JP2010135846A - Method of manufacturing semiconductor device and substrate processing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To promote the removal of an organic metal liquid raw material from a liquid raw material flow channel of a vaporizer and suppresses the liquid raw material flow channel from being blocked. <P>SOLUTION: A method of manufacturing semiconductor devices, includes a step of processing a substrate, by supplying multiple reactants several times into a processing chamber in which the substrate is placed, wherein at least one of the multiple reactants includes a source gas formed by vaporizing a liquid raw material in a vaporizer. In the step of processing the substrate, a vaporization operation is performed intermittently, in which a solvent capable of dissolving the liquid raw material is fed continuously to the vaporizer, and the liquid raw material is supplied to the vaporizer so that the liquid raw material is vaporized, and a flash operation is performed, when the liquid raw material vaporization operation is not performed, in which the solvent is flowed to the vaporizer, at a flow rate which is higher than the flow rate of the solvent supplied during the liquid raw material vaporizing operation, each time the liquid material vaporizing operation is performed by a predetermined number of times. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a semiconductor device for processing a substrate with a source gas obtained by vaporizing a liquid source, and a substrate processing apparatus.

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

  Here, as the first processing gas described above, for example, a gas obtained by vaporizing a liquid raw material that is liquid at room temperature may be used. And a vaporizer may be used as an apparatus which vaporizes a liquid raw material. The vaporizer includes, for example, a vaporization chamber that vaporizes a liquid raw material to generate a gas, a liquid raw material flow channel that is a flow path until the liquid raw material is discharged into the vaporization chamber, and a raw material gas generated in the vaporization chamber And a supply port for supplying to the outside.

  The liquid material flow path is provided with an open / close valve that controls the supply of the liquid material. In the above-described step (1), the supply of the liquid material to the vaporizing chamber is started by opening the opening / closing valve provided in the liquid material channel. In steps other than (1), the supply of the liquid raw material to the vaporizing chamber is stopped by closing the open / close valve, and the liquid raw material remaining in the liquid raw material flow path is altered to block the liquid raw material flow path. In order to prevent this, an inert gas is supplied into the liquid source flow path and purged.

  Here, as the above-described liquid raw material, for example, an organometallic liquid raw material containing an element such as Sr (strontium), Ba (barium), La (lanthanum) may be used. Since these organometallic liquid raw materials have low vapor pressure and high viscosity, they are often used after being diluted with a solvent (solvent) such as ECH (ethylcyclohexane) or THF (tetrahydrofuran). .

  However, the above-mentioned solvent has a higher vapor pressure than the organic metal liquid raw material that is a solute. Therefore, in steps other than the above (1), if an inert gas is supplied into the liquid source channel and purged, only the solvent evaporates first, and only the organometallic liquid source is in the liquid source channel. It may remain. And since the organometallic liquid raw material is highly viscous, it is difficult to remove it by supplying an inert gas into the liquid raw material channel and purging it, and the liquid raw material channel is blocked by the liquid raw material. May end up.

  A method of manufacturing a semiconductor device and a substrate processing apparatus according to the present invention are intended to promote removal of an organometallic liquid source from the liquid source channel of a vaporizer and suppress blockage in the liquid source channel. .

  According to one aspect of the present invention, a step of loading a substrate into a processing chamber, a step of processing the substrate by supplying a plurality of types of reactants into the processing chamber a plurality of times, and the processing of the substrate A step of unloading from a processing chamber, and at least one of the plurality of types of reactants includes a source gas obtained by vaporizing a liquid source in a vaporization unit, and in the step of processing the substrate, A vaporizing operation for supplying and vaporizing the liquid raw material to the vaporizing unit is intermittently performed, and a solvent capable of dissolving the liquid raw material in the vaporizing unit is at least at a time other than during the vaporizing operation of the liquid raw material. The liquid is flowed at a flow rate of 1 and the solvent is larger than the first flow rate in the vaporization unit every time the liquid raw material is vaporized for a predetermined number of times except during the vaporization operation. Second flow The method of manufacturing a semiconductor device to flow in is provided.

  According to another aspect of the present invention, a processing chamber for processing a substrate, a vaporization unit for vaporizing a liquid raw material, a liquid raw material supply system for supplying a liquid raw material to the vaporization unit, and the liquid raw material in the vaporization unit A source gas supply system for supplying the vaporized source gas into the processing chamber, a reaction gas supply system for supplying a reaction gas different from the source gas into the processing chamber, and a solvent capable of dissolving the liquid source A solvent supply system for supplying to the vaporization section, and a vaporization operation for performing the supply of the raw material gas and the reaction gas into the processing chamber a plurality of times and supplying the liquid raw material to the vaporization section for vaporization. At a time other than at the time of the vaporization operation of the liquid raw material, and at a time other than at the time of the vaporization operation of the liquid raw material, at a time other than at the time of the vaporization operation of the liquid raw material, The liquid material Each time the operation is performed a predetermined number of times, the liquid source supply system, the vaporization unit, the source gas supply system, and the solvent are supplied to the vaporization unit at a second flow rate that is larger than the first flow rate. There is provided a substrate processing apparatus having a supply system and a controller that controls the reaction gas supply system.

  According to the semiconductor device manufacturing method and the substrate processing apparatus according to the present invention, it is possible to promote the removal of the organometallic liquid source from the liquid source channel of the vaporizer and to suppress the blockage in the liquid source channel. .

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 schematic block diagram of the vertical processing furnace of the vertical ALD apparatus concerning 3rd Embodiment of this invention, (a) shows a processing furnace part with a longitudinal cross-section, (b) shows a processing furnace part (a ) Is a cross-sectional view taken along line AA of FIG. It is a block diagram of the gas supply system in the substrate processing apparatus concerning 2nd Embodiment of this invention. It is a sequence diagram which shows the timing of the raw material supply to a vaporizer, solvent supply, and flushing operation | movement in the substrate processing process concerning 2nd Embodiment of this invention. FIG. 9 is a modification of the sequence diagram shown in FIG. 9 and shows the solvent supply timing when the start timing of the flushing operation is delayed. FIG. 10 is a modification of the sequence diagram shown in FIG. 10, (a) shows the timing of solvent supply when no solvent is flown in each vaporization cycle, and (b) shows the solvent flow rate in the vaporization cycle and the solvent in the washing cycle. The timing of solvent supply in the case where the flow rate is lower than the flow rate is shown. FIG. 10 is a modified example of the sequence diagram shown in FIG. 10, (a) shows the timing of solvent supply when a large flow rate flushing operation is performed every time a vaporization cycle is performed, and (b) shows a small value every time a vaporization cycle is performed. The timing of solvent supply in the case where the flushing operation at a larger flow rate is performed every time the vaporization cycle is performed a predetermined number of times while performing the flushing operation at the flow rate is shown.

(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 a pressure regulator 262 such as an APC (Auto Pressure Controller) that controls the inside of the processing chamber 201 to a predetermined pressure, a raw material recovery trap 263, and The vacuum pump 264 is connected in series in order. An exhaust system (exhaust line) is mainly configured by the exhaust port 260, the exhaust pipe 261, the pressure regulator 262, the raw material recovery trap 263, and the vacuum pump 264.

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

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

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

On the other hand, a lower plate 205 is locked to the outer peripheral portion of the support base 203. The lower plate 205 includes a ring-shaped concave portion 205b and a flange portion 205a provided integrally on the inner upper portion of the concave portion 205b. The recess 205b is provided so as to block a gap between the outer peripheral portion of the support base 203 and the inner wall side surface of the processing chamber 201. A part of the bottom of the recess 205b near the exhaust port 260 is provided with a plate exhaust port 205c for 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 an exhaust duct 259 is formed with the inside of the recess 205b as a gas flow path region. . 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 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 etching of reaction products deposited on the inner wall of the exhaust duct 259. Is preferred.

