22d is extended, and contamination of the processing chamber 201 and the wafer 200 can be avoided.

[Second Embodiment]
Then, the structure of the processing furnace 202 concerning 2nd Embodiment of this invention is demonstrated mainly using FIG. 8 and FIG. In the second embodiment, the arrangement of the sheath heaters 22a, 22b, 22c, and 22d of the sheath heater assembly 419 and the arrangement of the gas outlets 248a provided in the porous nozzle 470a are different from those in the first embodiment. In the following description, different components of the sheath heater assembly 419 will be mainly described in detail. About the structure of other than that, the same code | symbol is attached | subjected to the component which has a function similar to the above-mentioned sheath heater assembly 319, and description is abbreviate | omitted.

FIG. 8A is a configuration diagram of the porous nozzle 470a and the sheath heater assembly 419 according to the present embodiment, and FIG. 8B is a configuration diagram showing the internal structure of the sheath heaters 22a, 22b, 22c, and 22d. FIG. 9 is a cross-sectional view of the multi-hole nozzle 470a and the sheath heater assembly 419 taken along the line C-C in FIG. 8A and 9, the right side of the drawing corresponds to the wafer 200 side. As shown in FIGS. 8A and 9, the gas outlet 248 a provided in the multi-hole nozzle 470 a is provided at a position rotated 90 ° horizontally with respect to the surface of the wafer 200 from a position facing the wafer 200. . The sheath heaters 22a, 22b, 22c, and 22d are also provided so as to surround the gas ejection port 248a in accordance with the position where the gas ejection port 419 is rotated. The sheath heaters 22 a, 22 b, 22 c, and 22 d have gaps through which O ₃ gas can pass so that the flow of O ₃ gas ejected from the gas ejection port 248 a is perpendicular to the outer peripheral edge of the wafer 200. . That is, the respective sheath heaters 22a, 22b, 22c, and 22d are arranged so that the O ₃ gas ejected from the gas ejection port 248a is supplied to the wafer 200 through the gap. Specifically, the sheath heaters 22a and 22b are provided at predetermined intervals on both sides of the gas ejection port 248a along the outer wall of the porous nozzle 270a. The sheath heaters 22c and 22d are arranged so as to draw a curve toward the wafer 200 adjacent to the sheath heater 22a while keeping a predetermined distance from the sheath heater 22b. As a result, the O ₃ gas ejected from the gas ejection port 248a flows along the curve formed by the sheath heaters 22a, 22c, and 22d, passes through the gap between the sheath heater 22b and the sheath heater 22d, and is activated in the wafer. 200 surfaces.

  Also in this embodiment, there exists an effect similar to the above-mentioned embodiment. Further, by disposing the gas outlets 248a included in the sheath heaters 22a, 22b, 22c and 22d of the sheath heater assembly 419 and the porous nozzle 470a as described above, for example, in the configuration of the processing furnace 202, the wafer 200 and the porous nozzle Even when the distance from 470a cannot be sufficiently secured, the sheath heater assembly 419 can be installed so as to obtain a desired effect.

[Third Embodiment]
Then, the structure of the processing furnace 202 concerning 3rd Embodiment of this invention is demonstrated mainly using FIG. In the present embodiment, the sheath heaters 22a, 22b, 22c, and 22d as the gas activation unit function not only as a heating body but also as a plasma discharge body. That is, the point that the sheath heater assembly 519 is further connected to the plasma generation unit is different from the above-described embodiment. In the following description, components different from the above of the sheath heater assembly 519 will be mainly described in detail. About the structure of other than that, the same code | symbol is attached | subjected to the component which has a function similar to the above-mentioned sheath heater assembly 319, and description is abbreviate | omitted.

10A is a configuration diagram of the porous nozzle 270a and the sheath heater assembly 519 according to the present embodiment, and FIG. 10B is a configuration diagram showing the internal structure of the sheath heaters 22a, 22b, 22c, and 22d. As shown in FIGS. 10A and 10B, any one of the sheaths 223a and 223c as the plasma discharge electrodes provided in the sheath heaters 22a and 22c, and the sheaths 223b and 223d as the plasma discharge electrodes provided in the sheath heaters 22b and 22d, respectively. One of these, for example, the sheaths 223c and 223d, is connected to a high-frequency power source 24 that applies high-frequency power via a matching unit 25, respectively. Power is supplied from the high-frequency power source 24 to the sheath heaters 22c and 22d, for example, the sheaths 223c and 223d made of a metal material such as SUS, and the spaces surrounded by the heater protection tubes 21a, 21b, 21c, and 21d made of a dielectric, for example. To generate plasma of O ₃ gas. That is, O ₃ gas passing through the gap between the sheath heaters 22a and 22b and the gap between the sheath heaters 22c and 22d is plasma-excited.

