JP5004890B2 - Vaporizer, substrate processing apparatus, and method for manufacturing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To inhibit the clogging of the spray nozzle of a vaporizer and the deposition of the raw material on the surface of the spray nozzle, thereby enhancing vaporization efficiency. <P>SOLUTION: The vaporizer includes a vaporizing chamber for vaporizing a liquid raw material, a heater for heating the interior of the vaporizing chamber, a mixer for mixing the liquid raw material and a carrier gas, a spray nozzle for spraying the liquid raw material which has been mixed with the carrier gas in the mixer into the vaporizing chamber, a cooling member for cooling the spray nozzle and the mixer, and a cover for covering a part of the surface of the leading edge of the spray nozzle so as to be separated from the vaporizing chamber and forming a flow path for delivering a purge gas around the leading edge of the spray nozzle. A projection is provided to the center of the most leading edge of the leading edge of the spray nozzle. A spraying aperture is formed at the leading edge surface of the projection. A portion of the cover corresponding to the leading edge surface of the projection is open. The side of the projection is covered by the cover. A discharge hole is provided in a clearance between the side of the projection and the cover to discharge the purge gas delivered around the leading edge of the spray nozzle inside the vaporizing chamber. <P>COPYRIGHT: (C)2010,JPO&amp;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. There is a vaporizer as an apparatus for vaporizing a liquid raw material. The vaporizer includes, for example, a vaporization chamber (vaporization tube) that vaporizes the liquid raw material to generate gas, a raw material flow path that carries the liquid raw material into the vaporization chamber, a spray nozzle that sprays the liquid raw material into the vaporization chamber, have.

  In a vaporizer that vaporizes liquid raw materials that are liquid at room temperature and solution raw materials obtained by diluting highly viscous liquid raw materials or solid raw materials with a solvent, in order to increase the vaporization speed, the particle size of the raw materials should be as small as possible Need to be sprayed on. In order to reduce the particle size of the liquid raw material, it is known that a two-fluid nozzle that mixes the carrier gas and the raw material and sprays the mixture into the vaporizing chamber is effective. As for the vaporizer that applies the two-fluid nozzle to the spray mechanism, an internal mixing type in which the carrier gas and the raw material are mixed on the upstream side of the raw material flow path into the vaporizing chamber and then sprayed (see Patent Document 1), There is an external mixing type in which a carrier gas and a raw material are mixed at the time of supply (see Patent Document 2). In general, the external mixing method can reduce the particle size of the liquid raw material.

JP 2006-108230 A JP 2007-46084 A

  By the way, the sprayed raw material must be completely vaporized in the vaporization chamber. Since there is a temperature drop due to the heat of vaporization, the vaporization chamber is generally heated and held at a constant temperature by a heater or the like in order to ensure the vapor pressure of the raw material. The configuration of these vaporizers has been subject to the following problems.

  In the case of a vaporizer having an external mixing type two-fluid nozzle, since the raw material before mixing with the carrier gas faces the high-temperature vaporization chamber, the raw material becomes hot, and preferential evaporation of the solvent (so-called jump-on phenomenon) Thermal decomposition of the raw material is likely to occur, which may cause clogging of the solution nozzle. As countermeasures, methods such as inserting a nozzle cleaning process with a solvent between the raw material vaporization processes such as after the film forming process, or decreasing the concentration by increasing the solvent dilution ratio are taken, but the throughput deteriorates due to the insertion of the cleaning process In addition, large consumption of solvents and reduction in vaporization are inevitable.

  On the other hand, in the case of the internal mixing method, although the particle size at the time of spraying is somewhat large, the raw material itself does not directly face the high temperature part, which is advantageous in terms of preventing clogging. However, the tip of the spray nozzle needs to have a narrower flow path and a pressure difference in order to prevent clogging due to solvent jump. Furthermore, a method is adopted in which the flow path between the carrier gas and the raw material is set to a temperature at which the raw material and the solvent do not boil or undergo thermal decomposition. Since the set temperature is lower than the vaporization tube (vaporization chamber) temperature set for raw material vaporization, the temperature at the tip of the spray nozzle must be lower than the inner surface temperature of the vaporization tube, and as a result, once vaporized. The raw material diffused in the vaporizing tube touches the low temperature region such as the tip of the spray nozzle and reliquefies. In the case of a solution raw material, a solid or highly viscous raw material is precipitated, and foreign matter is generated due to clogging of the spray nozzle or peeling of the precipitate. In order to prevent the deposition of raw materials, the suppression of deposits by heating, purging, and washing with a solvent are employed. Although the adhering matter can be suppressed by heating the tip of the nozzle to near the vaporization temperature, the raw material is thermally decomposed in the flow path, or the solvent jumps first, and the spray nozzle is blocked or foreign matter is generated. Further, when the heating temperature is low, the effect of preventing precipitation is low, and conversely, the deposited raw material is changed by heat and cannot be removed by purging or washing. Inhibiting the reattachment of raw material to the nozzle by flowing a gas such as an inert gas around the spray nozzle in the vaporizing tube and purging the nozzle part with the gas has a certain effect, but the raw material that vaporizes the nozzle in the vaporizing tube It is difficult to protect from contact with the gas, and increasing the gas flow rate in the vaporization tube causes vaporization failure due to pressure increase or temperature decrease in the vaporization tube. Also, cleaning with a solvent causes a deterioration in throughput and a large amount of solvent consumption as in the external mixing method.

