JP2010141076A - Wafer processing apparatus and method of manufacturing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wafer processing apparatus for suppressing suction of foreign matters onto a substrate. <P>SOLUTION: The wafer processing apparatus includes a first gas supply nozzle which is erected in a processing chamber along a stacking direction of substrates, and includes a plurality of gas supply ports and supplies a first processing gas produced by vaporizing a liquid material into the processing chamber, a vaporizer for vaporizing the liquid material, and a second gas supply nozzle which is erected adjacently to the first gas supply port, and includes a plurality of gas supply ports and supplies a second processing gas and an inert gas into the processing chamber, wherein the first processing gas and second processing gas are supplied alternately without being mixed with each other to form a desired film on a substrate and when the first processing gas is supplied, the inert gas is supplied from the second gas supply nozzle at a flow rate larger than the supply flow rate of the first processing gas. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

  As a process of manufacturing a semiconductor device such as an IC or a DRAM, a substrate processing process has been performed in which a gas is alternately supplied onto a substrate to process the substrate. In the substrate processing step, a processing chamber in which a plurality of substrates are stacked and accommodated, gas supply means for supplying gas from a plurality of gas supply nozzles standing in the processing chamber, and an atmosphere in the processing chamber are exhausted. And a substrate processing apparatus provided with an exhaust means. The substrate is carried into the processing chamber, and the substrate is processed by alternately supplying gas from each gas supply nozzle.

  However, when a substrate is processed using the above-described substrate processing apparatus, foreign matter (particles) is generated in the processing chamber, and the generated foreign matter is adsorbed on the surface of the substrate, so that the reliability of the semiconductor device is reduced. In some cases, the production yield of the product deteriorated.

  An object of the present invention is to provide a substrate processing apparatus and a semiconductor device manufacturing method capable of suppressing the adsorption of foreign substances onto the substrate.

  According to the first aspect of the present invention, a processing chamber that houses a plurality of substrates stacked thereon, a gas supply unit that supplies a desired gas into the processing chamber, and an exhaust unit that exhausts the atmosphere in the processing chamber. A control unit that controls at least the gas supply unit and the exhaust unit, and the gas supply unit is erected along the stacking direction of the substrate in the processing chamber and has a plurality of gas supply ports. A first gas supply nozzle for supplying a first processing gas obtained by vaporizing a liquid source into the processing chamber, a vaporizer for vaporizing the liquid source, and the first gas supply nozzle. A second gas supply nozzle that is erected and has a plurality of gas supply ports and supplies a second process gas and an inert gas into the process chamber, and the control unit includes the gas supply unit and The exhaust means is controlled to control the first When the process gas and the second process gas are alternately supplied so as not to mix with each other to form a desired film on the substrate and the first process gas is supplied, the first process gas is supplied. There is provided a substrate processing apparatus for supplying an inert gas from the second gas supply nozzle at a flow rate higher than the supply flow rate.

  According to the second aspect of the present invention, a processing chamber that houses a plurality of substrates stacked, a gas supply unit that supplies a desired gas into the processing chamber, and an exhaust unit that exhausts the atmosphere in the processing chamber. The gas supply means is installed in the process chamber along the stacking direction of the substrate, has a plurality of gas supply ports, and supplies the first process gas obtained by vaporizing a liquid source. A first gas supply nozzle for supplying the gas into the processing chamber; and a vaporizer configured to vaporize the liquid raw material, wherein the plurality of gas supply ports opened in the gas supply nozzle are more than the tangential direction of the substrate. There is provided a substrate processing apparatus that opens outward with respect to a substrate.

According to the third aspect of the present invention, a processing chamber that houses a plurality of substrates stacked thereon, a gas supply unit that supplies a desired gas into the processing chamber, and an exhaust unit that exhausts the atmosphere in the processing chamber. A control unit that controls at least the gas supply unit and the exhaust unit, and the gas supply unit is erected along the stacking direction of the substrate in the processing chamber, and is connected to the substrate from a tangent to the substrate. A first gas supply nozzle that has a plurality of gas supply ports opened to the outside and supplies a first processing gas obtained by vaporizing a liquid source into the processing chamber, and vaporization for vaporizing the liquid source And a second gas supply nozzle that is provided adjacent to the first gas supply nozzle, has a plurality of gas supply ports, and supplies a second processing gas and an inert gas into the processing chamber. The control unit includes the gas The supply means and the exhaust means are controlled to supply the first process gas and the second process gas alternately so as not to mix with each other, thereby forming a desired film on the substrate. When supplying the processing gas, there is provided a substrate processing apparatus for supplying an inert gas from the second gas supply nozzle at a flow rate higher than the supply flow rate of the first processing gas.

  According to the fourth aspect of the present invention, the first processing gas obtained by vaporizing the liquid raw material and the second processing gas different from the first processing gas are alternately supplied so as not to mix with each other. A method of manufacturing a semiconductor device for forming a desired film on a substrate, wherein when supplying the first processing gas, the gas supply nozzle for supplying the second processing gas into the processing chamber A method of manufacturing a semiconductor device that supplies an inert gas at a flow rate higher than a supply flow rate of a first process gas is provided.

  According to the fifth aspect of the present invention, the first processing gas obtained by vaporizing the liquid raw material and the second processing gas different from the first processing gas are alternately supplied so as not to mix with each other. There is provided a method of manufacturing a semiconductor device for forming a desired film on a substrate, wherein the first processing gas is supplied outward from a tangent line of the substrate to the substrate. Is done.

  According to the substrate processing apparatus and the semiconductor device manufacturing method of the present invention, it is possible to suppress the adsorption of foreign matter on the substrate.

  As described above, when the gas is supplied from the gas supply nozzle to process the substrate, foreign matter is generated in the processing chamber, and the generated foreign matter may be adsorbed on the surface of the substrate.

In FIG. 1, a conventional substrate processing apparatus is used to alternately supply TDMAS (SiH [N (CH ₃ ) ₂ ] ₃ ; trisdimethylaminosilane) gas and ozone (O ₃ ) gas onto a wafer to form an oxide film ( The foreign substance distribution (experimental result) on the wafer when the (SiO ₂ film) is formed is shown. In the experiment shown in FIG. 1, a wafer made of silicon is placed in a processing chamber, heated to 550 ° C., and TDMAS gas generated by supplying TDMA to the vaporizer at a flow rate of 3 g / min is supplied into the processing chamber for 30 seconds. A step of supplying and purging N ₂ gas into the processing chamber, a step of supplying O ₃ gas into the processing chamber at a flow rate of 6.5 slm for 7 seconds, and supplying and purging N ₂ gas into the processing chamber This process was repeated 27 times, and an oxide film (SiO ₂ film) was formed on the wafer. TDMAS gas and O ₃ gas were supplied from two gas supply nozzles provided upright in the processing chamber. Further, when supplying various gases into the processing chamber, the wafer was rotated in a horizontal posture. As a result, as shown in FIG. 1, many foreign matters were adsorbed on the wafer. In addition, 2428 foreign matters having a particle size of 0.08 μm or more and 0.13 μm or less were detected, and 79 foreign materials having a particle size exceeding 0.13 μm were detected.

The inventors have determined the distribution of foreign matter on the wafer (experimental results) for each of the case where only the TDMAS gas is supplied into the processing chamber and the case where only the O ₃ gas is supplied in order to specify the generation source of the foreign matter adsorbed on the wafer. Was measured.

FIG. 2 shows a foreign substance distribution (experimental result) on the wafer when only the TDMAS gas is supplied onto the wafer using a conventional substrate processing apparatus. In the experiment shown in FIG. 2, a step of supplying TDMAS gas generated by supplying TDMAS to the vaporizer at a flow rate of 3 g / min for 30 seconds, and a step of purging by supplying N ₂ gas into the processing chamber And this cycle was repeated 27 times. Other conditions are the same as in the experiment of FIG. As a result, a large number of foreign matters were adsorbed on the wafer as shown in FIG. In addition, 3137 foreign substances having a particle diameter of 0.08 μm or more and 0.13 μm or less were detected, and 119 foreign substances having a particle diameter exceeding 0.13 μm were detected.

