JP2010219421A - Vaporizer, substrate treatment device, and method of manufacturing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To uniformly form a passage width of a carrier gas ejection part throughout the carrier gas ejection part. <P>SOLUTION: The vaporizer includes: a vaporizing chamber for vaporizing a liquid material; a heater for heating the inside of the vaporizing chamber; a spray nozzle for spraying the liquid material into the vaporizing chamber; and a member for forming a carrier gas ejection part, which covers a portion of a surface of a tip part of the spray nozzle to form a carrier gas ejection part for spraying a carrier gas into the vaporizing chamber from a periphery of the tip part of the spray nozzle. A through-hole for housing the tip part of the spray nozzle therein is formed on the member for forming a carrier gas ejection part, and a plurality of projecting parts in contact with the tip part of the spray nozzle are formed at a plurality of parts on an inner wall surface of the through-hole. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

  As a method for forming a thin film in units of atomic layers on a substrate such as a wafer, there is an ALD (Atomic Layer Deposition) method. In the ALD method, for example, (1) a process of supplying a first processing gas into a processing chamber containing a substrate and adsorbing it on the surface of the substrate, and (2) removing the first processing gas remaining in the processing chamber. A process of introducing and purging an inert gas into the processing chamber, and (3) supplying a second processing gas into the processing chamber and reacting with the first processing gas adsorbed on the substrate surface to form a thin film And (4) 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 them in the vaporizing chamber is effective. As for the vaporizer in which the two-fluid nozzle is applied 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 when being supplied to (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

In the above-described external mixing method, a ring-shaped (annular, donut-shaped) carrier gas jetting portion is provided so as to surround the spray nozzle, and the raw material sprayed from the spray nozzle spray port and the carrier gas jet The particle size of the raw material is reduced by mixing with the carrier gas ejected from the part, and the vaporization of the raw material is promoted. In order to exert the effect of reducing the particle size of the raw material over the entire circumference of the carrier gas ejection part, the carrier gas ejection part width (flow channel width) is configured uniformly over the entire circumference of the carrier gas ejection part, and the carrier It is preferable that the flow rate of the carrier gas ejected from the gas ejection part is made uniform over the entire circumference of the carrier gas ejection part.

  However, the relative position of the carrier gas ejection part with respect to the spray port of the spray nozzle is biased due to the fitting tolerance of the members constituting the spray nozzle and its surroundings, and the channel width of the carrier gas ejection part is set to the entire circumference of the carrier gas ejection part. In some cases, it could not be configured evenly. Then, the flow rate of the carrier gas supplied from the carrier gas ejection part is not uniform over the entire circumference of the carrier gas ejection part, and the above-described effect of reducing the particle size of the raw material is applied to the entire circumference of the carrier gas ejection part. There was a case where it was not exhibited without leaking across. In some cases, the raw material having a large particle size is sprayed, resulting in poor vaporization of the raw material, generating particles due to poor vaporization, or clogging in the vicinity of the spray port.

  The object of the present invention is to easily configure the flow path width of the carrier gas ejection part over the entire circumference of the carrier gas ejection part, and to reduce the particle size of the raw material over the entire circumference of the carrier gas ejection part. An object of the present invention is to provide a vaporizer that can be sufficiently exerted. Another object of the present invention is to provide 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 process for processing the substrate with a raw material gas obtained by vaporizing the liquid raw material 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 raw material, a heater for heating the vaporizing chamber, a spray nozzle for spraying the liquid raw material into the vaporizing chamber, and a surface of a tip portion of the spray nozzle. A carrier gas ejection part forming member that covers a part and forms a carrier gas ejection part for ejecting a carrier gas from the periphery of the tip part of the spray nozzle into the vaporization chamber, and the carrier gas ejection part forming member Is provided with a through-hole for accommodating the tip portion of the spray nozzle, and a plurality of protrusions that are in contact with the tip portion of the spray nozzle are provided at a plurality of locations on the inner wall surface of the through-hole. A vaporizer 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 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 a reactive gas for supplying a reactive gas different from the raw material gas into the processing chamber A vaporizing chamber for vaporizing a liquid raw material, a heater for heating the vaporizing chamber, a spray nozzle for spraying the liquid raw material into the vaporizing chamber, and a tip portion of the spray nozzle. And a carrier gas ejection part forming member that forms a carrier gas ejection part for ejecting a carrier gas from the periphery of the tip part of the spray nozzle into the vaporization chamber. The carrier gas ejection portion forming member is provided with a through hole in which the tip portion of the spray nozzle is accommodated, and contacts the tip portion of the spray nozzle at a plurality of locations on the inner wall surface of the through hole. A substrate processing apparatus provided with a plurality of protrusions is provided.

According to still another aspect of the present invention, a step of carrying a substrate into the processing chamber, a vaporizing chamber for vaporizing the liquid source, a heater for heating the vaporizing chamber, and a spray nozzle for spraying the liquid source into the vaporizing chamber. And a carrier gas ejection part forming member that covers a part of the surface of the tip part of the spray nozzle and forms a carrier gas ejection part that ejects a carrier gas from the periphery of the tip part of the spray nozzle into the vaporization chamber; The carrier gas ejection portion forming member is provided with a through hole that accommodates the tip portion of the spray nozzle, and the spray nozzle is provided at a plurality of locations on the inner wall surface of the through hole. The sprayer is used while ejecting a carrier gas from the periphery of the tip portion of the spray nozzle into the vaporization chamber using a vaporizer provided with a plurality of protrusions that come into contact with the tip portion of the spray nozzle. A step of spraying a liquid raw material from the nozzle and vaporizing the liquid raw material in the vaporizing chamber; a step of supplying a raw material gas obtained by vaporizing the liquid raw material in the vaporizer into the processing chamber; And a step of unloading the semiconductor device from the processing chamber.

  According to the present invention, it is easy to uniformly configure the channel width of the carrier gas ejection section over the entire circumference of the carrier gas ejection section, and the effect of reducing the particle size of the raw material is achieved over the entire circumference of the carrier gas ejection section. It is possible to provide a vaporizer that can be sufficiently exerted. 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.

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 apparatus 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 a cross-sectional enlarged view of the spray nozzle periphery of the vaporizer | carburetor concerning 1st Embodiment of this invention. It is a cross-sectional perspective view around the spray nozzle of the vaporizer according to the first embodiment of the present invention. It is a cross-sectional perspective enlarged view around the spray nozzle of the vaporizer according to the first embodiment of the present invention. (A) is a top view of the nozzle cover of the vaporizer | carburetor concerning 1st Embodiment of this invention, (b) has shown sectional drawing. (A) is a perspective view of the nozzle cover of the vaporizer | carburetor concerning 1st Embodiment of this invention, (b) is a perspective enlarged view of a through-hole periphery. It is a schematic block diagram of the conventional vaporizer. It is a cross-sectional enlarged view around the spray nozzle of a conventional vaporizer. It is an arrow line view seen from the direction shown with the code | symbol B of FIG. 12, (a) has shown the state which has a spray nozzle in the center, (b) has shown the state which has a spray nozzle in the position biased from the center, respectively. . 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.