  An object of the present invention is to provide a vaporizer capable of suppressing vaporization nozzle blockage of a vaporizer and deposition of a raw material on the surface of the spray nozzle and increasing vaporization efficiency. 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 mixing unit for mixing the liquid source and a carrier gas, and a carrier gas mixed with the mixing unit. A spray nozzle for spraying the liquid raw material into the vaporizing chamber, a cooling member for cooling the spray nozzle and the mixing portion, and a part of the surface of the tip portion of the spray nozzle are covered so as to be isolated from the vaporizing chamber. And a cover that forms a flow path for allowing a purge gas to flow around the tip portion of the spray nozzle, and a protrusion is provided at a central tip of the tip portion of the spray nozzle. A spray port is formed on the tip surface of the cover, a portion corresponding to the tip surface of the projection of the cover is open, a side surface of the projection is covered by the cover, and a side surface of the projection Wherein a gap between the cover and the tip portion of the carburetor discharge port for discharging the purge gas was passed through the vaporization chamber around is provided in the spray nozzle is provided.

  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 purge gas supply system for supplying a purge gas to the vaporizer, a raw material gas supply system for supplying a raw material gas obtained by vaporizing the 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, a liquid source and a carrier gas. A mixing part for mixing the liquid source, a spray nozzle for spraying the liquid raw material mixed with the carrier gas in the mixing part into the vaporizing chamber, a cooling member for cooling the spray nozzle and the mixing part, and the spray nozzle A cover that covers a part of the surface of the tip portion of the spray nozzle so as to be isolated from the vaporizing chamber, and that forms a flow path for allowing purge gas to flow around the tip portion of the spray nozzle. A projection is provided at the center most distal end portion of the tip portion, a spray port is formed on the tip surface of the projection portion, and a portion corresponding to the tip surface of the projection portion of the cover is open, A side surface of the projection is covered with the cover, and a purge gas circulated around the tip portion of the spray nozzle is discharged into the vaporization chamber into a gap between the side of the projection and the cover. A substrate processing apparatus provided with a discharge port is provided.

  According to still another aspect of the present invention, the step of carrying the substrate into the processing chamber, the vaporizing chamber for vaporizing the liquid source, the heater for heating the vaporizing chamber, and the mixing unit for mixing the liquid source and the carrier gas. A spray nozzle that sprays the liquid raw material mixed with the carrier gas in the mixing section into the vaporization chamber, a cooling member that cools the spray nozzle and the mixing section, and a surface of the tip portion of the spray nozzle. And a cover that forms a flow path for circulating a purge gas around the tip portion of the spray nozzle, and covers the portion so as to be isolated from the vaporizing chamber, and the tip of the center of the tip portion of the spray nozzle The projection portion is provided on the portion, and a spray port is formed on the distal end surface of the projection portion, a portion corresponding to the distal end surface of the projection portion of the cover is open, and a side surface of the projection portion is Hippopotamus A vaporizer provided with a discharge port for discharging the purge gas circulated around the tip portion of the spray nozzle into the vaporization chamber in a gap between the side surface of the protrusion and the cover. A step of spraying a liquid raw material mixed with a carrier gas from the spraying port while discharging a purge gas from the discharge port into the vaporizing chamber and vaporizing the liquid raw material in the vaporizing chamber; and the vaporizer in the processing chamber A method for manufacturing a semiconductor device is provided, which includes a step of supplying a source gas obtained by vaporizing a liquid source and processing a substrate, and a step of unloading the processed substrate from the processing chamber.

  ADVANTAGE OF THE INVENTION According to this invention, the vaporizer which can suppress the spray nozzle obstruction | occlusion of a vaporizer and precipitation of the raw material to the spray nozzle surface, and can raise vaporization efficiency can be provided. Also, a substrate processing apparatus for processing a substrate with a raw material gas obtained by vaporizing a liquid raw material with the vaporizer, and a method for manufacturing a semiconductor device comprising a step of processing the substrate with a raw material gas obtained by vaporizing the liquid raw material with the vaporizer Can be provided.

(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 chamber>
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. Note that 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, and the spaces are supplied from the gas inlet 210. Function as a dispersion chamber (first buffer space) 240c for dispersing gas and a second buffer space 240d for diffusing the gas that has passed through the dispersion plate 240a.

<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 exhausting (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 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 FIGS. 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, and FIG. 6 is a schematic configuration of a vaporizer according to the first embodiment of the present invention. FIG. 7 is a partially enlarged view of the vicinity of the spray nozzle of the spray nozzle of the vaporizer of FIG.