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

  Next, the configuration of the gas supply system connected to the gas inlet 210 described above will be described with reference to FIGS. FIG. 1 is a configuration diagram of a gas supply system (gas supply line) included in the substrate processing apparatus according to the first embodiment of the present invention, and FIG. 6 is a schematic configuration of a vaporizer according to the first embodiment of the present invention. FIG.

  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 vaporizes the liquid material in the vaporization unit. A raw material gas supply system for supplying the raw material gas into the processing chamber 201, a reactive gas supply system for supplying a reactive gas different from the raw material gas into the processing chamber 201, and a cleaning liquid for supplying a cleaning liquid (solvent) to the vaporizer A supply system (solvent supply system). Furthermore, the substrate processing apparatus according to the first embodiment of the present invention has a purge gas supply system 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. In addition, it is preferable to use gas which does not react with a liquid raw material as pressurized gas, for example, inert gas, such as Ar gas, is used suitably.

  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. The open / close valves vs1, vb1, and vt1 are provided inside the vaporizers 229s, 229b, and 229t, 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).

<Vaporization part>
The vaporizers 229s, 229b, and 229t serving as vaporizers for vaporizing the liquid raw material generate the raw material gas by heating and vaporizing the liquid raw material with the heaters 23s, 23b, and 23t, as shown in detail in FIG. Vaporization chambers 20s, 20b, and 20t, and liquid source channels 21s, 21b, and 21t that are channels until the liquid source is discharged into the vaporization chambers 20s, 20b, and 20t,
The above-described on-off valves vs1, vb1, vt1 for controlling the supply of the liquid source into the vaporization chambers 20s, 20b, 20t, and the first source gas supply described later for the source gas generated in the vaporization chambers 20s, 20b, 20t. It has a pipe 213s, a second source gas supply pipe 213b, and source gas supply ports 22s, 22b, and 22t as outlets that supply the third source gas supply pipe 213t. The downstream end portions of the first liquid raw material supply pipe 211s, the second liquid raw material supply pipe 211b, and the third liquid raw material supply pipe 211t are respectively connected to the liquid raw material flow paths 21s, via the on-off valves vs1, vb1, and vt1, respectively. 21b, 21t is connected to the upstream end. Carrier liquid supply pipes 24s, 24b, and 24t as carrier gas supply systems (carrier gas supply lines) are connected to the liquid source flow paths 21s, 21b, and 21t, respectively. Ar in the vaporization chambers 20s, 20b, and 20t It is configured to supply a carrier gas such as.

<Raw gas supply system>
The source gas supply ports 22s, 22b, and 22t of the vaporizers 229s, 229b, and 229t have a first source gas supply pipe 213s, a second source gas supply pipe 213b, and a first source gas supply pipe 213b that supply source gas into the processing chamber 201, respectively. The upstream end portions of the three source gas supply pipes 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 is preferably used as the pressurized gas.

Further, a cleaning liquid supply pipe (solvent supply pipe) 212 is connected to the cleaning liquid supply source 220e. The upstream end of the cleaning liquid supply pipe 212 is immersed in the cleaning liquid stored in the cleaning liquid supply source 220e. The downstream end of the cleaning liquid supply pipe 212 is connected to be branched into three lines, that is, a first cleaning liquid supply pipe 212s, a second cleaning liquid supply pipe 212b, and a third cleaning liquid supply pipe 212t. The downstream end portions of the first cleaning liquid supply pipe 212s, the second cleaning liquid supply pipe 212b, and the third cleaning liquid supply pipe 212t are connected to the liquid source channels 21s, 21b, and 21t of the vaporizers 229s, 229b, and 229t, respectively. Yes. The first cleaning liquid supply pipe 212
s, the second cleaning liquid supply pipe 212b, and the third cleaning liquid supply pipe 212t include liquid flow rate controllers 222s, 222b, and 222t as flow rate control means for controlling the supply flow rate of the cleaning liquid, and an open / close valve vs2 that controls the supply of the cleaning liquid. , Vb2, and vt2 are provided. The open / close valves vs2, vb2, and vt2 are provided inside the vaporizers 229s, 229b, and 229t, respectively.

  With the above configuration, the liquid raw material of the vaporizers 229s, 229b, and 229t is supplied by supplying the pressurized gas from the cleaning liquid pressurized gas supply pipe 237e, closing the open / close valves vs1, vb1, and vt1, and opening the open / close valves vs2, vb2, and vt2. The cleaning liquid can be pumped (supplied) into the channels 21s, 21b, and 21t to clean the liquid source channels 21s, 21b, and 21t. 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, and 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 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 an ozone gas supply port 22o as an outlet 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 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 Ar gas supply source 230a includes a purge gas supply pipe 2
14 upstream ends are connected. 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 224s as a flow rate control means for controlling the supply flow rate of Ar gas. 224b, 224t, 224o and open / close valves vs4, vb4, vt4, vo4 for controlling the supply of Ar gas are provided, respectively. 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).

<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 transport 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 vs6, vb1. Controls the operations of vb6, vt1 to vt6, vo3 to vo6, liquid flow rate controllers 221s, 221b, 221t, 222s, 222b, 222t, flow rate controllers 224s, 224b, 224t, 221o, 222o, 224o and the like.

  As described above, the substrate processing apparatus according to the first embodiment of the present invention is configured.

(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, with the on-off valve vs2 closed, the on-off valve vs1 is opened, and the pumping gas is supplied from the first pumping gas supply pipe 237s, and the first liquid source is supplied from the first liquid source supply source 220s to the vaporizer 229s. The first liquid source is vaporized (supplied) and vaporized in the vaporizer 229s to generate the first source gas. 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, and the cleaning of the liquid raw material channels 21b and 21t of the vaporizers 229b and 229t is started. 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.

  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 21s of the vaporizer 229s. The inside of the passage 21s is washed. 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 into the liquid source channel 21s cleans the liquid source channel 21s and then enters the vaporization chamber 20s. To be vaporized. At this time, the first liquid source and the solvent remaining in the liquid source channel 21s are also supplied into the vaporizing chamber 20s 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 Note that the cleaning of the liquid source flow path 21s of the vaporizer 229s is continued, for example, until the next supply of the first liquid source to the vaporizer 229s is started (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, the open / close valve vt2 is closed and the open / close valve vt1 is opened, and the pressurized gas is supplied from the third pressurized gas supply pipe 237t to supply the third liquid material from the third liquid material supply source 220t to the vaporizer 229t. Then, the third liquid source is vaporized by the vaporizer 229t to generate a third source gas. In the ALD process (S6) using the first source gas, the third source gas is supplied into the processing chamber 201 by opening the on-off valve vt5 while operating the vacuum pump 264 and keeping the on-off valve vt3 closed. The process chamber 201 is bypassed and exhausted. In this way, the third source gas is generated in advance, and the opening and closing of the open / close valves vt3 and vt5 is switched in the ALD step (S7) using the third source gas described later, thereby changing the flow path of the third source gas. Switch. Thereby, in the ALD process (S7) using the third source gas, stable supply of the third source gas into the processing chamber 201 can be started or stopped quickly, which is preferable.

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

  After a predetermined time has elapsed after opening the on-off valve vt3 and starting the supply of the third source gas, the on-off valve vt3 is closed and the on-off valves vt4, vt5 are opened to supply the third source gas into the processing chamber 201. To stop. At the same time, the on-off valve vt1 is closed, and the supply of the third liquid material to the vaporizer 229t is also stopped.

  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 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 21t of the vaporizer 229t. The inside of the passage 21t is washed. 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 21t is cleaned in the liquid source channel 21t and then into the vaporization chamber 20t. To be vaporized. At this time, the third liquid source and the solvent remaining in the liquid source channel 21t are also supplied into the vaporizing chamber 20s 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 The cleaning of the liquid raw material flow path 21t of the vaporizer 229t is continued, for example, until the next supply of the third liquid raw 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, the first source gas supply pipe 213s and the second source gas supply pipe 2 are used.
13b, the open / close valves vs4, vb4, and vt4 are kept open to prevent the ozone gas from entering the third source gas supply pipe 213t and to promote the diffusion of the ozone gas in the processing chamber 201. It is preferable that Ar gas always flow in the chamber 201.