(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. In addition, the support base 203 is provided with through holes 208a through which the lift pins 208b pass, at positions corresponding to the lift pins 208b. When the support table 203 is lowered to the wafer transfer position, the upper ends of the lift pins 208b protrude 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 an APC (Au that controls the inside of the processing chamber 201 to a predetermined pressure is connected to the exhaust pipe 261.
pressure regulator 262 such as a pressure controller), a raw material recovery trap 263, and a vacuum pump 264 are connected in series in this 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 discharging (circulating) gas from the recess 205b to the exhaust port 260 side. The flange portion 205 a functions as a locking portion that locks on the upper outer periphery of the support base 203. When the flange portion 205 a is locked on the upper outer periphery of the support base 203, the lower plate 205 is moved up and down together with the support base 203 as the support base 203 is moved up and down.

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

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

  Next, the configuration of the gas supply system connected to the above-described gas inlet 210 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. FIG. 6 is a schematic configuration diagram of the vaporizer according to the first embodiment of the present invention, FIG. 7 is a partially enlarged view around the spray port of the spray nozzle of the vaporizer of FIG. 6, and FIG. FIG. 9 is a cross-sectional perspective view around the spray nozzle of the vaporizer of FIG. 6, FIG. 9 is a cross-sectional perspective enlarged view of the vicinity of the spray nozzle of the vaporizer of FIG. 6, and FIG. 10 (a) is the vaporizer of FIG. 10B is a cross-sectional view of the nozzle cover of the vaporizer of FIG. 6, and FIG. 11A is a perspective view of the nozzle cover of the vaporizer of FIG. 6. FIG. 11B is an enlarged perspective view of the periphery of the through hole of the nozzle cover 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 a Ti (titanium) element. A source 220t is provided. The first liquid raw material supply source 220s, the second liquid raw material supply source 220b, and the third liquid raw material supply source 220t are each configured as a tank (sealed container) capable of containing (filling) the liquid raw material therein. Each organometallic liquid raw material containing Sr, Ba, Ti elements is diluted to 0.05 mol / L to 0.2 mol / L with a solvent (solvent) such as ECH (ethylcyclohexane) or THF (tetrahydrofuran), for example. And then stored in the tank.

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

  In addition, the first liquid raw material supply source 220s, the second liquid raw material supply source 220b, and the third liquid raw material supply source 220t include a first liquid raw material supply pipe 211s, a second liquid raw material supply pipe 211b, and a third liquid raw material, respectively. A supply pipe 211t is connected to each other. Here, upstream end portions of the first liquid source supply pipe 211s, the second liquid source supply pipe 211b, and the third liquid source supply pipe 211t are respectively the first liquid source supply source 220s and the second liquid source supply source 220b. And the liquid raw material housed in the third liquid raw material supply source 220t. Further, the downstream end portions of the first liquid source supply pipe 211s, the second liquid source supply pipe 211b, and the third liquid source supply pipe 211t are 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 the N ₂ gas. , And open / close valves vs8, vb8, and vt8 for controlling the supply of N ₂ gas, respectively. Mainly, N ₂ gas supply source 230n, purge gas supply pipe 219, first purge gas supply pipe 219s, second purge gas supply pipe 219b, third purge gas supply pipe 219t, flow rate controllers 226s, 226b, 226t, open / close valves vs8, vb8, A purge gas supply system (purge gas supply line) is configured by vt8. In addition to the N ₂ gas, an inert gas such as Ar gas may be used as the purge gas.

<Vaporization part>
The vaporizers 229s, 229b, and 229t as vaporizers for vaporizing the liquid raw material mainly include vaporization chambers 51s, 51b, and 51t, heaters 61s, 61b, and 61t, and sprays, as shown in FIG. It has nozzles 31s, 31b, 31t, mixing pipe portions 21s, 21b, 21t, 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 the vaporization tubes 52s, 52b, and 52t as vaporization containers. Around the vaporization tubes 52s, 52b, and 52t, heaters 61s, 61b, and 61t are provided as heating means (heating mechanism). The heaters 61s, 61b, 61t are configured to heat and vaporize the liquid material sprayed in the vaporization chambers 51s, 51b, 51t. In the upper portions of the vaporization chambers 51s, 51b, and 51t, inlets 53s, 53b, and 53t for introducing a liquid material, a carrier gas, and a purge gas into the vaporization chambers 51s, 51b, and 51t are provided. Outlets 54s, 54b, and 54t that discharge the source gas generated in the vaporization chambers 51s, 51b, and 51t into the source gas supply pipes 213s, 213b, and 213t are provided in the lower portions of the vaporization chambers 51s, 51b, and 51t. ing. The vaporization chambers 51s, 51b, and 51t have a sufficient volume so that the liquid material droplets sprayed from the inlets 53s, 53b, and 53t are vaporized before reaching the inner walls of the vaporization chambers 51s, 51b, and 51t. Has been. That is, the height L of the vaporization chambers 51s, 51b, 51t and the width W of the vaporization chambers 51s, 51b, 51t are sufficiently secured.

  Spray nozzles 31s, 31b, and 31t as spraying portions are provided in the inlets 53s, 53b, and 53t of the vaporization chambers 51s, 51b, and 51t. The spray nozzles 31s, 31b, and 31t are provided on the lower surfaces of the mixing pipe portions 21s, 21b, and 21t, and vaporize chambers 51s and 51b with a fluid mixture of the liquid raw material and the carrier gas supplied from the mixing pipes 25s, 25b, and 25t. , 51t.

As shown in FIGS. 7 and 9, 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. Yes. 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 tip portions of the spray nozzles 31s, 31b, 31t are configured as protrusions (convex portions) provided at the center of the tip of the spray nozzles 31s, 31b, 31t (main body portions 32s, 32b, 32t). The main body portions 32s, 32b, 32t extend from the root portions of the spray nozzles 31s, 31b, 31t (portions joined to the lower surfaces of the mixing pipe portions 21s, 21b, 21t) to the tip portions of the spray nozzles 31s, 31b, 31t. Part. The outer shapes of the main body portions 32s, 32b, and 32t and the distal end portions 33s, 33b, and 33t are each formed in a cylindrical shape. That is, the main body portions 32s, 32b, and 32t and the distal end portions 33s, 33b, and 33t are each configured to have a constant outer diameter. The outer diameters of the tip portions 33s, 33b, and 33t are much smaller than the outer diameters of the main body portions 32s, 32b, and 32t. The most advanced portions 34s, 34b, and 34t have tapered surfaces. That is, the outermost portions 34s, 34b, and 34t are formed in a substantially conical shape, and the outermost portions 34s, 34b, and 34t are configured such that the outer diameter decreases toward the distal end side.