FIG. 3 shows the distribution of foreign matters (experimental results) on the wafer when only the O ₃ gas is supplied onto the wafer using a conventional substrate processing apparatus. In the experiment shown in FIG. 3, the process of supplying O ₃ gas into the process chamber at a flow rate of 6.5 slm for 7 seconds and the process of supplying N ₂ gas into the process chamber for purging are performed as one cycle. Repeated times. Other conditions are the same as in the experiment of FIG. As a result, as shown in FIG. 3, the number of foreign matters on the wafer was significantly reduced as compared with the cases of FIGS. Three foreign matters having a particle size of 0.08 μm or more and 0.13 μm or less were detected, and eight foreign matters having a particle size exceeding 0.13 μm were detected.

The inventors also measured the distribution of foreign matter (experimental results) on the wafer by reducing the supply flow rate of the TDMAS gas into the processing chamber. FIG. 4 shows the distribution of foreign matter on a wafer when an oxide film is formed by alternately supplying a smaller amount of TDMAS gas and O ₃ gas onto the wafer than in the case of FIG. 1 using a conventional substrate processing apparatus. (Experimental result) is shown. In the experiment shown in FIG. 2, a step of supplying TDMAS gas generated by supplying TDMAS to the vaporizer at a flow rate of 1.0 g / min for 8 seconds, and a step of purging by supplying N ₂ gas into the processing chamber, By repeating this cycle 163 times, the process of supplying O ₃ gas into the process chamber at a flow rate of 6.5 slm for 30 seconds and the process of supplying and purging N ₂ gas into the process chamber are performed 163 times. An oxide film (SiO ₂ film) was formed thereon. Other conditions are the same as in the experiment of FIG. As a result, as shown in FIG. 2, the foreign matter on the wafer was reduced as compared with the case of FIG. In addition, 155 foreign matters having a particle size of 0.08 μm or more and 0.13 μm or less were detected, and 6 foreign materials having a particle size exceeding 0.13 μm were detected.

  Based on the above experiment, the inventors have found that supplying the TDMAS gas from the gas supply nozzle into the processing chamber is one factor that adsorbs foreign matter on the substrate. It has also been determined that simply reducing the TDMAS gas supply flow rate will reduce the processing speed and increase the number of cycles, and it will not be sufficient to significantly suppress foreign matter adsorbed on the wafer. It was. As a result of earnest research, the inventors have obtained the knowledge that the amount of foreign matter adsorbed on the wafer can be greatly reduced by controlling the direction of the TDMAS gas flow supplied from the gas supply nozzle. It was. The present invention has been made based on such knowledge.

<One Embodiment of the Present Invention>
An embodiment of the present invention will be described below with reference to the drawings.

  FIG. 5 is a longitudinal sectional view of the processing furnace of the substrate processing apparatus according to one embodiment of the present invention. 6 is a cross-sectional view taken along the line AA of the processing furnace shown in FIG. FIG. 7 is a flow diagram illustrating a gas supply sequence in the substrate processing process according to this embodiment. FIG. 11 is a perspective perspective view of a substrate processing apparatus according to an embodiment of the present invention.

(1) Configuration of Substrate Processing Apparatus First, a configuration example of a substrate processing apparatus 101 according to an embodiment of the present invention will be described with reference to FIG.

As shown in FIG. 11, the substrate processing apparatus 101 according to this embodiment includes a housing 111. In order to transport a wafer (substrate) 200 made of silicon or the like 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 in front of the housing 111 (on the right side in the drawing). The cassette 110 is placed on the cassette stage 114 by an in-process transfer 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 the in-process transfer device. The cassette stage 114 rotates the cassette 110 90 degrees in the vertical direction toward the rear of the casing 111 to bring the wafer 200 in the cassette 110 into a horizontal posture, and the wafer loading / unloading port of the cassette 110 is placed behind the casing 111. It is configured to be able to face.

  A cassette shelf (substrate storage container mounting shelf) 105 is installed at a substantially central portion in the front-rear direction in the housing 111. 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. Further, a preliminary cassette shelf 107 is provided above the cassette stage 114, and is configured to store the cassette 110 in a preliminary manner.

  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 cooperative 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 transfer jig) 125c that holds the wafer 200 in a horizontal posture. By the cooperative 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 (charged) into a boat (substrate support member) 217 described later. Alternatively, the wafer 200 is detached from the boat 217 (discharged) 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 boat elevator (substrate support member lifting mechanism) 115 is provided as a lifting mechanism that lifts and lowers the boat 217 and transports 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 lid 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. ing.

  The boat 217 includes a plurality of holding members, and a plurality of (for example, about 50 to 150) 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. The detailed configuration of the boat 217 will be described later.

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

  In addition, a clean unit (not shown) provided with a supply fan and a dustproof filter so as to supply clean air to the left end portion of the housing 111 opposite to the wafer transfer device elevator 125b and the boat elevator 115 side. Is installed. Clean air blown out from the clean unit (not shown) is configured to be sucked into an exhaust device (not shown) and exhausted to the outside of the casing 111 after circulating around the wafer transfer device 125a and the boat 217. ing.

  Next, the operation of the substrate processing apparatus 101 according to this embodiment will be described.

  First, the cassette 110 is placed on the cassette stage 114 by an in-process transfer device (not shown) so that the wafer 200 is in a vertical posture and the wafer loading / unloading port of the cassette 110 faces upward. Thereafter, the cassette 110 is rotated 90 ° in the vertical direction 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.

  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 transporting device 118, delivered, temporarily stored, and then stored in the cassette shelf 105 or the spare cassette shelf. The sample is transferred from 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 (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 lower end portion of the processing furnace 202 closed by the furnace port shutter 147 is opened by the furnace port shutter 147. Subsequently, the seal cap 219 is raised by the boat elevator 115, so that the boat 217 holding the group of wafers 200 is loaded into the processing furnace 202. 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 discharged to the outside of the casing 111 by a procedure reverse to the above procedure.

(2) Configuration of Processing Furnace Next, the configuration of the processing furnace 202 according to an embodiment of the present invention will be described with reference to FIGS. 5 and 6.

(Processing room)
A processing furnace 202 according to an embodiment of the present invention includes 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 its upper end closed and its lower end open. The manifold 209 is made of a metal material such as SUS, for example, and has a cylindrical shape with an upper end and a lower end opened. The reaction tube 203 is supported vertically by the manifold 209 from the lower end side. The reaction tube 203 and the manifold 209 are arranged concentrically. The lower end portion of the manifold 209 is configured to be hermetically sealed by the seal cap 219 when the above-described boat elevator 115 is raised. A sealing member 220 such as an O-ring that hermetically seals the inside of the processing chamber 201 is provided between the lower end portion of the manifold 209 and the seal cap 219.

  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. A boat 217 serving as a substrate support unit is inserted into the processing chamber 201 from below. The inner diameters of the reaction tube 203 and the manifold 209 are configured to be larger than the maximum outer diameter of the boat 217 loaded with the wafers 200.

  The boat 217 is configured to hold a plurality of (for example, 75 to 100) wafers 200 in multiple stages with a predetermined gap (substrate pitch interval) in a substantially horizontal state. The boat 217 is mounted on a heat insulating cap 218 that blocks heat conduction from the boat 217. The heat insulating cap 218 is supported from below by the rotating shaft 255. The rotation shaft 255 is provided so as to penetrate the center portion of the seal cap 219 while maintaining airtightness in the processing chamber 201. A rotation mechanism 267 that rotates the rotation shaft 255 is provided below the seal cap 219. By rotating the rotation shaft 255 by the rotation mechanism 267, the boat 217 on which the plurality of wafers 200 are mounted can be rotated while maintaining the airtightness in the processing chamber 201.