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

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

  In the ALD process (S7) using the third source gas, a source gas (hereinafter referred to as a second source gas) obtained by vaporizing the second liquid source (organic metal liquid source containing Ba element) is generated in advance ( Pre-vaporization) (PT1-). That is, the on-off valve vb2 is closed and the on-off valve vb1 is opened, and the pressurized gas is supplied from the second pressurized gas supply pipe 237b to supply the second liquid source from the second liquid source supply source 220b to the vaporizer 229b. Then, the second liquid source is vaporized by the vaporizer 229b to generate the second source gas. In the ALD process (S7) using the third source gas, the second source gas is supplied into the processing chamber 201 by opening the on-off valve vb5 while operating the vacuum pump 264 and keeping the on-off valve vb3 closed. The process chamber 201 is bypassed and exhausted. In this way, the second source gas is generated in advance, and the opening and closing of the on-off valves vb3 and vb5 is switched in the ALD step (S8) using the second source gas, which will be described later. Switch. Thereby, in the ALD process (S8) using the second source gas, stable supply of the second source gas into the processing chamber 201 can be started or stopped quickly, which is preferable.

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

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

  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).

In addition, after closing the on-off valve vb1 and stopping the supply of the second liquid raw material, the vaporizer 229b
Starts cleaning (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 21b of the vaporizer 229b. The inside of the passage 21b is washed. 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 21b is cleaned in the liquid source channel 21b and then into the vaporization chamber 20b. To be vaporized. At this time, the second liquid source and the solvent remaining in the liquid source channel 21b are also supplied into the vaporizing chamber 20b and vaporized. The vaporized cleaning liquid, the second liquid source, and the solvent are exhausted from the vent pipe 215b by bypassing the processing chamber 201 without being supplied into the processing chamber 201 through the second source gas supply pipe 213b. The The cleaning of the liquid source flow path 21b of the vaporizer 229b is continued, for example, until the next supply of the second liquid source 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, the open / close valve vt2 is closed and the open / close valve vt1 is opened, and the pressurized gas is supplied from the third pressurized gas supply pipe 237t to supply the third liquid material from the third liquid material supply source 220t to the vaporizer 229t. Then, the third liquid source is vaporized by the vaporizer 229t to generate a third source gas. 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 (S6 to S9) using each source gas, the source gas is adsorbed on the wafer 200 without being thermally decomposed. Further, when ozone gas is supplied, the raw material gas molecules adsorbed on the wafer 200 react with the ozone gas, whereby a thin film of less than one atomic layer (less than 1 cm) is formed on the wafer 200. At this time, impurities such as C and H mixed in the thin film can be desorbed by ozone gas.

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

(3) Effects According to the First Embodiment According to the present embodiment, the vaporizer is used at a time other than when the raw material gas obtained by vaporizing the liquid raw material in the vaporizers 229s, 229b, and 229t is supplied into the processing chamber 201. The vaporizers 229s, 229s, 229b, and 229t are supplied with a solvent (ECH or the like) for diluting the liquid raw material, instead of supplying an inert gas into the liquid raw material flow paths 21s, 21b, and 21t of the 229s, 229b, and 229t. 229b and 229t are cleaned. Thereby, the inside of the liquid source flow paths 21s, 21b, and 21t can be cleaned in a low viscosity state while the liquid source is diluted with the solvent. That is, it can be suppressed that only the solvent evaporates first in the liquid source flow paths 21s, 21b, and 21t, and only the organometallic liquid source remains.

Further, according to the present embodiment, immediately after the on-off valves vs1, vb1, vt1 are closed, that is, immediately after the supply of the liquid material to the vaporizers 229s, 229b, 229t is stopped, the inside of the vaporizers 229s, 229b, 229t. Has started cleaning. Therefore, after the supply of the liquid source to the vaporizers 229s, 229b, and 229t is stopped, the organometallic liquid source remains in the liquid source channels 21s, 21b, and 21t, and the inside of the liquid source channels 21s, 21b, and 21t is organometallic. It is possible to suppress clogging with the liquid material.

  As described above, according to the present embodiment, the organometallic liquid source from the liquid source channels 21s, 21b, and 21t of the vaporizers 229s, 229b, and 229t when the supply of the liquid source to the vaporizers 229s, 229b, and 229t is stopped. Is promoted, and blockage in the liquid material flow paths 21s, 21b, and 21t due to the organometallic liquid material is suppressed.

<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, each vaporizer is supplied for each supply operation of each raw material gas to the processing chamber 201 (for each discharge operation of each liquid raw material to the vaporizers 229s, 229b, and 229t). Although the case where the liquid source flow paths 21s, 21b, and 21t of 229s, 229b, and 229t are cleaned has been described, the present invention is not limited to the above-described embodiment. That is, the cleaning of the liquid raw material flow paths 21s, 21b, and 21t of the vaporizers 229s, 229b, and 229t may be performed every plural supply operations of the respective raw material gases, for example, every two supply operations. . However, the cleaning in each supply operation as in the above-described embodiment promotes the cleaning of the liquid source flow paths 21s, 21b, and 21t of the vaporizers 229s, 229b, and 229t, and the liquid source This is preferable because the vaporization operation is more stable.

  Further, in the above-described embodiment, the cleaning operation in the liquid raw material flow paths 21s, 21b, and 21t of the vaporizers 229s, 229b, and 229t is always performed at times other than when the vaporization operation is performed. The invention is not limited to the embodiments described above. For example, the cleaning operation in the liquid material channels 21s, 21b, and 21t of the vaporizers 229s, 229b, and 229t is performed when the organometallic liquid material in the liquid material channels 21s, 21b, and 21t is removed. It may be stopped even when it is not performed.

Conversely, the cleaning operation in the liquid material flow paths 21s, 21b, and 21t of the vaporizers 229s, 229b, and 229t is performed not only when the liquid material is vaporized, but also when the liquid material is vaporized. You may make it carry out also when performing. In other words, the cleaning liquid may be continuously supplied into the liquid raw material flow paths 21s, 21b, and 21t 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 flow paths 21s, 21b, and 21t 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 during the liquid raw material vaporization operation. Each time a predetermined number of times is performed, a flushing operation may be performed in which the flow rate of the cleaning liquid is larger than the flow rate of the cleaning liquid supplied during the liquid material vaporization operation.

(Second Embodiment)
Next, a second embodiment of the present invention will be described. In the second embodiment, the above-described flushing operation and the like will be mainly described.

  As described above, when a thin film containing a metal element is formed in a semiconductor manufacturing process, an organometallic material in which carbon, hydrogen, nitrogen, or the like is chemically added to a metal atom may be used as a raw material. By using an organic metal, the vapor pressure increases, and the raw material can be handled as a liquid at a temperature near room temperature. Moreover, even if it is a solid organic metal or a liquid material having a very high viscosity at room temperature, if it is soluble in an organic solvent, it is diluted (dissolved) in the solvent and liquefied (hereinafter referred to as a liquefied raw material) By doing so, it can be handled as a low viscosity liquid. Such liquid raw materials and liquefied raw materials (in the present specification, these are collectively referred to simply as liquid raw materials) are vaporized by a vaporizer and then supplied into a reaction chamber of a semiconductor manufacturing apparatus. Although contributing to the membrane, conventional vaporizers have the following problems.