  In the spray nozzles 31s, 31b, and 31t, fluid flow paths 35s, 35b, and 35t through which a fluid in which a liquid raw material and a carrier gas are mixed are provided. The inner diameters of the fluid flow paths 35s, 35b, and 35t are reduced on the tip side. In the present embodiment, narrow tube portions 36s, 36b, and 36t having an inner diameter smaller than the inner diameters of the fluid channels 35s, 35b, and 35t are provided on the distal ends of the fluid channels 35s, 35b, and 35t. The tips of the narrow tube portions 36s, 36b, and 36t are opened at the center of the tip surfaces of the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t, and spray a fluid that is a mixture of a liquid source and a carrier gas. The spray ports 37s, 37b, and 37t are configured. The inner diameters of the spray ports 37s, 37b, and 37t are, for example, 0.5 to 1.0 mm. A predetermined pressure difference is generated between the fluid flow paths 35s, 35b, and 35t and the vaporization chambers 51s, 51b, and 51t because the inner diameters of the fluid flow paths 35s, 35b, and 35t are narrowed on the tip side. The spray nozzles 31s, 31b, 31t are prevented from being blocked by the preferential evaporation of the solvent (so-called solvent jump-on phenomenon). This pressure difference can be adjusted by changing the length and diameter of the narrow tube portions 36s, 36b, and 36t. The fluid flow paths 35s, 35b, and 35t and the narrow tube portions 36s, 36b, and 36t are not limited to the case where the inner diameters are gradually reduced as shown in FIGS. You may join so that an internal diameter may become small continuously as it goes. The fluid flow paths 35s, 35b, and 35t and the narrow tube portions 36s, 36b, and 36t are vertically arranged on the central axes of the main body portions 32s, 32b, and 32t, the distal end portions 33s, 33b, and 33t, and the most distal end portions 34s, 34b, and 34t. Is provided. The narrow tube portions 36s, 36b, 36t, the fluid flow paths 35s, 35b, 35t, the most distal portions 34s, 34b, 34t, the tip portions 33s, 33b, 33t, and the main body portions 32s, 32b, 32t are concentric with each other. It is configured.

Above the spray nozzles 31s, 31b, and 31t, mixing pipe portions 21s, 21b, and 21t are provided as mixing portions. The mixing pipe portions 21s, 21b, and 21t are configured to mix the liquid raw material and the carrier gas and introduce the mixed fluid into the spray nozzles 31s, 31b, and 31t (in the fluid flow paths 35s, 35b, and 35t). Has been. 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. Carrier gas supply pipes 218s, 218b, and 218t are connected to the carrier gas pipes 23s, 23b, and 23t. 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 raw material is supplied from the liquid raw material supply pipes 211s, 211b, and 211t into the mixing pipes 25s, 25b, and 25t via the liquid raw material pipes 22s, 22b, and 22t. The carrier gas is a carrier gas supply pipe 218s.
, 218b and 218t are 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. To be introduced.

  A cover (covering member) is provided below the mixing pipe portions 21s, 21b, and 21t and above the vaporization chambers 51s, 51b, and 51t and the heaters 61s, 61b, and 61t and around the spray nozzles 31s, 31b, and 31t. There are provided nozzle covers 41s, 41b, 41t which are also carrier gas ejection part forming members.

  The nozzle covers 41s, 41b, 41t are configured to cover part of the surface of the spray nozzles 31s, 31b, 31t. Specifically, the nozzle covers 41s, 41b, and 41t are the side surfaces and tip surfaces of the main body portions 32s, 32b, and 32t of the spray nozzles 31s, 31b, and 31t, the side surfaces and tip surfaces of the tip portions 33s, 33b, and 33t, and the most advanced. The side surfaces of the portions 34s, 34b, and 34t are provided so as to cover each.

  As shown in FIGS. 10 and 11, the portions of the nozzle covers 41s, 41b, and 41t (the nozzle covers 41s, 41b, and 41t of the nozzle covers 41s, 41b, and 41t correspond to the tip surfaces of the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t. In the central portion, through holes 44s, 44b, and 44t are provided. The upper and lower portions of the through holes 44s, 44b, and 44t are each formed in a tapered surface (conical shape). The upper inner wall surfaces of the through holes 44s, 44b, 44t are tapered surfaces (conical shapes) whose inner diameter gradually decreases stepwise or continuously from the upper part of the through holes 44s, 44b, 44t toward the intermediate side (downward side). ). The lower inner wall surface of the through holes 44s, 44b, 44t is a tapered surface (conical shape) whose inner diameter decreases stepwise or continuously from the tip of the through holes 44s, 44b, 44t to the intermediate part side (upward side). ). As shown in FIGS. 7 to 9, the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t are configured to be accommodated in the upper portions of the through holes 44s, 44b, and 44t. That is, the foremost portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t are configured to be accommodated in the through holes 44s, 44b, and 44t and not to protrude into the vaporization chambers 51s, 51b, and 51t.

  Thus, the nozzle covers 41s, 41b, and 41t are configured so as to follow the surface shape of the tip portions of the spray nozzles 31s, 31b, and 31t. The nozzle covers 41s, 41b, and 41t cover the surfaces of the spray nozzles 31s, 31b, and 31t to isolate them from the vaporization chambers 51s, 51b, and 51t, and are exposed to the vaporization chambers 51s, 51b, and 51t. , 31t is minimized.

  As shown in FIGS. 7 to 9, the nozzle covers 41s, 41b, and 41t are carrier gas jets that jet purge gas into the vaporization chambers 51s, 51b, and 51t from the periphery of the tip portions of the spray nozzles 31s, 31b, and 31t. It is comprised so that part 43s, 43b, 43t may be formed. As will be described later, in the vaporizers 229s, 229b, and 229t in the present embodiment, the particle size of the liquid raw material is reduced in two stages, and the purge gas ejected from the carrier gas ejection portions 43s, 43b, and 43t is Acts as a second stage carrier gas (externally mixed carrier gas).