  When the sheath heaters 22a, 22b, 22c, and 22d are arranged in the above-described second embodiment, any one of the sheaths 223a, 223c, and 223d included in the sheath heaters 22a, 22c, and 22d and the sheath 223b included in the sheath heater 22b are included. And a high-frequency power source 24 are connected. Preferably, the high frequency power supply 24 is connected to the sheath 223d and the sheath 223b.

  Mainly sheath heaters 22a, 22b, 22c, 22d as gas activating parts (plasma discharge bodies) having sheaths 223a, 223b, 223c, 223d as plasma discharge electrodes, and heater protection tubes 21a, 21b, 21c as protection tubes , 21d constitutes a sheath heater assembly 519, and a high-frequency power source 24 and a matching unit 25 mainly constitute a plasma generation unit. And the gas activation mechanism is mainly comprised by the sheath heater power supply 20 as a sheath heater assembly 519, a plasma production | generation part, and a gas heating part.

Next, the operation of the sheath heater assembly 519 provided with the plasma generation unit will be described. First, the sheath heater power source 20 provided in the sheath heater assembly 519 energizes and heats the heater main bodies 221a, 221b, 221c, and 221d of the sheath heaters 22a, 22b, 22c, and 22d. Next, O ₃ gas is ejected from the gas ejection port 248a of the porous nozzle 270a. At this time, sheathed heater from the high frequency power source 24 22c, the sheath 22d is provided 223c, respectively by applying a power to 223d, the heater protective tube 21a, 21b, 21c, an electric field is generated in the space surrounded by 21d, by the _{O 3} gas Plasma is generated. With such a configuration, oxygen radicals of higher concentration can be generated by heating by the sheath heaters 22a, 22b, 22c, and 22d and by converting the O ₃ gas itself into plasma. In this way, by supplying the O ₃ gas containing high-concentration oxygen radicals to the wafer 200 and performing substrate processing, the processing speed of the wafer 200 can be further increased.

  Also in this embodiment, there exists an effect similar to the above-mentioned embodiment.

Further, according to the present embodiment, the high frequency power source 24 and the matching unit 25 are connected to any of the sheaths 223a, 223b, 223c, and 223d, and the O ₃ gas ejected from the gas ejection port 248a is converted into plasma. It has a configuration. As a result, O ₃ gas containing a higher concentration of oxygen radicals can be supplied to the wafer 200. Therefore, the efficiency and productivity of the substrate processing process can be further improved.

According to the present embodiment, any of the sheaths 223a, 223b, 223c, and 223d constituting the sheath heaters 22a, 22b, 22c, and 22d is used as a plasma discharge electrode. Thereby, plasma of O ₃ gas can be generated without adding a new component.

Further, according to the present embodiment, the sheath heaters 22a, 22b, 22c, and 22d are configured to be covered with the heater protection tubes 21a, 21b, 21c, and 21d that are made of a dielectric. Thereby, even if plasma of O ₃ gas is generated in the vicinity of the sheath heaters 22a, 22b, 22c, and 22d, damage to the sheath heaters 22a, 22b, 22c, and 22d due to the plasma is reduced, and the sheath heaters 22a, 22b, 22c, and 22d are reduced. Can extend the lifespan.

  Furthermore, according to the present embodiment, the heater protection tubes 21a, 21b, 21c, and 21d are made of a dielectric, so that plasma discharge using the sheaths 223a, 223b, 223c, and 223d as plasma discharge electrodes is not hindered.

In the above-described embodiment, an example in which O ₃ gas is used as the oxidizing agent is described. However, the present invention is not limited to this, and O ₂ gas may be used as the oxidizing agent.

[Other embodiments]
As described above, in the above-described embodiment, the sheath heaters 22a, 22b, 22c, and 22d and the heater protection tubes 21a, 21b, 21c, and 21d included in the sheath heater assemblies 319, 419, and 519 are four each. The number of tubes is not limited to this, and it is only necessary to provide two or more sheath heaters and heater protective tubes so as to form a gap through which O ₃ gas passes.