  A heater 207 as a heating means (heating mechanism) is provided on the outer periphery of the reaction tube 203 concentrically with the reaction tube 203. The heater 207 has a cylindrical shape and is vertically installed by being supported by a heater base (not shown) as a holding plate.

  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 and has a disk 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. A rotation mechanism 267 that rotates the boat 217 is installed on the side of the seal cap 219 opposite to the processing chamber 201. A rotation shaft 255 of the rotation mechanism 267 passes through the seal cap 219 and supports the boat 217 from below, and is configured such that the wafer 200 can be rotated by operating the rotation mechanism 267. The seal cap 219 is configured to be moved up and down in the vertical direction by a boat elevator 215 as a lifting mechanism vertically disposed outside the reaction tube 203, thereby transporting the boat 217 into and out of the processing chamber 201. It is possible.

(Gas supply means)
The processing furnace 202 is erected in the processing chamber 201 along the stacking direction of the wafers 200, has a plurality of gas supply ports 250a, and serves as a first processing gas obtained by vaporizing TDMAS as a liquid source. A vaporized gas supply nozzle 250 is provided as a first gas supply nozzle that supplies TDMAS (SiH [N (CH ₃ ) ₂ ] ₃ ; trisdimethylaminosilane) gas into the processing chamber 201. Further, the processing furnace 202 is erected adjacent to the vaporized gas supply nozzle 250, has a plurality of gas supply ports 251a, and includes ozone (O ₃ ) gas as the second processing gas and N as the inert gas. _And a reactive gas supply nozzle 251 as a second gas supply nozzle for supplying _two gases into the processing chamber 201.

  The vaporized gas supply nozzle 250 and the reactive gas supply nozzle 251 are each configured in an L shape having a vertical portion and a horizontal portion. The vertical portions of the vaporized gas supply nozzle 250 and the reactive gas supply nozzle 251 are arranged in the vertical direction along the inner wall of the reaction tube 203. The horizontal portions of the vaporized gas supply nozzle 250 and the reactive gas supply nozzle 251 are provided so as to penetrate the side walls of the manifold 209.

  6 is a top view of an AA cross section of the processing furnace shown in FIG. As shown in FIG. 6, the vaporized gas supply nozzle 250 is erected on the upper side of the boat 217 (wafer 200) in the rotational direction 200d (upstream in the rotational direction 200d) from the reactive gas supply nozzle 251. It is configured. Note that the rotation direction 200d of the boat 217 (wafer 200) can be changed as appropriate, and more preferably, is opposite to the rotation direction 200d, and the vaporized gas supply nozzle 250 is lower than the reactive gas supply nozzle 251. You may rotate so that it becomes.

  A plurality of gas supply ports 250a and 251a are provided on the vertical side surfaces of the vaporized gas supply nozzle 250 and the reactive gas supply nozzle 251, respectively, so as to be arranged in the vertical direction. The gas supply ports 250a and 251a are configured to open between the stacked wafers 200, respectively. The shapes of the gas supply ports 250a and 251a are respectively configured as directional shapes, for example, formed in round holes. The gas supply ports 250a and 251a according to the present embodiment are configured so as to face substantially the center of the processing chamber 201 (substantially the center of the wafer 200 loaded into the processing chamber 201), respectively. The gas supplied from 251a is configured to be ejected toward the substantial center in the processing chamber 201. The gas supply ports 250 a and 251 a are configured to open between the stacked wafers 200. The opening diameters of the gas supply ports 250a and 251a 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.

A vaporized gas supply pipe 244a that supplies a TDMAS gas as the first processing gas is connected to the upstream end (horizontal end) of the vaporized gas supply nozzle 250. The vaporized gas supply pipe 244a is sequentially provided with a vaporizer 271 and an open / close valve 243a that vaporize TDMAS as a liquid raw material to generate TDMAS gas from the upstream side. The vaporizer 271 has, for example, a spray structure, and is configured to spray and vaporize liquid TDMAS using the spray structure. Connected to the vaporizer 271 are a liquid source supply pipe 244c for supplying TDMAS into the vaporizer 271 and a carrier gas supply pipe 244d for supplying an inert gas (N ₂ gas) as a carrier gas into the vaporizer 271. Has been. In the liquid source supply pipe 244c, a liquid source supply source 242c that supplies TDMAS as a liquid source, an LMFC (liquid flow rate controller) 241c, and an opening / closing valve 243c are provided in this order from the upstream side. The carrier gas supply pipe 244d is provided with an N ₂ gas supply source 242d, an MFC (flow rate controller) 241d, and an opening / closing valve 243d in order from the upstream side. By opening the on-off valve 243c, the TDMAS is supplied from the liquid source supply source 242c into the vaporizer 271 while controlling the flow rate by the LMFC 241c, and is vaporized by the vaporizer 271, thereby generating the TDMAS gas. Then, by opening the opening and closing valve 243 d, and the _{N 2} gas _is supplied from the _{N 2} gas supply source 242d to the vaporizer 271 while the flow rates were controlled by MFC 241 d, can promote the discharge of TDMAS gas from within the vaporizer 271 It is configured as follows. Then, by opening the opening / closing valve 243a, the TDMAS gas can be supplied from the vaporized gas supply nozzle 250 into the processing chamber 201 through the vaporized gas supply pipe 244a.

A reaction gas supply pipe 244b that supplies ozone gas as the second processing gas is connected to the upstream end (horizontal end) of the reaction gas supply nozzle 251. The reaction gas supply pipe 244b is provided with an ozonizer 102 for generating ozone gas, an MFC (flow rate controller) 241b, and an opening / closing valve 243b in this order from the upstream side. An oxygen gas supply pipe 244e that supplies oxygen (O ₂ ) gas is connected to the ozonizer 102. The oxygen gas supply pipe 244e is provided with an oxygen gas supply source 242e and an opening / closing valve 243e in order from the upstream side. When the opening / closing valve 243e is opened and oxygen gas is supplied from the oxygen gas supply source 242e to the ozonizer 102, the ozonizer 102 generates ozone gas. Then, by opening the opening / closing valve 243b, ozone gas can be supplied from the reaction gas supply nozzle 251 into the processing chamber 201 while controlling the flow rate by the MFC 241b.

A first purge gas pipe 244f for supplying an inert gas (N ₂ gas) as a purge gas is connected downstream of the open / close valve 243a of the vaporized gas supply pipe 244a. The first purge gas pipe 244f is provided with an N ₂ gas supply source 242f, an MFC (flow rate controller) 241f, and an opening / closing valve 243f in order from the upstream side. By opening the opening / closing valve 243f, N ₂ gas can be supplied from the vaporized gas supply nozzle 250 into the processing chamber 201 while controlling the flow rate by the MFC 241f. A second purge gas pipe 244g for supplying an inert gas (N ₂ gas) as a purge gas is connected to the downstream side of the open / close valve 243b of the reaction gas supply pipe 244b. The second purge gas pipe 244g is provided with an N ₂ gas supply source 242g, an MFC (flow rate controller) 241g, and an opening / closing valve 243g in order from the upstream side. By opening the on-off valve 243g, the N ₂ gas can be supplied from the reaction gas supply nozzle 251 into the processing chamber 201 while controlling the flow rate by the MFC 241g.

  The upstream side of the vent pipe 244h is connected to the upstream side of the open / close valve 243a of the vaporized gas supply pipe 244a (between the vaporizer 271 and the open / close valve 243a). The downstream side of the vent pipe 244h is connected to the downstream side of an exhaust pipe 231 described later (between an APC valve 231a and a vacuum pump 246 described later). The vent pipe 244h is provided with an open / close valve 243h. By closing the opening / closing valve 243a and opening the opening / closing valve 243h, the supply of the TDMAS gas into the processing chamber 201 can be stopped while the generation of the TDMAS gas in the vaporizer 271 is continued. Although a predetermined time is required to stably generate the TDMAS gas, the supply / stop of the TDMAS gas into the processing chamber 201 can be switched in a very short time by the opening / closing switching operation of the opening / closing valve 243a and the opening / closing valve 243h. It is configured to be able to.