Specifically, the nozzle covers 41 s, 41 b, 41 t flow purge gas around the main body portions 32 s, 32 b, 32 t and the tip portion of the spray nozzles 31 s, 31 b, 31 t, and the purge gas flows into the vaporization chambers 51 s, 51 b, 51 t. The purge gas flow paths 42s, 42b, and 42t for discharging to are formed. A part of the purge gas flow paths 42s, 42b, 42t is configured to form buffer spaces 47s, 47b, 47t around a part of the main body portions 32s, 32b, 32t of the spray nozzles 31s, 31b, 31t. . Purge gas supply pipes 219s, 219b, and 219t are connected to the buffer spaces 47s, 47b, and 47t. Further, the other part of the purge gas flow paths 42s, 42b, and 42t form carrier gas ejection portions 43s, 43b, and 43t that follow the shapes of the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t. It is configured.

  The carrier gas ejection portions 43s, 43b, and 43t are formed between the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t and the upper inner walls in the through holes 44s, 44b, and 44t of the nozzle covers 41s, 41b, and 41t. It is a space (gas flow path) sandwiched between them, and the horizontal cross-sectional shape is formed in a ring shape (annular shape, donut shape). The lower ends of the carrier gas ejection portions 43s, 43b, and 43t are carrier gas jets that discharge purge gas (carrier gas) from the vicinity of the spray ports 37s, 37b, and 37t of the spray nozzles 31s, 31b, and 31t into the vaporization chambers 51s, 51b, and 51t. It is configured as an exit. The carrier gas outlet is provided on substantially the same plane as the spray ports 37s, 37b, and 37t of the spray nozzles 31s, 31b, and 31t.

  The tip portions 33s, 33b, 33t and the tip portions 34s, 34b, 34t of the spray nozzles 31s, 31b, 31t and the through holes 44s, 44b, 44t of the nozzle covers 41s, 41b, 41t are concentric. It is configured. That is, the channel widths of the carrier gas ejection portions 43s, 43b, and 43t are configured to be uniform over the entire circumference of the carrier gas ejection portions 43s, 43b, and 43t. Further, the spray ports 37 s, 37 b, 37 t of the spray nozzles 31 s, 31 b, 31 t are arranged at the center of the carrier gas ejection parts 43 s, 43 b, 43 t. That is, the distances between the spray ports 37s, 37b, and 37t of the spray nozzles 31s, 31b, and 31t and the carrier gas ejection portions 43s, 43b, and 43t are uniform over the entire circumference of the carrier gas ejection portions 43s, 43b, and 43t. It is configured as follows. Regarding the mechanism for configuring the flow path width of the carrier gas ejection parts 43s, 43b, 43t and the positional relationship between the carrier gas ejection parts 43s, 43b, 43t and the spray ports 37s, 37b, 37t as described above with high reproducibility. It will be described later.

  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. Although 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 spray nozzles 31s, 31b, and 31t and the mixing pipe portions 21s, 21b, and 21t are provided with the above-described raw materials in order to suppress clogging due to the thermal decomposition of the raw materials in the pipes and the flow paths and the jumping-out phenomenon of the solvent. It is preferable that the temperature be maintained at a temperature that is not high enough to vaporize the gas. These members are preferably maintained at a temperature of 20 to 250 ° C., for example. That is, the temperature of the spray nozzles 31s, 31b, 31t, the mixing pipe portions 21s, 21b, 21t is lower than the temperatures of the vaporization chambers 51s, 51b, 51t, the heaters 61s, 61b, 61t, and the nozzle covers 41s, 41b, 41t. It is preferable to be held in Here, if the purge gas flow paths 42s, 42b, 42t are not provided between the high temperature member and the low temperature member, the high temperature members (vaporization chambers 51s, 51b, 51t, heaters 61s, 61b, 61t, nozzle covers 41s, 41b). , 41t), the heat easily moves from the low-temperature members (spray nozzles 31s, 31b, 31t, mixing pipe portions 21s, 21b, 21t). On the other hand, if the purge gas flow paths 42s, 42b, 42t are provided between the high temperature member and the low temperature member as in this embodiment and the purge gas is circulated through the purge gas flow paths 42s, 42b, 42t, It is possible to block the heat moving from the high temperature member to the low temperature member. And spray nozzle 31s, 31b
31t, the temperature of the mixing pipe sections 21s, 21b, 21t is maintained at a temperature lower than the temperatures of the vaporization chambers 51s, 51b, 51t, the heaters 61s, 61b, 61t, and the nozzle covers 41s, 41b, 41t, It is possible to suppress clogging due to the thermal decomposition of the raw material in the flow path or the solvent jumping phenomenon.

  The spray nozzles 31s, 31b, and 31t are set to a temperature lower than the temperatures of the vaporization tubes 52s, 52b, and 52t. Therefore, when the raw material that has been vaporized and diffused into the vaporization tubes 52s, 52b, and 52t flows backward toward the spray nozzles 31s, 31b, and 31t, the raw material comes into contact with the surfaces of the spray nozzles 31s, 31b, and 31t and is reliquefied. Will occur. On the other hand, if the purge gas is ejected from the lower ends (carrier gas ejection ports) of the carrier gas ejection portions 43s, 43b, 43t as in the present embodiment, the backflow of the vaporized material can be suppressed, and the spray nozzle 31s. , 31b, 31t can be prevented from contacting the vaporized raw material, and reliquefaction and precipitation of the raw material due to the contact. 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. Thereby, the area of the spray nozzles 31s, 31b, 31t exposed to the vaporization chambers 51s, 51b, 51t is minimized, and the purge effect by the purge gas is effectively utilized. Further, the most distal portions 34 s, 34 b, 34 t of the spray nozzles 31 s, 31 b, 31 t are configured to fit in the through holes 44 s, 44 b, 44 t and not to protrude into the vaporization tubes 52 s, 52 b, 52 t. Thereby, 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 shut-off function with the purge gas.

  As described above, the purge gas has a role of blocking the heat of the vaporizer components and preventing clogging of the spray nozzle due to the purge. In addition to these, the purge gas has a function of reducing the particle size of the raw material when the raw material is sprayed into the vaporization pipe (a function as a carrier gas that gives energy to the raw material). 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 ejected from the purge gas supply pipes 219s, 219b, 219t through the purge gas flow paths 42s, 42b, 42t and the carrier gas ejection parts 43s, 43b, 43t into the vaporization chambers 51s, 51b, 51t. The raw material and purge gas that have become a two-phase flow are mixed in the second mixing portions 46s, 46b, and 46t near the lower portions of the through holes 44s, 44b, and 44t (below the spray ports 37s, 37b, and 37t). 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 vaporization chambers 51 s, 51 b, 51 t under high vacuum temperature. The The sprayed raw material is vaporized by colliding with the inner walls of the vaporization tubes 52s, 52b, and 52t maintained at a high temperature by the heaters 61s, 61b, and 61t and by radiating heat from the inner walls of the vaporization tubes 52s, 52b, and 52t. The