  In the above-described embodiment, the configuration is such that plasma is generated by applying high-frequency power to the heater protection tubes 21a, 21b, 21c, and 21d while heating the sheath heaters 22a, 22b, 22c, and 22d. Only plasma discharge may be performed without heating 22b, 22c, and 22d. In this case, the sheath heaters 22a, 22b, 22c, and 22d are not energized from the sheath heater power source 20, and the high-frequency power to any of the sheaths 223a, 223b, 223c, and 223d included in the sheath heaters 22a, 22b, 22c, and 22d Only power from 24 is supplied.

In the above-described embodiment, the O ₃ gas is used as the oxidizing agent. However, in the configuration having the plasma generation unit, for example, O ₂ gas or other O atom-containing gas can be used.

In the above-described embodiment, the case where TEMAZ is used as the raw material for the ZrO film has been described in detail. However, the raw material for the ZrO film is not limited to TEMAZ, and Zr (O-tBu) ₄ , TDMAZ (tetrakisdimethylaminozirconium: Zr ( NMe ₂ ) ₄ ), TDEAZ (tetrakisdiethylaminozirconium: Zr (NEt ₂ ) ₄ ), Zr (MMP) _{4 and the} like can be used.

In the above-described embodiment, the ZrO film is formed. However, in the above-described substrate processing apparatus 101, not only the ZrO film but also a TiO film, an AlO film, an HfO film, an HfAlO film, a ZrAlO film, etc. Various films such as an insulating film containing various metal atoms, an SiO ₂ film, and an SiON film can be formed. In addition to the film formation process, various substrate processes such as an oxidation process, a substrate surface modification process, and a diffusion process can be performed. The processing gas supplied into the processing chamber 201 can be variously selected according to the desired substrate processing, but the present invention can be suitably used particularly when O ₃ gas is included as the processing gas.

  Further, the processing gas activated by the gas activating unit is not limited to the oxidizing agent and the raw material gas as described above, and may be other gases such as a nitriding agent, a reducing agent, and a carbonizing agent.

  In the above-described embodiment, the case where the substrate processing apparatus 101 is configured as a vertical heat treatment apparatus has been described, but the present invention is not limited to such a form. For example, the present invention can be suitably applied to a substrate processing apparatus including a processing chamber for processing a wafer or the like under reduced pressure, such as a horizontal heat treatment apparatus or a single wafer heat treatment apparatus.

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

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

The first aspect of the present invention is:
A processing chamber for storing a plurality of substrates stacked in multiple stages at a predetermined interval;
A processing gas supply unit for supplying a processing gas for processing the substrate into the processing chamber;
The processing gas supply unit includes a gas nozzle provided with a plurality of gas ejection ports for ejecting the processing gas to the surface of the substrate, and extending along the stacking direction of the substrate,
The gas jet port is provided outside the gas nozzle so as to surround the gas jet port with a gap through which the process gas can pass so that the flow of the process gas is perpendicular to the outer peripheral edge of the substrate. The substrate processing apparatus has a gas activation unit that activates the processing gas ejected from the gas and supplies the processing gas to the substrate.

The second aspect of the present invention is:
The said gas activation part is a substrate processing apparatus as described in a 1st aspect which is a heating body which heats the said process gas ejected from the said gas ejection port.

The third aspect of the present invention is:
The gas activation unit is the substrate processing apparatus according to the first aspect or the second aspect, which is a plasma discharge body that converts the processing gas ejected from the gas ejection port into plasma.

The fourth aspect of the present invention is:
The processing gas is ozone gas,
The gas activation unit is the substrate processing apparatus according to the first to third aspects in which ozone gas is decomposed to generate oxygen radicals.

According to a fifth aspect of the present invention,
A processing chamber for storing a plurality of substrates stacked in multiple stages at a predetermined interval;
A substrate heating unit for heating the substrate housed in the processing chamber;
A gas nozzle extending in the vicinity of the side surface of the substrate along the stacking direction of the substrate;
A plurality of gas jets provided in the gas nozzle and jetting a processing gas for processing the substrate to the surface of the substrate;
A heating element provided near the gas outlet;
A gas heating unit that supplies electric power to the heating body, activates the processing gas ejected from the gas ejection port by heating the heating body, and supplies the activated processing gas to the substrate; A substrate processing apparatus is provided.

The sixth aspect of the present invention is:
The substrate processing apparatus according to the fifth aspect, wherein the heating body is a sheath heater that is covered with a protective tube made of a dielectric and includes a heater body and a sheath that wraps the heater body.

