JP2011082196A - Vaporizer, substrate processing apparatus, and method of manufacturing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vaporizer for suppressing persistence of a liquid raw material within the vaporizer when stopping generating a source gas and for facilitating cleaning the inside of a liquid raw material supply path. <P>SOLUTION: The vaporizers 229s, 229b, 229t include: vaporizing chambers 51s, 51b, 51t for vaporizing the liquid raw material; heaters 61s, 61b, 61t for heating the inside of the vaporizing chambers; atomizing nozzles 31s, 31b, 31t for atomizing the liquid raw material into the vaporizing chambers; and a valve for controlling supply of a carrier gas, the liquid raw materials, and solvents into the atomizing nozzles. The valve is directly connected to the atomizing nozzles 31s, 31b, 31t. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a vaporizer for vaporizing a liquid raw material, particularly a vaporizer for an ALD film forming apparatus, a substrate processing apparatus for processing a substrate with a raw material gas obtained by vaporizing the liquid raw material in the vaporizer, and a liquid raw material in the vaporizer The present invention relates to a method for manufacturing a semiconductor device, which includes a step of processing a substrate with vaporized source gas.

  As a method for forming a thin film in units of atomic layers on a substrate such as a wafer, there is an ALD (Atomic Layer Deposition) method. In the ALD method, for example, (1) a process of supplying a first processing gas into a processing chamber containing a substrate and adsorbing it on the surface of the substrate, and (2) removing the first processing gas remaining in the processing chamber. A process of introducing and purging an inert gas into the processing chamber, and (3) supplying a second processing gas into the processing chamber and reacting with the first processing gas adsorbed on the substrate surface to form a thin film And (4) a process of introducing and purging an inert gas into the processing chamber to remove the second processing gas and reaction byproducts remaining in the processing chamber as one cycle. It has the process of repeating this cycle.

  Here, as the first processing gas described above, for example, a gas obtained by vaporizing a liquid raw material that is liquid at room temperature may be used. In addition, a gas obtained by vaporizing a solution raw material (liquefied raw material) obtained by diluting a highly viscous liquid raw material or solid raw material with a solvent to be liquefied may be used. For example, as a solution raw material, an organometallic liquid raw material containing elements such as Sr (strontium), Ba (barium), and La (lanthanum) having a low vapor pressure and high viscosity, ECH (ethylcyclohexane), THF (tetrahydrofuran), etc. Diluted with a solvent (solvent). In this specification, liquid raw materials and solution raw materials may be collectively referred to simply as liquid raw materials.

  A vaporizer is used as an apparatus for vaporizing a liquid raw material. The vaporizer includes a vaporization chamber (vaporization tube) that vaporizes a liquid raw material to generate gas, a heater that heats the vaporization chamber, a spray nozzle that supplies a carrier gas and sprays the liquid raw material into the vaporization chamber, A valve for controlling the supply of the liquid raw material and the solvent into the nozzle, and a joint portion for connecting the spray nozzle and the valve are provided. This valve is configured as a four-way four-way valve (hereinafter also referred to as a block valve), and includes a first port that receives the supply of the liquid raw material, a second port that receives the supply of the solvent, and the joint portion described above. A third port that is connected and supplies a solution raw material that is a mixed liquid of a liquid raw material and a solvent to the joint portion; and a fourth port that discharges the liquid raw material and the solvent to the outside of the vaporizer. Yes. In the block valve, a liquid raw material supply path connecting the first port and the third port, a solvent supply path connecting the second port and the third port, a first port, A liquid source discharge path connecting between the fourth port and a solvent discharge path connecting between the second port and the fourth port are provided. The liquid raw material supply path and the solvent supply path merge together in the vicinity of the third port. The liquid raw material discharge path and the solvent discharge path merge together in the vicinity of the fourth port. Each of the liquid raw material supply path, the solvent supply path, the liquid raw material discharge path, and the solvent discharge path is provided with an opening / closing valve. These routes can be switched, and the solvent route can be switched between the solvent supply route and the solvent discharge route.

When the source gas is generated, the open / close valve is switched to allow the liquid source supplied to the first port to flow through the liquid source supply path and to be supplied into the vaporization chamber via the third port, the joint portion, and the spray nozzle. Further, when the generation of the raw material gas is stopped, the supply of the liquid raw material supplied to the first port is stopped by switching the open / close valve. At this time, the liquid material may flow through the liquid material discharge path and be discharged out of the vaporizer through the fourth port.

  However, if the generation of the source gas is stopped by switching the path in the block valve as described above, the liquid source may remain in the liquid source supply path or the joint (hereinafter referred to as the liquid source). These areas where residuals can occur are also referred to as dead spaces). The liquid raw material remaining in the dead space may gradually enter the vaporizing chamber and unintentionally generate a raw material gas. Further, the liquid raw material remaining in the dead space may affect the concentration and flow rate of the raw material gas when restarting the generation of the raw material gas. In addition, the liquid raw material remaining in the dead space may cause clogging of the liquid raw material supply path and the joint, and may cause vaporization failure when resuming the generation of the raw material gas.

  To solve these problems, a method of cleaning the inside of the dead space with a solvent every time the generation of the source gas is stopped is also conceivable. In such a case, the opening / closing valve is switched to cause the solvent supplied to the second port to flow through the solvent supply path, and is introduced into the vaporization chamber via the third port, the joint portion, and the spray nozzle. However, since the block valve is configured as described above, it is difficult to sufficiently supply the solvent in the dead space (particularly in the liquid source supply path). Moreover, if it is necessary to clean the dead space every time the generation of the source gas is stopped, the liquid source and the solvent are wasted and it takes time to switch the stop and restart of the source gas generation. In some cases, the cost of substrate processing is increased or productivity is lowered.

  An object of the present invention is to provide a vaporizer capable of suppressing the residual liquid raw material in the vaporizer when the generation of the raw material gas is stopped and easily cleaning the liquid raw material supply path. . Another object of the present invention is to provide a substrate processing apparatus for processing a substrate with a source gas obtained by evaporating a liquid source with the vaporizer, and a process for processing the substrate with a source gas obtained by evaporating the liquid source with the vaporizer. It is an object of the present invention to provide a method for manufacturing a semiconductor device having the same.

  According to one aspect of the present invention, a vaporizing chamber for vaporizing a liquid source, a heater for heating the vaporizing chamber, a spray nozzle for spraying a liquid source into the vaporizing chamber, a carrier gas into the spray nozzle, and a liquid There is provided a vaporizer having a valve for controlling the supply of the raw material and the solvent, wherein the valve is directly connected to the spray nozzle.

  According to another aspect of the present invention, a processing chamber for processing a substrate, a vaporizer that vaporizes a liquid raw material, a liquid raw material supply system that supplies the liquid raw material to the vaporizer, and a carrier gas that is supplied to the vaporizer A carrier gas supply system, a solvent supply system for supplying a solvent to the vaporizer, a raw material gas supply system for supplying a raw material gas obtained by vaporizing a liquid raw material in the vaporizer into the processing chamber, and the raw material gas A reaction gas supply system for supplying different reaction gases into the processing chamber, and the vaporizer includes a vaporization chamber for vaporizing a liquid source, a heater for heating the vaporization chamber, and a liquid source for the vaporization chamber. There is provided a substrate processing apparatus having a spray nozzle for spraying, and a valve for controlling supply of carrier gas, liquid raw material and solvent into the spray nozzle, and the valve is directly connected to the spray nozzle. The

According to still another aspect of the present invention, a step of carrying a substrate into the processing chamber, a vaporizing chamber for vaporizing the liquid source, a heater for heating the vaporizing chamber, and a spray nozzle for spraying the liquid source into the vaporizing chamber. A vaporizer directly connected to the spray nozzle and controlling supply of carrier gas, liquid source and solvent into the spray nozzle, and supplying at least carrier gas and liquid source into the spray nozzle Spraying a liquid source from the spray nozzle and vaporizing the liquid source in the vaporizing chamber; and supplying a source gas obtained by vaporizing the liquid source in the vaporizer into the processing chamber and processing the substrate; And a step of carrying out a processed substrate from the processing chamber.

  ADVANTAGE OF THE INVENTION According to this invention, the vaporizer which can suppress the residue of the liquid raw material in the vaporizer when generation | occurrence | production of raw material gas is stopped, and can perform the washing | cleaning in a liquid raw material supply path | route easily is provided. In addition, according to the present invention, the substrate processing apparatus for processing the substrate with the source gas obtained by vaporizing the liquid source with the vaporizer, and the process for processing the substrate with the source gas obtained by vaporizing the liquid source with the vaporizer. A method for manufacturing a semiconductor device can be provided.

It is a block diagram of the gas supply system in the substrate processing apparatus concerning 1st Embodiment of this invention. It is a sequence diagram which shows the opening / closing timing of each valve | bulb in the substrate processing apparatus concerning 1st Embodiment of this invention. It is a section lineblock diagram at the time of wafer processing of a substrate processing device concerning a 1st embodiment of the present invention. It is a section lineblock diagram at the time of wafer conveyance of a substrate processing device concerning a 1st embodiment of the present invention. It is a flowchart of the substrate processing process concerning 1st Embodiment of this invention. It is a schematic block diagram of the vaporizer | carburetor concerning 1st Embodiment of this invention. It is the elements on larger scale around the spray mouth of the spray nozzle of the vaporizer | carburetor concerning 1st Embodiment of this invention. It is the figure which extracted the front-end | tip part and peripheral part of the spray nozzle in the modification of the vaporizer | carburetor concerning 1st Embodiment of this invention, (a) has shown the example which shortened the length of the thin tube part, (B) has shown the example which lengthened the length of the thin tube part. It is a figure which shows the discharge direction of the raw material discharged from a spray nozzle, and the discharge direction of the purge gas discharged from a discharge part, (a) shows the example whose discharge direction of a raw material and the discharge direction of purge gas are the same. (B) shows an example in which the discharge direction of the raw material and the discharge direction of the purge gas intersect. It is the figure which extracted the front-end | tip part and peripheral part of the spray nozzle in the modification of the vaporizer | carburetor concerning 1st Embodiment of this invention, (a) shortens the length of the most advanced part of a spray nozzle, and is the most. (B) is an example in which the length of the most advanced part of the spray nozzle is shortened, the discharge part parallel to the most advanced part is slightly provided, and This is an example in which the tip portion is eliminated and the spray nozzle is configured only by the main body portion and the most advanced portion. It is a schematic block diagram of the block valve concerning 1st Embodiment of this invention. It is a perspective view of the block valve concerning a 1st embodiment of the present invention. It is a schematic block diagram of the vertical processing furnace of the vertical ALD apparatus concerning 2nd Embodiment of this invention, (a) shows a processing furnace part with a longitudinal cross-section, (b) shows a processing furnace part (a ) Is a cross-sectional view taken along line AA of FIG. It is a schematic block diagram of the conventional block valve. It is a perspective view of the conventional block valve. It is the schematic which shows a mode that a liquid raw material, a solvent, and carrier gas are supplied to the conventional block valve. It is a cross-sectional view which shows the flow path of the block valve concerning 1st Embodiment of this invention.

<First Embodiment>
(1) Configuration of Substrate Processing Apparatus First, the configuration of the substrate processing apparatus according to the present embodiment will be described with reference to FIGS. FIG. 4 is a cross-sectional configuration diagram of the substrate processing apparatus according to the first embodiment of the present invention during wafer transfer, and FIG. 3 is a cross-sectional configuration of the substrate processing apparatus according to the first embodiment of the present invention during wafer processing. FIG.

(Processing room)
As shown in FIGS. 3 and 4, the substrate processing apparatus according to this embodiment includes a processing container 202. The processing container 202 is configured as a flat sealed container having a circular cross section, for example. The processing container 202 is made of a metal material such as aluminum (Al) or stainless steel (SUS). In the processing container 202, a processing chamber 201 for processing a wafer 200 as a substrate is configured.

A support table 203 that supports the wafer 200 is provided in the processing chamber 201. For example, quartz (SiO ₂ ), carbon, ceramics, silicon carbide (SiC), aluminum oxide (Al ₂ O ₃ ), or aluminum nitride (AlN) is formed on the upper surface of the support base 203 that the wafer 200 directly touches. A susceptor 217 is provided as a support plate. In addition, the support base 203 incorporates a heater 206 as a heating means for heating the wafer 200. Note that the lower end portion of the support base 203 passes through the bottom portion of the processing container 202.

  An elevating mechanism 207 b is provided outside the processing chamber 201. By operating the lifting mechanism 207b, the wafer 200 supported on the susceptor 217 can be lifted and lowered. The support table 203 is lowered to the position shown in FIG. 4 (wafer transfer position) when the wafer 200 is transferred, and is raised to the position shown in FIG. 3 (wafer processing position) when the wafer 200 is processed. Note that the lower end of the support base 203 and the periphery of the elevating mechanism 207b are covered with a bellows 203a, and the inside of the processing chamber 201 is kept airtight.

  Further, for example, three lift pins 208b are provided in the vertical direction on the bottom surface (floor surface) of the processing chamber 201. Further, the support base 203 is provided with through holes 208a for allowing the lift pins 208b to pass therethrough at positions corresponding to the lift pins 208b. When the support table 203 is lowered to the wafer transfer position, the upper end portion of the lift pins 208b protrudes from the upper surface of the support table 203, and the lift pins 208b support the wafer 200 from below. Further, when the support table 203 is raised to the wafer processing position, the lift pins 208b are buried from the upper surface of the support table 203, and the susceptor 217 provided on the upper surface of the support table 203 supports the wafer 200 from below. The In addition, since the lift pins 208b are in direct contact with the wafer 200, it is desirable to form the lift pins 208b with a material such as quartz or alumina.

(Wafer transfer port)
A wafer transfer port 250 for transferring the wafer 200 into and out of the process chamber 201 is provided on the inner wall side surface of the process chamber 201. The wafer transfer port 250 is provided with a gate valve 251. By opening the gate valve 251, the processing chamber 201 and the transfer chamber (preliminary chamber) 271 communicate with each other. The transfer chamber 271 is formed in a sealed container 272, and a transfer robot 273 for transferring the wafer 200 is provided in the transfer chamber 271. The transfer robot 273 includes a transfer arm 273 a that supports the wafer 200 when the wafer 200 is transferred. With the support table 203 lowered to the wafer transfer position, the gate valve 251 is opened so that the wafer 200 can be transferred between the processing chamber 201 and the transfer chamber 271 by the transfer robot 273. It is configured.
The wafer 200 transferred into the processing chamber 201 is temporarily placed on the lift pins 208b as described above.

(Exhaust system)
An exhaust port 260 for exhausting the atmosphere in the processing chamber 201 is provided on the inner wall side surface of the processing chamber 201 and on the opposite side of the wafer transfer port 250. An exhaust pipe 261 is connected to the exhaust port 260, and a pressure regulator 262 such as an APC (Auto Pressure Controller) that controls the inside of the processing chamber 201 to a predetermined pressure, a raw material recovery trap 263, and The vacuum pump 264 is connected in series in order. An exhaust system (exhaust line) is mainly configured by the exhaust port 260, the exhaust pipe 261, the pressure regulator 262, the raw material recovery trap 263, and the vacuum pump 264.

(Gas inlet)
A gas inlet 210 for supplying various gases into the processing chamber 201 is provided on the upper surface (ceiling wall) of a shower head 240 described later provided in the upper portion of the processing chamber 201. The configuration of the gas supply system connected to the gas inlet 210 will be described later.

(shower head)
A shower head 240 as a gas dispersion mechanism is provided between the gas inlet 210 and the wafer 200 at the wafer processing position. The shower head 240 disperses the gas introduced from the gas introduction port 210 and the gas that has passed through the dispersion plate 240 a are more uniformly dispersed and supplied to the surface of the wafer 200 on the support table 203. A shower plate 240b. The dispersion plate 240a and the shower plate 240b are provided with a plurality of vent holes. The dispersion plate 240 a is disposed so as to face the upper surface of the shower head 240 and the shower plate 240 b, and the shower plate 240 b is disposed so as to face the wafer 200 on the support table 203. Spaces are provided between the upper surface of the shower head 240 and the dispersion plate 240a, and between the dispersion plate 240a and the shower plate 240b, respectively. These spaces function as a dispersion chamber (first buffer space) 240c for dispersing the gas supplied from the gas inlet 210 and a second buffer space 240d for diffusing the gas that has passed through the dispersion plate 240a, respectively. To do.

(Exhaust duct)
On the inner wall side surface of the processing chamber 201, a step portion 201a is provided. The step portion 201a is configured to hold the conductance plate 204 in the vicinity of the wafer processing position. The conductance plate 204 is configured as a single donut-shaped (ring-shaped) disk in which a hole for accommodating the wafer 200 is provided in the inner periphery. A plurality of discharge ports 204 a arranged in the circumferential direction with a predetermined interval are provided on the outer periphery of the conductance plate 204. The discharge port 204 a is formed discontinuously so that the outer periphery of the conductance plate 204 can support the inner periphery of the conductance plate 204.