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 vaporizers 229s, 229b, and 229t in 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, respectively. Acts as a carrier gas (externally mixed 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 order to sufficiently exhibit the above-described effect of reducing the particle size of the raw material over the entire circumference of the spray nozzles 31 s, 31 b, and 31 t, the vaporization chambers 51 s, through the carrier gas ejection portions 43 s, 43 b, and 43 t. It is preferable that the flow rate of the purge gas (second stage carrier gas) supplied into 51b and 51t is made uniform over the entire circumference of the carrier gas ejection parts 43s, 43b and 43t. Further, the amount of the purge gas (carrier gas) mixed (collised) with the raw material sprayed from the spray ports of the spray nozzles 31s, 31b, 31t may be made uniform over the entire circumference of the carrier gas ejection portions 43s, 43b, 43t. preferable. That is, it is preferable that the flow path widths of the ring-shaped carrier gas ejection portions 43s, 43b, and 43t are made uniform over the entire circumference of the carrier gas ejection portions 43s, 43b, and 43t. Further, the spray ports 37 s, 37 b, 37 t of the spray nozzles 31 s, 31 b, 31 t are preferably positioned at the center of the carrier gas ejection portions 43 s, 43 b, 43 t.

  Further, in order to increase the flow rate of the purge gas acting as the second-stage carrier gas and reduce the particle size of the raw material more efficiently, the channel widths of the carrier gas ejection portions 43s, 43b, and 43t are provided at the carrier gas ejection port. It is preferable to configure so that the flow path width at the throttle and the carrier gas outlet becomes the narrowest as it goes. For example, when the flow rate of Ar gas as the purge gas is about 200 to 1500 sccm, the channel width at the carrier gas outlet is preferably about 0.02 to 0.15 mm. If the flow path width at the carrier gas outlet is not so narrow, the flow rate of the purge gas (second-stage carrier gas) needs to be significantly increased.

  However, it has been difficult in the past to configure the channel widths at the carrier gas ejection portions 43s, 43b, and 43t (carrier gas ejection ports) uniformly over the entire circumference while configuring the channel width at the carrier gas ejection port to be narrow. there were. The carrier gas ejection portions 43s, 43b, and 43t can be configured by fitting, for example, the spray nozzles 31s, 31b, and 31t and the nozzle covers 41s, 41b, and 41t, but the spray nozzles 31s and 31b with respect to the through holes 44s, 44b, and 44t. This is because the relative positions of the most distal end portions 34s, 34b, and 34t of 31t tend to be biased due to fitting tolerances. For example, when an attempt is made to configure the flow path width at the carrier gas outlet uniformly to about 0.02 to 0.15 mm over the entire circumference, if a fitting tolerance of about 0.01 to 0.05 mm occurs, the spray nozzle The side surfaces (tapered surfaces) of the tip portions 34s, 34b, and 34t of 31s, 31b, and 31t and the upper inner wall surfaces of the through holes 44s, 44b, and 44t are extremely close to each other or come into contact with each other. In this case, the flow rate of the purge gas (second stage carrier gas) supplied into the vaporization chambers 51s, 51b, 51t through the carrier gas ejection parts 43s, 43b, 43t is uniform over the entire circumference of the carrier gas ejection port. It will disappear (deviation will occur in the flow rate). And the above-mentioned effect which makes the particle size of a raw material smaller will not be exhibited without omission over spray nozzle 31s, 31b, 31t whole circumference. Then, a vaporization failure of the raw material occurs, and the raw material (droplet) adheres to the inner walls of the vaporization chambers 51s, 51b, 51t and generates particles. Further, the raw material (droplet) having a large particle size is difficult to be blown off by the purge gas (second-stage carrier gas), and the tips of the most advanced portions 34s, 34b, 34t of the spray nozzles 31s, 31b, 31t and the through holes 44s, 44b, Since it tends to stay on the inner wall of 44t or the like, there is a case where clogging of the raw material occurs near the spray ports 37s, 37b, 37t, or particles are generated due to this.

In contrast, in the present embodiment, the above-described problems are solved by providing a plurality of protrusions 45s, 45b, and 45t at a plurality of locations on the inner wall surfaces of the through holes 44s, 44b, and 44t.

  That is, in the present embodiment, a plurality of protrusions 45s, 45b, and 45t that contact the tip portions of the spray nozzles 31s, 31b, and 31t are provided at a plurality of locations on the inner wall surfaces of the through holes 44s, 44b, and 44t. The plurality of protrusions 45s, 45b, 45t are provided at equal intervals. Specifically, the plurality of protrusions 45s, 45b, and 45t are formed of three protrusions provided on the upper inner wall surface of the through holes 44s, 44b, and 44t, and are respectively formed at the centers of the through holes 44s, 44b, and 44t. On the other hand, the central angles are set to be approximately equal to 120 °. The plurality of protrusions 45s, 45b, and 45t are configured to have the same height. The spray nozzles 31s, 31b, and 31t and the nozzle covers 41s, 41b, and 41t are connected to the side surfaces (tapered surfaces) of the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t, and the nozzle covers 41s, 41b, The carrier gas ejection portions 43s, 43b, and 43t are configured by combining (fitting) the plurality of projection portions 45s, 45b, and 45t of 41t so as to come into contact with each other (to be pressed against each other).

  With this configuration, the relative positions of the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t and the through holes 44s, 44b, and 44t are set to the side surfaces of the most distal portions 34s, 34b, and 34t ( It is uniquely determined according to the outer diameter and angle of the tapered surface), the inner diameters of the through holes 44s, 44b, and 44t, the heights and intervals of the plurality of protrusions 45s, 45b, and 45t.

  Each time the spray nozzles 31s, 31b, 31t and the nozzle covers 41s, 41b, 41t are combined (fitted together), the side surfaces of the most distal portions 34s, 34b, 34t of the spray nozzles 31s, 31b, 31t, and the through holes 44s, 44b, and 44t can be configured concentrically with good reproducibility. That is, the distances between the side surfaces (tapered surfaces) of the most distal portions 34s, 34b, 34t of the spray nozzles 31s, 31b, 31t and the upper inner wall surfaces of the through holes 44s, 44b, 44t are evenly distributed over the entire circumference. It becomes possible.

  Further, the spray ports 37s, 37b, and 37t of the spray nozzles 31s, 31b, and 31t can be arranged with high reproducibility in the center of the carrier gas ejection portions 43s, 43b, and 43t. That is, the distance between the spray ports 37s, 37b, and 37t of the spray nozzles 31s, 31b, and 31t and the carrier gas ejection parts 43s, 43b, and 43t is reproducible over the entire circumference of the carrier gas ejection parts 43s, 43b, and 43t. It becomes possible to configure evenly.