The seventh aspect of the present invention is
A processing chamber for storing a plurality of substrates stacked in multiple stages at a predetermined interval;
A substrate heating unit for heating the substrate housed in the processing chamber;
A gas nozzle extending in the vicinity of the side surface of the substrate along the stacking direction of the substrate;
A plurality of gas jets provided in the gas nozzle for jetting a processing gas for processing the substrate to the surface of the substrate;
A plasma discharge electrode provided in the vicinity of the gas outlet;
A plasma generation unit that supplies power to the plasma discharge electrode, activates the processing gas ejected from the gas ejection port into plasma by the plasma discharge electrode, and supplies the activated processing gas to the substrate And a substrate processing apparatus.

The eighth aspect of the present invention is
The plasma discharge electrode is a sheath made of a metal material provided in a sheath heater,
The substrate processing apparatus according to an eighth aspect, wherein the sheath heater is covered with a protective tube made of a dielectric, and includes a heater body and the sheath that wraps the heater body.

The ninth aspect of the present invention provides
A processing chamber for storing a plurality of substrates stacked in multiple stages at a predetermined interval;
A processing gas supply unit having a gas nozzle extending into the processing chamber along the stacking direction of the substrates, and supplying a processing gas for processing the substrate into the processing chamber;
A plurality of gas jets provided in the gas nozzle and jetting the processing gas to the surface of the substrate;
A gas activation portion extending along the gas nozzle;
A gas activation mechanism connected to the gas activation unit;
A control unit for controlling at least the processing gas supply unit and the gas activation mechanism,
The gas activation unit connected to the gas activation mechanism has a gap extending in the stacking direction of the substrate and allowing the processing gas ejected from the gas ejection port to pass through.
The controller is
The process gas is ejected from the gas jet port by the process gas supply unit, and the process gas is passed through the gap of the gas activation unit,
The substrate processing apparatus, wherein the processing gas passing through the gap by the gas activation mechanism is activated via the gas activation unit and supplied to the substrate.

The tenth aspect of the present invention provides
A step of laminating a plurality of substrates in a multi-stage at a predetermined interval and carrying them into the processing chamber;
A gas activation unit provided outside the gas nozzle so as to eject the processing gas from a plurality of gas outlets provided in a gas nozzle extending in the processing chamber along the stacking direction of the substrate and surround the gas outlet The process gas is passed through the gap so that the flow of the process gas is perpendicular to the outer peripheral edge of the substrate, and the process gas passing through the gap is activated by the gas activation unit to the substrate. And a step of processing the substrate.

The eleventh aspect of the present invention is
Carrying a plurality of substrates into the processing chamber;
Supplying a processing gas for processing the substrate into a processing chamber from a gas nozzle provided with a plurality of gas outlets for jetting the processing gas to the surface of the substrate and extending along the stacking direction of the substrate;
A gas outlet is provided by a gas activation part provided outside the gas nozzle so as to surround the gas outlet while leaving a gap through which the processing gas can pass so that the flow of the processing gas is perpendicular to the outer peripheral edge of the substrate Activating the process gas ejected from the substrate and supplying the activated gas to the substrate;
A step of unloading the substrate from the processing chamber;
A method of manufacturing a semiconductor device having

101 substrate processing apparatus 200 wafer (substrate)
201 processing chamber 270a, 270b perforated nozzle (gas nozzle)
248a, 248b Gas outlet 22a, 22b, 22c, 22d Sheath heater (gas activation part)

Claims (2)

A processing chamber for storing a plurality of substrates stacked in multiple stages at a predetermined interval;
A processing gas supply unit for supplying a processing gas for processing the substrate into the processing chamber;
The processing gas supply unit includes a gas nozzle provided with a plurality of gas ejection ports for ejecting the processing gas to the surface of the substrate, and extending along the stacking direction of the substrate,
The gas jet port is provided outside the gas nozzle so as to surround the gas jet port with a gap through which the process gas can pass so that the flow of the process gas is perpendicular to the outer peripheral edge of the substrate. A substrate processing apparatus comprising: a gas activation unit that activates the processing gas ejected from the substrate and supplies the activated processing gas to the substrate. Carrying a plurality of substrates into the processing chamber;
Supplying a processing gas for processing the substrate into the processing chamber from a gas nozzle provided with a plurality of gas outlets for jetting the processing gas to the surface of the substrate and extending in the stacking direction of the substrate;
A gas activation unit provided outside the gas nozzle so as to surround the gas outlet while leaving a gap through which the process gas can pass so that the flow of the process gas is perpendicular to the outer peripheral edge of the substrate. The step of activating the processing gas ejected from the gas ejection port and supplying it to the substrate,
And unloading the substrate from the processing chamber.
A method for manufacturing a semiconductor device.

Images