  In the case of a vaporizer that performs vaporization with a spray mechanism such as a spray, the raw material is atomized and vaporized by spraying the liquid raw material into the vaporizing chamber through a thin pipe (nozzle). Therefore, when a viscous raw material is vaporized, the raw material may be adsorbed and remain in the thin pipe of the sprayer, causing the pipe to be blocked. The vaporization chamber is usually kept at a high temperature to vaporize the atomized raw material, but even if it is a low viscosity liquid, the liquid raw material in the vicinity of the spray mechanism is decomposed by the thermal radiation, and the decomposition products are connected to the piping. In some cases, it was occluded. Decomposition products often do not dissolve in the solvent, and removal can only be done by means such as decomposition cleaning.

  Further, even in the liquefied raw material, the pipe clogging due to the so-called “first jump” phenomenon often occurs. This is because the inside of the vaporization chamber is normally kept at a reduced pressure, whereas the raw material is supplied at a normal pressure, so the inside of the fine pipe of the sprayer is reduced in pressure as it approaches the vaporization chamber, and the solvent that is easy to vaporize first. This is because the solid raw material which is a solute or the liquid raw material having a high viscosity remains in the thin pipe. This solid or highly viscous liquid caused blockage of the piping.

  In this embodiment, the clogging in the liquid raw material flow path is particularly achieved by the operation method of the vaporizer for stably vaporizing the material that is likely to be clogged in the spray mechanism of the vaporizer for a long period of time, that is, by the flushing operation or the like. The method of further suppressing will be described.

  FIG. 8 shows a configuration example of a gas supply system of the substrate processing apparatus in the second embodiment. Note that the gas supply system of the substrate processing apparatus in the second embodiment shown in FIG. 8 is the two raw material supply lines of the gas supply system of the substrate processing apparatus in the first embodiment shown in FIG. Part of a line for supplying a raw material), a line for supplying a Ti raw material (third raw material), and a line for further supplying ozone gas (reactive gas) are extracted. The configuration of each supply line and substrate processing apparatus in the second embodiment is the same as the configuration of each supply line and substrate processing apparatus in the first embodiment. In FIG. 8, elements that are substantially the same as those described in FIG. 1 are given the same reference numerals, and descriptions thereof are omitted.

The vaporizer in this embodiment includes a pipe for supplying a liquid source (liquid source supply pipe), a pipe for supplying a solvent capable of dissolving the source (solvent supply pipe), and a carrier gas pipe (carrier gas supply). Pipes) are each connected via a flow regulator. In the present embodiment, two vaporizers having this configuration are used. That is, the vaporizers 229t and 229s in this embodiment include liquid source supply pipes 211t and 211s, solvent supply pipes (cleaning liquid supply pipes) 212t and 212s, and carrier gas supply pipes 218t and 218s, respectively. 221s, 222t, 222s, 225t, and 225s.

  Hereinafter, using the substrate processing apparatus of the second embodiment described above, as a process of manufacturing a semiconductor device, using two types of raw materials, a substrate processing process of forming a thin film on a wafer by the ALD method, This will be described with reference to FIG. FIG. 9 is a timing chart showing the timing of the vaporization operation by supplying the raw materials to the vaporizers 229t and 229s, the cleaning operation by supplying the solvent, and the flushing operation by supplying a large amount of solvent in the substrate processing process according to the second embodiment of the present invention. FIG. In this timing chart, the horizontal axis represents time, and the vertical axis represents the raw material and solvent flow rates. In FIG. 9, the timing of supplying the carrier gas is omitted. This figure also shows the flow of each step (A, B, P) performed in the processing chamber 201. A, B, and P showing the steps performed in the processing chamber 201 are the supply of the raw material A (Ti raw material), the supply of the raw material B (Sr raw material), the purge, and the supply of the oxidizing agent (purging / oxidizing agent). Supply / purge). In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 280.

  The substrate processing step in the second embodiment is different from the substrate processing step in the first embodiment in the steps S6 to S10 of the substrate processing steps in the first embodiment, that is, the step of substantially forming a thin film. It is only a certain film forming process, and the other processes are the same. Hereinafter, the film forming process will be described.

  When starting the vaporization operation for film formation, first, the valves vt2, vs2, vt7, and vs7 are opened, and the flow rate is adjusted by the flow rate regulators 222t and 222s of the solvent supply pipes 212t and 212s in both the raw materials A and B systems, respectively. The solvent is supplied into the vaporization chambers 20t and 20s of the vaporizers 229t and 229s together with the carrier gas whose flow rate is adjusted by the flow rate regulators 225t and 225s of the carrier gas supply pipes 218t and 218s, respectively. At this time, since the valves vt3 and vs3 are closed and the valves vt5 and vs5 are opened, the evaporated solvent is exhausted to the vent lines 215t and 215s. At this time, the solvent is allowed to flow through the vaporization chambers 20t and 20s at the first flow rate.

  Next, the valve vt1 of the liquid raw material supply pipe 211t for supplying the raw material A is opened, and the raw material A whose flow rate is adjusted by the flow rate controller 221t is introduced into the vaporizing chamber 20t of the vaporizer 229t and vaporized (vaporization cycle). At this time, the valve vt2 is kept open, the solvent supplied from the solvent supply pipe 212t into the vaporizing chamber 20t is kept flowing, and a mixed gas of the raw material A and the solvent is generated in the vaporizing chamber 20t. At this time, the valve vt7 is also kept open. At this time, since the valves vt3 and vs3 are closed and the valves vt5 and vs5 are kept open, the mixed gas of the raw material A and the solvent is exhausted to the vent line 215t. Also at this time, the solvent is allowed to flow into the vaporizing chamber 20t at the first flow rate. However, when the liquid raw material is a liquefied raw material obtained by dissolving a solid or viscous liquid in a solvent, since the raw material already contains the solvent, the solvent supply pipe 212t in the vaporization cycle into the vaporization chamber 20t is used. The solvent supply is not essential and may be omitted.

  Next, the valves vt5 and vt3 of the vent line 215t and the source gas supply pipe 213t are switched. That is, the mixed gas of the raw material A and the solvent is introduced into the processing chamber 201 by closing the valve vt5 of the vent line 215t and opening the valve vt3 of the raw material gas supply pipe 213t (A).

  When the predetermined time elapses, the source gas supply pipe 213t and the valves vt3 and vt5 of the vent line 215t are switched. That is, by closing the valve vt3 of the source gas supply pipe 213t and opening the valve vt5 of the vent line 215t, the introduction of the mixed gas of the source A and the solvent into the processing chamber 201 is stopped. At the same time, the purge gas is introduced into the processing chamber 201 by opening the valve vt4 of the purge gas supply pipe 214t. On the vaporizer 229t side, the valve vt1 is closed to stop the supply of the raw material A into the vaporization chamber 20t, and only the solvent and the carrier gas are supplied into the vaporization chamber 20t while the valves vt2 and vt7 are kept open. The raw material remaining in the vicinity of the vessel 229t, particularly in the vicinity of the spray pipe (liquid raw material flow path 21t) as a spray mechanism is washed away (cleaning cycle). Also at this time, the solvent is allowed to flow into the vaporizing chamber 20t at the first flow rate. The cleaning cycle is continued until the next vaporization cycle, that is, the time when the raw material A is next fed into the vaporization chamber 20t of the vaporizer 229t. During this time, the residual gas of the raw material A in the processing chamber 201 is purged by the purge gas. After purging, the oxidizing agent (ozone gas) is supplied into the processing chamber 201, and after a predetermined time has passed, Purge with a purge gas (P).

  Next, the valve vs1 of the liquid material supply pipe 211s for supplying the material B is opened, and the material B whose flow rate is adjusted by the flow rate controller 221s is introduced into the vaporizing chamber 20s of the vaporizer 229s and vaporized (vaporization cycle). At this time, the valve vs2 is kept open, and the solvent supplied from the solvent supply pipe 212s into the vaporizing chamber 20s continues to flow without stopping, and a mixed gas of the raw material B and the solvent is generated in the vaporizing chamber 20s. At this time, the valve vs7 is also kept open. At this time, since the valves vt3 and vs3 are closed and the valves vt5 and vs5 are kept open, the mixed gas of the raw material B and the solvent is exhausted to the vent line 215s. Also at this time, the solvent is allowed to flow into the vaporizing chamber 20s at the first flow rate. However, when the liquid raw material is a liquefied raw material in which a solid or viscous liquid is dissolved in a solvent, since the raw material already contains the solvent, the solvent supply pipe 212s in the vaporization cycle enters the vaporizing chamber 20s. The solvent supply is not essential and may be omitted.