  The gas supply system of the substrate processing apparatus according to the first embodiment of the present invention includes a vaporization unit that vaporizes a liquid material, a liquid material supply system that supplies the liquid material to the vaporization unit, and a carrier gas that is supplied to the vaporization unit. A carrier gas supply system, a purge gas supply system for supplying a purge gas to the vaporization section (for the vaporization section), a cleaning liquid supply system for supplying a cleaning liquid (solvent) to the vaporization section (solvent supply system), and a liquid source in the vaporization section A source gas supply system that supplies the vaporized source gas into the process chamber 201 and a reaction gas supply system that supplies a reaction gas different from the source gas into the process chamber 201 are provided. Furthermore, the substrate processing apparatus according to the first embodiment of the present invention has a purge gas supply system (for piping and processing chambers) and a vent (bypass) system. Below, the structure of each part is demonstrated.

<Liquid 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 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. 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 connected to vaporizers 229s, 229b, and 229t as vaporizers that vaporize the liquid source. Each is connected. 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 and open / close valves vs1, vb1 and vt1 for controlling the supply of the liquid raw material are provided, respectively.

  With the above configuration, the first and second pressure-feeding gas supply pipes 237s, the second pressure-feeding gas supply pipe 237b, and the third pressure-feeding gas supply pipe 237t are supplied with the first and second pressure-feeding gas supply pipes 237s and 237t. The liquid material can be pumped (supplied) from the liquid material supply source 220s, the second liquid material supply source 220b, and the third liquid material supply source 220t to the vaporizers 229s, 229b, and 229t. 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, respectively. The first carrier gas supply pipe 218s, the second carrier gas supply pipe 218b, and the third carrier gas supply pipe 218t include flow rate controllers (MFCs) 225s and 225b as flow rate control means for controlling the supply flow rate of N ₂ gas. , 225t, and open / close valves vs7, vb7, vt7 for controlling the supply of N ₂ gas, respectively. 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 vaporization section)>
The N ₂ gas supply source 230n provided outside the processing chamber 201 also serves as a purge gas supply source for purging the components of the vaporizer as the 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, and 226t as flow rate control means for controlling the supply flow rate of 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.

<Vaporization part>
As shown in FIG. 6, the vaporizers 229s, 229b, and 229t as vaporizers that vaporize the liquid raw material mainly include vaporization chambers 51s, 51b, and 51t, heaters 61s, 61b, and 61t, It has spray nozzles 31s, 31b, 31t, mixing pipe sections 21s, 21b, 21t, low temperature plates 11s, 11b, 11t, and nozzle covers 41s, 41b, 41t.

  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 vaporization tubes 52s, 52b, and 52t as vaporization containers. Heaters 61s, 61b, 61t as heating means (heating mechanisms) are provided around the vaporization tubes 52s, 52b, 52t, and the liquid raw material sprayed in the vaporization chambers 51s, 51b, 51t is heated and vaporized. It is configured as follows. 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, 54t for discharging the source gas into the source gas supply pipes 213s, 213b, 213t are provided.

  Spray nozzles 31s, 31b, and 31t as spray sections are provided in the inlets 53s, 53b, and 53t of the vaporization tubes 52s, 52b, and 52t, and the spray nozzles 31s, 31b, and 31t are disposed in the vaporization chambers 51s, 51b, and 51t. The liquid raw material is sprayed on. 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, and 31t, that is, the tip portions 33s, 33b, and 33t and the tip portions 34s, 34b, and 34t protrude into the vaporization tubes 52s, 52b, and 52t (vaporization chambers 51s, 51b, and 51t). Arranged not to.

  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 to prevent the spray nozzles 31s, 31b, and 31t from being blocked due to the solvent jumping phenomenon. 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 portions corresponding to the main body portions 32s, 32b, and 32t and the tip portions 33s, 33b, and 33t, The thin tube portions 36s, 36b, and 36t are provided in portions corresponding to the tip portions 33s, 33b, and 33t and the most distal 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.

  Above the spray nozzles 31s, 31b, 31t, mixing pipe parts 21s, 21b, 21t are provided as mixing parts. The mixing pipe parts 21s, 21b, 21t mix liquid raw material and carrier gas. The mixed fluid is introduced into the spray nozzles 31s, 31b, 31t. In the mixing pipe portions 21s, 21b, and 21t, liquid raw material pipes 22s, 22b, and 22t that supply liquid raw materials, carrier gas pipes 23s, 23b, and 23t that supply carrier gas, and liquid raw material pipes 22s, 22b, and 22t, Mixing pipes 25s, 25b, and 25t formed by joining the carrier gas pipes 23s, 23b, and 23t are provided. Liquid source supply pipes 211s, 211b, and 211t are connected to the liquid source pipes 22s, 22b, and 22t, and carrier gas supply pipes 218s, 218b, and 218t are connected to the carrier gas pipes 23s, 23b, and 23t. Yes. In addition, fluid flow paths 35s, 35b, and 35t of spray nozzles 31s, 31b, and 31t are connected to the mixing pipes 25s, 25b, and 25t. The liquid source is supplied from the liquid source supply pipes 211s, 211b, and 211t to the mixing pipes 25s, 25b, and 25t via the liquid source pipes 22s, 22b, and 22t, and the carrier gas is supplied from the carrier gas supply pipes 218s, 218b, and 218t. It is supplied into the mixing pipes 25s, 25b and 25t via the carrier gas pipes 23s, 23b and 23t. The liquid raw material and the carrier gas are mixed in the first mixing sections 24s, 24b, and 24t and supplied into the mixing pipes 25s, 25b, and 25t, and the fluid flow paths 35s, 35b, and 35t of the spray nozzles 31s, 31b, and 31t are supplied. be introduced.