  Then, the flow rate of the purge gas (second stage carrier gas) supplied into the vaporization chambers 51 s, 51 b, 51 t through the carrier gas ejection portions 43 s, 43 b, 43 t is made uniform over the entire circumference of the carrier gas ejection port. It becomes possible. Further, the amount of the purge gas (carrier gas) mixed (collised) with the raw material sprayed from the spray ports of the spray nozzles 31s, 31b, 31t may be made uniform over the entire circumference of the carrier gas ejection portions 43s, 43b, 43t. It becomes possible. As a result, the above-described effect of reducing the particle size of the raw material can be sufficiently and evenly exhibited over the entire circumference of the carrier gas ejection port. Then, the vaporization of the raw material (droplets) can be promoted, and the generation of particles and the clogging around the spray ports 37s, 37b, 37t can be suppressed.

  The dimensions of the carrier gas ejection portions 43s, 43b, and 43t are the outer diameter and angle of the side surfaces (tapered surfaces) of the most distal portions 34s, 34b, and 34t, the inner diameters of the through holes 44s, 44b, and 44t, and the plurality of protrusions 45s. , 45b, 45t can be arbitrarily adjusted according to the height, interval and the like. The flow rate and flow rate of the purge gas (second-stage carrier gas) supplied from the carrier gas ejection parts 43s, 43b, 43t can be freely adjusted by adjusting the dimensions of the carrier gas ejection parts 43s, 43b, 43t. Is possible.

<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 a 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. The source gas supply system (source gas supply) is mainly constituted by the first source gas supply pipe 213s, the second source gas supply pipe 213b, the third source gas supply pipe 213t, the source gas supply pipe 213, and the open / close valves vs3, vb3, 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.

  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 accommodated in the cleaning liquid supply source 220e. The downstream end of the cleaning liquid supply pipe 212 is connected to be branched to 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 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 on-off valves vs1, vb1, and vt1, and opening the on-off valves vs2, vb2, and vt2. Raw material flow paths, that is, liquid raw material pipes 22s, 22b, 22t, mixing pipes 25s, 25b, 25t, spray nozzles 31s, 31
It is possible to wash (inject) the cleaning liquid into the fluid flow paths 35 s, 35 b, 35 t and the narrow pipe portions 36 s, 36 b, 36 t in b, 31 t to clean the liquid source flow paths. 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.

  An 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.

  An 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 branches 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 and second source gas supply pipes 213s, 213b and 213b are closed 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 through the supply pipe 213t and the ozone gas supply pipe 213o can be bypassed through the process chamber 201 without being supplied into the process chamber 201, and exhausted out of 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 combined into a vent pipe 216, and the vent pipe 216 is an exhaust pipe. It is connected to the downstream side of the raw material recovery trap 263 and the upstream side of the vacuum pump 264. The fifth vent pipe 216s, the sixth vent pipe 216b, the seventh vent pipe 216t, and the eighth vent pipe 216o are provided with open / close valves vs6, vb6, vt6, and vo6 for controlling gas supply, respectively.

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

<Controller>
Note that the substrate processing apparatus according to the present embodiment includes a controller 280 that controls the operation of each unit of the substrate processing apparatus. The controller 280 includes a gate valve 251, an elevating mechanism 207b, a transfer robot 273, a heater 206, a pressure regulator (APC) 262, vaporizers 229s, 229b 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 in the vaporizer 229s or to stably generate the ozone gas in 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, the switching of the open / close valve is preferable because stable supply of the first source gas and ozone gas into the processing chamber 201 can be started or stopped quickly.

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 and closing valves vb7 and vt7 are opened to supply the carrier gas (N ₂ gas) from the N ₂ gas supply source 230n to the vaporizers 229b and 229t, and the opening and closing valves vb8 and vt8 are opened to supply the N ₂ gas. Purge gas (N ₂ gas) is supplied from the source 230n to the vaporizers 229b and 229t. The supply of the carrier gas and the supply of the purge gas are preferably performed prior to the supply of the cleaning liquid. The 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 on-off valve vs1 is closed, and the supply of the first liquid raw material to the vaporizer 229s is also stopped. The open / close valve vs7 and open / close 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.

  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. Thus, 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 forms 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. As a result, ozone gas and reaction byproducts 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, which will be described later. 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.

  After a predetermined time has elapsed after opening the on-off valve vb3 and starting the supply of the second source gas, the on-off valve vb3 is closed and the on-off valves vb4, vb5 are opened to supply the second source gas into the processing chamber 201. To stop. At the same time, the on-off valve vb1 is closed and the supply of the second liquid material to the vaporizer 229b is also stopped. 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.

  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. As a result, 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).

  Moreover, after closing the opening / closing valve vb1 and stopping the supply of the second liquid raw material, cleaning of 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 raw material and the solvent remaining in the liquid raw material flow path are also supplied into the vaporizing chamber 51b and vaporized. Then, the vaporized cleaning liquid, the second liquid raw material, 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 raw material gas supply pipe 213b. The Also at this time, the opening / closing valve vb7 and the opening / closing valve vb8 are kept open 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 of the second liquid raw material to the vaporizer 229b is started (until the next Ti in S7).

  When the purge in the processing chamber 201 is completed, the opening / closing valves vo4, vo5 are closed, the opening / closing valve vo3 is opened, and supply of ozone gas into the processing chamber 201 is started (OxB). The ozone gas is dispersed by the shower head 240, is uniformly supplied onto the wafer 200 in the processing chamber 201, reacts with the 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. As a result, ozone gas and reaction byproducts 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 (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 A pressurized 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. 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 (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.

  Note that when 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 is not self-decomposed. In this case, when supplying each source gas in the ALD process (S 6 to S 9) using each source gas, the source gas is adsorbed onto the wafer 200. 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) Effect concerning 1st Embodiment According to this embodiment, there exists one or several effect shown below.

(A) According to the present embodiment, a plurality of protrusions 45s, 45b, and 45t that contact the tip portions of the spray nozzles 31s, 31b, and 31t are provided at a plurality of locations on the inner wall surfaces of the through holes 44s, 44b, and 44t. It is said. The plurality of protrusions 45s, 45b, 45t are provided at equal intervals. The spray nozzles 31s, 31b, and 31t and the nozzle covers 41s, 41b, and 41t are connected to the side surfaces (tapered surfaces) of the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t, and the nozzle covers 41s, 41b, The carrier gas ejection portions 43s, 43b, and 43t are configured by combining (fitting) the plurality of projection portions 45s, 45b, and 45t of 41t so as to come into contact with each other (to be pressed against each other).