  Next, the valves vs5 and vs3 of the vent line 215s and the source gas supply pipe 213s are switched. That is, by closing the valve vs5 of the vent line 215s and opening the valve vs3 of the raw material gas supply pipe 213s, the mixed gas of the raw material B and the solvent is introduced into the processing chamber 201 (B).

  When the predetermined time has elapsed, the valves vs3 and vs5 of the source gas supply pipe 213s and the vent line 215s are switched. That is, by closing the valve vs3 of the source gas supply pipe 213s and opening the valve vs5 of the vent line 215s, the introduction of the mixed gas of the source B and the solvent into the processing chamber 201 is stopped. At the same time, the valve vs4 of the purge gas supply pipe 214s is opened to introduce the purge gas into the processing chamber 201. On the vaporizer 229s side, the valve vs1 is closed to stop the supply of the raw material B into the vaporization chamber 20s, and only the solvent and the carrier gas are supplied into the vaporization chamber 20s with the valves vs2 and vs7 open. The raw material remaining in the vicinity of the vessel 229s, in particular, the spray pipe (liquid raw material channel 21s) as a spray mechanism is washed away (cleaning cycle). Also at this time, the solvent is allowed to flow into the vaporizing chamber 20s at the first flow rate. The cleaning cycle is continued until the next vaporization cycle, that is, the time when the raw material B is next supplied into the vaporization chamber 20s of the vaporizer 229s. During this time, the residual gas of the raw material B in the processing chamber 201 is purged with a purge gas, and after purging, an oxidizing agent (ozone gas) is supplied into the processing chamber 201, and after a predetermined time has passed, the inside of the processing chamber 201 is returned again. Purge with a purge gas (P).

As shown in FIG. 9, in the processing chamber 201, supply of the raw material A (A), purge, supply of oxidant, purge (P), supply of raw material B (B), purge, supply of oxidant, purge ( P) is one cycle (film formation cycle), and this cycle is repeated a predetermined number of times. As a result, an STO (strontium titanate) thin film, that is, a SrTiO ₃ thin film having a desired film thickness is formed on the wafer 200. During this time, in the vaporizers 229t and 229s, the vaporization cycle and the cleaning cycle are alternately repeated. In the film forming cycle, the supply of the raw material A (A), the purge, the supply of the oxidant, the purge (P), the supply of the raw material B (B), the purge, the supply of the oxidant, and the purge (P) are performed in one cycle. As the (film formation cycle), this cycle is repeated a predetermined number of times. For example, the supply of the raw material A (A), the purge, the supply of the raw material B (B), the purge, the supply of the oxidizing agent, and the purge are performed in one cycle. As the (film formation cycle), this cycle may be repeated a predetermined number of times. Also in these cases, in the vaporizers 229t and 229s, the vaporization cycle and the cleaning cycle are alternately repeated. In the case of FIG. 9, since the solvent continuously flows through the vaporizers 229t and 229s even in the vaporization cycle, the vaporizers 229t and 229s are cleaned simultaneously with the vaporization of the raw material. That is, regardless of the vaporization cycle and the cleaning cycle, the vaporizers 229t and 229s are continuously cleaned.

  As described above, the clogging of the vaporizers 229t and 229s can be suppressed by the cleaning cycle after the vaporization cycle. However, depending on the nature of the raw material, the solvent is continuously supplied to the vaporizers 229t and 229s during the vaporization cycle, or the solvent As described above, the valve may be closed without flowing or the flow rate may be changed.

  Hereinafter, a flushing operation for further suppressing the blockage of the vaporizers 229t and 229s will be described. The flushing operation is a time other than the vaporization cycle, that is, the cleaning cycle, and every time the vaporization cycle is performed a predetermined number of times, the flow rate of the solvent supplied to the vaporizers 229t and 229s is changed during the normal cleaning cycle and the vaporization cycle. This is an operation of cleaning the vaporizers 229t and 229s as the flow rate of the solvent to be supplied, that is, the second flow rate that is larger than the first flow rate. FIG. 9 shows an example in which the flushing operation is performed in the film formation cycle (4) in the processing chamber 201, that is, an example in which the flushing operation is performed every four vaporization cycles. In FIG. 9, in the cleaning cycle after the vaporization cycle in the film formation cycle (4), the solvent flow rate is temporarily supplied to the vaporizers 229t and 229s with at least twice the flow rate of the normal cleaning cycle or the vaporization cycle. is doing. At this time, the flow rate of the carrier gas may be changed.

  It may be difficult to completely remove the raw material residue adhering to or remaining in the vaporizers 229t and 229s only by performing a normal cleaning cycle for each vaporization cycle. If the vaporization cycle and the cleaning cycle are regularly repeated without completely removing the raw material residue, the raw material residue in the vaporizers 229t and 229s may increase cumulatively with the repetition. is there. On the other hand, each time a predetermined number of vaporization cycles are performed, the cleaning effect is usually achieved by flowing a larger amount of solvent at a higher speed than usual in the spray mechanism portions (liquid raw material flow paths 21t, 21s) of the vaporizers 229t, 229s. The cleaning effect in the cleaning cycle is much greater than that in the cleaning cycle, and it is possible to remove raw material residues that could not be removed in the normal cleaning cycle. In other words, if the flushing operation is performed every time a predetermined number of vaporization cycles are performed, the steady repetition of the vaporization cycle and the cleaning cycle can be changed, and the vaporization that has increased cumulatively. The raw material residue in the vessels 229t and 229s can be removed. And the maintenance period of vaporizer 229t, 229s can be lengthened.

  This operation cycle is called a flushing cycle. Since the frequency, time, and solvent flow rate of the flushing cycle with respect to the normal cleaning cycle vary depending on the physical properties of the raw material, they are determined experimentally, but it is effective to perform the frequency approximately every tens of vaporization cycles. It is.

As the temperature, pressure, solvent (ECH) flow rate, and carrier gas flow rate in the vaporizers 229t and 229s (vaporization chambers 20t and 20s) in each of the vaporization cycle and the normal cleaning cycle of the present embodiment,
Temperature in vaporizer (vaporization chamber): about 250 ° C,
Vaporizer (vaporization chamber) pressure: several to 10 Torr,
Solvent supply flow rate (first flow rate): 0.05 to 0.5 cc / min,
Carrier gas supply flow rate: 1-4 slm,
Is exemplified.

In addition, as the temperature, pressure, solvent (ECH) flow rate, and carrier gas flow rate in the vaporizers 229t and 229s (vaporization chambers 20t and 20s) in the flushing cycle of the present embodiment,
Temperature in vaporizer (vaporization chamber): about 250 ° C,
Vaporizer (vaporization chamber) internal pressure: several to 10 Torr or more,
Solvent supply flow rate (second flow rate): 2 to 20 times, preferably 2 to 10 times the first flow rate,
Carrier gas supply flow rate: 1-10 slm,
Is exemplified. In the flushing cycle, since the flow rate of the solvent supplied to the vaporizers 229t and 229s is increased, the pressure in the vaporizers 229t and 229s is higher than that in the vaporization cycle and the cleaning cycle.