Mainly, a vaporized gas supply nozzle 250, a reactive gas supply nozzle 251, a vaporized gas supply pipe 244a, a reactive gas supply pipe 244b, a liquid source supply pipe 244c, a carrier gas supply pipe 244d, an oxygen gas supply pipe 244e, and a first purge gas pipe 244f. , Second purge gas pipe 244g, vent pipe 244h, liquid source supply source 242c, oxygen gas supply source 242e, N ₂ gas supply source 242d, 242f, 242g, vaporizer 271, ozonizer 102, LMFC 241c, MFC 241b, 241d, 241f, 241g The gas supply means for supplying a desired gas into the processing chamber 201 is constituted by the open / close valves 243a to 243f.

(Exhaust means)
An exhaust pipe 231 is connected to the side wall of the manifold 209. A pressure sensor 245 as a pressure detector, an APC (Auto Pressure Controller) valve 231a as a pressure regulator, and a vacuum pump 246 as a vacuum exhaust device are provided in the exhaust pipe 231 in order from the upstream side. The interior of the processing chamber 201 can be set to a desired pressure by adjusting the opening degree of the opening / closing valve of the APC valve 231a while operating the vacuum pump 246. The exhaust pipe 231, the pressure sensor 245, the APC valve 231 a, and the vacuum pump 246 mainly constitute exhaust means for exhausting the atmosphere in the processing chamber 201.

(controller)
The controller 280 as a control unit (control means) includes a heater 207, an APC valve 231a, a vacuum pump 246, a rotation mechanism 267, a boat elevator 215, a vaporizer 271, an ozonizer 102, an LMFC 241c, MFCs 241b, 241d, 241f, and 241g. 243a-243f etc. are connected. The controller 280 adjusts the temperature of the heater 207, opens and closes the APC valve 231a and adjusts the pressure, starts and stops the vacuum pump 246, adjusts the rotation speed of the rotating mechanism 267, moves up and down the boat elevator 215, and vaporizes the carburetor 271. The ozone generation operation of the ozonizer 102, the flow rate adjustment operation of the LMFC 241c and the MFCs 241b, 241d, 241f, and 241g, and the opening / closing operations of the opening / closing valves 243a to 243f are controlled.

The controller 280 is configured to control the gas supply means and the exhaust means to supply the TDMAS gas and the ozone gas alternately into the processing chamber 201 so as not to mix with each other, thereby forming a desired film on the wafer 200. Has been. The controller 280 is configured to supply N ₂ gas from the reaction gas supply nozzle 251 at a flow rate higher than the supply flow rate of the TDMAS gas when supplying the TDMAS gas into the processing chamber 201. This operation will be described later.

(3) Substrate Processing Step Next, a substrate processing step as one embodiment of the present invention will be described with reference to FIGS. FIG. 7 is a flow diagram illustrating a gas supply sequence in the substrate processing process according to this embodiment. In the substrate processing process according to the present embodiment, an oxide film made of, for example, SiO ₂ is formed on the surface of the wafer 200 by using an ALD (Atomic Layer Deposition) method which is one of CVD (Chemical Vapor Deposition) methods. This is a film forming method, and is performed as one step of a semiconductor device manufacturing process. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 280.

(Substrate loading process)
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 215 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 O-ring 220b. In the substrate carry-in process, the open / close valve 243f and the open / close valve 243g are opened, and the supply of N ₂ gas (purge gas) into the process chamber 201 is continued to reduce the oxygen concentration in the process chamber 201.

(Decompression and temperature rise process)
Subsequently, the APC valve 231 a is opened and the inside of the processing chamber 201 is evacuated by the vacuum pump 246 so that the inside of the processing chamber 201 has a desired pressure (degree of vacuum). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the opening degree of the APC valve 231a is feedback-controlled based on the measured pressure. Further, the inside of the processing chamber 201 is heated by the heater 207 so that the inside of the processing chamber 201 has a desired temperature. At this time, feedback control of the energization state to the heater 207 is performed based on the temperature information detected by the temperature sensor so that the inside of the processing chamber 201 has a desired temperature distribution. Then, the boat 217 is rotated by the rotation mechanism 267 to rotate the wafer 200.

(Film formation process)
Subsequently, a film forming process is performed. In the film forming process, the TDMAS gas and the ozone gas are alternately supplied into the processing chamber 201 so as not to mix with each other, and a desired film is formed on the wafer 200. Note that when the TDMAS gas is supplied into the processing chamber 201, the N ₂ gas is supplied from the reaction gas supply nozzle 251 at a flow rate higher than the supply flow rate of the TDMAS gas. Specifically, a step of stabilizing the flow rate of the TDMAS gas (Step 1), a step of stopping and sealing the exhaust of the processing chamber 201 (Step 2), a TDMAS gas and a large flow rate in the processing chamber 201 A process of supplying N ₂ gas (step 3), a process of purging the inside of the processing chamber 201 (step 4), a process of supplying ozone gas into the processing chamber 201 (step 5), and a purge of the inside of the processing chamber 201 This process is repeated a predetermined number of times. Hereinafter, Step 1 to Step 6 will be described.

In step 1, the open / close valve 243 c is opened, and TDMAS is supplied into the vaporizer 271 at a flow rate of 3 g / min, for example. Further, the open / close valve 243d is opened, and N ₂ gas (carrier gas) is supplied into the vaporizer 271 at a flow rate of, for example, 0.3 slm. Until the flow rate of the TDMAS gas from the vaporizer 271 is stabilized, the open / close valve 243h is opened while the open / close valve 243a is closed, and the TDMAS gas is exhausted from the vent pipe 244h without being supplied into the processing chamber 201. Keep it. Further, the open / close valve 243f and the open / close valve 243g are opened, and N ₂ gas (purge gas) is supplied into the processing chamber 201 from the vaporized gas supply nozzle 250 and the reactive gas supply nozzle 251 at a flow rate of, for example, 0.3 slm. The opening / closing valve 243b is closed. The time required for Step 1 is, for example, about 6 seconds.

  In step 2, the APC valve 231a is closed and the exhaust of the processing chamber 201 is stopped. As a result, the inside of the processing chamber 201 is sealed in a decompressed state. The time required for Step 2 is, for example, about 1 second.

In step 3, the open / close valve 243 h is closed and the open / close valve 243 a is opened to supply the TDMAS gas from the vaporized gas supply nozzle 250 into the processing chamber 201. Further, when supplying the TDMAS gas into the processing chamber 201, the MFC 241g is adjusted, and the N ₂ gas is supplied into the processing chamber 201 from the reaction gas supply nozzle 251 at a flow rate higher than the supply flow rate of the TDMAS gas. For example, when TDMAS gas is generated by supplying 3 g / min TDMAS into the vaporizer 271 as described above, N ₂ gas is supplied from the reaction gas supply nozzle 251 at a flow rate of 1.0 slm. .

  As described above, the TDMAS gas supplied into the processing chamber 201 is approximately at the center in the processing chamber 201 from the gas supply port 250a of the vaporized gas supply nozzle 250 (substantially the center of the wafer 200 loaded into the processing chamber 201). Erupted toward. Such a situation is illustrated by reference numeral f1 in FIG. According to the above-described experimental results by the inventors, the supply of the TDMAS gas from the vaporized gas supply nozzle 250 into the processing chamber 201 becomes a factor for adsorbing foreign matter onto the wafer 200. Therefore, when the TDMAS gas is supplied from the gas supply port 250a along the direction of reference numeral f1, the wafer 200 is directly exposed to the TDMAS gas (TDMAS gas containing foreign matter) injected from the gas supply port 250a. Foreign matter will be adsorbed.