  With this configuration, the relative positions of the most distal portions 34s, 34b, and 34t of the spray nozzles 31s, 31b, and 31t and the through holes 44s, 44b, and 44t are set to the side surfaces of the most distal portions 34s, 34b, and 34t ( It is uniquely determined according to the outer diameter and angle of the tapered surface), the inner diameters of the through holes 44s, 44b, and 44t, the heights and intervals of the plurality of protrusions 45s, 45b, and 45t. Each time the spray nozzles 31s, 31b, 31t and the nozzle covers 41s, 41b, 41t are combined (fitted together), the side surfaces of the most distal portions 34s, 34b, 34t of the spray nozzles 31s, 31b, 31t, and the through holes 44s, 44b, and 44t can be configured concentrically with good reproducibility. That is, the distances between the side surfaces (tapered surfaces) of the most distal portions 34s, 34b, 34t of the spray nozzles 31s, 31b, 31t and the upper inner wall surfaces of the through holes 44s, 44b, 44t are evenly distributed over the entire circumference. It becomes possible. Further, the spray ports 37s, 37b, and 37t of the spray nozzles 31s, 31b, and 31t can be arranged with high reproducibility in the center of the carrier gas ejection portions 43s, 43b, and 43t. That is, the distance between the spray ports 37s, 37b, and 37t of the spray nozzles 31s, 31b, and 31t and the carrier gas ejection parts 43s, 43b, and 43t is reproducible over the entire circumference of the carrier gas ejection parts 43s, 43b, and 43t. It becomes possible to configure evenly. Then, the flow rate of the purge gas (second stage carrier gas) supplied into the vaporization chambers 51 s, 51 b, 51 t through the carrier gas ejection portions 43 s, 43 b, 43 t is made uniform over the entire circumference of the carrier gas ejection port. It becomes possible. Further, the amount of the purge gas (carrier gas) mixed (collised) with the raw material sprayed from the spray ports of the spray nozzles 31s, 31b, 31t may be made uniform over the entire circumference of the carrier gas ejection portions 43s, 43b, 43t. It becomes possible. As a result, the above-described effect of reducing the particle size of the raw material can be sufficiently and evenly exhibited over the entire circumference of the carrier gas ejection port. Then, the vaporization of the raw material (droplets) can be promoted, and the generation of particles and the clogging around the spray ports 37s, 37b, 37t can be suppressed.

  For reference, the configuration of the conventional vaporizer 529 will be described with reference to FIGS. FIG. 12 is a schematic configuration diagram of a conventional vaporizer 529. FIG. 13 is a partially enlarged view around the spray port 537 of the spray nozzle 531 of the conventional vaporizer 529. FIG. 14 is a view as seen from the direction indicated by the symbol B in FIG. 12, where (a) shows a state where the spray nozzle 531 is at the center, and (b) shows a position where the spray nozzle 531 is deviated from the center. Each state is shown. As shown in FIGS. 12 and 13, in the conventional vaporizer 529, the inner wall surface of the through hole 544 is not provided with a protrusion that contacts the tip portion of the spray nozzle 531. Therefore, when the carrier nozzle 543 is configured by fitting the spray nozzle 531 and the nozzle cover 541 together, as shown in FIG. 14B, the tip 533 of the spray nozzle 531 with respect to the through-hole 544 and the most advanced In some cases, the relative position of the portion 534 is not uniquely determined and may be biased due to the fitting tolerance. As a result, the flow rate of the purge gas (carrier gas) supplied from the carrier gas ejection portion 543 is not uniform over the entire circumference of the carrier gas ejection portion 543 (the flow rate varies), and the particle size of the raw material The above-described effect of reducing the size of the carrier gas is not exhibited without leakage over the entire circumference of the carrier gas ejection portion 543. Then, raw materials (droplets) having a large particle size are sprayed, resulting in poor vaporization of the raw materials, generating particles due to poor vaporization, or clogging near the spraying port 537 in some cases. .

(B) According to the present embodiment, the dimensions of the carrier gas ejection portions 43s, 43b, and 43t are changed according to the outer diameter and angle of the side surfaces (taper surfaces) of the most distal end portions 34s, 34b, and 34t, the through holes 44s, 44b, and 44t. Can be arbitrarily adjusted according to the inner diameter, the height of the plurality of protrusions 45s, 45b, 45t, the interval, and the like. The flow rate and flow rate of the purge gas (second-stage carrier gas) supplied from the carrier gas ejection parts 43s, 43b, 43t can be freely adjusted by adjusting the dimensions of the carrier gas ejection parts 43s, 43b, 43t. is there.

(C) 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 purge gas is supplied to the purge gas flow paths 42s, 42b, 42t. Since it is made to distribute | circulate, the heat which goes to a low temperature member from a high temperature member can be interrupted | blocked.

(D) 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 from the carrier gas ejection portions 43s, 43b, and 43t into the vaporization tubes 52s, 52b, and 52t, the vaporized raw material is sprayed by the back flow. Contact with the nozzles 31s, 31b, and 31t, 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.

(E) According to the present embodiment, clogging of the spray nozzles 31s, 31b, and 31t can be prevented by the above-described heat blocking effect by the purge gas and the purge effect of the spray nozzle.

(F) According to the present embodiment, in the vaporizers 229s, 229b, and 229t, the particle size of the liquid raw material is set in two stages by the carrier gas acting as the first stage carrier gas and the purge gas acting as the second stage carrier gas. By making it small and vaporizing, the particle size of the raw material can be made finer, vaporization failure can be prevented, and the vaporization speed and vaporization efficiency can be increased.

(G) According to the present embodiment, the carrier gas ejection portions 43s, 43b, 43t for flowing the purge gas acting as the second-stage carrier gas are throttled toward the carrier gas ejection port, and the flow at the carrier gas ejection port The road is the narrowest. Therefore, the flow rate of the purge gas acting as the second stage carrier gas can be increased, and the energy given to the raw material can be increased. Thereby, the particle size of a raw material can be reduced more efficiently, vaporization failure can be prevented, and the vaporization speed and vaporization efficiency can be increased.

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

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

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

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

  In the above-described embodiment, each vaporizer is supplied for each supply operation to the processing chamber 201 (for each discharge operation of each liquid 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, the cleaning in each of the vaporizers 229s, 229b, and 229t is facilitated by performing the cleaning for each supply operation (vaporization operation) as in the above-described embodiment, and the vaporization operation of the liquid raw material becomes 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 times other than when the vaporizing 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 each of 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 material, the cleaning liquid supplied into the liquid material channel also functions as a part of the solvent for diluting the liquid material. 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 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. 15 is a schematic configuration diagram of a vertical processing furnace of a vertical ALD apparatus suitably used in the second embodiment. FIG. 15A is a vertical cross section of the processing furnace 302, and FIG. The furnace 302 part is shown by the AA sectional view of FIG.