  According to the present embodiment, by constantly flowing the solvent to the vaporizer, it is possible to further suppress the blockage of the vaporizer, particularly the spray mechanism portion, caused by the raw material. In addition, by periodically performing a flushing operation on the vaporizer, it is possible to effectively remove the raw material that remains and accumulates in the spray mechanism portion even though a normal pipe cleaning cycle is performed. Blockage of the spray mechanism portion can be further suppressed. Due to the above effect, the time to reach the piping blockage can be greatly extended, so that the downtime of the apparatus due to maintenance when the vaporizer is closed can be greatly reduced.

  In the substrate processing step shown in FIG. 9, the raw material may remain in the liquid raw material flow paths 21t and 21s of the vaporizers 229t and 229s immediately after the vaporization cycle is completed. In such a case, if the flushing operation is performed immediately after the start of the flushing cycle (immediately after the end of the vaporization cycle), the raw material remaining in the liquid raw material flow paths 21t and 21s has a second flow rate higher than the first flow rate. The solvent at the flow rate causes the solvent to be swept into the vaporization chambers 20t and 20s at a stretch, and the concentration of the raw material in the vaporization chambers 20t and 20s is temporarily increased. And the raw material density | concentration in vaporization chamber 20t, 20s exceeds the vaporization capability of vaporizer 229t, 229s, a raw material cannot be completely vaporized and vaporization defect may generate | occur | produce.

  Therefore, in the present embodiment, when the solvent is caused to flow through the vaporizers 229t and 229s at the second flow rate (when the flushing cycle is performed in the film formation cycle (4)), the solvent is temporarily supplied to the vaporizers 229t and 229s. The flow rate may be smaller than the flow rate, and then the supply of the solvent at the second flow rate to the vaporizers 229t and 229s may be started. In this case, the second flow rate of the solvent having a capacity comparable to the pipe capacity in the liquid raw material flow paths 21t and 21s from the open / close valves vt1 and vs1 to the vaporization chambers 20t and 20s is temporarily supplied to the vaporizers 229t and 229s. After flowing at a smaller flow rate, it is preferable to start supplying the solvent at the second flow rate to the vaporizers 229t and 229s.

FIG. 10 is a modification of the sequence diagram shown in FIG. 9 and shows the solvent supply timing when the start timing of the flushing operation is delayed. According to FIG. 10, when a solvent is caused to flow through the vaporizers 229t and 229s at a second flow rate, the solvent is once caused to flow through the vaporizers 229t and 229s at a first flow rate, and then supplied to the vaporizers 229t and 229s. The flow rate is changed from the first flow rate to the second flow rate to start the flushing operation. As described above, immediately after the start of the flushing cycle (immediately after the end of the vaporization cycle), the solvent is supplied at the first flow rate into the vaporization chambers 229t and 229s in the same manner as in the normal cleaning cycle, and the liquid raw material channels 21t and 2
By extruding the raw material remaining in 1 s into the vaporization chambers 20 t and 20 s and replacing it with the solvent, the raw material concentration in the vaporization chambers 20 t and 20 s exceeds the vaporization capacity of the vaporizers 229 t and 229 s. Can be suppressed, the occurrence of vaporization failure can be suppressed, and the blockage in the liquid raw material flow paths 21t and 21s can be suppressed.

  The delay time of the start timing of the flushing operation, that is, the time from the start of the flushing cycle (at the end of the vaporization cycle) to the start of the flushing operation is, for example, from the open / close valves vt1 and vs1 to the vaporization chambers 20t and 20s. It can be calculated on the basis of the time required to flow a solvent having a capacity comparable to the pipe capacity in the liquid material flow paths 21t and 21s. In FIG. 10, the flow rate of the solvent supplied to the vaporizers 229t and 229s immediately after the start of the flushing cycle (immediately after the end of the vaporization cycle) (the flow rate of the solvent supplied to the vaporizers 229t and 229s until the flushing operation is started). Is not necessarily limited to the first flow rate as long as the flow rate can moderately increase the raw material concentration in the vaporization chambers 20t and 20s and suppress the occurrence of vaporization failure.

  In the second embodiment, the solvent is always allowed to flow in the vaporization chambers 20t and 20s at the first flow rate in the vaporization cycle and the normal cleaning cycle, but the present invention is not limited to such a form. That is, the flushing cycle is also suitable when no solvent is allowed to flow in the vaporization chambers 20t and 20s in the vaporization cycle or when the solvent is allowed to flow in the vaporization chambers 20t and 20s in the vaporization cycle at a flow rate lower than the first flow rate. It can be implemented. FIG. 11 is a modification of the sequence diagram shown in FIG. 10 and shows the timing of the vaporization cycle, the cleaning cycle, and the flushing cycle for one of the vaporizers 229t and 229s in FIG. FIG. 11A shows the timing of solvent supply when no solvent is flown in each vaporization cycle, and FIG. 11B shows the solvent when the solvent flow rate in the vaporization cycle is less than the solvent flow rate in the washing cycle. The timing of supply is shown. In either case, the start timing of the flushing operation can be delayed as shown in FIG.

  In the second embodiment, the flushing cycle is performed every time the vaporization cycle is performed a predetermined number of times, but the present invention is not limited to such a form. That is, this invention is good also as implementing a flushing cycle whenever it performs a vaporization cycle. At this time, the flow rate of the solvent flowing in each flushing operation is not limited to a constant amount, and may be changed. For example, a large flow flushing operation may be performed each time a vaporization cycle is performed, and a large flow flushing operation is performed every predetermined number of vaporization cycles while a small flow flushing operation is performed each time a vaporization cycle is performed. It is good to do. FIG. 12 is a modification of the sequence diagram shown in FIG. 10, in which the timings of the vaporization cycle, the cleaning cycle, and the flushing cycle for one of the vaporizers 229t and 229s in FIG. 10 are extracted. (A) of FIG. 12 shows the timing of supplying the solvent when a large flow rate flushing operation is performed every time the vaporization cycle is performed, and (b) is performed while performing a small flow rate flushing operation every time the vaporization cycle is performed. The timing of supplying the solvent when performing a flushing operation with a larger flow rate every time the vaporization cycle is performed a predetermined number of times is shown. In either case, the start timing of the flushing operation can be delayed as shown in FIG.

(Third embodiment)
Next, a third embodiment of the present invention will be described. In the first embodiment and the second embodiment described above, an example in which film formation is performed using a single-wafer type ALD apparatus that processes one substrate at a time as a substrate processing apparatus has been described. It is not limited to the 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. 7 is a schematic configuration diagram of a vertical processing furnace of a vertical ALD apparatus preferably used in the third embodiment. FIG. 7A shows a processing furnace 302 portion in a vertical cross section, and FIG. The furnace 302 portion is shown in the cross-sectional view along the line AA in FIG.

  As shown in FIG. 7A, 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 opposite to the connection side of the exhaust pipe 331 with the manifold 309. The vacuum pump 346 is connected so that the pressure in the processing chamber 301 can be evacuated to a predetermined pressure (degree of vacuum). The APC valve 342 is opened and closed so that the processing chamber 301 can be evacuated and stopped by evacuation, and the pressure in the processing chamber 301 can be adjusted by adjusting the valve opening. It is a valve.

  Below the manifold 309, a seal cap 319 is provided as a furnace port lid that can airtightly close the lower end opening of the manifold 309. The seal cap 319 is brought into contact with the lower end of the manifold 309 from the lower side in the vertical direction. The seal cap 319 is made of a metal such as stainless steel and is formed in a 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. Similar to the first nozzle 333a and the second nozzle 333b, the temperature sensor 363 is provided along the inner wall of the process tube 303.

  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, open / close valves vs1 to vs6, vb1 to vb6, vt1 to vt6, The operations of vo3 to vo6, liquid flow rate controllers 221s, 221b, 221t, 222s, 222b, 222t, flow rate controllers 224s, 224b, 224t, 221o, 222o, 224o and the like are 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). 7A, 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. . Alternatively, as in the second embodiment described above, supply of raw material A (A), purge, supply of oxidant, purge (P), supply of raw material B (B), purge, supply of oxidant, purge (P ) Is defined as one cycle, and this cycle is repeated a predetermined number of times to form a SrTiO 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).