  Low temperature plates 11s, 11b, and 11t as cooling means (cooling mechanisms) are provided below the mixing pipe portions 21s, 21b, and 21t and around the main body portions 32s, 32b, and 32t of the spray nozzles 31s, 31b, and 31t. It has been. The low temperature plates 11s, 11b, and 11t, which are cooling members, are provided so as to be in contact with both the mixing pipe portions 21s, 21b, and 21t and the spray nozzles 31s, 31b, and 31t. The low temperature plates 11s, 11b, and 11t are configured to circulate cooling water inside, for example, and cool the spray nozzles 31s, 31b, and 31t and the mixing pipe portions 21s, 21b, and 21t, and spray nozzles 31s, 31b. , 31t and the temperature of the liquid raw material and the solvent in the mixing pipe portions 21s, 21b, 21t are set so as not to boil or pyrolyze. 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 11s, 11b, and 11t and above the vaporization chambers 51s, 51b, and 51t and the heaters 61s, 61b, and 61t and around the tip portion side of the spray nozzles 31s, 31b, and 31t. 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 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. Purge gas supply pipes 219s, 219b, and 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. 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, and pass through the narrow tube portions 36s, 36b, 36t. The liquid raw material mixed with the carrier gas and the purge gas that has passed through the discharge 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 first mixing parts 24s, 24b, 24t is this part, that is, the discharge parts 43s, 43b, 43t of the purge gas flow paths 42s, 42b, 42t and the spray nozzle 31s. , 31b and 31t are mixed with an inert gas as a purge gas at the portions of the inlets 53s, 53b and 53t of the vaporizing tubes 52s, 52b and 52t provided with the narrow tube portions 36s, 36b and 36t. 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 11s, 11b, and 11t, the spray nozzles 31s, 31b, and 31t, and the mixing pipe portions 21s, 21b, and 21t suppress clogging due to the thermal decomposition of the raw material in the pipe and the flow path and the jumping phenomenon of the solvent. Therefore, it is kept 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 11s, 11b, and 11t, the spray nozzles 31s, 31b, and 31t, and the mixing pipe portions 21s, 21b, and 21t are the vaporization chambers 51s, 51b, and 51t, the heaters 61s, 61b, and 61t, and the nozzle covers 41s and 41b. , 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 11s, 11b, 11t, spray nozzle 31s, 31b). , 31t, and the mixing pipes 21s, 21b, 21t), it is considered that the purge gas flow paths 42s, 42b, 42t are provided between the high temperature member and the low temperature member, and the purge gas flow path 42s. , 42b, and 42t, the heat from the high temperature member to the low temperature member is blocked by flowing the purge gas.

  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 liquid source supply pipes 211s, 211b, and 211t into the liquid source pipes 22s, 22b, and 22t, and the carrier gas is supplied from the carrier gas supply pipes 218s, 218b, and 218t to the carrier gas pipes 23s and 23b. , 23t, the liquid raw material and the carrier gas are mixed in the first mixing sections 24s, 24b, 24t. 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 pipes 25s, 25b, and 25t, 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 is discharged from the purge gas supply pipes 219s, 219b, and 219t into the vaporization chambers 51s, 51b, and 51t through the purge gas flow paths 42s, 42b, and 42t and the discharge portions 43s, 43b, and 43t. 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.

<Raw gas supply system>
A first source gas supply pipe 213s for supplying a source gas into the processing chamber 201 and a second source gas supply are supplied to the outlets 54s, 54b, 54t of the vaporizer tubes 52s, 52b, 52t of the vaporizers 229s, 229b, 229t. The upstream end of the pipe 213b and the third source gas supply pipe 213t are 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 source is vaporized by the vaporizers 229s, 229b, and 229t to generate the source gas, and the first source gas supply pipe 213s and the second source 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).

<Cleaning liquid supply system (solvent supply system)>
In addition, a cleaning liquid supply source (solvent 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 cleaning liquid supply source 220e is configured as a tank (sealed container) capable of containing (filling) the cleaning liquid therein. The cleaning liquid is not limited to ECH, and a solvent such as THF (tetrahydrofuran) can be used.