  On the other hand, a lower plate 205 is locked to the outer peripheral portion of the support base 203. The lower plate 205 includes a ring-shaped concave portion 205b and a flange portion 205a provided integrally on the inner upper portion of the concave portion 205b. The recess 205b is provided so as to block a gap between the outer peripheral portion of the support base 203 and the inner wall side surface of the processing chamber 201. A part of the bottom of the recess 205b near the exhaust port 260 is provided with a plate exhaust port 205c for discharging (circulating) gas from the recess 205b to the exhaust port 260 side. The flange portion 205 a functions as a locking portion that locks on the upper outer periphery of the support base 203. When the flange portion 205 a is locked on the upper outer periphery of the support base 203, the lower plate 205 is moved up and down together with the support base 203 as the support base 203 is moved up and down.

  When the support table 203 is raised to the wafer processing position, the lower plate 205 is also raised to the wafer processing position. As a result, the conductance plate 204 held in the vicinity of the wafer processing position closes the upper surface portion of the recess 205b of the lower plate 205, and the exhaust duct 259 having the gas passage region inside the recess 205b is formed. . At this time, due to the exhaust duct 259 (the conductance plate 204 and the lower plate 205) and the support base 203, the inside of the processing chamber 201 is above the processing chamber above the exhaust duct 259 and the processing chamber below the exhaust duct 259. It will be partitioned into a lower part. Note that the conductance plate 204 and the lower plate 205 are made of a material that can be maintained at a high temperature, for example, high temperature resistant high load quartz, in consideration of the case where the reaction product deposited on the inner wall of the exhaust duct 259 is etched. Is preferred.

  Here, the flow of gas in the processing chamber 201 during wafer processing will be described. First, the gas supplied from the gas inlet 210 to the upper part of the shower head 240 enters the second buffer space 240d through a large number of holes in the dispersion plate 240a via the dispersion chamber (first buffer space) 240c, and further the shower. It passes through a large number of holes in the plate 240 b and is supplied into the processing chamber 201, and is uniformly supplied onto the wafer 200. The gas supplied onto the wafer 200 flows radially outward of the wafer 200 in the radial direction. Then, surplus gas after contacting the wafer 200 flows radially on the exhaust duct 259 (that is, on the conductance plate 204) provided on the outer periphery of the support base 203 toward the radially outer side of the wafer 200, and is exhausted. The gas is discharged from the discharge port 204a provided on the duct 259 into the gas flow path region (in the recess 205b) in the exhaust duct 259. Thereafter, the gas flows through the exhaust duct 259 and is exhausted to the exhaust port 260 via the plate exhaust port 205c. As described above, the gas is prevented from flowing into the lower portion of the processing chamber 201, that is, the back surface of the support base 203 and the bottom surface side of the processing chamber 201.

  Next, the configuration of the gas supply system connected to the gas inlet 210 described above will be described mainly with reference to FIG. FIG. 1 is a configuration diagram of a gas supply system (gas supply line) included in the substrate processing apparatus according to the first embodiment of the present invention.

  The gas supply system included in the substrate processing apparatus according to the first embodiment of the present invention includes vaporizers 229s, 229b, and 229t that vaporize liquid raw materials, and a liquid raw material supply system that supplies liquid raw materials to the vaporizers 229s, 229b, and 229t. A carrier gas supply system that supplies carrier gas to the vaporizers 229s, 229b, and 229t, a purge gas supply system that supplies purge gas to the vaporizers 229s, 229b, and 229t (for the vaporizers 229s, 229b, and 229t), and a vaporizer A solvent supply system (cleaning liquid supply system) that supplies a solvent (cleaning liquid) to 229s, 229b, and 229t, and a raw material gas that supplies a raw material gas obtained by vaporizing a liquid raw material in the vaporizers 229s, 229b, and 229t into the processing chamber 201 A supply system, and a reaction gas supply system that supplies a reaction gas different from the source gas into the processing chamber 201. . Furthermore, the substrate processing apparatus according to the first embodiment of the present invention has a purge gas supply system (for piping and processing chamber 201) and a vent (bypass) system. Below, the structure of each part is demonstrated.

(Liquid raw material supply system)
Outside the processing chamber 201, a first liquid source supply source 220s that supplies an organometallic liquid source (hereinafter referred to as a first liquid source) containing an Sr (strontium) element as a liquid source, and an organic containing a Ba (barium) element. A second liquid source supply source 220b that supplies a metal liquid source (hereinafter referred to as a second liquid source) and a third liquid source supply that supplies an organometallic liquid source (hereinafter referred to as a third liquid source) containing a Ti (titanium) element. A source 220t is provided. The first liquid raw material supply source 220s, the second liquid raw material supply source 220b, and the third liquid raw material supply source 220t are each configured as a tank (sealed container) capable of containing (filling) the liquid raw material therein. Each organometallic liquid raw material containing Sr, Ba, Ti elements is diluted to 0.05 mol / L to 0.2 mol / L with a solvent (solvent) such as ECH (ethylcyclohexane) or THF (tetrahydrofuran), for example. And then stored in the tank.

Here, the first liquid source supply source 220s, the second liquid source supply source 220b, and the third liquid source supply source 220t include a first pumping gas supply pipe 237s, a second pumping gas supply pipe 237b, and a third pumping, respectively. Gas supply pipes 237t are connected to each other. A pumping gas supply source (not shown) is connected to upstream ends of the first pumping gas supply pipe 237s, the second pumping gas supply pipe 237b, and the third pumping gas supply pipe 237t. The downstream ends of the first pressurized gas supply pipe 237s, the second pressurized gas supply pipe 237b, and the third pressurized gas supply pipe 237t are respectively a first liquid source supply source 220s, a second liquid source supply source 220b, The third liquid source supply source 220t communicates with a space in the upper part, and is configured to supply a pressure gas into this space. As the pressurized gas, it is preferable to use a gas that does not react with the liquid material, for example an inert gas such as Ar gas or N ₂ gas is preferably used.

  In addition, the first liquid raw material supply source 220s, the second liquid raw material supply source 220b, and the third liquid raw material supply source 220t include a first liquid raw material supply pipe 211s, a second liquid raw material supply pipe 211b, and a third liquid raw material, respectively. A supply pipe 211t is connected to each other. Here, upstream end portions of the first liquid source supply pipe 211s, the second liquid source supply pipe 211b, and the third liquid source supply pipe 211t are respectively the first liquid source supply source 220s and the second liquid source supply source 220b. And the liquid raw material housed in the third liquid raw material supply source 220t. Further, the downstream end portions of the first liquid source supply pipe 211s, the second liquid source supply pipe 211b, and the third liquid source supply pipe 211t are vaporizers that vaporize the liquid source via the block valves 10s, 10b, and 10t. 229s, 229b, and 229t, respectively. The configuration of the block valves 10s, 10b, and 10t and the vaporizers 229s, 229b, and 229t will be described later. The first liquid source supply pipe 211s, the second liquid source supply pipe 211b, and the third liquid source supply pipe 211t include a liquid flow rate controller (LMFC) 221s as a flow rate control unit that controls the supply flow rate of the liquid source. 221b and 221t are provided, respectively. The block valves 10s, 10b, and 10t are provided with opening / closing valves vs1, vb1, and vt1, respectively, for controlling the supply of the liquid material.

  With the above configuration, the opening / closing valves vs1, vb1, and vt1 of the block valves 10s, 10b, and 10t are opened, and the pumping gas is supplied from the first pumping gas supply pipe 237s, the second pumping gas supply pipe 237b, and the third pumping gas supply pipe 237t. , The liquid source can be pumped (supplied) from the first liquid source supply source 220s, the second liquid source supply source 220b, and the third liquid source supply source 220t to the vaporizers 229s, 229b, and 229t. It becomes possible. Mainly, the first liquid raw material supply source 220s, the second liquid raw material supply source 220b, the third liquid raw material supply source 220t, the first pressurized gas supply pipe 237s, the second pressurized gas supply pipe 237b, and the third pressurized gas supply pipe 237t. , The first liquid source supply pipe 211s, the second liquid source supply pipe 211b, the third liquid source supply pipe 211t, the liquid flow rate controllers 221s, 221b, 221t, and the open / close valves vs1, vb1, vt1 (liquid source supply system). Line).

(Carrier gas supply system)
Outside the processing chamber 201, an N ₂ gas supply source 230n for supplying N ₂ gas as a carrier gas is provided. The upstream end of the carrier gas supply pipe 218 is connected to the N ₂ gas supply source 230n. The downstream side of the carrier gas supply pipe 218 is branched into three lines, that is, a first carrier gas supply pipe 218s, a second carrier gas supply pipe 218b, and a third carrier gas supply pipe 218t. The downstream end portions of the first carrier gas supply pipe 218s, the second carrier gas supply pipe 218b, and the third carrier gas supply pipe 218t are connected to the vaporizers 229s, 229b, and 229t through the block valves 10s, 10b, and 10t, respectively. Has been. The first carrier gas supply pipe 218s and the second carrier gas supply pipe 21
8b, the third carrier gas supply pipe 218t, flow controller (MFC) 225s as a flow rate control means for controlling the supply flow rate of _{N 2} gas, 225b, 225T and-off valve controls the supply of the _{N 2} gas VS7, vb7 and vt7 are provided. Mainly, N ₂ gas supply source 230n, carrier gas supply pipe 218, first carrier gas supply pipe 218s, second carrier gas supply pipe 218b, third carrier gas supply pipe 218t, flow rate controllers 225s, 225b, 225t, open / close valves A carrier gas supply system (carrier gas supply line) is configured by vs7, vb7, and vt7. In addition to the N ₂ gas, an inert gas such as Ar gas may be used as the carrier gas.

(Purge gas supply system (for vaporizer))
The N ₂ gas supply source 230n provided outside the processing chamber 201 also serves as a purge gas supply source for purging components of the vaporizer as a vaporizer. A purge gas supply pipe 219 is connected to the N ₂ gas supply source 230 n via a carrier gas supply pipe 218. The downstream side of the purge gas supply pipe 219 is branched into three lines, that is, a first purge gas supply pipe 219s, a second purge gas supply pipe 219b, and a third purge gas supply pipe 219t. The downstream end portions of the first purge gas supply pipe 219s, the second purge gas supply pipe 219b, and the third purge gas supply pipe 219t are connected to the vaporizers 229s, 229b, and 229t, respectively. The first purge gas supply pipe 219s, the second purge gas supply pipe 219b, and the third purge gas supply pipe 219t include flow rate controllers (MFC) 226s, 226b, 226t as flow rate control means for controlling the supply flow rate of the N ₂ gas. , And open / close valves vs8, vb8, and vt8 for controlling the supply of N ₂ gas, respectively. Mainly, N ₂ gas supply source 230n, purge gas supply pipe 219, first purge gas supply pipe 219s, second purge gas supply pipe 219b, third purge gas supply pipe 219t, flow rate controllers 226s, 226b, 226t, open / close valves vs8, vb8, A purge gas supply system (purge gas supply line) is configured by vt8. In addition to the N ₂ gas, an inert gas such as Ar gas may be used as the purge gas.

(Raw gas supply system)
The outlets 54s, 54b, and 54t of the vaporizers 229s, 229b, and 229t include a first source gas supply pipe 213s, a second source gas supply pipe 213b, and a third source gas that supply the source gas into the processing chamber 201. The upstream end of the supply pipe 213t is connected to each other. The downstream end portions of the first source gas supply pipe 213s, the second source gas supply pipe 213b, and the third source gas supply pipe 213t are unified so as to be merged into the source gas supply pipe 213, which is unified. The source gas supply pipe 213 is connected to the gas inlet 210. The first source gas supply pipe 213s, the second source gas supply pipe 213b, and the third source gas supply pipe 213t are provided with opening / closing valves vs3, vb3, and vt3 that control the supply of the source gas into the processing chamber 201. Each is provided.

  With the above configuration, the liquid raw material is vaporized by the vaporizers 229s, 229b, and 229t to generate the raw material gas, and the first raw material gas supply pipe 213s and the second raw material gas are opened by opening the on-off valves vs3, vb3, and vt3. The source gas can be supplied from the supply pipe 213b and the third source gas supply pipe 213t into the processing chamber 201 through the source gas supply pipe 213. A source gas supply system (source gas supply) is mainly configured by a first source gas supply pipe 213s, a second source gas supply pipe 213b, a third source gas supply pipe 213t, a source gas supply pipe 213, and open / close valves vs3, vb3, and vt3. Line).

(Solvent supply system (cleaning liquid supply system))
In addition, a solvent supply source (cleaning liquid supply source) 220 e that supplies ECH (ethylcyclohexane) that is a solvent (solvent) as a cleaning liquid is provided outside the processing chamber 201. The solvent supply source 220e is configured as a tank (sealed container) capable of containing (filling) a solvent (cleaning liquid) therein. The solvent (cleaning solution) is not limited to ECH, and a solvent such as THF (tetrahydrofuran) can be used.

Here, a solvent supply gas supply pipe 237e is connected to the solvent supply source 220e. A non-illustrated pressurized gas supply source is connected to the upstream end of the solvent pressurized gas supply pipe 237e. Further, the downstream side end portion of the solvent pressurized gas supply pipe 237e communicates with a space existing in the upper part in the solvent supply source 220e, and is configured to supply the pressurized gas into this space. Note that an inert gas such as Ar gas or N ₂ gas is preferably used as the pressurized gas.

  A solvent supply pipe (cleaning liquid supply pipe) 212 is connected to the solvent supply source 220e. The upstream end of the solvent supply pipe 212 is immersed in a solvent (cleaning liquid) accommodated in the solvent supply source 220e. The downstream end of the solvent supply pipe 212 is connected to branch into three lines, that is, a first solvent supply pipe 212s, a second solvent supply pipe 212b, and a third solvent supply pipe 212t. The downstream end portions of the first solvent supply pipe 212s, the second solvent supply pipe 212b, and the third solvent supply pipe 212t are connected to the vaporizers 229s, 229b, and 229t via the block valves 10s, 10b, and 10t, respectively. Yes. The first solvent supply pipe 212s, the second solvent supply pipe 212b, and the third solvent supply pipe 212t have liquid flow rate controllers (LMFC) 222s, 222b, and 222t as flow rate control means for controlling the supply flow rate of the cleaning liquid. Each is provided. The block valves 10s, 10b, and 10t are provided with opening / closing valves vs2, vb2, and vt2 for controlling the supply of the cleaning liquid, respectively. The block valves 10s, 10b, and 10t further control the discharge pipes 217s, 217b, and 217t for discharging the liquid raw material and the cleaning liquid, and the discharge of the liquid raw material and the cleaning liquid performed through the discharge pipes 217s, 217b, and 217t. Opening and closing valves vs9, vb9, vt9, vs10, vb10, and vt10 are provided.

  Mainly, a solvent supply source 220e, a solvent pressurized gas supply pipe 237e, a solvent supply pipe 212, a first solvent supply pipe 212s, a second solvent supply pipe 212b, a third solvent supply pipe 212t, liquid flow rate controllers 222s, 222b, 222t, The opening / closing valves vs2, vb2, and vt2 constitute a cleaning liquid supply system (solvent supply system), that is, a cleaning liquid supply line (solvent supply line).

(Reactive gas supply system)
Further, an oxygen gas supply source 230o for supplying oxygen (O ₂ ) gas is provided outside the processing chamber 201. The upstream end of the first oxygen gas supply pipe 211o is connected to the oxygen gas supply source 230o. The downstream end of the first oxygen gas supply pipe 211o is connected to an ozonizer 229o that generates a reaction gas (reactant), that is, ozone gas as an oxidant, from oxygen gas by plasma. The first oxygen gas supply pipe 211o is provided with a flow rate controller (MFC) 221o as flow rate control means for controlling the supply flow rate of oxygen gas.

  The upstream end of an ozone gas supply pipe 213o as a reaction gas supply pipe is connected to the outlet 22o of the ozonizer 229o. The downstream end of the ozone gas supply pipe 213o is connected so as to join the source gas supply pipe 213. That is, the ozone gas supply pipe 213o is configured to supply ozone gas as a reaction gas into the processing chamber 201. The ozone gas supply pipe 213o is provided with an open / close valve vo3 that controls the supply of ozone gas into the processing chamber 201.

The upstream end of the second oxygen gas supply pipe 212o is connected to the upstream side of the flow rate controller 221o of the first oxygen gas supply pipe 211o. The downstream end of the second oxygen gas supply pipe 212o is connected to the upstream side of the open / close valve vo3 of the ozone gas supply pipe 213o. The second oxygen gas supply pipe 212o is provided with a flow rate controller (MFC) 222o as flow rate control means for controlling the supply flow rate of oxygen gas.

  With the above configuration, oxygen gas is supplied to the ozonizer 229o to generate ozone gas, and ozone gas can be supplied into the processing chamber 201 by opening the opening / closing valve vo3. Note that if the oxygen gas is supplied from the second oxygen gas supply pipe 212o during the supply of the ozone gas into the processing chamber 201, the ozone gas supplied into the processing chamber 201 is diluted with the oxygen gas to obtain an ozone gas concentration. Can be adjusted. The reaction gas supply system (mainly) is constituted by an oxygen gas supply source 230o, a first oxygen gas supply pipe 211o, an ozonizer 229o, a flow rate controller 221o, an ozone gas supply pipe 213o, an open / close valve vo3, a second oxygen gas supply pipe 212o, and a flow rate controller 222o. A reaction gas supply line).