<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 step of loading a substrate into a processing chamber, a step of processing the substrate by supplying a plurality of types of reactants into the processing chamber a plurality of times, and the processing of the substrate A step of unloading from a processing chamber, and at least one of the plurality of types of reactants includes a source gas obtained by vaporizing a liquid source in a vaporization unit, and in the step of processing the substrate, A vaporizing operation for supplying and vaporizing the liquid raw material to the vaporizing unit is intermittently performed, and a solvent capable of dissolving the liquid raw material in the vaporizing unit is at least at a time other than during the vaporizing operation of the liquid raw material. The liquid is flowed at a flow rate of 1 and the solvent is larger than the first flow rate in the vaporization unit every time the liquid raw material is vaporized for a predetermined number of times except during the vaporization operation. Second flow The method of manufacturing a semiconductor device to flow in is provided.

  Preferably, in the step of processing the substrate, the solvent is continuously flowed to the vaporization section after the vaporization operation of the liquid material is performed once until the vaporization operation is performed next.

  Preferably, in the step of processing the substrate, the solvent is continuously flowed to the vaporization section regardless of the vaporization operation of the liquid raw material.

  Preferably, the solvent that has flowed into the vaporizing section is exhausted without being supplied into the processing chamber at times other than during the vaporizing operation of the liquid raw material.

  Also preferably, the second flow rate is at least twice the first flow rate.

  Preferably, when flowing the solvent at the second flow rate through the vaporization unit, the flow rate of the solvent supplied to the vaporization unit is once set after flowing the solvent through the vaporization unit at the first flow rate. The first flow rate is changed to the second flow rate.

  Further preferably, when the solvent is caused to flow through the vaporization unit at the second flow rate, the solvent is once caused to flow through the vaporization unit at a flow rate smaller than the second flow rate, and then the first to the vaporization unit. Begin feeding the solvent at a flow rate of 2.

  According to another aspect of the present invention, a processing chamber for processing a substrate, a vaporization unit for vaporizing a liquid raw material, a liquid raw material supply system for supplying a liquid raw material to the vaporization unit, and the liquid raw material in the vaporization unit A source gas supply system for supplying the vaporized source gas into the processing chamber, a reaction gas supply system for supplying a reaction gas different from the source gas into the processing chamber, and a solvent capable of dissolving the liquid source A solvent supply system for supplying to the vaporization section, and a vaporization operation for performing the supply of the raw material gas and the reaction gas into the processing chamber a plurality of times and supplying the liquid raw material to the vaporization section for vaporization. At a time other than at the time of the vaporization operation of the liquid raw material, and at a time other than at the time of the vaporization operation of the liquid raw material, at a time other than at the time of the vaporization operation of the liquid raw material, The liquid material Each time the operation is performed a predetermined number of times, the liquid source supply system, the vaporization unit, the source gas supply system, and the solvent are supplied to the vaporization unit at a second flow rate that is larger than the first flow rate. There is provided a substrate processing apparatus having a supply system and a controller that controls the reaction gas supply system.

  According to still another aspect of the present invention, there is provided a semiconductor device manufacturing method including a step of processing a substrate by supplying a plurality of types of reactants a plurality of times into a processing chamber in which the substrate is accommodated. At least one of the reactants includes a source gas obtained by vaporizing a liquid source in a vaporization unit, and in the step of processing the substrate, the liquid source is intermittently supplied to the vaporization unit and vaporized. In addition, a solvent capable of dissolving the liquid raw material is continuously supplied and vaporized, and the liquid raw material is supplied a predetermined number of times other than when the liquid raw material is supplied to the vaporization unit. In addition, there is provided a method for manufacturing a semiconductor device that performs a flushing operation in which the solvent is supplied to the vaporizing section at a flow rate larger than the flow rate of the solvent supplied when the liquid raw material is supplied.

  According to still another aspect of the present invention, the processing chamber for processing the substrate, the vaporizing unit for vaporizing the liquid raw material, the liquid raw material supply pipe for supplying the liquid raw material to the vaporizing unit, and the vaporizing unit A source gas supply pipe for supplying a source gas vaporized from a liquid source into the processing chamber; a reaction gas supply pipe for supplying a reaction gas different from the source gas into the processing chamber; and the liquid source in the vaporizing section. A solvent supply pipe that supplies a solvent that can be dissolved, and the substrate gas is controlled to be processed by performing the supply of the source gas and the reaction gas into the processing chamber a plurality of times, and the vaporization is performed at that time. The liquid raw material is intermittently supplied to the part and vaporized, and the solvent is continuously supplied to vaporize, and the liquid raw material is supplied at a time other than the time when the liquid raw material is supplied to the vaporizing part. Every time a certain number of times The solvent vaporization unit, and a controller for controlling to perform the flushing operation flow a large flow rate than the flow rate of the solvent supplied when supplying the liquid raw material, a substrate processing apparatus having a provided.

  According to still another aspect of the present invention, a liquid raw material vaporizer used in a semiconductor manufacturing apparatus and having a spray mechanism therein is mixed and supplied with a liquid raw material and a solvent capable of dissolving the raw material, or In the operation of supplying by separate system and mixing and vaporizing inside, the supply of raw materials is intermittently performed as necessary on the semiconductor manufacturing equipment side, while the solvent is continuously supplied and vaporized regardless of the supply cycle of the raw materials. The operation method of the vaporizer | carburetor which suppresses obstruction | occlusion of the spray mechanism part by the raw material which remain | survived near the spray mechanism or its decomposition product by continuing conversion is provided.

  Here, when the raw material is a liquefied raw material obtained by dissolving a solid raw material or a highly viscous liquid raw material in a solvent, the raw material itself contains a solvent, so the solvent is continuous regardless of the supply / vaporization cycle of the raw material. In addition to continuing supply and vaporization, supply and vaporization of the solvent only in cycles where no liquefied raw material is supplied prevents clogging of the spray mechanism due to the raw material remaining in the vicinity of the spray mechanism and its decomposition products You can also.

Preferably, in a cycle in which only the solvent is flowed, the flow rate of the solvent near the vaporizing nozzle is changed by flowing a solvent at a flow rate at least twice that of the solvent flow rate in the raw material vaporization cycle to effectively remain in the vicinity of the nozzle. The flushing operation for cleaning the raw material to be performed is performed. More preferably, the cleaning efficiency is improved by mixing and flowing a purge gas such as nitrogen in the solvent. More preferably, the flushing cleaning operation is performed for each raw material vaporization cycle or each time the raw material vaporization cycle is repeated several times within a range not to block the spray mechanism.

  According to still another aspect of the present invention, there is provided a semiconductor device manufacturing method including a step of processing a substrate by supplying a plurality of types of reactants a plurality of times into a processing chamber in which the substrate is accommodated. At least one of the reactants includes a source gas obtained by vaporizing a liquid source in a vaporization unit, and after the operation of supplying the source gas vaporized in the vaporization unit into the processing chamber at least once, Next, a method for manufacturing a semiconductor device is provided in which the vaporizing part is cleaned with a cleaning liquid before the liquid source is vaporized in the vaporizing part.

  Preferably, the vaporizer is cleaned every time the raw material gas is supplied. Preferably, the liquid raw material is diluted with a solvent, and the cleaning liquid is the solvent for diluting the liquid raw material. Preferably, the solvent is ethylcyclohexane or tetrahydrofuran. Preferably, when the vaporizing unit is cleaned, the cleaning liquid is vaporized by the vaporizing unit, and the vaporized cleaning liquid is exhausted out of the processing chamber. Preferably, the liquid material is a liquid material containing at least one of Sr, Ba, and Ti. Preferably, the liquid material includes an Sr liquid material, a Ba liquid material, and a Ti liquid material.