Here, a cleaning liquid supply gas supply pipe 237e is connected to the cleaning liquid supply source 220e. A pressure gas supply source (not shown) is connected to the upstream end of the cleaning liquid pressure gas supply pipe 237e. The downstream end of the cleaning liquid pressure feed gas supply pipe 237e communicates with a space existing in the upper part of the cleaning liquid supply source 220e, and is configured to supply the pressure gas into this space. Note that an inert gas such as Ar gas or N ₂ gas is preferably used as the pressurized gas.

  Further, a cleaning liquid supply pipe (solvent supply pipe) 212 is connected to the cleaning liquid supply source 220e. The upstream end of the cleaning liquid supply pipe 212 is immersed in the cleaning liquid stored in the cleaning liquid supply source 220e. The downstream end of the cleaning liquid supply pipe 212 is connected to be branched into three lines, that is, a first cleaning liquid supply pipe 212s, a second cleaning liquid supply pipe 212b, and a third cleaning liquid supply pipe 212t. The downstream ends of the first cleaning liquid supply pipe 212s, the second cleaning liquid supply pipe 212b, and the third cleaning liquid supply pipe 212t are the first liquid raw material supply pipe 211s and the second liquid raw material supply before the vaporizers 229s, 229b, and 229t. The pipe 211b and the third liquid source supply pipe 211t are connected to each other. The first cleaning liquid supply pipe 212s, the second cleaning liquid supply pipe 212b, and the third cleaning liquid supply pipe 212t include liquid flow rate controllers (LMFC) 222s, 222b, and 222t as flow rate control means for controlling the supply flow rate of the cleaning liquid. Open / close valves vs2, vb2, and vt2 for controlling the supply of the cleaning liquid are respectively provided.

  With the above configuration, the liquid in the vaporizers 229s, 229b, and 229t is supplied by supplying the pressurized gas from the cleaning liquid pressurized gas supply pipe 237e, closing the open / close valves vs1, vb1, and vt1, and opening the open / close valves vs2, vb2, and vt2. Cleaning fluid in the raw material passages, that is, the liquid raw material pipes 22s, 22b, and 22t, the mixing pipes 25s, 25b, and 25t, the fluid passages 35s, 35b, and 35t in the spray nozzles 31s, 31b, and 31t, and the narrow pipe portions 36s, 36b, and 36t. These liquid source channels can be cleaned by pressure feeding (supply). Mainly, a cleaning liquid supply source 220e, a cleaning liquid pressure feed gas supply pipe 237e, a cleaning liquid supply pipe 212, a first cleaning liquid supply pipe 212s, a second cleaning liquid supply pipe 212b, a third cleaning liquid 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.

  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. 261 is connected to the downstream side of the raw material recovery trap 263 and to 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 and 229t, an ozonizer 229o, a vacuum pump 264, open / close valves vs1 to vs8, vb1. vb8, vt1 to vt8, 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 Etc. are controlled.

(2) 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 Placement 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 adjusting step (S3), temperature raising 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, while the on-off valve vs2 is closed, the on-off valve vs1 is opened, and the pressurized gas is supplied from the first pressurized gas supply pipe 237s, and the first liquid source is supplied from the first liquid source supply source 220s to the vaporizer 229s. Is pumped (supplied). 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. In this manner, the first liquid source is vaporized by the vaporizer 229s to generate the first source gas. 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. Therefore, in the present 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 execution of the preliminary vaporization step, the on-off valves vb2 and vt2 are opened, the cleaning liquid (solvent) is supplied into the liquid raw material flow paths of the vaporizers 229b and 229t, and cleaning of the vaporizers 229b and 229t is started. At this time, the opening / closing valves vb7, vt7 are opened to supply the carrier gas (N ₂ gas) from the N ₂ gas supply source 230n to the vaporizers 229b, 229t, and the opening / closing valves vb8, vt8 are further 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 on-off valves vb7 and vt7 and the on-off valves vb8 and vt8 are always kept open 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 in the vaporizer 229b. , 229t. 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 is closed, and the supply of the first liquid material to the vaporizer 229s is also stopped. The open / close valve vs7 and open / close 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 opening / closing valve vs1 and stopping the supply of the first liquid raw material, cleaning of the vaporizer 229s is started (PS1 to PS1). That is, while supplying the pressurized gas from the cleaning liquid pressurized gas supply pipe 237e, the open / close valve vs2 is opened while the open / close valve vs1 is closed, and the cleaning liquid is supplied into the liquid raw material flow path of the vaporizer 229s. The inside of the liquid source flow path is cleaned. 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 are exhausted from the vent pipe 215s by bypassing the processing chamber 201 without being supplied into the processing chamber 201 through the first source gas supply pipe 213s. The 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. In addition, 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, the supply of the carrier gas and the purge gas to the vaporizer 229t is continued, the on-off valve vt2 is closed, the on-off valve vt1 is opened, and the third pressurized gas supply A pressurized gas is supplied from the tube 237t, a third liquid source is supplied from the third liquid source supply source 220t to the vaporizer 229t, and the third liquid source is vaporized by the vaporizer 229t. 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 on-off valve vt1 is closed, and the supply of the third liquid material to the vaporizer 229t is also stopped. 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).