On the other hand, in step 3, when supplying the TDMAS gas into the processing chamber 201, the N ₂ gas is supplied into the processing chamber 201 from the reaction gas supply nozzle 251 at a flow rate higher than the supply flow rate of the TDMAS gas. As a result, the TDMAS gas ejected from the gas supply port 250a undergoes trajectory correction by the large flow rate of N ₂ gas supplied from the reaction gas supply nozzle 251 and is bent in the outer direction (for example, tangential direction) of the wafer 200. It becomes. Such a situation is illustrated by reference numeral f2 in FIG. As a result, the wafer 200 becomes difficult to be directly exposed to the TDMAS gas (TDMAS gas containing foreign matter) injected from the gas supply port 250a, and the foreign matter adsorption to the wafer 200 is suppressed. Even if it becomes difficult for the wafer 200 to be directly exposed to the TDMAS gas injected from the gas supply port 250a, the TDMAS gas is diffused in the processing chamber 201 and supplied onto the wafer 200. It is possible to obtain film speed and film quality. By executing Step 3, the gas molecules of the TDMAS gas are adsorbed on the surface of the wafer 200. The time required for step 3 is about 30 seconds, for example.

In step 4, the APC valve 231a is opened to resume exhausting the processing chamber 201. Further, the open / close valve 243c is closed to stop the generation of the TEMAS gas in the vaporizer 271. Note that without stopping the generation of the TEMAS gas, the on-off valve 243a may be closed to stop the supply of the TDMAS gas into the processing chamber 201, and the TDMAS gas may be exhausted from the vent pipe 244h. Further, the MFC 241g is adjusted to return the flow rate of the N ₂ gas supplied from the reaction gas supply nozzle 251 from 1.0 slm to 0.3 slm. While evacuating the inside of the processing chamber 201, N ₂ gas is supplied from the vaporized gas supply nozzle 250 and the reactive gas supply nozzle 251 at a flow rate of 0.3 slm, whereby the inside of the processing chamber 201, the vaporized gas supply nozzle 250, Residual gases in the gas supply nozzle 251, the vaporized gas supply pipe 244a, the reaction gas supply pipe 244b, etc. are purged. The time required for step 4 is, for example, about 7 seconds.

In step 5, while continuing the exhaust in the processing chamber 201, the open / close valves 243e and 243b are opened, and ozone gas is supplied from the reaction gas supply nozzle 251 into the processing chamber 201 at a flow rate of, for example, 6.5 slm. Note that when ozone gas is supplied into the processing chamber 201, the open / close valve 243 g is closed to stop the supply of N ₂ gas from the reaction gas supply nozzle 251. Note that the opening and closing valve 243f is not closed, and the supply of the N ₂ gas from the vaporized gas supply nozzle 250 is continued, thereby suppressing the ozone gas from entering the vaporized gas supply nozzle 250. The ozone gas supplied into the processing chamber 201 is supplied onto the wafer 200, reacts with gas molecules of the TEMAS gas adsorbed on the surface of the wafer 200, and one to several atomic layers of SiO ₂ film are formed on the surface of the wafer 200. Generated. The time required for step 5 is, for example, about 7 seconds.

In step 6, while the exhausting of the processing chamber 201 is continued, the on-off valves 243 e and 243 b are closed to stop the supply of ozone gas into the processing chamber 201 and the on-off valve 243 g is opened to open the reaction gas supply nozzle 251. The supply of N ₂ gas is resumed. While evacuating the inside of the processing chamber 201, N ₂ gas is supplied from the vaporized gas supply nozzle 250 and the reactive gas supply nozzle 251 at a flow rate of 0.3 slm, whereby the inside of the processing chamber 201, the vaporized gas supply nozzle 250, Residual gases and reaction products in the gas supply nozzle 251, the vaporized gas supply pipe 244a, the reaction gas supply pipe 244b, etc. are purged. The time required for step 6 is, for example, about 3 seconds.

As described above, step 1 to step 6 are set as one cycle, and this cycle is repeated a predetermined number of times to form a SiO ₂ film having a desired thickness on the wafer 200, and the film forming process is completed. Note that the flow rate of the N ₂ gas supplied from the reactive gas supply nozzle 251 may be increased to 1.0 slm only in step 3 as described above, or may be always 1.0 slm in steps 1 to 6. .

(Atmospheric pressure recovery process, substrate unloading process)
Subsequently, the opening / closing valves 243a and 243b are closed, and the opening / closing valves 243f and 243g are kept open, and the opening degree of the APC valve 231a is reduced, so that the pressure in the processing chamber 201 becomes atmospheric pressure. N ₂ gas (purge gas) is supplied. Then, the film-formed wafer 200 is unloaded from the processing chamber 201 by the reverse procedure of the substrate loading process, and the substrate processing process according to the present embodiment is completed. In the substrate unloading process, by opening the opening / closing valve 243f and the opening / closing valve 243g and continuously supplying N ₂ gas into the processing chamber 201,
The oxygen concentration in the processing chamber 201 is reduced.

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

(A) In Step 3 of the film forming process according to this embodiment, when supplying the TDMAS gas into the processing chamber 201, the N ₂ gas is supplied from the reactive gas supply nozzle 251 at a flow rate higher than the supply flow rate of the TDMAS gas. . As a result, the TDMAS gas ejected from the gas supply port 250a undergoes trajectory correction by the large flow rate of N ₂ gas supplied from the reaction gas supply nozzle 251 and is bent in the outer direction (for example, tangential direction) of the wafer 200. It becomes. As a result, the wafer 200 becomes difficult to be directly exposed to the TDMAS gas (TDMAS gas containing foreign matter) injected from the gas supply port 250a, and the foreign matter adsorption to the wafer 200 is suppressed.

(B) In Step 5 of the film forming process according to the present embodiment, the ozone gas into the vaporized gas supply nozzle 250 is maintained by continuing the supply of N ₂ gas from the vaporized gas supply nozzle 250 without closing the on-off valve 243f. The entry of is suppressed. As a result, a film forming reaction or the like in the vaporized gas supply nozzle 250 and the reactive gas supply pipe 244b is less likely to occur, the generation of foreign matters is suppressed, and the foreign matter adsorption to the wafer 200 is suppressed.

(C) In Step 4 and Step 6 of the film forming process according to the present embodiment, N ₂ gas is supplied from the vaporized gas supply nozzle 250 and the reactive gas supply nozzle 251 while exhausting the inside of the processing chamber 201, respectively. Residual gases and reaction products in the processing chamber 201, the vaporized gas supply nozzle 250, the reactive gas supply nozzle 251, the vaporized gas supply pipe 244a, the reactive gas supply pipe 244b, etc. are purged. As a result, a film formation reaction or the like hardly occurs in the vaporized gas supply nozzle 250, the reactive gas supply nozzle 251, the vaporized gas supply pipe 244a, and the reactive gas supply pipe 244b, and the generation of foreign matters is suppressed. Foreign matter adsorption is suppressed.

<Other Embodiments of the Present Invention>
In the substrate processing apparatus according to the above-described embodiment, the gas supply ports 250a and 251a are each configured to face substantially the center in the processing chamber 201 (substantially the center of the wafer 200 loaded into the processing chamber 201). . However, the present invention is not limited to such a form. In other words, the plurality of gas supply ports 250a opened in the vaporized gas supply nozzle 250 may be opened toward the outer side (opposite to the gas supply port 251a) with respect to the wafer 200 with respect to the tangential direction of the wafer 200. Good. For example, as shown in FIG. 9, the direction connecting the center of the wafer 200 and the center of the horizontal section of the vaporized gas supply nozzle 250 is the radial direction dr of the wafer 200, and the direction perpendicular to the radial direction dr is the tangent to the wafer. When the direction dt is set, the plurality of gas supply ports 250 a opened in the vaporized gas supply nozzle 250 are between the tangential direction dt of the wafer 200 and the radial direction dr of the wafer 200 and outside the wafer 200. You may make it open toward (on the opposite side to the gas supply port 251a).