  According to still another aspect of the present invention, a processing chamber for processing a substrate, a vaporization unit for vaporizing a liquid raw material, a liquid raw material supply pipe for supplying the liquid raw material to the vaporization unit, and a liquid raw material in the vaporization unit A source gas supply pipe for supplying a source gas vaporized into the processing chamber, a reactant supply pipe for supplying a reactant different from the source gas into the processing chamber, and a cleaning liquid supply for supplying a cleaning liquid to the vaporizing section And controlling the substrate to be processed by performing a plurality of times of supply of the raw material gas into the processing chamber and supply of the reactant into the processing chamber, and at least one supply operation of the raw material gas And a controller for controlling the vaporization unit to be cleaned by supplying the cleaning liquid to the vaporization unit until the liquid source is vaporized by the vaporization unit. Provided .

  Preferably, the controller controls the vaporizer to be cleaned every time the source gas is supplied. Preferably, the liquid raw material is diluted with a solvent, and the cleaning liquid is the solvent for diluting the liquid raw material. Preferably, the solvent is ethylcyclohexane or tetrahydrofuran. Preferably, the controller controls the vaporizing unit to vaporize the cleaning liquid and exhaust the vaporized cleaning liquid to the outside of the processing chamber when the vaporizing unit is cleaned. Preferably, the liquid material is a liquid material containing at least one of Sr, Ba, and Ti. Preferably, the liquid material includes an Sr liquid material, a Ba liquid material, and a Ti liquid material.

  According to still another aspect of the present invention, the step of supplying one reactant onto the substrate and the step of supplying another reactant onto the substrate are set as one cycle, and this cycle is repeated a plurality of times. A method of manufacturing a semiconductor device including a step of processing the substrate, wherein at least one of the reactants includes a source gas obtained by vaporizing a liquid source in a vaporization unit, and the liquid source is supplied to the vaporization unit. A method for manufacturing a semiconductor device is provided in which the vaporizing section is cleaned with another liquid after at least one supply operation.

According to still another aspect of the present invention, a processing chamber for processing a substrate, a vaporization unit for vaporizing a liquid raw material, a liquid raw material supply pipe for supplying the liquid raw material to the vaporization unit, and a liquid raw material in the vaporization unit A source gas supply pipe for supplying a source gas vaporized into the processing chamber, a reactant supply pipe for supplying a reactant different from the source gas into the processing chamber, and a cleaning liquid supply for supplying a cleaning liquid to the vaporizing section And controlling the substrate to be processed by performing the supply of the source gas and the reactant in the processing chamber a plurality of times, and at least one of the liquid source to the vaporization section. There is provided a substrate processing apparatus including a controller that controls the vaporization unit to be cleaned by supplying the cleaning liquid to the vaporization unit after the supply operation.

  According to still another aspect of the present invention, a step of supplying a source gas obtained by vaporizing a liquid source in a vaporization section into a processing chamber containing a substrate, and a step of supplying an oxidizing agent into the processing chamber are performed a plurality of times. A method of manufacturing a semiconductor device including a step of processing the substrate by repeating, wherein after the operation of supplying the source gas vaporized in the vaporization section into the processing chamber at least once, and then the liquid source A method of manufacturing a semiconductor device is provided in which the vaporizing section is cleaned with a cleaning liquid before the vaporizing section is vaporized.

  According to still another aspect of the present invention, a step of supplying a plurality of types of source gases obtained by separately vaporizing a plurality of types of liquid raw materials in different vaporization sections into a processing chamber containing a substrate; A step of processing the substrate by repeating the step of supplying the oxidant a plurality of times, after at least one supply operation of the respective source gases into the processing chamber Then, a method of manufacturing a semiconductor device is provided in which each of the liquid raw materials is cleaned with a cleaning liquid before each of the liquid raw materials is vaporized by the respective vaporizing units.

200 wafer (substrate)
201 processing chamber 211s first liquid source supply pipe 211b second liquid source supply pipe 211t third liquid source supply pipe 212s first cleaning liquid supply pipe 212b second cleaning liquid supply pipe 212t third cleaning liquid supply pipe 213s first source gas supply pipe 213b Second source gas supply pipe 213t Third source gas supply pipe 213o Ozone gas supply pipe (reactant supply pipe)
229s vaporizer 229b vaporizer 229t vaporizer 280 controller

Claims (8)

A method for manufacturing a semiconductor device comprising a step of processing a substrate by supplying a plurality of types of reactants a plurality of times into a processing chamber containing the substrate,
At least one of the plurality of types of reactants includes a raw material gas obtained by vaporizing a liquid raw material in a vaporization section,
In the step of processing the substrate, a solvent capable of dissolving the liquid raw material is continuously flowed to the vaporization unit, and the vaporization operation for supplying and vaporizing the liquid raw material to the vaporization unit is intermittently performed.
The solvent is supplied to the vaporizing unit during the vaporizing operation of the liquid raw material every time the liquid raw material is vaporized for a predetermined number of times except during the vaporizing operation of the liquid raw material. A method for manufacturing a semiconductor device, characterized by performing a flushing operation in which a flow rate is larger than a flow rate. 2. The semiconductor device according to claim 1, wherein the flow rate of the solvent that flows to the vaporization unit during the flushing operation is equal to or more than twice the flow rate of the solvent that is supplied to the vaporization unit during the vaporization operation of the liquid raw material. Manufacturing method. The flow rate of the solvent that flows through the vaporization unit during the flushing operation is 2 to 20 times the flow rate of the solvent that is supplied to the vaporization unit during the vaporization operation of the liquid raw material. A method for manufacturing a semiconductor device. 2. The method of manufacturing a semiconductor device according to claim 1, wherein the solvent flowed to the vaporizing unit is exhausted without being supplied into the processing chamber at a time other than the vaporizing operation of the liquid material. When flowing the solvent to the vaporization unit at the large flow rate during the flushing operation, the solvent is once flowed to the vaporization unit at the flow rate of the solvent supplied during the vaporization operation of the liquid raw material, and then to the vaporization unit. 2. The method of manufacturing a semiconductor device according to claim 1, wherein the flow rate of the solvent to be supplied is changed to the large flow rate. When flowing the solvent through the vaporization unit at the large flow rate during the flushing operation, the solvent is once flowed through the vaporization unit at a smaller flow rate, and then the flow rate of the solvent supplied to the vaporization unit is increased. The method of manufacturing a semiconductor device according to claim 1, wherein the flow rate is changed. When flowing the solvent through the vaporization unit at the large flow rate during the flushing operation, the solvent is once flowed through the vaporization unit at a smaller flow rate, and then the solvent at the large flow rate is supplied to the vaporization unit. 2. The method of manufacturing a semiconductor device according to claim 1, wherein supply is started. A processing chamber for processing the substrate;
A vaporizing section for vaporizing the liquid raw material;
A liquid raw material supply system for supplying a liquid raw material to the vaporization unit;
A raw material gas supply system for supplying a raw material gas obtained by vaporizing the liquid raw material in the vaporizing section into the processing chamber;
A reaction gas supply system for supplying a reaction gas different from the source gas into the processing chamber;
A solvent supply system for supplying a solvent capable of dissolving the liquid raw material to the vaporization unit;
The supply of the source gas into the processing chamber and the supply of the reaction gas are performed a plurality of times. At this time, the solvent is continuously supplied to the vaporization unit, and the liquid source is supplied to the vaporization unit and vaporized. The vaporizing operation is intermittently performed, and the solvent is supplied to the vaporizing unit every time the vaporizing operation of the liquid raw material is performed a predetermined number of times except during the vaporizing operation of the liquid raw material. The liquid raw material supply system, the vaporizer, the raw material gas supply system, the solvent supply system, and the reaction gas supply system so as to perform a flushing operation that flows at a flow rate larger than the flow rate of the solvent supplied during the vaporization operation. And a controller that controls the substrate processing apparatus.