  In addition, after closing the opening / closing valve vt1 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 cleaning liquid pressurized gas supply pipe 237e, the open / close valve vt2 is opened while the open / close valve vt1 is closed, and the cleaning liquid is supplied into the liquid raw material flow path of the vaporizer 229t. Clean inside. 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 are exhausted from the vent pipe 215t by bypassing the processing chamber 201 without being supplied into the processing chamber 201 through the third source gas supply pipe 213t. The 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, with the opening / closing valve vb7 and the opening / closing valve vb8 kept open, the supply of the carrier gas and the purge gas to the vaporizer 229b is continued, the opening / closing valve vb2 is closed, the opening / closing valve vb1 is opened, and the second pressure gas supply The pumping gas is supplied from the tube 237b, the second liquid source is supplied from the second liquid source supply source 220b to the vaporizer 229b, the second liquid source is vaporized by the vaporizer 229b, and the second source gas is supplied. Let it be generated. 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.

  When 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 on-off valve vb1 is closed and the supply of the second liquid material to the vaporizer 229b is also stopped. 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 on-off valve vb1 and stopping the supply of the second liquid raw material, cleaning in the vaporizer 229b is started (PB1). That is, while supplying the pressurized gas from the cleaning liquid pressurized gas supply pipe 237e, the open / close valve vb2 is opened while the open / close valve vb1 is closed, and the cleaning liquid is supplied into the liquid raw material flow path of the vaporizer 229b. Clean inside. 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 are exhausted from the vent pipe 215b by bypassing the processing chamber 201 without being supplied into the processing chamber 201 through the second source gas supply pipe 213b. The 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 cleaning of the vaporizer 229b is continued, for example, until the next supply start of the second liquid material to the vaporizer 229b (until the next Ti in S7).

  When the purge in the processing chamber 201 is completed, the on-off valves vo4 and vo5 are closed, the on-off 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. In addition, 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 ~). That is, with the on-off valve vt7 and the on-off valve vt8 kept open, the supply of the carrier gas and the purge gas to the vaporizer 229t is continued, the on-off valve vt2 is closed, the on-off valve vt1 is opened, and the third pressurized gas supply The pumping gas is supplied from the tube 237t, the third liquid source is supplied from the third liquid source supply source 220t to the vaporizer 229t, the third liquid source is vaporized by the vaporizer 229t, and the third source gas is supplied. Let it be generated. In the ALD process (S8) using the second 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. As described above, 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 (S9) using the third source gas, which will be described later. Switch. Thereby, in the ALD process (S9) 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 (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.

<Repetition 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.

(3) Effects according to the first embodiment 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 path 42s. , 42b, 42t, the purge gas is circulated, so that heat from the high temperature member to the low temperature member can be blocked.

  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 are provided around the spray nozzles 31s, 31b, 31t. Since the purge gas is circulated through the purge gas flow paths 42s, 42b, and 42t and discharged into the vaporization tubes 52s, 52b, and 52t from the discharge portions 43s, 43b, and 43t, the spray nozzles 31s and 31b due to the backflow of the vaporized raw material are used. , 31t, and thereby 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.

  Moreover, according to this embodiment, the spray nozzles 31s, 31b, and 31t can be prevented from being clogged by the above-described heat blocking effect by the purge gas and the purge effect of the spray nozzle.

  Further, according to the present embodiment, in the vaporizers 229s, 229b, and 229t, the particle size of the liquid raw material is reduced in two stages 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 vaporizing, 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.

  In addition, according to the present embodiment, the purge gas flow paths 42s, 42b, and 42t through which the purge gas that acts as the second-stage carrier gas flows are narrowed toward the discharge units 43s, 43b, and 43t, and the discharge units 43s and 43b. , 43t, the flow path 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.

  Further, 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, 43t of the purge gas flow paths 42s, 42b, 42t. Are parallel to each other 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. Thus, the particle size of the raw material can be reduced more efficiently, vaporization failure can be prevented, and the vaporization speed and vaporization efficiency can be increased.

  Further, according to the present embodiment, when the supply of the liquid material to the vaporizers 229s, 229b, and 229t is stopped, a solvent (ECH or the like) that dilutes the liquid material is supplied into the liquid material channel of the vaporizers 229s, 229b, and 229t. Since the vaporizers 229s, 229b, and 229t are cleaned, the removal of the organometallic liquid source from the liquid source channel is promoted, and the blockage in the liquid source channel by the organometallic liquid source is suppressed. . 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 times 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 during 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 liquid material vaporization operation.