  With this configuration, when the TDMAS gas is supplied from the gas supply port 250 a into the processing chamber 201, the TDMAS gas is ejected outward with respect to the wafer 200 from the tangential direction dt of the wafer 200. It becomes. As a result, the wafer 200 becomes difficult to be directly exposed to the TDMAS gas (TDMAS gas containing foreign matter) injected from the gas supply port 250a, and the foreign matter adsorption to the wafer 200 is suppressed.

Note that the flow rate of the N ₂ gas supplied from the reaction gas supply nozzle 251 in this embodiment does not necessarily increase in step 3 (for example, the flow rate of the N ₂ gas supplied from the reaction gas supply nozzle 251 in step 3 is It may be about 0.3 slm). Further, the flow rate of the N ₂ gas supplied from the reactive gas supply nozzle 251 may be increased to, for example, 1.0 slm only in step 3 as in the above-described embodiment, It may be increased to 0 slm. As a result, the wafer 200 is more difficult to be exposed to the TDMAS gas (TDMAS gas containing foreign matter) injected from the gas supply port 250a, and foreign matter adsorption to the wafer 200 is further suppressed.

<Example 1>
Next, Example 1 of the present invention will be described together with a comparative example with reference to FIG. FIG. 8 is a schematic diagram for explaining Example 1 of the present invention together with a comparative example, and the foreign substance distribution and film thickness distribution on the wafer 200 when the supply flow rate of N ₂ gas from the reaction gas supply nozzle 251 is changed. Indicates.

In this example, when supplying the TDMAS gas into the processing chamber 201, the N ₂ gas was supplied from the reaction gas supply nozzle 251 at a flow rate higher than the supply flow rate of the TDMAS gas. The gas supply ports 250a and 251a are each configured to face approximately the center in the process chamber 201 (approximately the center of the wafer 200 loaded into the process chamber 201). Further, the rotation by the rotation mechanism 267 was stopped.

Specifically, the wafer 200 made of silicon was accommodated in the processing chamber 201 and heated to 550 ° C., and the above-described steps 1 to 6 were set as one cycle, and this cycle was repeated 163 times. In Step 1, TDMAS was supplied into the vaporizer 271 at a flow rate of 1.0 g / min, and N ₂ gas was supplied into the vaporizer 271 at a flow rate of 0.3 slm. Further, N ₂ gas was supplied from the vaporized gas supply nozzle 250 and the reactive gas supply nozzle 251 at a flow rate of 0.3 slm, respectively. In Step 2, the exhaust of the processing chamber 201 was stopped, and the processing chamber 201 was sealed with the pressure reduced. In Step 3, TDMAS gas was supplied from the vaporized gas supply nozzle 250 for 8 seconds. Further, when supplying the TDMAS gas, N ₂ gas was supplied from the reaction gas supply nozzle 251 at a flow rate of 1.0 slm, and the TDMAS gas was bent toward the outside of the wafer 200 (for example, tangential direction). In step 4, the exhausting of the processing chamber 201 was resumed, and the generation of the TEMAS gas in the vaporizer 271 was stopped. N ₂ gas was supplied from the vaporized gas supply nozzle 250 and the reaction gas supply nozzle 251 at a flow rate of 0.3 slm. In step 5, ozone gas was supplied from the reaction gas supply nozzle 251 into the processing chamber 201 at a flow rate of 6.5 slm for 30 seconds while continuing to exhaust the processing chamber 201. When supplying ozone gas into the processing chamber 201, supply of N ₂ gas from the reaction gas supply nozzle 251 was stopped. In step 6, the supply of ozone gas into the processing chamber 201 is stopped while exhausting the processing chamber 201 is continued, and N ₂ at a flow rate of 0.3 slm from the vaporized gas supply nozzle 250 and the reactive gas supply nozzle 251, respectively. Gas was supplied.

The column of Example 1 in FIG. 8 shows the foreign material distribution and the SiO ₂ film thickness distribution on the wafer 200 in this example. According to FIG. 8, it was confirmed that the adsorption of foreign matter to the wafer 200 was suppressed. Specifically, only 28 foreign matters having a particle size of 0.08 μm or more and 0.13 μm or less were detected, and no foreign matter having a particle size exceeding 0.13 μm was detected. Further, it was confirmed that the film thickness and flatness of the SiO ₂ film were hardly changed as compared with Comparative Examples 1 and 2 described later. That is, even if it becomes difficult for the wafer 200 to be directly exposed to the TDMAS gas injected from the gas supply port 250a, the TDMAS gas is diffused in the processing chamber 201 and supplied onto the wafer 200. It was confirmed that the film speed and film quality can be obtained. Specifically, the average film thickness of the SiO ₂ film was 103.9 mm, and the flatness was 5.33%.

(Comparative Example 1)
In this comparative example, when supplying the TDMAS gas into the processing chamber 201 in Step 3, the flow rate of N ₂ gas supplied from the reactive gas supply nozzle 251 is set to 0.3 slm. Other conditions are the same as those in the first embodiment.

The column of Comparative Example 1 in FIG. 8 shows the foreign material distribution and the SiO ₂ film thickness distribution on the wafer 200 in this comparative example. According to FIG. 8, it was confirmed that a large number of foreign matters were adsorbed on the wafer 200. Specifically, 164 foreign matters having a particle size of 0.08 μm or more and 0.13 μm or less were detected, and 32 foreign matters having a particle size exceeding 0.13 μm were detected. Further, it was confirmed that the thickness and flatness of the SiO ₂ film were almost the same as those of Example 1. Specifically, the average film thickness of the SiO ₂ film was 106.2 mm, and the flatness was 4.84%.

(Comparative Example 2)
In this comparative example, in Step 1 to Step 6, the flow rate of N ₂ gas supplied from the vaporized gas supply nozzle 250 was increased to 1.0 slm. In step 3, when the TDMAS gas is supplied into the processing chamber 201, the flow rate of N ₂ gas supplied from the reactive gas supply nozzle 251 is set to 0.3 slm without increasing. Other conditions are the same as those in the first embodiment.

The column of Comparative Example 2 in FIG. 8 shows the foreign material distribution and the SiO ₂ film thickness distribution on the wafer 200 in this comparative example. According to FIG. 8, it was confirmed that a large number of foreign matters were adsorbed on the wafer 200. Specifically, 147 foreign matters having a particle size of 0.08 μm or more and 0.13 μm or less were detected, and 39 foreign matters having a particle size exceeding 0.13 μm were detected. Further, it was confirmed that the thickness and flatness of the SiO ₂ film were almost the same as those of Example 1. Specifically, the average film thickness of the SiO ₂ film was 104.2 mm, and the flatness was 6.14%.

<Example 2>
Next, Example 2 of the present invention will be described together with a comparative example with reference to FIG. It is the schematic explaining Example 2 of this invention with a comparative example, and shows the foreign material distribution and film thickness distribution on a wafer when the supply direction of TDMAS gas is changed.

In this embodiment, a plurality of gas supply ports 250a opened in the vaporized gas supply nozzle 250 are opened toward the outer side (opposite to the gas supply port 251a) with respect to the wafer 200 than the tangential direction of the wafer 200. It was. Note that when the TDMAS gas was supplied into the processing chamber 201, the flow rate of the N ₂ gas supplied from the reaction gas supply nozzle 251 was maintained without increasing.

Specifically, the wafer 200 made of silicon was accommodated in the processing chamber 201, heated to 550 ° C., rotated by the rotating mechanism 267, and this cycle was repeated 27 times with Step 1 to Step 6 as one cycle. In Step 1, TDMAS was supplied into the vaporizer 271 at a flow rate of 3.0 g / min. Further, N ₂ gas was supplied into the vaporizer 271 at a flow rate of 0.3 slm. N ₂ gas was supplied from the vaporized gas supply nozzle 250 and the reaction gas supply nozzle 251 at a flow rate of 0.3 slm. In Step 2, the exhaust of the processing chamber 201 was stopped, and the processing chamber 201 was sealed with the pressure reduced. In step 3, the TDMAS gas was supplied from the vaporized gas supply nozzle 250 to the wafer 200 outward from the tangential direction of the wafer 200 for 30 seconds. Further, when supplying the TDMAS gas into the processing chamber 201, the flow rate of N ₂ gas supplied from the reaction gas supply nozzle 251 was set to 0.3 slm. In step 4, the exhausting of the processing chamber 201 was resumed, and the generation of the TEMAS gas in the vaporizer 271 was stopped. N ₂ gas was supplied from the vaporized gas supply nozzle 250 and the reaction gas supply nozzle 251 at a flow rate of 0.3 slm. In step 5, ozone gas was supplied from the reaction gas supply nozzle 251 into the processing chamber 201 at a flow rate of, for example, 6.5 slm for 7 seconds while continuing to exhaust the processing chamber 201. When supplying ozone gas into the processing chamber 201, supply of N ₂ gas from the reaction gas supply nozzle 251 was stopped. In step 6, the supply of ozone gas into the processing chamber 201 is stopped while exhausting the processing chamber 201 is continued, and N ₂ at a flow rate of 0.3 slm from the vaporized gas supply nozzle 250 and the reactive gas supply nozzle 251, respectively.
Gas was supplied.

The column of Example 2 in FIG. 11 shows the foreign material distribution and the SiO ₂ film thickness distribution on the wafer 200 in this example. According to FIG. 8, it was confirmed that the adsorption of foreign matter to the wafer 200 was suppressed. Specifically, only 476 foreign matters having a particle size of 0.08 μm or more and 0.13 μm or less were detected, and only 42 foreign matters having a particle size exceeding 0.13 μm were detected. Further, it was confirmed that the film thickness and flatness of the SiO ₂ film were hardly changed as compared with Comparative Example 3 described later. That is, even if the wafer 200 is not directly exposed to the TDMAS gas injected from the gas supply port 250a, the TDMAS gas is diffused in the processing chamber 201 and supplied onto the wafer 200, and the film formation rate and the same as the conventional one are obtained. It was confirmed that film quality could be obtained. Specifically, the average film thickness of the SiO ₂ film was 62.07 mm, and the flatness was 0.93%.

(Comparative Example 3)
In this comparative example, the gas supply ports 250a and 251a are each configured to face substantially the center in the processing chamber 201 (substantially the center of the wafer 200 loaded into the processing chamber 201). Further, when the TDMAS gas was supplied into the processing chamber 201, the flow rate of the N ₂ gas supplied from the reaction gas supply nozzle 251 was maintained without increasing.

The column of Comparative Example 2 in FIG. 8 shows the foreign material distribution and the SiO ₂ film thickness distribution on the wafer 200 in this comparative example. According to FIG. 8, it was confirmed that a large number of foreign matters were adsorbed on the wafer 200. Specifically, 2428 foreign matters having a particle size of 0.08 μm or more and 0.13 μm or less were detected, and 79 foreign materials having a particle size exceeding 0.13 μm were detected. Further, it was confirmed that the thickness and flatness of the SiO ₂ film were almost the same as those in Example 2. Specifically, the average film thickness of the SiO ₂ film was 62.58 mm, and the flatness was 0.50%.

<Still another embodiment of the present invention>
In the above-described embodiment, the case where a gas obtained by vaporizing TEMAS (TEMAS gas) is used as the first processing gas, but the present invention is not limited to such a configuration. For example, as the first processing gas, BTBAS (SiH ₂ [NH (C ₄ H ₉ )] ₂ ; Bistally butylaminosilane), TEMAH (Hf [N (CH ₃ ) CH ₂ CH ₃ ] ₄ ; tetrakismethylethylaminohafnium ), TEMAZ (Zr [N (CH ₃ ) CH ₂ CH ₃ ] ₄ ; tetrakisethylmethylaminozirconium), TiCl ₄ (titanium tetrachloride), and the like, the present invention can be suitably applied. It is. Moreover, although the above-mentioned embodiment demonstrated the case where ozone gas was used as 2nd process gas, this invention is not limited to the structure which concerns. For example, the present invention can be suitably applied to the case where oxygen (O ₂ ) gas, oxygen nitride (N ₂ O) gas, water vapor (H ₂ O), or ammonia (NH ₃ ) gas is used as the second processing gas. is there.

  In the above-described embodiment, the case where the ALD method for alternately supplying the vaporized gas and the reactive gas onto the wafer 200 has been described, but the present invention is not limited to such a configuration. That is, as long as a vaporized gas obtained by vaporizing a liquid material is used, the present invention can be suitably applied to a method such as a CVD method or a PVD (Physical Vapor Deposition) method. Further, the present invention is not limited to the case of forming an oxide film, and can be suitably applied to a substrate processing apparatus that forms other films such as a nitride film, a metal film, and a semiconductor film.

  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.

According to a first aspect of the invention,
A processing chamber for stacking and housing a plurality of substrates;
Gas supply means for supplying a desired gas into the processing chamber;
Exhaust means for exhausting the atmosphere in the processing chamber;
A control unit for controlling at least the gas supply means and the exhaust means,
The gas supply means includes
A first gas supply that is provided in the processing chamber along the stacking direction of the substrates, has a plurality of gas supply ports, and supplies a first processing gas obtained by vaporizing a liquid source into the processing chamber. A nozzle,
A vaporizer for vaporizing the liquid raw material;
A second gas supply nozzle that is erected adjacent to the first gas supply nozzle, has a plurality of gas supply ports, and supplies a second processing gas and an inert gas into the processing chamber. ,
The controller is
The gas supply means and the exhaust means are controlled to supply the first processing gas and the second processing gas alternately so as not to mix with each other to form a desired film on the substrate, When supplying one processing gas, there is provided a substrate processing apparatus for supplying an inert gas from the second gas supply nozzle at a flow rate higher than a supply flow rate of the first processing gas.

  Preferably, the vaporizer has a spray structure.

Preferably,
Substrate support means for supporting the plurality of substrates;
A rotation mechanism for rotating the substrate support means,
The first gas supply nozzle is erected on the lower side of the second gas supply nozzle with respect to the rotation direction of the substrate support means.

  Preferably, the shapes of the plurality of gas supply ports respectively opened in the first gas supply nozzle and the second gas supply nozzle are directional shapes.

  Preferably, the shape of the gas supply port is a round hole.

Preferably, the liquid material is TDMAS, BTBAS, TEMAH, TEMAZ, either TiCl _4.

Preferably, the second processing gas is any one of O ₂ , O ₃ , N ₂ O, H ₂ O, and NH ₃ .

According to a second aspect of the invention,
A processing chamber for stacking and housing a plurality of substrates;
Gas supply means for supplying a desired gas into the processing chamber;
An exhaust means for exhausting the atmosphere in the processing chamber,
The gas supply means includes
A first gas supply that is provided in the processing chamber along the stacking direction of the substrates, has a plurality of gas supply ports, and supplies a first processing gas obtained by vaporizing a liquid source into the processing chamber. A nozzle,
A vaporizer for vaporizing the liquid raw material,
The substrate processing apparatus may be provided in which the plurality of gas supply ports opened in the gas supply nozzle are opened outward with respect to the substrate rather than in a tangential direction of the substrate.

Preferably,
A second gas supply nozzle that is erected adjacent to the gas supply nozzle, has a plurality of gas supply ports, and supplies a second processing gas and an inert gas into the processing chamber;
A control unit for controlling at least the gas supply means and the exhaust means,
The control unit controls the gas supply unit and the exhaust unit to supply the first processing gas and the second processing gas alternately so as not to mix with each other, thereby forming a desired film on the substrate. Form.

  Preferably, the plurality of gas supply ports open between the tangential direction of the substrate and the radial direction of the substrate and outward toward the substrate.

  Preferably, the vaporizer has a spray structure.

Preferably,
Substrate support means for supporting the plurality of substrates;
A rotation mechanism for rotating the substrate support means,
The first gas supply nozzle is erected in a lower direction than the second gas supply nozzle with respect to the rotation direction of the substrate support means.

  Preferably, the shapes of the plurality of gas supply ports respectively opened in the first gas supply nozzle and the second gas supply nozzle are directional shapes.

  Preferably, the shape of the gas supply port is a round hole.

Preferably, the liquid material is TDMAS, BTBAS, TEMAH, TEMAZ, either TiCl _4.

Preferably, the second processing gas is any one of O ₂ , O ₃ , N ₂ O, H ₂ O, and NH ₃ .

According to a third aspect of the invention,
A processing chamber for stacking and housing a plurality of substrates;
Gas supply means for supplying a desired gas into the processing chamber;
Exhaust means for exhausting the atmosphere in the processing chamber;
A control unit for controlling at least the gas supply means and the exhaust means,
The gas supply means includes
A plurality of gas supply ports which are erected in the processing chamber along the stacking direction of the substrate and open outward from the tangent line of the substrate with respect to the substrate; A first gas supply nozzle for supplying a processing gas into the processing chamber;
A vaporizer for vaporizing the liquid raw material;
A second gas supply nozzle that is erected adjacent to the first gas supply nozzle, has a plurality of gas supply ports, and supplies a second processing gas and an inert gas into the processing chamber. ,
The control unit controls the gas supply unit and the exhaust unit to supply the first processing gas and the second processing gas alternately so as not to mix with each other, thereby forming a desired film on the substrate. When the first processing gas is formed and supplied, a substrate processing apparatus is provided that supplies an inert gas from the second gas supply nozzle at a flow rate higher than the supply flow rate of the first processing gas. .

According to a fourth aspect of the invention,
A semiconductor that forms a desired film on a substrate by alternately supplying a first processing gas obtained by vaporizing a liquid source and a second processing gas different from the first processing gas so as not to mix with each other. A device manufacturing method comprising:
When supplying the first processing gas, an inert gas is supplied from a gas supply nozzle that supplies the second processing gas into the processing chamber in a supply amount larger than the supply amount of the first processing gas. A method for manufacturing a semiconductor device is provided.

According to a fifth aspect of the present invention,
A semiconductor that forms a desired film on a substrate by alternately supplying a first processing gas obtained by vaporizing a liquid source and a second processing gas different from the first processing gas so as not to mix with each other. A device manufacturing method comprising:
A method for manufacturing a semiconductor device is provided in which the first processing gas is supplied outward from a tangent to the substrate.

It is a foreign material distribution diagram on a wafer when a TDMAS gas and an O ₃ gas are alternately supplied onto a wafer by using a conventional substrate processing apparatus to form an oxide film. It is a foreign substance distribution map on a wafer when only TDMAS gas is supplied on a wafer using the conventional substrate processing apparatus. Using conventional substrate processing apparatus is a foreign material distributions on a wafer when supplying the O ₃ gas only on the wafer. FIG. 10 is a distribution diagram of foreign matters on a wafer when an oxide film is formed by alternately supplying a smaller amount of TDMAS gas and O ₃ gas than the case of FIG. 1 on a wafer using a conventional substrate processing apparatus. It is a longitudinal cross-sectional view of the processing furnace of the substrate processing apparatus which concerns on one Embodiment of this invention. It is AA sectional drawing of the processing furnace shown in FIG. It is a flowchart which illustrates the gas supply sequence of the substrate processing process which concerns on this embodiment. It is a schematic view for explaining an embodiment 1 of the present invention together with comparative examples, showing the foreign material distribution and thickness distribution on the wafer when changing the supply flow rate of N ₂ gas from the reaction gas nozzle. It is the schematic which illustrates arrangement | positioning of the gas supply nozzle of the substrate processing apparatus which concerns on other embodiment of this invention. It is the schematic explaining Example 2 of this invention with a comparative example, and shows the foreign material distribution and film thickness distribution on a wafer when the supply direction of TDMAS gas is changed. 1 is a perspective perspective view of a substrate processing apparatus according to an embodiment of the present invention.

Explanation of symbols

101 substrate processing apparatus 200 wafer (substrate)
201 processing chamber 250 vaporized gas supply nozzle (first gas supply nozzle)
250a Gas supply port 251 Reaction gas supply nozzle (second gas supply nozzle)
251a Gas supply port 255 Rotating shaft 267 Rotating mechanism 271 Vaporizer 280 Controller (control unit)

Claims (5)

A processing chamber for stacking and housing a plurality of substrates;
Gas supply means for supplying a desired gas into the processing chamber;
Exhaust means for exhausting the atmosphere in the processing chamber;
A control unit for controlling at least the gas supply means and the exhaust means,
The gas supply means includes
A first gas supply that is provided in the processing chamber along the stacking direction of the substrates, has a plurality of gas supply ports, and supplies a first processing gas obtained by vaporizing a liquid source into the processing chamber. A nozzle,
A vaporizer for vaporizing the liquid raw material;
A second gas supply nozzle that is erected adjacent to the first gas supply nozzle, has a plurality of gas supply ports, and supplies a second processing gas and an inert gas into the processing chamber. ,
The controller is
The gas supply means and the exhaust means are controlled to supply the first processing gas and the second processing gas alternately so as not to mix with each other to form a desired film on the substrate, A substrate processing apparatus for supplying an inert gas from the second gas supply nozzle at a flow rate higher than a supply flow rate of the first process gas when supplying one process gas. A processing chamber for stacking and housing a plurality of substrates;
Gas supply means for supplying a desired gas into the processing chamber;
An exhaust means for exhausting the atmosphere in the processing chamber,
The gas supply means includes
A first gas supply that is provided in the processing chamber along the stacking direction of the substrates, has a plurality of gas supply ports, and supplies a first processing gas obtained by vaporizing a liquid source into the processing chamber. A nozzle,
A vaporizer for vaporizing the liquid raw material,
The substrate processing apparatus, wherein the plurality of gas supply ports opened in the gas supply nozzle are opened outward with respect to the substrate rather than in a tangential direction of the substrate. A processing chamber for stacking and housing a plurality of substrates;
Gas supply means for supplying a desired gas into the processing chamber;
Exhaust means for exhausting the atmosphere in the processing chamber;
A control unit for controlling at least the gas supply means and the exhaust means,
The gas supply means includes
A plurality of gas supply ports which are erected in the processing chamber along the stacking direction of the substrate and open outward from the tangent line of the substrate with respect to the substrate; A first gas supply nozzle for supplying a processing gas into the processing chamber;
A vaporizer for vaporizing the liquid raw material;
A second gas supply nozzle that is erected adjacent to the first gas supply nozzle, has a plurality of gas supply ports, and supplies a second processing gas and an inert gas into the processing chamber. ,
The control unit controls the gas supply unit and the exhaust unit to supply the first processing gas and the second processing gas alternately so as not to mix with each other, thereby forming a desired film on the substrate. A substrate processing apparatus that forms and supplies the inert gas from the second gas supply nozzle at a flow rate higher than the supply flow rate of the first process gas when supplying the first process gas. A semiconductor that forms a desired film on a substrate by alternately supplying a first processing gas obtained by vaporizing a liquid source and a second processing gas different from the first processing gas so as not to mix with each other. A device manufacturing method comprising:
When supplying the first processing gas, a semiconductor that supplies an inert gas at a flow rate higher than the supply flow rate of the first processing gas from a gas supply nozzle that supplies the second processing gas into the processing chamber. Device manufacturing method. A semiconductor that forms a desired film on a substrate by alternately supplying a first processing gas obtained by vaporizing a liquid source and a second processing gas different from the first processing gas so as not to mix with each other. A device manufacturing method comprising:
A method of manufacturing a semiconductor device, wherein the first processing gas is supplied outward from a tangent to the substrate with respect to the substrate.