(Purge gas supply system)
In addition, an Ar gas supply source 230 a for supplying Ar gas as a purge gas is provided outside the processing chamber 201. The upstream end of the purge gas supply pipe 214 is connected to the Ar gas supply source 230a. The downstream end of the purge gas supply pipe 214 is branched into four lines, that is, a first purge gas supply pipe 214s, a second purge gas supply pipe 214b, a third purge gas supply pipe 214t, and a fourth purge gas supply pipe 214o. It is connected to the. The downstream ends of the first purge gas supply pipe 214s, the second purge gas supply pipe 214b, the third purge gas supply pipe 214t, and the fourth purge gas supply pipe 214o are the first source gas supply pipe 213s and the second source gas supply pipe 213b. The third source gas supply pipe 213t and the ozone gas supply pipe 213o are connected to the downstream sides of the open / close valves vs3, vb3, vt3, and vo3, respectively. The first purge gas supply pipe 214s, the second purge gas supply pipe 214b, the third purge gas supply pipe 214t, and the fourth purge gas supply pipe 214o have a flow rate controller (MFC) as a flow rate control means for controlling the supply flow rate of Ar gas. ) 224s, 224b, 224t, 224o and open / close valves vs4, vb4, vt4, vo4 for controlling the supply of Ar gas are provided. Mainly, Ar gas supply source 230a, purge gas supply pipe 214, first purge gas supply pipe 214s, second purge gas supply pipe 214b, third purge gas supply pipe 214t, and fourth purge gas supply pipe 214o, flow rate controllers 224s, 224b, and 224t. , 224o and open / close valves vs4, vb4, vt4, and vo4 constitute a purge gas supply system (purge gas supply line). Note that N ₂ gas may be used as the purge gas.

(Vent (bypass) system)
Further, the first vent on the upstream side of the open / close valves vs3, vb3, vt3, vo3 of the first source gas supply pipe 213s, the second source gas supply pipe 213b, the third source gas supply pipe 213t, and the ozone gas supply pipe 213o is provided. The upstream ends of the pipe 215s, the second vent pipe 215b, the third vent pipe 215t, and the fourth vent pipe 215o are connected to each other. Further, the downstream end portions of the first vent pipe 215s, the second vent pipe 215b, the third vent pipe 215t, and the fourth vent pipe 215o are unified so as to be merged into a vent pipe 215, and the vent pipe 215 is an exhaust pipe. 261 is connected upstream of the raw material recovery trap 263. The first vent pipe 215s, the second vent pipe 215b, the third vent pipe 215t, and the fourth vent pipe 215o are provided with open / close valves vs5, vb5, vt5, and vo5 for controlling gas supply, respectively.

  With the above configuration, the first source gas supply pipe 213s, the second source gas supply pipe 213b, and the third source gas are opened by closing the on-off valves vs3, vb3, vt3, and vo3 and opening the on-off valves vs5, vb5, vt5, and vo5. The gas flowing in the supply pipe 213t and the ozone gas supply pipe 213o can be bypassed and exhausted out of the process chamber 201 without being supplied into the process chamber 201.

  Further, the flow rate controller 224s is upstream of the opening / closing valves vs4, vb4, vt4, and vo4 of the first purge gas supply pipe 214s, the second purge gas supply pipe 214b, the third purge gas supply pipe 214t, and the fourth purge gas supply pipe 214o. , 224b, 224t, and 224o are connected to the fifth vent pipe 216s, the sixth vent pipe 216b, the seventh vent pipe 216t, and the eighth vent pipe 216o, respectively. Further, the downstream end portions of the fifth vent pipe 216s, the sixth vent pipe 216b, the seventh vent pipe 216t, and the eighth vent pipe 216o are unified so as to be merged into a vent pipe 216, and the vent pipe 216 is an exhaust pipe. It is connected to the downstream side of the raw material recovery trap 263 and the upstream side of the vacuum pump 264. The fifth vent pipe 216s, the sixth vent pipe 216b, the seventh vent pipe 216t, and the eighth vent pipe 216o are provided with open / close valves vs6, vb6, vt6, and vo6 for controlling gas supply, respectively.

  With the above configuration, the first and second purge gas supply pipes 214s, 214b, 214b, and 214t are opened by closing the open / close valves vs4, vb4, vt4, and vo4 and opening the open / close valves vs6, vb6, vt6, and vo6. In addition, the Ar gas flowing in the fourth purge gas supply pipe 214o can be bypassed through the processing chamber 201 without being supplied into the processing chamber 201, and exhausted out of the processing chamber 201. Note that the first source gas supply pipe 213s, the second source gas supply pipe 213b, and the third source gas supply pipe are opened by closing the on-off valves vs3, vb3, vt3, and vo3 and opening the on-off valves vs5, vb5, vt5, and vo5. When the gas flowing in the ozone gas supply pipe 213o is bypassed into the processing chamber 201 without being supplied into the processing chamber 201 and exhausted to the outside of the processing chamber 201, the open / close valves vs4, vb4, vt4 By opening vo4, Ar gas is introduced into the first source gas supply pipe 213s, the second source gas supply pipe 213b, the third source gas supply pipe 213t, and the ozone gas supply pipe 213o, and inside each source gas supply pipe It is set to purge. The open / close valves vs6, vb6, vt6, and vo6 are set so as to perform the reverse operation of the open / close valves vs4, vb4, vt4, and vo4. When Ar gas is not supplied into each source gas supply pipe, the processing is performed. The chamber 201 is bypassed and the Ar gas is exhausted. Mainly, the first vent pipe 215s, the second vent pipe 215b, the third vent pipe 215t, the fourth vent pipe 215o, the vent pipe 215, the fifth vent pipe 216s, the sixth vent pipe 216b, the seventh vent pipe 216t, The 8 vent pipe 216o, the vent pipe 216, the open / close valves vs5, vb5, vt5, vo5, and the open / close valves vs6, vb6, vt6, vo6 constitute a vent system (bypass system), that is, a vent line (bypass line).

(controller)
Note that the substrate processing apparatus according to the present embodiment includes a controller 280 that controls the operation of each unit of the substrate processing apparatus. The controller 280 includes a gate valve 251, an elevating mechanism 207b, a transfer robot 273, a heater 206, a pressure regulator (APC) 262, vaporizers 229s, 229b, 229t, an ozonizer 229o, a vacuum pump 264, block valves 10s, 10b, 10t, Open / close valves vs1 to vs10, vb1 to vb10, vt1 to vt10, vo3 to vo6, liquid flow controllers 221s, 221b, 221t, 222s, 222b, 222t, flow controllers 224s, 224b, 224t, 225s, 225b, 225t, 226s, 226b , 226t, 221o, 222o, 224o and the like are controlled.

(2) Configuration of Vaporizer and Block Valve Next, the configuration of the above-described vaporizers 229s, 229b, and 229t and the block valves 10s, 10b, and 10t will be described in detail with reference to FIGS. 6 to 12 and FIG.

FIG. 6 is a schematic configuration diagram of the vaporizers 229s, 229b, and 229t and the block valves 10s, 10b, and 10t according to the first embodiment of the present invention. FIG. 7 is a partially enlarged view around the spray nozzles 31s, 31b, and 31t of the vaporizers 229s, 229b, and 229t according to the first embodiment of the present invention. FIG. 8 is a diagram in which the tip portions of the spray nozzles 31s, 31b, and 31t and the peripheral portions thereof are extracted in a modified example of the vaporizers 229s, 229b, and 229t according to the first embodiment of the present invention. The example which shortened the length of the thin tube parts 36s, 36b, 36t is shown, (b) has shown the example which lengthened the length of the thin tube parts 36s, 36b, 36t. FIG. 9 is a diagram showing the discharge direction of the raw material discharged from the spray nozzles 31s, 31b, and 31t and the discharge direction of the purge gas discharged from the discharge portion. FIG. 9A shows the discharge direction of the raw material and the discharge of the purge gas. An example in which the direction is the same is shown, and (b) shows an example in which the discharge direction of the raw material and the discharge direction of the purge gas intersect. FIG. 10 is a diagram in which the tip portions of the spray nozzles 31s, 31b, and 31t and the peripheral portions thereof are extracted in a modified example of the vaporizers 229s, 229b, and 229t according to the first embodiment of the present invention. The spray nozzles 31s, 31b, and 31t have the shortest lengths 34s, 34b, and 34t, and are slightly provided with a discharge portion parallel to the leading edges 34s, 34b, and 34t. The tip portions 34s, 34b, and 34t of the nozzles 31s, 31b, and 31t are shortened, a discharge portion parallel to the tip portions 34s, 34b, and 34t is slightly provided, and the tips of the spray nozzles 31s, 31b, and 31t are provided. This is an example in which the spray nozzles 31s, 31b, and 31t are configured only by the main body portions 32s, 32b, and 32t and the most advanced portions 34s, 34b, and 34t without the portions 33s, 33b, and 33t. FIG. 11 is a schematic configuration diagram of the block valves 10s, 10b, and 10t according to the first embodiment of the present invention. FIG. 12 is a perspective view of the block valves 10s, 10b, and 10t according to the first embodiment of the present invention. FIG. 17 is a cross-sectional view showing the flow paths of the block valves 10s, 10b, and 10t according to the first embodiment of the present invention.

  As shown in FIG. 6, the vaporizers 229 s, 229 b, and 229 t mainly include vaporization chambers 51 s, 51 b, and 51 t, heaters 61 s, 61 b, and 61 t, spray nozzles 31 s, 31 b, and 31 t, and a block. It has valves 10s, 10b, 10t, low temperature plates 71s, 71b, 71t, and nozzle covers 41s, 41b, 41t.

(Vaporization room)
The vaporization chambers 51s, 51b, and 51t are chambers that heat and vaporize the liquid raw material to generate a raw material gas, and are formed in the vaporization tubes 52s, 52b, and 52t as vaporization containers. Around the vaporization tubes 52s, 52b, and 52t, heaters 61s, 61b, and 61t are provided as heating means (heating mechanism). The heaters 61s, 61b, 61t are configured to heat and vaporize the liquid material sprayed in the vaporization chambers 51s, 51b, 51t. The vaporization tubes 52s, 52b, and 52t are generated in the vaporization chambers 51s, 51b, and 51t, inlets 53s, 53b, and 53t for introducing a liquid raw material, a carrier gas, and a purge gas into the vaporization chambers 51s, 51b, and 51t. Outlets 54s, 54b, and 54t that discharge the source gas into the first source gas supply pipe 213s, the second source gas supply pipe 213b, and the third source gas supply pipe 213t are provided.

(Spray nozzle)
Spray nozzles 31s, 31b, and 31t as spraying portions are provided in the inlets 53s, 53b, and 53t of the vaporizing tubes 52s, 52b, and 52t. The spray nozzles 31s, 31b, 31t are configured to spray the liquid raw material into the vaporization chambers 51s, 51b, 51t. The spray nozzles 31s, 31b, and 31t have main body portions 32s, 32b, and 32t, tip portions 33s, 33b, and 33t, and most advanced portions 34s, 34b, and 34t. The tip portions of the spray nozzles 31s, 31b, and 31t are constituted by the tip portions 33s, 33b, and 33t and the most distal end portions 34s, 34b, and 34t. The main body portions 32s, 32b, and 32t are portions from the root portion to the tip portion of the spray nozzles 31s, 31b, and 31t. The most advanced portions 34s, 34b, 34t are configured as protrusions (convex portions) provided at the center most distal portion of the tip portions of the spray nozzles 31s, 31b, 31t. The outer shape of the main body portions 32s, 32b, and 32t is a cylindrical shape, the outer shape of the tip portions 33s, 33b, and 33t is a substantially conical shape, and the outer shape of the most distal portions 34s, 34b, and 34t is a cylindrical shape. That is, the main body portions 32s, 32b, and 32t are configured to have a constant outer diameter, and the distal end portions 33s, 33b, and 33t are configured to decrease in outer diameter toward the distal end side. The portions 34s, 34b, and 34t are configured so that the outer diameter is constant. Note that the outer diameters of the most advanced portions 34s, 34b, and 34t are much smaller than the outer diameters of the main body portions 32s, 32b, and 32t. The tip portions of the spray nozzles 31s, 31b, 31t, that is, the tip portions 33s, 33b, 33t and the most distal portions 34s, 34b, 34t are in the vaporization tubes 52s, 52b, 52t (vaporization chambers 51s, 51b, 51t). It is arranged so as not to protrude.

  In the spray nozzles 31s, 31b, and 31t, fluid flow paths 35s, 35b, and 35t are provided for flowing a fluid in which a liquid source and a carrier gas are mixed. The fluid flow paths 35s, 35b, and 35t are narrowed on the tip side, and thin tube portions 36s, 36b, and 36t are provided on the tip side. Thus, by providing the narrow tube portions 36s, 36b, 36t having an inner diameter smaller than the inner diameter of the fluid flow paths 35s, 35b, 35t on the tip side of the spray nozzles 31s, 31b, 31t, the fluid flow paths 35s, 35b, 35t are provided. A predetermined pressure difference is provided between the inside and the vaporization chambers 51s, 51b, and 51t, and blockage of the spray nozzles 31s, 31b, and 31t due to the preferential evaporation of the solvent (so-called solvent first jump) phenomenon is prevented. Yes. As shown in FIG. 8, this pressure difference can be adjusted by changing the lengths and diameters of the narrow tube portions 36s, 36b, and 36t. FIG. 8A shows an example in which the lengths of the narrow tube portions 36s, 36b, and 36t are shortened, and FIG. 8B shows an example in which the lengths of the narrow tube portions 36s, 36b, and 36t are lengthened. FIG. 8 is a view in which only the tip portions of the spray nozzles 31s, 31b, and 31t and their peripheral portions are extracted. 6 and 8A, the fluid flow paths 35s, 35b, and 35t include main body portions 32s, 32b, and 32t, tip portions 33s, 33b, and 33t, and most advanced portions 34s, 34b, and 34t. The narrow tube portions 36s, 36b, and 36t are provided in portions corresponding to some of the most distal end portions 34s, 34b, and 34t. In the example of FIG. 8B, the fluid flow paths 35s, 35b, and 35t are provided in the main body portions 32s, 32b, and 32t and portions corresponding to part of the tip portions 33s, 33b, and 33t. The narrow tube portions 36s, 36b, and 36t are provided at a part of the tip portions 33s, 33b, and 33t and portions corresponding to the most distal end portions 34s, 34b, and 34t. It can be said that the main body portions 32s, 32b, and 32t and the most advanced portions 34s, 34b, and 34t are cylindrical. The narrow tube portions 36s, 36b, and 36t constitute the spray ports of the spray nozzles 31s, 31b, and 31t. That is, the spray port is formed on the front end surfaces of the most advanced portions 34s, 34b, and 34t as the protrusions.

(Block valve)
Block valves 10s, 10b, and 10t for controlling the supply of carrier gas, liquid source, and solvent into the spray nozzles 31s, 31b, and 31t are provided above the spray nozzles 31s, 31b, and 31t.

The block valves 10s, 10b, and 10t are first ports 11s, 11b, and 11t that receive the supply of the liquid raw material, second ports 12s, 12b, and 12t that receive the supply of the solvent, and a third port that receives the supply of the carrier gas. Ports 13s, 13b, and 13t, fourth ports 14s, 14b, and 14t for supplying fluid and solvent mixed with the liquid source and carrier gas to the spray nozzles 31s, 31b, and 31t, and the liquid source and solvent for vaporizer 229s, 229b, and 229t, and fifth ports 15s, 15b, and 15t that discharge to the outside. The first ports 11s, 11b, and 11t are connected to the downstream ends of the first liquid source supply pipe 211s, the second liquid source supply pipe 211b, and the third liquid source supply pipe 211t, respectively. The downstream ends of the first solvent supply pipe 212s, the second solvent supply pipe 212b, and the third solvent supply pipe 212t are connected to the second ports 12s, 12b, and 12t, respectively. The downstream ends of the first carrier gas supply pipe 218s, the second carrier gas supply pipe 218b, and the third carrier gas supply pipe 218t are connected to the third ports 13s, 13b, and 13t, respectively. The above-mentioned spray nozzles 31s, 31b, and 31t (the upper ends of the fluid flow paths 35s, 35b, and 35t) are directly connected to the fourth ports 14s, 14b, and 14t without using joints or the like. The upstream ends of the discharge pipes 217s, 217b, and 217t are connected to the fifth ports 15s, 15b, and 15t, respectively.