(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 preferably 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 reaction 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 reaction 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. The heat insulating member 318 may be composed of 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 boat rotation mechanism 367, a boat elevator 315, vaporizers 229s, 229b, and 229t, an ozonizer 229o, an open / close valve vs1. To vs8, vb1 to vb8, vt1 to vt8, 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, The operation of 221o, 222o, 224o, etc. is 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). Then, as shown in FIG. 11A, the boat 317 holding the 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 an evacuation device 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 pressure regulator 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 mixing unit for mixing the liquid source and a carrier gas, and a carrier gas mixed with the mixing unit. A spray nozzle for spraying the liquid raw material into the vaporizing chamber, a cooling member for cooling the spray nozzle and the mixing portion, and a part of the surface of the tip portion of the spray nozzle are covered so as to be isolated from the vaporizing chamber. And a cover that forms a flow path for allowing a purge gas to flow around the tip portion of the spray nozzle, and a protrusion is provided at a central tip of the tip portion of the spray nozzle. A spray port is formed on the tip surface of the cover, a portion corresponding to the tip surface of the projection of the cover is open, a side surface of the projection is covered by the cover, and a side surface of the projection Wherein a gap between the cover and the tip portion of the carburetor discharge port for discharging the purge gas was passed through the vaporization chamber around is provided in the spray nozzle is provided.

Preferably, the projection of the spray nozzle is cylindrical.
Preferably, a base portion of the spray nozzle is cylindrical, and the protrusion has a cylindrical shape having an outer diameter smaller than that of the root portion.
Further preferably, the base portion of the spray nozzle has a shape with a constant outer diameter, the tip portion has a shape with a smaller outer diameter toward the tip side, and the protrusion has a shape with a constant outer diameter. The outer diameter is smaller than the root portion.
Preferably, the spray port and the discharge port have the same spray direction of the liquid material mixed with the carrier gas sprayed from the spray port and the discharge direction of the purge gas discharged from the discharge port. Composed.
Preferably, the protrusion of the spray nozzle is configured not to protrude into the vaporization chamber.
Preferably, the spray port and the discharge port are provided on the same plane.
Preferably, the cover is configured to follow the surface shape of the tip portion of 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 purge gas supply system for supplying a purge gas to the vaporizer, a raw material gas supply system for supplying a raw material gas obtained by vaporizing the 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, a liquid source and a carrier gas. A mixing part for mixing the liquid source, a spray nozzle for spraying the liquid raw material mixed with the carrier gas in the mixing part into the vaporizing chamber, a cooling member for cooling the spray nozzle and the mixing part, and the spray nozzle A cover that covers a part of the surface of the tip portion of the spray nozzle so as to be isolated from the vaporizing chamber, and that forms a flow path for allowing purge gas to flow around the tip portion of the spray nozzle. A projection is provided at the center most distal end portion of the tip portion, a spray port is formed on the tip surface of the projection portion, and a portion corresponding to the tip surface of the projection portion of the cover is open, A side surface of the projection is covered with the cover, and a purge gas circulated around the tip portion of the spray nozzle is discharged into the vaporization chamber into a gap between the side of the projection and the cover. A substrate processing apparatus provided with a discharge port is provided.

  According to still another aspect of the present invention, the step of carrying the substrate into the processing chamber, the vaporizing chamber for vaporizing the liquid source, the heater for heating the vaporizing chamber, and the mixing unit for mixing the liquid source and the carrier gas. A spray nozzle that sprays the liquid raw material mixed with the carrier gas in the mixing section into the vaporization chamber, a cooling member that cools the spray nozzle and the mixing section, and a surface of the tip portion of the spray nozzle. And a cover that forms a flow path for circulating a purge gas around the tip portion of the spray nozzle, and covers the portion so as to be isolated from the vaporizing chamber, and the tip of the center of the tip portion of the spray nozzle The projection portion is provided on the portion, and a spray port is formed on the distal end surface of the projection portion, a portion corresponding to the distal end surface of the projection portion of the cover is open, and a side surface of the projection portion is Hippopotamus A vaporizer provided with a discharge port for discharging the purge gas circulated around the tip portion of the spray nozzle into the vaporization chamber in a gap between the side surface of the protrusion and the cover. A step of spraying a liquid raw material mixed with a carrier gas from the spraying port while discharging a purge gas from the discharge port into the vaporizing chamber and vaporizing the liquid raw material in the vaporizing chamber; and the vaporizer in the processing chamber A method for manufacturing a semiconductor device is provided, which includes a step of supplying a source gas obtained by vaporizing a liquid source and processing a substrate, and a step of unloading the processed substrate from the processing chamber.

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) is the example which shortened the length of the thin tube parts 36s, 36b, and 36t. (B) has shown the example which lengthened the length of the thin tube parts 36s, 36b, and 36t. 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) has shown the example with the same discharge direction of a raw material and the discharge direction of purge gas. (B) has shown the example which the discharge direction of a raw material and the discharge direction of purge gas cross | intersect. It is the figure which extracted the front-end | tip part of the spray nozzle and its peripheral part 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 advanced (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 the tip of the spray nozzle is provided. This is an example in which the spray nozzle is configured with only the main body portion and the most advanced portion without the portion. 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.