  As shown in FIG. 15A, 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 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 of the exhaust pipe 331 opposite to the connection side 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 configured to open and close the valve so that the processing chamber 301 can be evacuated and stopped, and the valve opening can be adjusted to adjust the pressure in the processing chamber 301. 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 disc shape. On the upper surface of the seal cap 319, an O-ring 320b is provided as a seal member that contacts 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 lifted and lowered in the vertical direction by a boat elevator 315 as a lifting mechanism vertically disposed outside the process tube 303, thereby bringing the boat 317 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 step of forming a thin film on the wafer 200 by the ALD method will be described as one step of the semiconductor device manufacturing process using the vertical ALD apparatus processing furnace 302 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. 15A, 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 the desired film thickness is formed is held by 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).

(Other embodiments of the present invention)
As mentioned above, although embodiment of this invention was described concretely, this invention is not limited to the above-mentioned embodiment, Various changes are possible in the range which does not deviate from the summary. For example, the present invention can be suitably applied not only to a semiconductor manufacturing apparatus that processes a wafer but also to an apparatus that processes a photomask, a printed wiring board, a glass substrate such as an LCD device, a compact disk, and a magnetic disk. is there. Further, the configuration of the process chamber is not limited to the above-described embodiment.

<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 raw material, a heater for heating the vaporizing chamber, a spray nozzle for spraying the liquid raw material into the vaporizing chamber, and a surface of a tip portion of the spray nozzle. A carrier gas ejection part forming member that covers a part and forms a carrier gas ejection part for ejecting a carrier gas from the periphery of the tip part of the spray nozzle into the vaporization chamber, and the carrier gas ejection part forming member Is provided with a through-hole for accommodating the tip portion of the spray nozzle, and a plurality of protrusions that are in contact with the tip portion of the spray nozzle are provided at a plurality of locations on the inner wall surface of the through-hole. A vaporizer is provided.

Preferably, the tip portion of the spray nozzle has a tapered surface, and the plurality of protrusions are in contact with the tapered surface.
Preferably, the plurality of protrusions are provided at equal intervals.
Preferably, the plurality of protrusions include three protrusions, which are provided at equal intervals.

  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 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 a reactive gas for supplying a reactive gas different from the raw material gas into the processing chamber A vaporizing chamber for vaporizing a liquid raw material, a heater for heating the vaporizing chamber, a spray nozzle for spraying the liquid raw material into the vaporizing chamber, and a tip portion of the spray nozzle. And a carrier gas ejection part forming member that forms a carrier gas ejection part for ejecting a carrier gas from the periphery of the tip part of the spray nozzle into the vaporization chamber. The carrier gas ejection portion forming member is provided with a through hole in which the tip portion of the spray nozzle is accommodated, and contacts the tip portion of the spray nozzle at a plurality of locations on the inner wall surface of the through hole. A substrate processing apparatus provided with a plurality of protrusions is provided.

  According to still another aspect of the present invention, a step of carrying a substrate into the processing chamber, a vaporizing chamber for vaporizing the liquid source, a heater for heating the vaporizing chamber, and a spray nozzle for spraying the liquid source into the vaporizing chamber. And a carrier gas ejection part forming member that covers a part of the surface of the tip part of the spray nozzle and forms a carrier gas ejection part that ejects a carrier gas from the periphery of the tip part of the spray nozzle into the vaporization chamber; The carrier gas ejection portion forming member is provided with a through hole that accommodates the tip portion of the spray nozzle, and the spray nozzle is provided at a plurality of locations on the inner wall surface of the through hole. The sprayer is used while ejecting a carrier gas from the periphery of the tip portion of the spray nozzle into the vaporization chamber using a vaporizer provided with a plurality of protrusions that come into contact with the tip portion of the spray nozzle. A step of spraying a liquid raw material from the nozzle and vaporizing the liquid raw material in the vaporizing chamber; a step of supplying a raw material gas obtained by vaporizing the liquid raw material in the vaporizer into the processing chamber; And a step of unloading the semiconductor device from the processing chamber.

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 Capillary tube Part 41s, 41b, 41t Nozzle cover (carrier gas ejection part forming member)
43s, 43b, 43t Carrier gas ejection part 44s, 44b, 44t Through hole 45s, 45b, 45t Protrusion part 51s, 51b, 51t Vaporization chamber 61s, 61b, 61t Heater 229s, 229b, 229t Vaporizer

Claims (3)

A vaporization chamber for vaporizing the liquid raw material;
A heater for heating the vaporization chamber;
A spray nozzle for spraying a liquid raw material into the vaporization chamber;
A carrier gas ejection part forming member for covering a part of the surface of the tip part of the spray nozzle and forming a carrier gas ejection part for ejecting a carrier gas from the periphery of the tip part of the spray nozzle into the vaporization chamber; Have
The carrier gas ejection portion forming member is provided with a through hole in which the tip portion of the spray nozzle is accommodated, and contacts the tip portion of the spray nozzle at a plurality of locations on the inner wall surface of the through hole. A vaporizer comprising a plurality of protrusions. 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 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 covers a part of the surface of the vaporization chamber for vaporizing the liquid raw material, a heater for heating the vaporization chamber, a spray nozzle for spraying the liquid raw material into the vaporization chamber, and a tip portion of the spray nozzle. A carrier gas ejection portion forming member that forms a carrier gas ejection portion for ejecting a carrier gas from the periphery of the tip portion of the spray nozzle into the vaporization chamber, and the carrier gas ejection portion forming member includes A through hole for receiving the tip portion of the spray nozzle is provided, and a plurality of protrusions that come into contact with the tip portion of the spray nozzle are provided at a plurality of locations on the inner wall surface of the through hole. A substrate processing apparatus. 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 spray nozzle for spraying the liquid source into the vaporizing chamber, a portion of the surface of the tip portion of the spray nozzle, A carrier gas ejection portion forming member that forms a carrier gas ejection portion for ejecting a carrier gas from the periphery of the tip portion into the vaporization chamber, and the carrier gas ejection portion forming member includes: Using a vaporizer provided with a plurality of protrusions that are in contact with the tip portion of the spray nozzle at a plurality of locations on the inner wall surface of the through-hole in which the tip portion is accommodated. The liquid material is sprayed from the spray nozzle while jetting a carrier gas from the periphery of the tip portion of the spray nozzle into the vaporization chamber, and the liquid material is vaporized in the vaporization chamber. And a step,
Supplying a source gas obtained by vaporizing a liquid source with the vaporizer into the processing chamber and processing the substrate;
And a step of unloading the processed substrate from the processing chamber.

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