  In the block valves 10s, 10b, and 10t, liquid source supply paths 21s, 21b, 21t, 21s ′, 21b ′, and 21t ′, solvent supply paths 22s, 22b, 22t, 22s ′, 22b ′, and 22t ′, carrier gas Supply path 23s, 23b, 23t, mixing path 24s, 24b, 24t, liquid source discharge path 25s, 25b, 25t, 25s′25b′25t ′, solvent discharge path 26s, 26b, 26t, 26s ′, 26b ′, 26t ′ Is provided. Open / close valves vs1, vb1, vt1 are provided between the liquid source supply paths 21s, 21b, 21t and the liquid source supply paths 21s', 21b ', 21t'. On-off valves vs2, vb2, and vt2 are provided between the solvent supply paths 22s, 22b, and 22t and the solvent supply paths 22s', 22b ', and 22t'. Open / close valves vs10, vb10, vt10 are provided between the liquid source discharge paths 25s, 25b, 25t and the liquid source discharge paths 25s'25b'25t '. Open / close valves vs9, vb9, vt9 are provided between the solvent discharge paths 26s, 26b, 26t and the solvent discharge paths 26s', 26b ', 26t'. The upstream side of the liquid source supply paths 21s, 21b, and 21t is connected to the first ports 11s, 11b, and 11t. The upstream side of the carrier gas supply paths 23s, 23b, and 23t is connected to the third ports 13s, 13b, and 13t. The downstream side of the liquid source supply paths 21s', 21b ', 21t' and the downstream side of the carrier gas supply paths 23s, 23b, 23t are connected to the upstream side of the mixing paths 24s, 24b, 24t, respectively. The downstream sides of the mixing paths 24s, 24b, and 24t are connected to the fourth ports 14s, 14b, and 14t. The upstream side of the solvent supply paths 22s, 22b, and 22t is connected to the second ports 12s, 12b, and 12t. The downstream side of the solvent supply paths 22s ', 22b', 22t 'is connected to the vicinity of the on-off valves vs1, vb1, vt1 in the liquid source supply paths 21s', 21b ', 21t'. The upstream side of the liquid source discharge paths 25s, 25b, and 25t is connected to the liquid source supply paths 21s, 21b, and 21t. The upstream side of the solvent discharge paths 26s, 26b, and 26t is connected to the solvent supply paths 22s, 22b, and 22t. The downstream of the liquid material discharge paths 25s ′, 25b ′, and 25t ′ and the downstream of the solvent discharge paths 26s ′, 26b ′, and 26t ′ are unified so that the unified piping is the fifth. Port 15s, 15b, 15t.

  According to the above configuration, the liquid source is supplied to the first ports 11s, 11b, and 11t and the carrier gas is supplied to the third ports 13s, 13b, and 13t, and the on-off valves vs1, vb1, and vt1 are operated. The liquid source and carrier gas are mixed in the mixing paths 24s, 24b, and 24t by flowing the liquid source through the liquid source supply paths 21s, 21b, 21t, 21s ′, 21b ′, and 21t ′. A fluid obtained by mixing the liquid raw material and the carrier gas is supplied into the vaporization chambers 51 s, 51 b, 51 t through the fourth ports 14 s, 14 b, 14 t and the spray nozzles 31 s, 31 b, 31 t to generate the raw material gas. I can do it.

Further, according to the above configuration, while supplying the liquid material to the first ports 11s, 11b, and 11t, the open / close valves vs1, vb1, and vt1 are operated (closed) and the open / close valves vs10, vb10, and vt10 are operated. The liquid material is allowed to flow (open) through the liquid material discharge paths 25s, 25b, 25t, 25t ′, 25b ′, and 25t ′, so that the liquid material is discharged from the fifth ports 15s, 15b, and 15t to the discharge pipes 217s, 217b, and 217t. Through the vaporizers 229s, 229b, and 229t, and the supply of the liquid raw material into the vaporization chambers 51s, 51b, and 51t can be stopped. As described above, the fourth ports 14s, 14b, and 14t are directly connected to the spray nozzles 31s, 31b, and 31t without passing through the joints and the like, and the vaporizers 229s,
229b, 229t liquid source flow paths (flow paths from the first ports 11s, 11b, 11t to the vaporization chambers 51s, 51b, 51t (particularly liquid source supply paths 21s ′, 21b ′, 21t ′)) Is structured short. Therefore, even if the on-off valves vs1, vb1, vt1 and the on-off valves vs10, vb10, vt10 are operated as described above to stop the supply of the liquid raw material into the vaporization chambers 51s, 51b, 51t, the vaporizers 229s, 229b. , 229t, the residual liquid material can be suppressed (remaining amount can be reduced).

  Further, according to the above configuration, while supplying the solvent to the second ports 12s, 12b, and 12t, the open / close valves vs2, vb2, and vt2 are operated (opened) so that the solvent is supplied to the solvent supply paths 22s, 22b, 22t, By flowing through 22s ′, 22b ′, and 22t ′, the solvent is sprayed in the liquid source supply paths 21s ′, 21b ′, and 21t ′, in the mixing paths 24s, 24b, and 24t, in the fourth ports 14s, 14b, and 14t. The liquid material remaining in the nozzles 31s, 31b, 31t and the vaporizing chambers 51s, 51b, 51t can be removed. The downstream ends of the solvent supply paths 22s ′, 22b ′, and 22t ′ are connected in the vicinity of the on-off valves vs1, vb1, and vt1 in the liquid source supply paths 21s ′, 21b ′, and 21t ′, and the liquid source supply path Since the distances between the connection points of the solvent supply paths 22s ′, 22b ′, and 22t ′ in the 21s ′, 21b ′, and 21t ′ and the open / close valves vs1, vb1, and vt1 are the minimum length, Space can be minimized. With this configuration, the solvent can be sufficiently supplied from the upstream side of the liquid source supply paths 21s ′, 21b ′, 21t ′ to the entire liquid source supply paths 21s ′, 21b ′, 21t ′, and the liquid source supply path 21s. The liquid raw material remaining in ', 21b' and 21t 'can be efficiently removed.

  Further, according to the above configuration, while supplying the solvent to the second ports 12s, 12b, and 12t, the open / close valves vs2, vb2, and vt2 are operated (closed) and the open / close valves vs9, vb9, and vt9 are operated. By flowing the solvent through the solvent discharge paths 26s, 26b, 26t, 26s ′, 26b ′, and 26t ′ (open), the solvent is discharged from the fifth ports 15s, 15b, and 15t through the discharge pipes 217s, 217b, and 217t. The vaporizers 229s, 229b, and 229t are discharged to the outside, and the cleaning in the vaporizers 229s, 229b, and 229t can be stopped.

(Low temperature plate and nozzle cover)
Low temperature plates 71s, 71b, 71t as cooling means (cooling mechanism) are provided below the block valves 10s, 10b, 10t and around the body portions 32s, 32b, 32t of the spray nozzles 31s, 31b, 31t. ing. The low-temperature plates 71s, 71b, 71t, which are cooling members, are provided in contact with both the block valves 10s, 10b, 10t and the spray nozzles 31s, 31b, 31t. The low temperature plates 71s, 71b, 71t are configured to circulate cooling water inside, for example, and cool the spray nozzles 31s, 31b, 31t and the block valves 10s, 10b, 10t to spray nozzles 31s, 31b, The temperature is set so that the liquid raw material and solvent in 31t and block valves 10s, 10b, and 10t are not boiled or thermally decomposed. Since the set temperature is lower than the vaporization tube temperature set for vaporizing the raw material, the temperature of the spray nozzles 31s, 31b, 31t is lower than the inner surface temperature of the vaporization tubes 52s, 52b, 52t.

A cover (covering member) is provided below the low temperature plates 71 s, 71 b, 71 t and above the vaporization chambers 51 s, 51 b, 51 t and the heaters 61 s, 61 b, 61 t and around the tip portion side of the spray nozzles 31 s, 31 b, 31 t. Nozzle covers 41s, 41b, and 41t are provided. The nozzle covers 41s, 41b, and 41t are formed by a part of the main body portions 32s, 32b, and 32t of the spray nozzles 31s, 31b, and 31t and the tip portions (the tip portions 33s, 33b, and 33t and the most advanced portions 34s, 34b, and 34t). It is provided so as to cover a part. The nozzle covers 41s, 41b, and 41t cover part of the surface of the tip of the spray nozzles 31s, 31b, and 31t so as to be isolated from the vaporization chambers 51s, 51b, and 51t, and the spray nozzles 31s, 31b, and 31t. It is comprised so that the surface shape of the front-end | tip part may be followed. In addition, the part corresponding to the front-end | tip surface of the spray nozzles 31s, 31b, and 31t of the nozzle nozzles 41s, 41b, and 41t is open | released, and the tip part of the spray nozzles 31s, 31b, and 31t The side surfaces of 34s, 34b, and 34t are covered with nozzle covers 41s, 41b, and 41t. As described above, the nozzle covers 41s, 41b, and 41t are configured to minimize the areas of the spray nozzles 31s, 31b, and 31t exposed to the vaporization chambers 51s, 51b, and 51t. The tip surfaces of the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t and the bottom surfaces of the nozzle covers 41s, 41b, and 41t are provided on the same plane.

  The nozzle covers 41s, 41b, and 41t flow purge gas around a part of the main body portions 32s, 32b, and 32t and the tip of the spray nozzles 31s, 31b, and 31t, and the purge gas flows into the vaporization chambers 51s, 51b, and 51t. The purge gas flow paths 42s, 42b, and 42t for discharging to are formed. A first purge gas supply pipe 219s, a second purge gas supply pipe 219b, and a third purge gas supply pipe 219t are connected to the purge gas flow paths 42s, 42b, and 42t. A part of the purge gas passages 42s, 42b, 42t is configured to form a buffer space around a part of the main body portions 32s, 32b, 32t of the spray nozzles 31s, 31b, 31t. Further, the other part of the purge gas flow paths 42s, 42b, and 42t substantially conforms to the shape of the tip portions 33s, 33b, and 33t of the spray nozzles 31s, 31b, and 31t, and the most advanced portions 34s, 34b, and 34t. It is comprised so that the shape of this may be followed. Discharge portions 43s, 43b, and 43t that discharge purge gas into the vaporization chambers 51s, 51b, and 51t are formed in portions along the shape of the most distal portions 34s, 34b, and 34t of the purge gas flow paths 42s, 42b, and 42t. That is, a discharge unit that discharges the purge gas into the vaporization chambers 51s, 51b, 51t in the gaps between the side surfaces of the most advanced portions 34s, 34b, 34t of the spray nozzles 31s, 31b, 31t and the nozzle covers 41s, 41b, 41. 43s, 43b, and 43t are formed, and the discharge ports 43s, 43b, and 43t form discharge ports. That is, the discharge ports for the purge gas into the vaporization chambers 51s, 51b, 51t are formed on the bottom surfaces of the nozzle covers 41s, 41b, 41. In addition, since the tip end surfaces 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t and the bottom surfaces of the nozzle covers 41s, 41b, and 41t are provided on the same plane, the discharge portions 43s, 43b, and The 43t discharge port and the spray nozzles 31s, 31b, and 31t are provided on the same plane. Further, the purge gas flow paths 42s, 42b, and 42t are narrowed toward the discharge portions 43s, 43b, and 43t, and the flow paths in the discharge portions 43s, 43b, and 43t are configured to be the narrowest. . In the example of FIG. 6, the surfaces of the tip portions 33s, 33b, and 33t of the spray nozzles 31s, 31b, and 31t and the inner surfaces of the nozzle covers 41s, 41b, and 41t adjacent thereto are not parallel, and approach the tip side. As shown in the example of FIG. 8A and the example of FIG. 8B, the surfaces of the tip portions 33s, 33b, and 33t of the spray nozzles 31s, 31b, and 31t, and the nozzles adjacent thereto You may comprise so that the cover 41s, 41b, and 41t inner surface may become parallel. In addition, about the front-end | tip part 34s, 34b, 34t surface of spray nozzle 31s, 31b, 31t, and nozzle cover 41s, 41b, 41t inner surface adjacent to it, FIG. 6, FIG. 8 (a), FIG. 8 (b). In any example, it is comprised so that it may become parallel.

The discharge parts 43s, 43b, 43t to the vaporization chambers 51s, 51b, 51t of the purge gas flow paths 42s, 42b, 42t are provided in the inlets 53s, 53b, 53t of the vaporization pipes 52s, 52b, 52t. As shown in FIG. 7, the discharge sections (discharge ports) 43s, 43b, 43t of the purge gas flow paths 42s, 42b, 42t are formed in a ring shape (annular shape) in the flow path cross section, and the spray nozzle 31s. , 31b, 31t are provided concentrically around the most distal portions 34s, 34b, 34t and the most distal portions 34s, 34b, 34t and narrow tube portions (spray ports) 36s, 36b, 36t. Narrow tube portions 36s, 3 of the spray nozzles 31s, 31b, 31t
6b, 36t and the discharge portions 43s, 43b, 43t of the purge gas flow paths 42s, 42b, 42t are provided in parallel, and the liquid raw material mixed with the carrier gas passing through the narrow tube portions 36s, 36b, 36t, and the discharge The purge gases that have passed through the portions 43s, 43b, and 43t are discharged in the same direction. The purge gas that has passed through the discharge portions 43s, 43b, and 43t is discharged from around the liquid source in which the carrier gas discharged from the narrow tube portions 36s, 36b, and 36t is mixed. The liquid raw material mixed with the inert gas as the carrier gas in the mixing paths 24s, 24b, and 24t is this portion, that is, the discharge portions 43s, 43b, and 43t of the purge gas flow paths 42s, 42b, and 42t and the spray nozzles 31s, In the portions of the inlets 53s, 53b, 53t of the vaporization tubes 52s, 52b, 52t provided with the narrow tube portions 36s, 36b, 36t of 31b, 31t, the inert gas as the purge gas is mixed. That is, this portion is configured as the second mixing portions 44s, 44b, and 44t.

  Here, the action of flowing the purge gas through the purge gas passages 42s, 42b, and 42t will be described. The purge gas that flows through the purge gas flow paths 42s, 42b, and 42t has a role of heat shielding and purging of the vaporizer components.

  The vaporization chambers 51s, 51b and 51t, the heaters 61s, 61b and 61t, and the nozzle covers 41s, 41b and 41t are maintained at a high temperature necessary for sufficiently vaporizing the raw material. Depending on the vaporization temperature of the raw material, these members are maintained at a temperature of 100 to 350 ° C., for example. On the other hand, the low temperature plates 71 s, 71 b, 71 t, the spray nozzles 31 s, 31 b, 31 t, and the block valves 10 s, 10 b, 10 t suppress clogging due to the thermal decomposition of the raw material in the pipe and the flow path and the solvent jumping phenomenon. Therefore, it is maintained at a temperature that does not become a high temperature necessary for vaporizing the raw material as described above. These members are maintained at a temperature of 20 to 250 ° C., for example. The temperatures of the low temperature plates 71s, 71b, 71t, the spray nozzles 31s, 31b, 31t, the block valves 10s, 10b, 10t are the vaporization chambers 51s, 51b, 51t, the heaters 61s, 61b, 61t, the nozzle covers 41s, 41b, The temperature is kept lower than the temperature of 41t. In such a structure, from a high temperature member (vaporization chamber 51s, 51b, 51t, heater 61s, 61b, 61t, nozzle cover 41s, 41b, 41t) to a low temperature member (low temperature plate 71s, 71b, 71t, spray nozzle 31s, 31b). , 31t, and block valves 10s, 10b, and 10t), the purge gas flow paths 42s, 42b, and 42t are provided between the high temperature member and the low temperature member, and the purge gas flow paths 42s, By flowing purge gas through 42b and 42t, the heat from the high temperature member toward the low temperature member is blocked.

  Further, since the spray nozzles 31s, 31b, and 31t are set to a temperature lower than the temperature of the vaporization tubes 52s, 52b, and 52t, the raw material that has vaporized and diffused into the vaporization tubes 52s, 52b, and 52t flows backward. The raw material reliquefies when it comes into contact with the spray nozzles 31s, 31b, 31t, but the purge gas is circulated through the purge gas flow paths 42s, 42b, 42t provided around the spray nozzles 31s, 31b, 31t, and the discharge parts 43s, 43b, Since 43t is discharged into the vaporization tubes 52s, 52b, and 52t, it prevents the vaporized raw material from contacting the spray nozzles 31s, 31b, and 31t due to the back flow, and thereby prevents reliquefaction of the raw material and precipitation of the raw material. Like to do. Further, the nozzle covers 41 s, 41 b, 41 t completely cover the portions other than the portions corresponding to the tip surfaces of the most distal portions 34 s, 34 b, 34 t of the spray nozzles 31 s, 31 b, 31 t, and fill the vaporizing chambers 51 s, 51 b, 51 t. By minimizing the areas of the exposed spray nozzles 31s, 31b, and 31t, the purge effect by the purge gas is effectively utilized. Further, by preventing the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t from protruding into the vaporization tubes 52s, 52b, and 52t, the purge effect by the purge gas is not impaired. Clogging of the spray nozzle can be prevented by the purge function of the spray nozzle with the purge gas and the above-described heat blocking function with the purge gas.

  As described above, the purge gas has the role of blocking the heat of the vaporizer components and preventing the clogging of the spray nozzle due to the purge. In addition, the purge gas functions to reduce the particle size of the raw material when spraying the raw material into the vaporization pipe. There is. Hereinafter, this effect will be described together with the vaporizing operation in the vaporizers 229s, 229b, and 229t.

  The liquid source (or solution source) is supplied from the first liquid source supply pipe 211s, the second liquid source supply pipe 211b, and the third liquid source supply pipe 211t into the liquid source supply paths 21s, 21b, 21t, and the carrier gas is supplied. When the first carrier gas supply pipe 218s, the second carrier gas supply pipe 218b, and the third carrier gas supply pipe 218t are supplied into the carrier gas supply paths 23s, 23b, and 23t, the liquid raw material and the carrier gas are mixed into the mixing path 24s, 24b and 24t are mixed. At this time, the liquid raw material collides with the carrier gas, whereby the liquid is torn off, resulting in a two-phase flow with a particle size of about 10 μm to 200 μm. The raw material that has become a two-phase flow is conveyed into the spray nozzles 31s, 31b, and 31t via the mixing paths 24s, 24b, and 24t, and the fluid flow paths 35s, 35b, and 35t in the spray nozzles 31s, 31b, and 31t. Then, they are discharged (sprayed) into the vaporizing chambers 51s, 51b, 51t through the narrow pipe portions 36s, 36b, 36t. At the same time, the purge gas passes from the first purge gas supply pipe 219s, the second purge gas supply pipe 219b, and the third purge gas supply pipe 219t to the purge gas flow paths 42s, 42b, 42t and the discharge portions 43s, 43b, 43t, and the vaporization chambers 51s, 51b. , 51t. The raw material that has become a two-phase flow and the purge gas are mixed in the second mixing sections 44s, 44b, and 44t. At this time, the raw material that has become a two-phase flow is further reduced in particle size by colliding with the purge gas (the particle size becomes about 10 μm to 100 μm), and sprayed into the vaporizing chambers 51 s, 51 b, 51 t under high vacuum temperature. Is done. The sprayed raw material is vaporized by obtaining collisions with the walls of the vaporization tubes 52s, 52b, and 52t maintained at a high temperature by the heaters 61s, 61b, and 61t and radiant heat from the inner walls of the vaporization tubes 52s, 52b, and 52t.

  Thus, the purge gas has a function of further reducing the particle diameter of the raw material whose particle diameter is reduced by mixing the liquid raw material and the carrier gas. That is, in the vaporizer according to the present embodiment, the particle size of the liquid raw material is reduced in two stages, and the carrier gas and the purge gas are the first-stage carrier gas (internal mixed carrier gas) and the second-stage carrier gas (external mixing), respectively. Acts as a carrier gas). Thus, by reducing the particle size of the liquid raw material in two steps and vaporizing, the particle size of the raw material can be made finer than in the case of reducing the particle size of the liquid raw material in one step, resulting in poor vaporization. Can be prevented, and the vaporization speed and vaporization efficiency can be increased.

  In this embodiment, as shown in FIG. 9A, the narrow tube portions 36s, 36b, 36t of the spray nozzles 31s, 31b, 31t and the discharge portions 43s, 43b, 43t of the purge gas flow paths 42s, 42b, 42t. Are provided in parallel so that the two-phase raw material discharged from the narrow tube portions 36s, 36b, and 36t and the purge gas discharged from the discharge portions 43s, 43b, and 43t have the same discharge direction. It is configured. With this configuration, the raw material liquid can be more efficiently torn and the particle size can be reduced. That is, the raw material can be allowed to flow uniformly in the vaporization tubes 52s, 52b, and 52t without reducing the flow velocity, and the discharge portions 43s, The purge gas discharged from 43b and 43t can provide uniform energy (flow velocity and flow rate), and the particle size of the raw material can be reduced more efficiently.

On the other hand, for example, as shown in FIG. 9B, the discharge portions 43s, 43b, and 43t of the purge gas flow paths 42s, 42b, and 42t have the shapes of the tip portions 33s, 33b, and 33t of the spray nozzles 31s, 31b, and 31t. The raw material that is oriented in the direction along which the two-phase flow discharged from the narrow tube portions 36s, 36b, and 36t intersects with the discharge direction of the purge gas discharged from the discharge portions 43s, 43b, and 43t. This liquid is not torn off and the flow of the raw material is disturbed. When the flow of the raw material is disturbed, it is considered that the raw material does not uniformly collide with the walls of the vaporization tubes 52s, 52b, 52t, and vaporization spots are generated. In addition, when the carrier gases collide with each other, that is, the carrier gas as the first-stage carrier gas (internal mixed carrier gas) and the purge gas as the second-stage carrier gas (external mixed carrier gas), the flow velocity becomes slow and the energy decreases. However, the particle size cannot be reduced. This also shows the advantage of having the same discharge direction of the purge gas and the raw material that has become a two-phase flow.

  In this embodiment, in order to make the discharge direction of the purge gas and the raw material that has become a two-phase flow, the most advanced portion 34s on the tip side of the tip portions 33s, 33b, and 33t of the spray nozzles 31s, 31b, and 31t. , 34b, 34t, and discharge portions 43s, 43b, 43t are provided in parallel with the most advanced portions 34s, 34b, 34t, and the narrow tube portions 36s, 36b, 36t and the discharge portions 43s, 43b, 43t are provided in parallel. I have to. As shown in FIG. 10A, the lengths of the discharge portions 43s, 43b, and 43t, that is, the lengths of the most distal portions 34s, 34b, and 34t are shortened and parallel to the most distal portions 34s, 34b, and 34t. Even if the discharge portions 43s, 43b, and 43t are slightly provided, the same effect as in the case of FIG. 6 can be obtained. Further, as shown in FIG. 10B, the substantially conical tip portions 33s, 33b, and 33t are eliminated, and the spray nozzles 31s, 31b, and 31t are formed only by the main body portions 32s, 32b, and 32t and the most advanced portions 34s, 34b, and 34t. You may make it comprise. FIG. 10B is also an example in which the lengths of the most advanced portions 34s, 34b, and 34t are shortened and the discharge portions 43s, 43b, and 43t that are parallel to the most advanced portions 34s, 34b, and 34t are slightly provided. . In addition, FIG. 10 is the figure which extracted only the front-end | tip part and its peripheral part of spray nozzle 31s, 31b, 31t.

(3) Substrate Processing Step Subsequently, as a step of the manufacturing process of the semiconductor device according to the first embodiment of the present invention, a substrate processing step of forming a thin film on the wafer by the ALD method using the substrate processing apparatus described above. This will be described with reference to FIGS. 5 and 2. FIG. 5 is a flowchart of the substrate processing process according to the first embodiment of the present invention. FIG. 2 is a sequence diagram as a timing chart showing the opening / closing timing of each valve included in the substrate processing apparatus according to the first embodiment of the present invention. In this timing chart, the High level indicates that the valve is open, and the Low level indicates that the valve is closed. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 280.

(Substrate loading step (S1), Substrate placing step (S2))
First, the elevating mechanism 207b is operated to lower the support table 203 to the wafer transfer position shown in FIG. Then, the gate valve 251 is opened to allow the processing chamber 201 and the transfer chamber 271 to communicate with each other. Then, the wafer 200 to be processed is loaded from the transfer chamber 271 into the processing chamber 201 by the transfer robot 273 while being supported by the transfer arm 273a (S1). The wafer 200 carried into the processing chamber 201 is temporarily placed on the lift pins 208 b protruding from the upper surface of the support table 203. When the transfer arm 273a of the transfer robot 273 returns from the processing chamber 201 to the transfer chamber 271, the gate valve 251 is closed.

  Subsequently, the elevating mechanism 207b is operated to raise the support table 203 to the wafer processing position shown in FIG. As a result, the lift pins 208b are buried from the upper surface of the support table 203, and the wafer 200 is placed on the susceptor 217 on the upper surface of the support table 203 (S2).

(Pressure adjustment step (S3), temperature rise step (S4))
Subsequently, the pressure regulator (APC) 262 controls the pressure in the processing chamber 201 to be a predetermined processing pressure (S3). Further, the power supplied to the heater 206 is adjusted to control the surface temperature of the wafer 200 to a predetermined processing temperature (S4).

In the substrate carrying-in process (S1), the substrate placing process (S2), the pressure adjusting process (S3), and the temperature raising process (S4), the open / close valves vs3, vb3, vt3 are operated while operating the vacuum pump 264. By closing vo3 and opening the on-off valves vs4, vb4, vt4, and vo4, Ar gas is always allowed to flow into the processing chamber 201 (idle). Thereby, adhesion of particles on the wafer 200 can be suppressed.

In parallel with the steps S1 to S4, a raw material gas (hereinafter referred to as a first raw material gas) obtained by vaporizing the first liquid raw material (organic metal liquid raw material containing Sr element) is generated (preliminary vaporization) (Set up). ). That is, with the open / close valve vs2 of the block valve 10s closed, the open / close valve vs1 of the block valve 10s is opened, and a pressurized gas is supplied from the first pressurized gas supply pipe 237s, and a vaporizer is supplied from the first liquid source supply source 220s. The first liquid material is pumped (supplied) to 229 s. At this time, by opening the closing valve vs7 supplying carrier gas _{(N 2} gas) to the vaporizer 229s from _{N 2} gas supply source 230n, further vaporizer 229s by opening the opening and closing valve vs8 from _{N 2} gas supply source 230n A purge gas (N ₂ gas) is supplied to the gas. The supply of the carrier gas and the supply of the purge gas are preferably performed prior to the supply of the first liquid raw material. The first liquid source flows in the liquid source supply paths 21s and 21s' and is mixed with the carrier gas in the mixing path 24s. Then, a fluid formed by mixing the first liquid source and the carrier gas is supplied into the vaporization chamber 51s via the fourth port 14s and the spray nozzle 31s to vaporize the first liquid source, and the first source gas is supplied. Let it occur. After that, the on-off valve vs7 and the on-off valve vs8 are always opened regardless of the vaporizing operation or the cleaning operation in the vaporizer 229s, and the carrier gas and the purge gas are always supplied to the vaporizer 229s. And In this preliminary vaporization step, the process chamber 201 is bypassed without supplying the first source gas into the process chamber 201 by opening the open / close valve vs5 while operating the vacuum pump 264 and keeping the open / close valve vs3 closed. And exhaust.

  In parallel with the steps S1 to S4, it is preferable to generate ozone gas as a reactant (Set up). That is, oxygen gas is supplied from the oxygen gas supply source 230o to the ozonizer 229o, and ozone gas is generated in the ozonizer 229o. At this time, while the vacuum pump 264 is operated, the open / close valve vo5 is opened while the open / close valve vo3 is closed, thereby bypassing the process chamber 201 and exhausting it without supplying ozone gas into the process chamber 201.

  A predetermined time is required to stably generate the first source gas by the vaporizer 229s or to stably generate the ozone gas by the ozonizer 229o. For this reason, in this embodiment, the first source gas or ozone gas is generated in advance, and the opening and closing valves vs3, vs5, vo3, and vo5 are switched to switch the flow path of the first source gas and ozone gas. As a result, it is preferable that the stable supply of the first source gas and ozone gas into the processing chamber 201 can be started or stopped quickly by switching the opening / closing valve.

Simultaneously with the preliminary vaporization step, the open / close valves vb2 and vt2 of the block valves 10b and 10t are opened, the cleaning liquid (solvent) is supplied to the second ports 12b and 12t of the block valves 10b and 10t, and the cleaning liquid (solvent) is supplied. The solvent is supplied to the solvent supply paths 22b, 22t, 22b ′, and 22t ′. Then, the cleaning liquid (solvent) is supplied into the liquid source supply paths 21b ′ and 21t ′, the mixing paths 24b and 24t, the fourth ports 14b and 14t, the spray nozzles 31b and 31t, and the vaporization chambers 51b and 51t. The remaining liquid raw material is removed (the insides of the vaporizers 229b and 229t are washed). At this time, the opening and closing valves vb7 and vt7 are opened to supply the carrier gas (N ₂ gas) from the N ₂ gas supply source 230n to the vaporizers 229b and 229t, and the opening and closing valves vb8 and vt8 are opened to supply the N ₂ gas. Purge gas (N ₂ gas) is supplied from the source 230n to the vaporizers 229b and 229t. The supply of the carrier gas and the supply of the purge gas are preferably performed prior to the supply of the cleaning liquid. The open / close valves vb7, vt7,
Thereafter, the on-off valves vb8 and vt8 are always opened regardless of the vaporizing operation and the cleaning operation in the vaporizers 229b and 229t, and the carrier gas and the purge gas are always supplied to the vaporizers 229b and 229t. And The details of the cleaning method will be described later.

(ALD process using first source gas (S6))
Subsequently, the open / close valves vs4 and vs5 are closed and the open / close valve vs3 is opened while the vacuum pump 264 is operated, and the supply of the first source gas into the processing chamber 201 is started (Sr). The first source gas is dispersed by the shower head 240 and uniformly supplied onto the wafer 200 in the processing chamber 201, and the gas molecules of the first source gas are adsorbed on the surface of the wafer 200. Excess first source gas flows through the exhaust duct 259 and is exhausted to the exhaust port 260. Note that when the first source gas is supplied into the processing chamber 201, the first source gas is prevented from entering the second source gas supply pipe 213b, the third source gas supply pipe 213t, and the ozone gas supply pipe 213o. In addition, it is preferable that the open / close valves vb4, vt4, and vo4 are kept open so that Ar gas is allowed to constantly flow into the processing chamber 201 so as to promote diffusion of the first source gas in the processing chamber 201.

  After a predetermined time has elapsed after opening the on-off valve vs3 and starting the supply of the first source gas, the on-off valve vs3 is closed and the on-off valves vs4 and vs5 are opened to supply the first source gas into the processing chamber 201. To stop. At the same time, the opening / closing valve vs1 of the block valve 10s is closed, and the supply of the first liquid material to the vaporizer 229s is also stopped. At this time, the open / close valve vs10 of the block valve 10s is operated (opened) to flow the first liquid material into the liquid material discharge paths 25s, 25s ′, and the first liquid material is discharged from the vaporizer 229s through the fifth port 15s. You may make it discharge | emit. By switching the flow path of the first liquid source using the on-off valves vs1 and vs10, the supply and stop of the supply of the first liquid source into the vaporization chamber 51s can be performed quickly. Note that, as described above, the fourth port 14s is directly connected to the spray nozzle 31s without using a joint portion or the like, and the flow path of the first liquid source in the vaporizer 229s (from the first port 11s to the vaporization chamber 51s). The flow path up to the above, particularly the liquid raw material supply path 21s') is configured to be short. Therefore, even if the on-off valve vs1 is operated as described above to stop the supply of the first liquid raw material into the vaporizing chamber 51s, the liquid raw material remains in the vaporizer 229s (remaining amount is reduced). be able to. Thereafter, the opening / closing valve vs7 and the opening / closing valve vs8 are opened without being closed, and the supply of the carrier gas and the purge gas to the vaporizer 229s is continued.

  Here, after the on-off valve vs3 is closed and the supply of the first source gas is stopped, the on-off valves vs4, vb4, vt4, and vo4 are kept open, and the Ar gas is always allowed to flow into the processing chamber 201. As a result, the first source gas remaining in the processing chamber 201 is removed, and the inside of the processing chamber 201 is purged with Ar gas (PS1).

In addition, after closing the open / close valve vs1 of the block valve 10s and stopping the supply of the first liquid raw material, cleaning in the vaporizer 229s is started (PS1). That is, while supplying the pressurized gas from the solvent pressurized gas supply pipe 237e, with the open / close valve vs1 of the block valve 10s closed, the open / close valve vs2 of the block valve 10s is opened, and the cleaning liquid ( Solvent) and flowing the cleaning liquid (solvent) through the solvent supply paths 22s and 22s ′, thereby allowing the cleaning liquid (solvent) to flow into the liquid raw material supply path 21s ′, the mixing path 24s, the fourth port 14s, and the spray nozzle. 31s is supplied into the vaporizing chamber 51s (hereinafter also simply referred to as a liquid source flow path), and the remaining first liquid source is removed (the inside of the vaporizer 229s is cleaned). Since the downstream end of the solvent supply path 22s ′ is connected to the vicinity of the opening / closing valve vs1 in the liquid source supply path 21s ′, it extends from the upstream side of the liquid source supply path 21s ′ to the entire liquid source supply path 21s ′. The cleaning liquid (solvent) can be sufficiently supplied, and the first liquid raw material remaining in the liquid raw material supply path 21s ′ can be efficiently removed. At this time, the on-off valves vs1 and vs3 are closed and the on-off valves vs2 and vs5 are opened, so that the cleaning liquid supplied in the liquid source channel is supplied into the vaporization chamber 51s after cleaning the liquid source channel. Being vaporized. At this time, the first liquid source and the solvent remaining in the liquid source channel are also supplied into the vaporizing chamber 51s and vaporized. The vaporized cleaning liquid, the first liquid source, and the solvent bypass the process chamber 201 from the first vent pipe 215s without being supplied into the process chamber 201 through the first source gas supply pipe 213s. Exhausted. Also at this time, the opening / closing valve vs7 and the opening / closing valve vs8 are kept open without being closed, and the supply of the carrier gas and the purge gas to the vaporizer 229s is continued. The cleaning of the vaporizer 229s is continued, for example, until the next supply of the first liquid raw material to the vaporizer 229s (until Ti in S9).

  When the purge in the processing chamber 201 is completed, the opening / closing valves vo4, vo5 are closed, the opening / closing valve vo3 is opened, and supply of ozone gas into the processing chamber 201 is started (OxS). The ozone gas is dispersed by the shower head 240 and uniformly supplied onto the wafer 200 in the processing chamber 201, reacts with the gas molecules of the first source gas adsorbed on the surface of the wafer 200, and the Sr element on the wafer 200. An SrO film is produced as a thin film containing Excess ozone gas and reaction byproducts flow through the exhaust duct 259 and are exhausted to the exhaust port 260. When supplying ozone gas into the processing chamber 201, in order to prevent ozone gas from entering the first source gas supply pipe 213s, the second source gas supply pipe 213b, and the third source gas supply pipe 213t, It is preferable to keep the open / close valves vs4, vb4, and vt4 open so that the ozone gas is diffused in the processing chamber 201 and to keep Ar gas flowing in the processing chamber 201 at all times.

  After a predetermined time has elapsed after opening the opening / closing valve vo3 and starting the supply of ozone gas, the opening / closing valve vo3 is closed and the opening / closing valves vo4, vo5 are opened to stop the supply of ozone gas into the processing chamber 201.

  After the opening / closing valve vo3 is closed and the supply of ozone gas is stopped, the opening / closing valves vs4, vb4, vt4, vo4 are kept open, and Ar gas is always allowed to flow into the processing chamber 201. Thereby, ozone gas and reaction by-products remaining in the processing chamber 201 are removed, and the inside of the processing chamber 201 is purged with Ar gas (PS2).

  In the ALD process (S6) using the first source gas, a source gas (hereinafter referred to as a third source gas) obtained by vaporizing the third liquid source (organometallic liquid source containing Ti element) is generated in advance ( Pre-vaporization) (PS1). That is, with the on-off valve vt7 and the on-off valve vt8 kept open and the supply of the carrier gas and the purge gas to the vaporizer 229t is continued, the on-off valve vt2 of the block valve 10t is closed and the on-off valve vt1 of the block valve 10t is closed. The third liquid source is supplied from the third liquid source supply source 220t to the vaporizer 229t by opening and supplying the pressurized gas from the third pressurized gas supply pipe 237t. The third liquid source flows through the liquid source supply paths 21t and 21t ′, is mixed with the carrier gas in the mixing path 24t, and the fluid formed by mixing the third liquid source and the carrier gas is the fourth port 14t, The third liquid source is vaporized by supplying it into the vaporizing chamber 51t via the spray nozzle 31t, and a third source gas is generated. In the ALD process (S6) using the first source gas, the third source gas is supplied into the processing chamber 201 by opening the on-off valve vt5 while operating the vacuum pump 264 and keeping the on-off valve vt3 closed. The process chamber 201 is bypassed and exhausted. In this way, the third source gas is generated in advance, and the opening and closing of the open / close valves vt3 and vt5 is switched in the ALD step (S7) using the third source gas described later, thereby changing the flow path of the third source gas. Switch. Thereby, in the ALD process (S7) using the third source gas, stable supply of the third source gas into the processing chamber 201 can be started or stopped quickly, which is preferable.

(ALD process using third source gas (S7))
Subsequently, the open / close valves vt4 and vt5 are closed and the open / close valve vt3 is opened while the vacuum pump 264 is operated, and supply of the third source gas into the processing chamber 201 is started (Ti). The third source gas is dispersed by the shower head 240 and uniformly supplied onto the wafer 200 in the processing chamber 201, and the gas molecules of the third source gas are adsorbed on the surface of the wafer 200. Excess third source gas flows through the exhaust duct 259 and is exhausted to the exhaust port 260. When the third source gas is supplied into the processing chamber 201, the third source gas is prevented from entering the first source gas supply pipe 213s, the second source gas supply pipe 213b, and the ozone gas supply pipe 213o. Further, it is preferable that the open / close valves vs4, vb4, and vo4 are kept open so that Ar gas flows constantly in the processing chamber 201 so as to promote diffusion of the third source gas in the processing chamber 201.

  After a predetermined time has elapsed after opening the on-off valve vt3 and starting the supply of the third source gas, the on-off valve vt3 is closed and the on-off valves vt4, vt5 are opened to supply the third source gas into the processing chamber 201. To stop. At the same time, the opening / closing valve vt1 of the block valve 10t is closed, and the supply of the third liquid material to the vaporizer 229t is also stopped. At this time, the open / close valve vt10 of the block valve 10t is operated (opened) to flow the third liquid material to the liquid material discharge paths 25t, 25t ′, whereby the third liquid material is vaporized from the fifth port 15t to the vaporizer 229t. You may make it discharge | emit outside. By switching the flow path of the third liquid material using the opening / closing valves vt1 and vt10, the supply and stop of the supply of the third liquid material into the vaporization chamber 51t can be performed quickly. As described above, the fourth port 14t is directly connected to the spray nozzle 31t without passing through the joint portion or the like, and the third liquid source flow path (from the first port 11t to the vaporization chamber 51t in the vaporizer 229t). The flow path up to the point, particularly the liquid raw material supply path 21t ′) is configured to be short. Therefore, even if the on-off valve vt1 is operated as described above to stop the supply of the third liquid source into the vaporizing chamber 51t, the liquid source remains in the vaporizer 229t (remaining amount is reduced). be able to. The open / close valve vt7 and open / close valve vt8 are opened without being closed, and the supply of the carrier gas and the purge gas to the vaporizer 229t is continued.

  Here, after the on-off valve vt3 is closed and the supply of the third source gas is stopped, the on-off valves vs4, vb4, vt4, and vo4 are kept open, and the Ar gas is always allowed to flow into the processing chamber 201. Thereby, the third source gas remaining in the processing chamber 201 is removed, and the inside of the processing chamber 201 is purged with Ar gas (PT1).

Further, after closing the opening / closing valve vt1 of the block valve 10t and stopping the supply of the third liquid raw material, cleaning of the vaporizer 229t is started (PT1). That is, while supplying the pressurized gas from the solvent pressurized gas supply pipe 237e, the open / close valve vt2 of the block valve 10t is opened while the open / close valve vt1 of the block valve 10t is closed, and the cleaning liquid ( Solvent) and flowing the cleaning liquid (solvent) through the solvent supply paths 22t and 22t ′, thereby allowing the cleaning liquid (solvent) to flow into the liquid raw material supply path 21t ′, the mixing path 24t, the fourth port 14t, and the spray nozzle. 31t is supplied into the vaporizing chamber 51t (hereinafter also simply referred to as a liquid source flow path), and the remaining third liquid source is removed (the inside of the vaporizer 229t is cleaned). Since the downstream end of the solvent supply path 22t ′ is connected to the vicinity of the opening / closing valve vt1 in the liquid source supply path 21t ′, the downstream end of the solvent supply path 22t ′ extends from the upstream side of the liquid source supply path 21t ′ to the entire liquid source supply path 21t ′. The cleaning liquid (solvent) can be sufficiently supplied, and the third liquid raw material remaining in the liquid raw material supply path 21t ′ can be efficiently removed. At this time, the on-off valves vt1 and vt3 are closed and the on-off valves vt2 and vt5 are opened, so that the cleaning liquid supplied into the liquid source channel is supplied into the vaporization chamber 51t after cleaning the liquid source channel. Being vaporized. At this time, the third liquid source and the solvent remaining in the liquid source channel are also supplied into the vaporizing chamber 51t and vaporized. Then, the vaporized cleaning liquid, the third liquid source, and the solvent pass through the third source gas supply pipe 213t and are not supplied into the processing chamber 201, but bypass the processing chamber 201 from the third vent pipe 215t. Exhausted. Also at this time, the on-off valve vt7 and the on-off valve vt8 are kept open without being closed, and the supply of the carrier gas and the purge gas to the vaporizer 229t is continued. The cleaning of the vaporizer 229t is continued, for example, until the next supply of the third liquid material to the vaporizer 229t is started (until Ba in S8).

When the purge in the processing chamber 201 is completed, the opening / closing valves vo4, vo5 are closed, the opening / closing valve vo3 is opened, and supply of ozone gas into the processing chamber 201 is started (OxT). The ozone gas is dispersed by the shower head 240, is uniformly supplied onto the wafer 200 in the processing chamber 201, reacts with gas molecules of the third source gas adsorbed on the surface of the wafer 200, and Ti element is formed on the wafer 200. A TiO ₂ film is produced as a thin film containing Excess ozone gas and reaction byproducts flow through the exhaust duct 259 and are exhausted to the exhaust port 260. When supplying ozone gas into the processing chamber 201, in order to prevent ozone gas from entering the first source gas supply pipe 213s, the second source gas supply pipe 213b, and the third source gas supply pipe 213t, It is preferable to keep the open / close valves vs4, vb4, and vt4 open so that the ozone gas is diffused in the processing chamber 201 and to keep Ar gas flowing in the processing chamber 201 at all times.

  After a predetermined time has elapsed after opening the opening / closing valve vo3 and starting the supply of ozone gas, the opening / closing valve vo3 is closed and the opening / closing valves vo4, vo5 are opened to stop the supply of ozone gas into the processing chamber 201.

  After the opening / closing valve vo3 is closed and the supply of ozone gas is stopped, the opening / closing valves vs4, vb4, vt4, vo4 are kept open, and Ar gas is always allowed to flow into the processing chamber 201. Thereby, ozone gas and reaction by-products remaining in the processing chamber 201 are removed, and the inside of the processing chamber 201 is purged with Ar gas (PT2).

  In the ALD process (S7) using the third source gas, a source gas (hereinafter referred to as a second source gas) obtained by vaporizing the second liquid source (organic metal liquid source containing Ba element) is generated in advance ( Pre-vaporization) (PT1-). That is, the on-off valve vb7 and the on-off valve vb8 are kept open, the carrier valve and the purge gas are continuously supplied to the vaporizer 229b, the on-off valve vb2 of the block valve 10b is closed, and the on-off valve vb1 of the block valve 10b is opened. While being opened, pressurized gas is supplied from the second pressurized gas supply pipe 237b, and the second liquid source is supplied from the second liquid source supply source 220b to the vaporizer 229b. The second liquid source flows in the liquid source supply paths 21b and 21b ′, is mixed with the carrier gas in the mixing path 24b, and the fluid formed by mixing the second liquid source and the carrier gas is the fourth port 14b. Then, the gas is supplied into the vaporizing chamber 51b through the spray nozzle 31b, and the second liquid source is vaporized to generate the second source gas. In the ALD process (S7) using the third source gas, the second source gas is supplied into the processing chamber 201 by opening the on-off valve vb5 while operating the vacuum pump 264 and keeping the on-off valve vb3 closed. The process chamber 201 is bypassed and exhausted. In this way, the second source gas is generated in advance, and the opening and closing of the on-off valves vb3 and vb5 is switched in the ALD step (S8) using the second source gas, which will be described later. Switch. Thereby, in the ALD process (S8) using the second source gas, stable supply of the second source gas into the processing chamber 201 can be started or stopped quickly, which is preferable.

(ALD process using second source gas (S8))
Subsequently, the open / close valves vb4 and vb5 are closed and the open / close valve vb3 is opened while the vacuum pump 264 is operated, and supply of the second source gas into the processing chamber 201 is started (Ba). The second source gas is dispersed by the shower head 240 and uniformly supplied onto the wafer 200 in the processing chamber 201, and the gas molecules of the second source gas are adsorbed on the surface of the wafer 200. Excess second source gas flows in the exhaust duct 259 and is exhausted to the exhaust port 260. When the second source gas is supplied into the processing chamber 201, the second source gas is prevented from entering the first source gas supply pipe 213s, the third source gas supply pipe 213t, and the ozone gas supply pipe 213o. Further, it is preferable to keep the open / close valves vs4, vt4, and vo4 open and to keep Ar gas flowing in the processing chamber 201 so as to promote diffusion of the second source gas in the processing chamber 201.

  After a predetermined time has elapsed after opening the on-off valve vb3 and starting the supply of the second source gas, the on-off valve vb3 is closed and the on-off valves vb4, vb5 are opened to supply the second source gas into the processing chamber 201. To stop. At the same time, the opening / closing valve vb1 of the block valve 10b is closed, and the supply of the second liquid raw material to the vaporizer 229b is also stopped. At this time, by operating (opening) the opening / closing valve vb10 of the block valve 10b, the second liquid source is allowed to flow through the liquid source discharge paths 25b, 25 ′, whereby the second liquid source is vaporized from the fifth port 15b. You may make it discharge | emit outside. By switching the flow path of the second liquid material using the opening / closing valves vb1 and vb10, the supply and stop of the supply of the second liquid material to the vaporization chamber 51b can be performed quickly. As described above, the fourth port 14b is directly connected to the spray nozzle 31b without using a joint portion or the like, and the second liquid raw material flow path (from the first port 11b to the vaporizing chamber 51b) in the vaporizer 229b. The flow path up to the above, particularly the liquid raw material supply path 21b ′) is configured to be short. Therefore, even if the on-off valve vb1 is operated as described above to stop the supply of the second liquid raw material into the vaporizing chamber 51b, the liquid raw material remains in the vaporizer 229b (remaining amount is reduced). be able to. The on-off valve vb7 and the on-off valve vb8 are opened without being closed, and the supply of the carrier gas and the purge gas to the vaporizer 229b is continued.

  Here, after the on-off valve vb3 is closed and the supply of the second source gas is stopped, the on-off valves vs4, vb4, vt4, and vo4 are kept open, and Ar gas is always allowed to flow into the processing chamber 201. Thereby, the second source gas remaining in the processing chamber 201 is removed, and the inside of the processing chamber 201 is purged with Ar gas (PB1).

In addition, after closing the opening / closing valve vb1 of the block valve 10b and stopping the supply of the second liquid raw material, cleaning of the vaporizer 229b is started (PB1 to PB1). That is, while supplying the pressurized gas from the solvent pressurized gas supply pipe 237e, the open / close valve vb2 of the block valve 10b is opened while the open / close valve vb1 of the block valve 10b is closed, and the cleaning liquid ( Solvent) and flowing the cleaning liquid (solvent) through the solvent supply paths 22b and 22b ′, thereby allowing the cleaning liquid (solvent) to flow into the liquid source supply path 21b ′, the mixing path 24b, the fourth port 14b, and the spray nozzle. 31b and the vaporizing chamber 51b (hereinafter also simply referred to as a liquid source flow path) are supplied to remove the remaining second liquid source (clean the inside of the vaporizer 229b). Since the downstream end of the solvent supply path 22b ′ is connected to the vicinity of the opening / closing valve vb1 in the liquid source supply path 21b ′, the upstream end of the liquid source supply path 21b ′ extends into the entire liquid source supply path 21b ′. The cleaning liquid (solvent) can be sufficiently supplied, and the second liquid source remaining in the liquid source supply path 21b ′ can be efficiently removed. At this time, the on-off valves vb1 and vb3 are closed and the on-off valves vb2 and vb5 are opened, so that the cleaning liquid supplied into the liquid source channel is supplied into the vaporization chamber 51b after cleaning the liquid source channel. Being vaporized. At this time, the second liquid source and the solvent remaining in the liquid source channel are also supplied into the vaporization chamber 51b and vaporized. The vaporized cleaning liquid, the second liquid source, and the solvent pass through the second source gas supply pipe 213b and are not supplied into the processing chamber 201, but bypass the processing chamber 201 from the second vent pipe 215b. Exhausted. Also at this time, the opening / closing valve vb7 and the opening / closing valve vb8 are opened without being closed, and the supply of the carrier gas and the purge gas to the vaporizer 229b is continued. The vaporizer 229
The cleaning of b is continued, for example, until the next supply of the second liquid material to the vaporizer 229b is started (until the next Ti of S7).

  When the purge in the processing chamber 201 is completed, the opening / closing valves vo4, vo5 are closed, the opening / closing valve vo3 is opened, and supply of ozone gas into the processing chamber 201 is started (OxB). The ozone gas is dispersed by the shower head 240 and uniformly supplied onto the wafer 200 in the processing chamber 201, reacts with gas molecules of the second source gas adsorbed on the surface of the wafer 200, and Ba element is formed on the wafer 200. BaO film is formed as a thin film containing Excess ozone gas and reaction byproducts flow through the exhaust duct 259 and are exhausted to the exhaust port 260. When supplying ozone gas into the processing chamber 201, in order to prevent ozone gas from entering the first source gas supply pipe 213s, the second source gas supply pipe 213b, and the third source gas supply pipe 213t, It is preferable to keep the open / close valves vs4, vb4, and vt4 open so that the ozone gas is diffused in the processing chamber 201 and to keep Ar gas flowing in the processing chamber 201 at all times.

  After a predetermined time has elapsed after opening the opening / closing valve vo3 and starting the supply of ozone gas, the opening / closing valve vo3 is closed and the opening / closing valves vo4, vo5 are opened to stop the supply of ozone gas into the processing chamber 201.

  After the opening / closing valve vo3 is closed and the supply of ozone gas is stopped, the opening / closing valves vs4, vb4, vt4, vo4 are kept open, and Ar gas is always allowed to flow into the processing chamber 201. Thereby, ozone gas and reaction by-products remaining in the processing chamber 201 are removed, and the inside of the processing chamber 201 is purged with Ar gas (PB2).

  In the ALD process (S8) using the second source gas, a source gas (hereinafter referred to as a third source gas) obtained by vaporizing the third liquid source (an organometallic liquid source containing Ti element) is generated in advance ( Pre-vaporization) (PB1 ~). The preliminary vaporization is performed in the same procedure as described above.

(ALD process using third source gas (S9))
Subsequently, the same process as the ALD process (S7) using the third source gas described above is performed again to generate a TiO ₂ film as a thin film containing Ti element on the wafer 200.

(Repeating step (S10))
After the ALD step (S9) using the third source gas, steps S6 to S9 are defined as one cycle, and this cycle is repeated a predetermined number of times, whereby a BST (barium strontium titanate) thin film having a desired thickness is formed on the wafer 200. That is, a (Ba, Sr) TiO ₃ thin film is formed.

(Substrate unloading step (S11))
Thereafter, the wafer 200 after forming a thin film with a desired film thickness is transferred from the processing chamber 201 to the transfer chamber 271 by a procedure reverse to the procedure shown in the substrate carry-in step (S1) and the substrate placement step (S2). The substrate processing step according to this embodiment is completed.

  In the case where the thin film forming process is performed by the ALD method, the processing temperature is controlled so as to be a temperature range in which the source gas does not self-decompose. In this case, when supplying each source gas in the ALD process (S6 to S9) using each source gas, the source gas is adsorbed on the wafer 200 without being thermally decomposed. Further, when ozone gas is supplied, the raw material gas molecules adsorbed on the wafer 200 react with the ozone gas, whereby a thin film of less than one atomic layer (less than 1 cm) is formed on the wafer 200. At this time, impurities such as C and H mixed in the thin film can be desorbed by ozone gas.

As a processing condition of the wafer 200 in the present embodiment, for example, when forming a thin film of (Ba, Sr) TiO ₃ ,
Processing temperature: 250-450 ° C.
Processing pressure: 10 to 200 Pa,
First liquid raw material Sr (C ₁₄ O ₄ H ₂₅ ) ₂ (abbreviation: Sr (METHD) ₂ ) 0.1 mol / L ECH dilution) Supply flow rate: 0.01 to 0.5 cc / min,
Second liquid raw material Ba (C ₁₄ O ₄ H ₂₅ ) ₂ (abbreviation: Ba (METHD) ₂ ) 0.1 mol / L ECH dilution) Supply flow rate: 0.01 to 0.5 cc / min,
Third liquid raw material Ti (C ₆ O ₂ H ₁₁ ) (C ₁₁ O ₂ H ₁₉ ) ₂ (abbreviation: Ti (MPD) (THD) ₂ ) 0.1 mol / L ECH dilution) Supply flow rate: 0.01 to 0 .5cc / min,
Reactant (ozone gas) supply flow rate: 500 to 2000 sccm (ozone concentration 20 to 200 g / Nm ³ ),
Cleaning liquid (ECH) supply flow rate: 0.05 to 0.5 cc / min,
High temperature member temperature of vaporizer: 100-350 ° C.
Low temperature temperature of vaporizer: 20-250 ° C,
Vaporization chamber pressure: several to 10 Torr
Is exemplified. In the present embodiment, the same substance (ECH) is used as a solvent for diluting each liquid raw material and a cleaning liquid.

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

(A) According to this embodiment, the fourth port is operated by operating the on-off valves vs1, vb1, vt1 while supplying the liquid raw material to the first ports 11s, 11b, 11t of the block valves 10s, 10b, 10t. Supply of the liquid raw material from 14s, 14b, and 14t into vaporization chamber 51s, 51b, and 51t is stopped. Here, the fourth ports 14s, 14b, and 14t are directly connected to the spray nozzles 31s, 31b, and 31t without passing through the joints or the like, and the flow path of the liquid material (first first) in the vaporizers 229s, 229b, and 229t. The channels from the ports 11s, 11b, and 11t to the vaporization chambers 51s, 51b, and 51t, particularly the liquid source supply channels 21s ′, 21b ′, and 21t ′) are configured to be short. Therefore, even if the on-off valves vs1, vb1, vt1 are operated as described above to stop the supply of the liquid material into the vaporization chambers 51s, 51b, 51t, the liquid material remains in the vaporizers 229s, 229b, 229t. (Residual amount can be reduced). Further, waste of the liquid material can be avoided, and an increase in substrate processing cost can be prevented. Further, after the supply of the liquid raw material into the vaporization chambers 51s, 51b, 51t is stopped, the remaining liquid raw material flows into the vaporization chambers 51s, 51b, 51t, and the raw material gas is generated unintentionally. Can be reduced. Further, when the generation of the source gas is restarted, the concentration and flow rate of the source gas after the restart of generation can be stabilized. Further, the occurrence of clogging in the liquid material supply paths 21s', 21b ', 21t', etc. can be suppressed, and the occurrence of vaporization failure can be avoided.

(B) According to the present embodiment, the solvent supply path is operated by operating the on-off valves vs2, vb2, and vt2 while supplying the solvent to the second ports 12s, 12b, and 12t of the block valves 10s, 10b, and 10t. 22s, 22b, 22t, 22s ′, 22b ′, and 22t ′ allow the solvent to flow, so that the liquid source supply paths 21s ′, 21b ′, and 21t ′, the mixing paths 24s, 24b, and 24t, the fourth port 14s, 14b, 14t, the spray nozzles 31s, 31b, 31t, and the vaporization chambers 51s, 51b, 51t are supplied with a solvent to remove the remaining liquid material (the vaporizers 229s, 229b, 229t are cleaned). . Here, since the downstream ends of the solvent supply paths 22s ′, 22b ′, and 22t ′ are connected in the vicinity of the on-off valves vs1, vb1, and vt1 in the liquid source supply paths 21s ′, 21b ′, and 21t ′, the liquid source The solvent can be sufficiently supplied to the entire supply paths 21s ′, 21b ′, and 21t ′ (the solvent can be supplied from the upstream side of the liquid source supply paths 21s ′, 21b ′, and 21t ′). As a result, the concentration and flow rate when the liquid raw material remains in the vaporizers 229s, 229b, and 229t (residual amount is reduced), the generation of unintended raw material gas is avoided, and the generation of the raw material gas is resumed. And the occurrence of clogging in the liquid material supply paths 21s ′, 21b ′, 21t ′ and the like can be suppressed, and the occurrence of vaporization defects can be avoided. Further, since the solvent can be supplied from the upstream side of the liquid source supply paths 21s ′, 21b ′, and 21t ′, the cleaning can be performed efficiently. Then, even when the vaporizers 229s, 229b, and 229t are cleaned each time the generation of the source gas is stopped, the consumption of the solvent can be reduced. In addition, the time required for switching between stopping and restarting the generation of the source gas (time required for cleaning the vaporizers 229s, 229b, and 229t) can be shortened. Thereby, it is possible to prevent an increase in substrate processing cost and a decrease in productivity.

(C) According to this embodiment, the fourth valve is operated by operating the on-off valves vs2, vb2, vt2 while supplying the solvent to the second ports 12s, 12b, 12t of the block valves 10s, 10b, 10t. By stopping the supply of the solvent from the ports 14s, 14b, and 14t to the vaporizers 229s, 229b, and 229t, the cleaning in the vaporizers 229s, 229b, and 229t is stopped. Here, as described above, the fourth ports 14s, 14b, and 14t are directly connected to the spray nozzles 31s, 31b, and 31t without passing through the joints and the like, and the solvent flow paths (the vaporizers 229s, 229b, and 229t ( The flow path from the second ports 12s, 12b, and 12t to the vaporization chambers 51s, 51b, and 51t) is configured to be short. Therefore, even if the supply of the solvent into the vaporizers 229s, 229b, and 229t is stopped by operating the open / close valves vs2, vb2, and vt2 as described above, residual solvent in the vaporizers 229s, 229b, and 229t is suppressed. (Residual amount can be reduced). And when resuming the generation of the raw material gas, it is possible to suppress the newly supplied liquid raw material from being diluted by the remaining solvent, and to stabilize the concentration and flow rate of the raw material gas after the resumption of the generation. Can do.

  For reference, the configuration of a conventional block valve will be described with reference to FIGS. FIG. 14 is a schematic configuration diagram of a conventional block valve 410 and a spray nozzle 431. FIG. 15 is a perspective view of a conventional block valve 410. FIG. 16 is a schematic view showing a state in which a liquid raw material, a solvent, and a carrier gas are supplied to a block valve 410 included in a conventional vaporizer.

A block valve 410 included in a conventional vaporizer is configured as a four-way four-way valve, and includes a first port 411 that receives supply of a liquid raw material, a second port 412 that receives supply of a solvent, and a joint portion 480. And a third port 413 for supplying the solution raw material, which is a mixed liquid of the liquid raw material and the solvent, to the joint portion 480, and a fourth port 414 for discharging the liquid raw material and the solvent to the outside of the vaporizer. Have. In the block valve 410, a liquid raw material supply path 421, 421 ′ connecting between the first port 411 and the third port 413 and a solvent connecting between the second port 412 and the third port 413. The supply path 422, 422 ′, the liquid raw material discharge path 423, 423 ′ connecting the first port 411 and the fourth port 414, and the second port 412 and the fourth port 414 are connected. Solvent discharge paths 424, 424 'are provided. The liquid source supply path 421 ′ and the solvent supply path 422 ′ merge together in the vicinity of the third port 413 to be unified. The liquid source discharge path 423 ′ and the solvent discharge path 424 ′ merge together in the vicinity of the fourth port 414 to be unified. An open / close valve 501 is provided between the liquid source supply path 421 and the liquid source supply path 421 ′. An open / close valve 502 is provided between the liquid source supply path 422 and the liquid source supply path 422 ′. An open / close valve 503 is provided between the liquid source supply path 424 and the liquid source supply path 424 ′. An open / close valve 504 is provided between the liquid source supply path 423 and the liquid source supply path 423 ′. The third port 413 and the spray nozzle 431 are connected via a joint portion 480. A carrier gas is supplied into the spray nozzle 431 from the fifth port 433. The liquid raw material supplied from the third port 413 through the joint portion 480 is mixed with the carrier gas supplied from the fifth port 433 in the spray nozzle 431, and the liquid raw material is supplied from the tip of the spray nozzle 431. And a fluid in which the carrier gas is mixed are sprayed.

  When the raw material gas is generated in the conventional vaporizer, the open / close valve 501 is switched to allow the liquid raw material supplied to the first port 411 to flow to the liquid raw material supply path 421, 421 ′, the third port 413, the joint The gas was supplied into the vaporizing chamber via the part 480 and the spray nozzle 431. Further, when the generation of the raw material gas is stopped, the opening / closing valve 501 is closed. At this time, the on-off valve 504 is switched so that the liquid material supplied to the first port 411 flows through the liquid material discharge paths 423 and 423 ′ and is discharged to the outside of the vaporizer through the fourth port 414. It was.

  However, if the generation of the source gas is stopped by switching the path in the block valve 410 as described above, the liquid source may remain in the liquid source supply path 421 ′ or the joint portion 480. (These places where the liquid raw material may remain are called dead spaces. Dead spaces are indicated by hatching in FIG. 16). In some cases, the liquid material remaining in the dead space gradually enters the vaporization chamber and unintentionally generates a raw material gas. In addition, the liquid raw material remaining in the dead space sometimes affects the concentration and flow rate of the raw material gas when the generation of the raw material gas is resumed. For example, when a raw material gas is generated by supplying a predetermined concentration of solvent raw material at a flow rate of 1 cc / min into the vaporization chamber, the liquid raw material remaining in the dead space is mixed with the newly supplied liquid raw material, In some cases, the concentration and flow rate of the source gas are affected. Further, the liquid raw material remaining in the dead space may cause clogging of the liquid raw material supply path 421 ′ and the joint portion 480, and may cause vaporization failure when resuming the generation of the raw material gas.

  To deal with these problems, a method of cleaning the inside of the liquid source supply path 421 ′ and the joint portion 480 with a solvent every time the generation of the source gas is stopped is also conceivable. In such a case, the on-off valve 502 is switched to allow the solvent supplied to the second port 412 to flow through the solvent supply path 422, 422 ′, and enter the vaporizing chamber via the third port 413, the joint portion 480, and the spray nozzle 431. Introduce. However, since the block valve is configured as described above, it has been difficult to sufficiently supply the solvent in the dead space (particularly in the liquid source supply path 421 '). Moreover, if it is necessary to clean the dead space every time the generation of the source gas is stopped, the liquid source and the solvent are wasted and it takes time to switch the stop and restart of the source gas generation. In some cases, the substrate processing cost is increased or the productivity is lowered.

  On the other hand, according to the present embodiment, the fourth ports 14s, 14b, and 14t are directly connected to the spray nozzles 31s, 31b, and 31t without passing through the joints and the like, and the inside of the vaporizers 229s, 229b, and 229t. The flow path of the liquid source (the flow path from the first ports 11s, 11b, and 11t to the vaporization chambers 51s, 51b, and 51t) is configured to be short. Further, according to the present embodiment, the downstream ends of the solvent supply paths 22s ′, 22b ′, and 22t ′ are connected to the vicinity of the on-off valves vs1, vb1, and vt1 in the liquid source supply paths 21s ′, 21b ′, and 21t ′. Therefore, the solvent can be sufficiently supplied to the entire liquid source supply paths 21s ′, 21b ′, and 21t ′ (the solvent is supplied from the upstream side of the liquid source supply paths 21s ′, 21b ′, and 21t ′). Is possible). Therefore, it is possible to solve the above-described problem that has occurred in the conventional vaporizer.

(D) Further, according to the present embodiment, the purge gas flow paths 42s, 42b, 42t are provided between the high temperature member and the low temperature member of the vaporizers 229s, 229b, 229t, and the purge gas flow paths 42s, 42b, 42t are provided. Since the purge gas is circulated, the heat from the high temperature member to the low temperature member can be blocked.

(E) Further, according to the present embodiment, the tip portions of the spray nozzles 31s, 31b, 31t of the vaporizers 229s, 229b, 229t are covered with the nozzle covers 41s, 41b, 41t, and the periphery of the spray nozzles 31s, 31b, 31t. Since the purge gas is circulated through the purge gas passages 42s, 42b, and 42t provided in the nozzle and discharged from the discharge portions 43s, 43b, and 43t into the vaporization pipes 52s, 52b, and 52t, the spray nozzle is generated by the backflow of the vaporized raw material. Contact with 31s, 31b, and 31t, and re-liquefaction of the raw material, and precipitation of the raw material can be prevented. The nozzle covers 41s, 41b, and 41t completely cover portions other than the portions corresponding to the tip surfaces of the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t, and fill the vaporizing chambers 51s, 51b, and 51t. Since the areas of the exposed spray nozzles 31s, 31b, and 31t are minimized, the purge effect by the purge gas can be effectively utilized. Further, since the most advanced portions 34s, 34b, 34t of the spray nozzles 31s, 31b, 31t are not projected into the vaporization tubes 52s, 52b, 52t, the purge effect by the purge gas can be effectively utilized.

(F) Further, according to the present embodiment, the spray nozzles 31s, 31b, and 31t can be prevented from being clogged by the above-described heat shielding effect by the purge gas and the purge effect of the spray nozzle.

(G) Further, according to the present embodiment, in the vaporizers 229s, 229b, and 229t, the particle size of the liquid raw material is set to 2 by the carrier gas that acts as the first stage carrier gas and the purge gas that acts as the second stage carrier gas. By reducing and vaporizing in stages, the particle size of the raw material can be made fine, vaporization failure can be prevented, and the vaporization speed and vaporization efficiency can be increased.

(H) According to the present embodiment, the purge gas flow paths 42s, 42b, and 42t for flowing the purge gas that acts as the second-stage carrier gas are throttled toward the discharge parts 43s, 43b, and 43t, and the discharge parts 43s, Since the flow paths at 43b and 43t are the narrowest, the flow rate of the purge gas acting as the second-stage carrier gas can be increased, and the energy given to the raw material can be increased. Thereby, the particle size of a raw material can be reduced more efficiently, vaporization failure can be prevented, and the vaporization speed and vaporization efficiency can be increased.

(I) According to the present embodiment, the narrow tube portions 36s, 36b, 36t of the spray nozzles 31s, 31b, 31t of the vaporizers 229s, 229b, 229t, and the discharge portions 43s, 43b of the purge gas flow paths 42s, 42b, 42t, 43t is provided in parallel so that the two-phase material discharged from the narrow tube portions 36s, 36b, and 36t and the purge gas discharged from the discharge portions 43s, 43b, and 43t have the same discharge direction. Therefore, the particle diameter of the raw material can be reduced more efficiently, vaporization failure can be prevented, and the vaporization speed and vaporization efficiency can be increased.

(J) According to the present embodiment, the solvent (ECH or the like) for diluting the liquid source into the liquid source flow path of the vaporizers 229s, 229b, 229t when the supply of the liquid source to the vaporizers 229s, 229b, 229t is stopped. Since the vaporizers 229s, 229b, and 229t are supplied and cleaned, the removal of the organometallic liquid source from the liquid source channel is promoted, and the blockage of the organometallic liquid source in the liquid source channel is suppressed. The Note that the cleaning of the vaporizers 229s, 229b, and 229t is performed during film formation and at a time other than the vaporization operation, so that the throughput is not affected. Further, since the amount of the solvent used for the cleaning is set to the minimum necessary, a large amount of the solvent is not consumed.

<Other embodiments of the present invention>
In the above-described embodiment, the downstream end portions of the first source gas supply pipe 213s, the second source gas supply pipe 213b, and the third source gas supply pipe 213t are unified so as to merge, and the source gas supply pipe 213 is joined. Thus, the unified source gas supply pipe 213 is connected to the gas inlet 210, but the present invention is not limited to the above-described embodiment. That is, downstream end portions of the first source gas supply pipe 213s, the second source gas supply pipe 213b, and the third source gas supply pipe 213t are directly connected to the upper surface (ceiling wall) of the shower head 240, respectively. Also good.

  In the above-described embodiment, the downstream end of the ozone gas supply pipe 213o is connected so as to join the source gas supply pipe 213, but the present invention is not limited to the above-described embodiment. That is, the downstream end of the ozone gas supply pipe 213o may be directly connected to the upper surface (ceiling wall) of the shower head 240.

In the above-described embodiment, an example in which a BST (barium strontium titanate) thin film, that is, a (Ba, Sr) TiO ₃ thin film, is formed on the wafer 200 has been described. However, the present invention is not limited to the above-described embodiment. That is, an STO (strontium titanate) thin film, that is, a SrTiO ₃ thin film may be formed on the wafer 200, and another film may be formed.

  In the above-described embodiment, each vaporizer is supplied for each supply operation of each raw material gas to the processing chamber 201 (for each discharge operation of each liquid raw material to the vaporizers 229s, 229b, and 229t). Although the case where the inside of 229s, 229b, and 229t is cleaned has been described, the present invention is not limited to the above-described embodiment. That is, the cleaning in the vaporizers 229s, 229b, and 229t may be performed every plural supply operations (vaporization operations) of each source gas, for example, every two supply operations (vaporization operations). However, cleaning in each of the vaporizers 229s, 229b, and 229t is facilitated by performing cleaning for each supply operation (vaporization operation) as in the above-described embodiment, and the liquid material vaporization operation is more stable. Therefore, it is preferable.

  In the above-described embodiment, the cleaning operation in each of the vaporizers 229s, 229b, and 229t is always performed except when the vaporizing operation is performed. However, the present invention is not limited to the above-described embodiment. For example, the cleaning operation in each of the vaporizers 229s, 229b, and 229t may be stopped at any time other than when the vaporization operation is performed as long as the organometallic liquid source in the liquid source channel is removed.

  Conversely, the cleaning operation in each of the vaporizers 229s, 229b, and 229t may be performed not only when the liquid raw material is vaporized but also when the liquid raw material is vaporized. That is, the cleaning liquid may be continuously supplied into the vaporizers 229s, 229b, and 229t regardless of whether or not the liquid raw material is vaporized. In that case, when performing the vaporization operation of the liquid source, the cleaning liquid supplied into the liquid source channel also functions as a part of the solvent for diluting the liquid source. In this case, as in the above-described embodiment, it is preferable that the solvent for diluting the liquid material and the cleaning liquid are the same substance. When supplying the cleaning liquid during the vaporization operation of the liquid source, the amount of the liquid source, the dilution solvent, and the cleaning liquid are adjusted so that the supply flow rate and concentration of the source gas supplied into the processing chamber 201 become a desired value. It is preferable to adjust the ratio appropriately. In that case, for example, the flow rate of the cleaning liquid supplied at a time other than the liquid material vaporizing operation is larger than the flow rate of the cleaning liquid supplied at the time of the liquid raw material vaporizing operation. You may make it wash | clean actively. In addition, the flow rate of the cleaning liquid supplied during the liquid material vaporization operation and the flow rate of the cleaning liquid supplied at a time other than during the liquid raw material vaporization operation are constant, and the liquid raw material vaporization operation is performed at a time other than the liquid raw material vaporization operation. Each time a predetermined number of times is performed, a flushing operation may be performed in which the flow rate of the cleaning liquid is larger than the flow rate of the cleaning liquid supplied during the vaporizing operation of the liquid material.

Second Embodiment
Next, a second embodiment of the present invention will be described. In the first embodiment described above, an example of forming a film using a single-wafer type ALD apparatus that processes one substrate at a time as a substrate processing apparatus has been described, but the present invention is not limited to the above-described embodiment. . For example, the film may be formed using a batch type vertical ALD apparatus that processes a plurality of substrates at a time as a substrate processing apparatus. The vertical ALD apparatus will be described below.

  FIG. 11 is a schematic configuration diagram of a vertical processing furnace of a vertical ALD apparatus suitably used in the second embodiment. FIG. 11A shows a processing furnace 302 portion in a vertical cross section, and FIG. The furnace 302 part is shown by the AA sectional view of FIG.

  As shown in FIG. 11A, the processing furnace 302 has a heater 307 as a heating means (heating mechanism). The heater 307 has a cylindrical shape and is vertically installed by being supported by a heater base (not shown) as a holding plate.

Inside the heater 307, a process tube 303 as a reaction tube is disposed concentrically with the heater 307. The process tube 303 is made of a heat-resistant material such as quartz (SiO ₂ ) or silicon carbide (SiC), and has a cylindrical shape with the upper end closed and the lower end opened. A processing chamber 301 is formed in a cylindrical hollow portion of the process tube 303 so that wafers 200 as substrates can be accommodated in a state of being aligned in multiple stages in a vertical posture in a horizontal posture by a boat 317 described later.

  A manifold 309 is disposed below the process tube 303 concentrically with the process tube 303. The manifold 309 is made of, for example, stainless steel and is formed in a cylindrical shape with an upper end and a lower end opened. The manifold 309 is engaged with the process tube 303 and is provided to support the process tube 303. An O-ring 320a as a seal member is provided between the manifold 309 and the process tube 303. Since the manifold 309 is supported by the heater base, the process tube 303 is vertically installed. A reaction vessel is formed by the process tube 303 and the manifold 309.

  In the manifold 309, a first nozzle 333a as a first gas introduction part and a second nozzle 333b as a second gas introduction part penetrate through the side wall of the manifold 309, and a part thereof is a processing chamber. 301 is connected so as to communicate with each other. Each of the first nozzle 333 a and the second nozzle 333 b has an L shape having a horizontal portion and a vertical portion, the horizontal portion is connected to the manifold 309, and the vertical portion of the process tube 303 constituting the processing chamber 301. An arc-shaped space between the inner wall and the wafer 200 is provided on the inner wall above the lower portion of the process tube 303 along the loading direction of the wafer 200. A first gas supply hole 348a and a second gas supply hole 348b, which are supply holes for supplying gas, are provided on the side surfaces of the vertical portions of the first nozzle 333a and the second nozzle 333b, respectively. The first gas supply hole 348a and the second gas supply hole 348b have the same opening area from the lower part to the upper part, and are provided at the same opening pitch.

  The gas supply system connected to the first nozzle 333a and the second nozzle 333b is the same as in the above-described embodiment. However, the present embodiment is different from the above-described embodiment in that the source gas supply pipe 213 is connected to the first nozzle 333a and the ozone gas supply pipe 213o is connected to the second nozzle 333b. That is, in this embodiment, source gas (1st source gas, 2nd source gas, 3rd source gas) and ozone gas are supplied by a separate nozzle. In addition, you may make it supply each raw material gas with a separate nozzle.

  The manifold 309 is provided with an exhaust pipe 331 that exhausts the atmosphere in the processing chamber 301. As a vacuum exhaust device, a pressure sensor 345 as a pressure detector and an APC (Auto Pressure Controller) valve 342 as a pressure regulator are provided on the downstream side opposite to the connection side of the exhaust pipe 331 with the manifold 309. The vacuum pump 346 is connected so that the pressure in the processing chamber 301 can be evacuated to a predetermined pressure (degree of vacuum). The APC valve 342 is opened and closed so that the processing chamber 301 can be evacuated and stopped by evacuation, and the pressure in the processing chamber 301 can be adjusted by adjusting the valve opening. It is a valve.

  Below the manifold 309, a seal cap 319 is provided as a furnace port lid that can airtightly close the lower end opening of the manifold 309. The seal cap 319 is brought into contact with the lower end of the manifold 309 from the lower side in the vertical direction. The seal cap 319 is made of a metal such as stainless steel and is formed in a disk shape. On the upper surface of the seal cap 319, an O-ring 320b is provided as a seal member that comes into contact with the lower end of the manifold 309. On the opposite side of the seal cap 319 from the processing chamber 301, a rotation mechanism 367 for rotating a boat 317 described later is installed. A rotation shaft 355 of the rotation mechanism 367 passes through the seal cap 319 and is connected to the boat 317, and is configured to rotate the wafer 200 by rotating the boat 317. The seal cap 319 is configured to be moved up and down in the vertical direction by a boat elevator 315 as an elevating mechanism disposed vertically outside the process tube 303, whereby the boat 317 is carried into and out of the processing chamber 301. It is possible to do.

  The boat 317 as a substrate holder is made of a heat-resistant material such as quartz or silicon carbide, and is configured to hold a plurality of wafers 200 in a horizontal posture and in a state where the centers are aligned with each other and held in multiple stages. Yes. A heat insulating member 318 made of a heat resistant material such as quartz or silicon carbide is provided at the lower part of the boat 317 so that heat from the heater 307 is not easily transmitted to the seal cap 319 side. Note that the heat insulating member 318 may be configured by a plurality of heat insulating plates made of a heat resistant material such as quartz or silicon carbide, and a heat insulating plate holder that holds the heat insulating plates in a horizontal posture in multiple stages. A temperature sensor 363 as a temperature detector is installed in the process tube 303, and the temperature in the processing chamber 301 is adjusted by adjusting the power supply to the heater 307 based on the temperature information detected by the temperature sensor 363. Is configured to have a predetermined temperature distribution. The temperature sensor 363 is provided along the inner wall of the process tube 303, similarly to the first nozzle 333a and the second nozzle 333b.

  The controller 380 as a control unit (control means) includes an APC valve 342, a heater 307, a temperature sensor 363, a vacuum pump 346, a rotation mechanism 367, a boat elevator 315, vaporizers 229s, 229b, and 229t, an ozonizer 229o, a block valve 10s, 10b, 10t, open / close valves vs1 to vs10, vb1 to vb10, vt1 to vt10, vo3 to vo6, liquid flow rate controllers 221s, 221b, 221t, 222s, 222b, 222t, flow rate controllers 224s, 224b, 224t, 225s, 225b, 225t , 226s, 226b, 226t, 221o, 222o, 224o and the like are controlled.

  Next, a substrate processing process for forming a thin film on the wafer 200 by the ALD method will be described as one process of the manufacturing process of the semiconductor device using the processing furnace 302 of the vertical ALD apparatus according to the above configuration. In the following description, the operation of each part constituting the vertical ALD apparatus is controlled by the controller 380.

A plurality of wafers 200 are loaded into the boat 317 (wafer charge). And FIG.
As shown in (a), the boat 317 holding a plurality of wafers 200 is lifted by the boat elevator 315 and loaded into the processing chamber 301 (boat loading). In this state, the seal cap 319 is in a state of sealing the lower end of the manifold 309 via the O-ring 320b.

  The processing chamber 301 is evacuated by a vacuum pump 346 so that a desired pressure (degree of vacuum) is obtained. At this time, the pressure in the processing chamber 301 is measured by the pressure sensor 345, and the APC valve 342 is feedback-controlled based on the measured pressure. In addition, heating is performed by the heater 307 so that the inside of the processing chamber 301 has a desired temperature. At this time, feedback control of the power supply to the heater 307 is performed based on the temperature information detected by the temperature sensor 363 so that the inside of the processing chamber 301 has a desired temperature distribution. Then, the wafer 200 is rotated by rotating the boat 317 by the rotation mechanism 367.

Thereafter, as in the first embodiment, the ALD process (S6) using the first source gas, the ALD process (S7) using the third source gas, and the ALD process (S8) using the second source gas. The ALD process (S9) using the third source gas is set as one cycle, and this cycle is repeated a predetermined number of times (S10), thereby forming a (Ba, Sr) TiO ₃ thin film having a desired film thickness on the wafer 200. .

  Thereafter, the seal cap 319 is lowered by the boat elevator 315 to open the lower end of the manifold 309, and the lower end of the manifold 309 is held in the state where the wafer 200 after the thin film having a desired film thickness is held on the boat 317. From the process tube 303 to the outside (boat unloading). Thereafter, the processed wafer 200 is taken out from the boat 317 (wafer discharge).

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

  According to one aspect of the present invention, a vaporizing chamber for vaporizing a liquid source, a heater for heating the vaporizing chamber, a spray nozzle for spraying a liquid source into the vaporizing chamber, a carrier gas into the spray nozzle, and a liquid There is provided a vaporizer having a valve for controlling the supply of the raw material and the solvent, wherein the valve is directly connected to the spray nozzle.

  According to another aspect of the present invention, a processing chamber for processing a substrate, a vaporizer that vaporizes a liquid raw material, a liquid raw material supply system that supplies the liquid raw material to the vaporizer, and a carrier gas that is supplied to the vaporizer A carrier gas supply system, a solvent supply system for supplying a solvent to the vaporizer, a raw material gas supply system for supplying a raw material gas obtained by vaporizing a liquid raw material in the vaporizer into the processing chamber, and the raw material gas A reaction gas supply system for supplying different reaction gases into the processing chamber, and the vaporizer includes a vaporization chamber for vaporizing a liquid source, a heater for heating the vaporization chamber, and a liquid source for the vaporization chamber. There is provided a substrate processing apparatus having a spray nozzle for spraying, and a valve for controlling supply of carrier gas, liquid raw material and solvent into the spray nozzle, and the valve is directly connected to the spray nozzle. The

According to still another aspect of the present invention, a step of carrying a substrate into the processing chamber, a vaporizing chamber for vaporizing the liquid source, a heater for heating the vaporizing chamber, and a spray nozzle for spraying the liquid source into the vaporizing chamber. A vaporizer directly connected to the spray nozzle and controlling supply of carrier gas, liquid source and solvent into the spray nozzle, and supplying at least carrier gas and liquid source into the spray nozzle Spraying a liquid source from the spray nozzle and vaporizing the liquid source in the vaporizing chamber; and supplying a source gas obtained by vaporizing the liquid source in the vaporizer into the processing chamber and processing the substrate; And a step of carrying out a processed substrate from the processing chamber.

10s, 10b, 10t Valve 31s, 31b, 31t Spray nozzle 51b, 51b, 51t Evaporation chamber 61b, 61b, 61t Heater 200 Wafer (substrate)
201 processing chamber 229s, 229b, 229t vaporizer

Claims (3)

A vaporization chamber for vaporizing the liquid raw material;
A heater for heating the vaporization chamber;
A spray nozzle for spraying a liquid raw material into the vaporization chamber;
A valve for controlling the supply of carrier gas, liquid raw material and solvent into the spray nozzle,
The vaporizer is characterized in that the valve is directly connected to the spray nozzle. A processing chamber for processing the substrate;
A vaporizer for vaporizing the liquid raw material;
A liquid source supply system for supplying a liquid source to the vaporizer;
A carrier gas supply system for supplying a carrier gas to the vaporizer;
A solvent supply system for supplying a solvent to the vaporizer;
A raw material gas supply system for supplying a raw material gas obtained by vaporizing a liquid raw material in the vaporizer into the processing chamber;
A reaction gas supply system for supplying a reaction gas different from the source gas into the processing chamber,
The vaporizer includes a vaporizing chamber for vaporizing a liquid raw material, a heater for heating the vaporizing chamber, a spray nozzle for spraying the liquid raw material into the vaporizing chamber, a carrier gas, a liquid raw material, and a solvent into the spray nozzle. A valve for controlling the supply,
The substrate processing apparatus, wherein the valve is directly connected to the spray nozzle. A step of carrying the substrate into the processing chamber;
A vaporizing chamber for vaporizing a liquid source, a heater for heating the vaporizing chamber, a spray nozzle for spraying the liquid source into the vaporizing chamber, a carrier gas, a liquid source and a solvent directly connected to the spray nozzle and into the spray nozzle And at least a carrier gas and a liquid raw material are supplied into the spray nozzle, the liquid raw material is sprayed from the spray nozzle, and the liquid raw material is vaporized in the vaporization chamber. Process,
Supplying a source gas obtained by vaporizing a liquid source with the vaporizer into the processing chamber and processing the substrate;
And a step of unloading the processed substrate from the processing chamber.