Explanation of symbols

11s, 11b, 11t Low temperature plate 21s, 21b, 21t Mixing part 31s, 31b, 31t Spray nozzle 32s, 32b, 32t Body part 33s, 33b, 33t Tip part 34s, 34b, 34t Most advanced part 35s, 35b, 35t Fluid flow Path 36s, 36b, 36t Narrow tube part 41s, 41b, 41t Nozzle cover 42s, 42b, 42t Purge gas flow path 43s, 43b, 43t Discharge part 51s, 51b, 51t Evaporation chamber 61s, 61b, 61t Heater 229s, 229b, 229t Vaporizer

Claims (10)

A vaporization chamber for vaporizing the liquid raw material;
A heater for heating the vaporization chamber;
A mixing section for mixing the liquid raw material and the carrier gas;
A spray nozzle for spraying the liquid raw material mixed with the carrier gas in the mixing section into the vaporization chamber;
A cooling member for cooling the spray nozzle and the mixing unit;
Covering a part of the surface of the tip portion of the spray nozzle so as to be isolated from the vaporization chamber, and forming a flow path for flowing purge gas around the tip portion of the spray nozzle,
A projection is provided at the central frontmost portion of the tip portion of the spray nozzle, a spray port is formed at the tip surface of the projection, and a portion corresponding to the tip surface of the projection of the cover is open. The side surface of the projection is covered with the cover, and the purge gas circulated around the tip portion of the spray nozzle in the gap between the side surface of the projection and the cover is vaporized. A vaporizer characterized by being provided with a discharge port for discharging into the room.   The vaporizer according to claim 1, wherein the protrusion of the spray nozzle is cylindrical.   The vaporizer according to claim 1, wherein a base portion of the spray nozzle is cylindrical, and the protrusion has a cylindrical shape having an outer diameter smaller than that of the root portion.   The base portion of the spray nozzle has a shape with a constant outer diameter, the tip portion has a shape with a smaller outer diameter toward the tip side, and the protrusion has a shape with a constant outer diameter than the root portion. The carburetor according to claim 1, wherein the outer diameter is small.   The spray port and the discharge port are configured such that the spray direction of the liquid material mixed with the carrier gas sprayed from the spray port and the discharge direction of the purge gas discharged from the discharge port are the same. The vaporizer according to any one of claims 1 to 4, wherein the vaporizer is provided.   The vaporizer according to claim 1, wherein the protrusion of the spray nozzle is configured not to protrude into the vaporization chamber.   The vaporizer according to claim 1, wherein the spray port and the discharge port are provided on the same plane.   The vaporizer according to any one of claims 1 to 7, wherein the cover is configured to follow a surface shape of the tip portion of 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 purge gas supply system for supplying a purge gas to the vaporizer;
A raw material gas supply system for supplying a raw material gas obtained by vaporizing the 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 source, a heater for heating the vaporizing chamber, a mixing unit for mixing the liquid source and a carrier gas, and a liquid source mixed with a carrier gas in the mixing unit. A spray nozzle for spraying into the vaporizing chamber, a cooling member for cooling the spray nozzle and the mixing portion, a part of the surface of the tip portion of the spray nozzle so as to be isolated from the vaporizing chamber, and the spray nozzle A cover for forming a flow path for allowing purge gas to flow around the tip portion of the spray nozzle, and a projection is provided at a central frontmost portion of the tip portion of the spray nozzle. The spray port is formed, the portion of the cover corresponding to the tip surface of the protrusion is open, the side surface of the protrusion is covered by the cover, the side surface of the protrusion and the cover A substrate processing apparatus in the gap, wherein the discharge port is provided for discharging said was circulated around the tip portion of the spray nozzle purge gas into the vaporizing chamber between. A step of carrying the substrate into the processing chamber;
A vaporizing chamber for vaporizing the liquid source, a heater for heating the vaporizing chamber, a mixing unit for mixing the liquid source and the carrier gas, and a liquid source mixed with the carrier gas in the mixing unit are sprayed into the vaporizing chamber. The spray nozzle, a cooling member that cools the spray nozzle and the mixing portion, a part of the surface of the tip portion of the spray nozzle is covered so as to be isolated from the vaporization chamber, and the tip portion of the spray nozzle is And a cover that forms a flow path for the purge gas to flow around, and a protrusion is provided at the center most distal end of the tip of the spray nozzle, and a spray port is formed at the tip of the protrusion A portion of the cover corresponding to the tip surface of the protrusion is open, a side surface of the protrusion is covered with the cover, and a gap between the side surface of the protrusion and the cover And a vaporizer provided with a discharge port for discharging the purge gas circulated around the tip portion of the spray nozzle into the vaporization chamber, and discharging the purge gas from the discharge port into the vaporization chamber while the carrier is discharged from the spray port. Spraying a liquid material mixed with a gas, and evaporating the liquid material in the vaporization chamber;
Supplying a source gas obtained by vaporizing a liquid source with the vaporizer into the processing chamber and processing the substrate;
Unloading the processed substrate from the processing chamber;
A method for manufacturing a semiconductor device, comprising: