JP2020088085A - Substrate processing method and substrate processing apparatus - Google Patents

Abstract

To reduce the reduction amount of a processing liquid in a tank due to the adjustment of dissolved oxygen concentration.SOLUTION: A low oxygen gas having the oxygen concentration lower than the oxygen concentration in the air is supplied into a first gas generation tank 122 that stores a processing liquid, and bubbles of the low oxygen gas are generated in the processing liquid in the first gas generation tank 122. As a result, a first adjustment gas containing the low oxygen gas and the processing liquid is generated. Then, the first adjustment gas is dissolved in the processing liquid in a first supply tank 72A to adjust the dissolved oxygen concentration of the processing liquid in the first supply tank 72A. After that, the processing liquid in the first supply tank 72A is supplied to a substrate W.SELECTED DRAWING: Figure 7

Description

The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. The substrate to be processed is, for example, a semiconductor wafer, an FPD (Flat Panel Display) substrate such as a liquid crystal display device and an organic EL (electroluminescence) display device, an optical disk substrate, a magnetic disk substrate, a magneto-optical disk substrate, or a photo substrate. It includes a mask substrate, a ceramic substrate, a solar cell substrate, and the like.

A substrate processing apparatus for processing a substrate such as a semiconductor wafer or a glass substrate is used in a manufacturing process of a semiconductor device, an FPD or the like. Patent Document 1 discloses a substrate processing apparatus that supplies TMAH (Tetramethyl ammonium hydroxide) to a substrate. In this substrate processing apparatus, at least one of nitrogen gas and dry air is supplied into the tank that stores TMAH. Thereby, the dissolved oxygen concentration of TMAH is adjusted. The gas supplied into the tank that stores TMAH is discharged to the outside of the tank through the exhaust line.

JP, 2013-258391, A

In the substrate processing apparatus described in Patent Document 1, in order to adjust the dissolved oxygen concentration in TMAH, at least one of nitrogen gas and dry air is supplied into the tank to form a large number of bubbles in TMAH. This is called bubbling.
The gas in TMAH floats up to the liquid surface of TMAH, and then is discharged to the exhaust line together with the gas in the tank. The exhaust gas discharged from the tank contains at least one of nitrogen gas and dry air, as well as TMAH vapor and TMAH mist. Although the TMAH contained in the exhaust gas is extremely small, the TMAH in the tank is gradually discharged through the exhaust line when bubbling is continued. Therefore, the frequency of supplying new TMAH to the tank increases, and the running cost required for processing the substrate increases.

Further, when the treatment liquid in the tank contains a plurality of components, the vapor pressures of these components are different from each other, and thus, when bubbling is continued, the concentration of the treatment liquid gradually changes. In particular, when the treatment liquid contains components that are easily vaporized, the concentration of the treatment liquid changes significantly. When the concentration of the processing liquid changes with time, the quality of the substrate processed by the processing liquid also changes with time. Therefore, the stability of the quality of the substrate is impaired.

Therefore, one of the objects of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of reducing the decrease amount of the processing liquid in the tank due to the adjustment of the dissolved oxygen concentration.

The invention according to claim 1 for achieving the above object is the invention according to claim 1, in which the oxygen concentration in the air is higher than the oxygen concentration in the air in the first gas generation tank that stores the first liquid containing the first substance. A low oxygen gas having a low oxygen concentration is supplied to form bubbles of the low oxygen gas in the first liquid in the first gas generation tank, the low oxygen gas and the first substance being included. A first gas generating step of generating a first adjusted gas; and dissolving the first adjusted gas in a first processing liquid containing the first substance stored in a first supply tank, It is a substrate processing method including a first final adjusting step of adjusting a dissolved oxygen concentration of a first processing liquid, and a processing liquid supplying step of supplying the first processing liquid in the first supply tank to a substrate.

According to this method, the low oxygen gas having an oxygen concentration lower than the oxygen concentration in the air is supplied into the first gas generation tank. The first liquid containing the first substance is stored in the first gas generation tank. The low oxygen gas is dispersed in the first liquid in the first gas generation tank to form a large number of bubbles. After that, the low oxygen gas floats in the first liquid to the liquid surface of the first liquid and mixes with the gas on the liquid surface of the first liquid. In the process up to this point, the vapor and mist of the first substance contained in the first liquid are dispersed in the low oxygen gas. As a result, the first adjusted gas containing the low oxygen gas and the first substance is generated.

The first adjusted gas is supplied to the first supply tank that stores the first processing liquid, and dissolves in the first processing liquid in the first supply tank. The first adjustment gas contains low oxygen gas. Therefore, due to the dissolution of the first adjusted gas, oxygen in the first processing liquid is discharged, and the dissolved oxygen concentration of the first processing liquid decreases. As a result, the dissolved oxygen concentration of the first treatment liquid in the first supply tank is adjusted.

Furthermore, since the first substance is contained in both the first adjustment gas and the first processing liquid, even if the first adjustment gas is continuously supplied to the first supply tank, the first substance in the first supply tank It is difficult to reduce the processing liquid. As a result, the frequency of supplying the new first processing liquid to the first supply tank can be reduced. Furthermore, even when a plurality of components are contained in the first processing liquid, it is possible to suppress the change in the concentration of the first processing liquid. As a result, it is possible to suppress changes in the quality of the substrate with the passage of time.

The first substance may be one atom or a molecule. The same applies to the second substance described later. The first liquid containing the first substance may be a liquid of the first substance (a liquid containing 100% of the first substance) or a liquid containing the first substance and a substance other than the first substance. It may be. The same applies to the preconditioning liquid and the second liquid described later.
In the invention according to claim 2, the concentration of the first substance in the first adjusted gas is higher than the concentration of the first substance in the low oxygen gas before being supplied to the first gas generation tank. The substrate processing method according to claim 1.

According to this method, the low oxygen gas having a low concentration of the first substance is supplied into the first gas generation tank. As described above, the low oxygen gas forms a large number of bubbles in the first liquid in the first gas generation tank and floats in the first liquid to the liquid level of the first liquid. As a result, a first adjustment gas having a high concentration of the first substance (for example, a first adjustment gas having a concentration of the first substance at or near the saturation concentration) is generated. Then, the first adjusted gas having a high concentration of the first substance is supplied to the first supply tank. As a result, the reduction amount of the first processing liquid in the first supply tank can be effectively reduced.

The invention according to claim 3 is the substrate processing method according to claim 1 or 2, wherein the first gas generation tank is a tank for storing the first processing liquid.
According to this method, the first processing liquid is stored not only in the first supply tank but also in the first gas generation tank. Therefore, the first adjusted gas containing the first processing liquid is generated in the first gas generation tank and supplied to the first supply tank. Even if the liquid component of the first adjustment gas dissolves in the first processing liquid, the concentration of the first processing liquid in the first supply tank remains unchanged or hardly changes. Thereby, the change in the concentration of the first treatment liquid in the first supply tank can be suppressed.

In the invention according to claim 4, a recovery step of recovering the first processing liquid after being supplied to the substrate into the first supply tank via a recovery tank, and a preconditioning liquid containing the first substance. The low oxygen gas is supplied into a pre-gas generation tank that stores, to form bubbles of the low oxygen gas in the pre-conditioning liquid in the pre-gas generation tank. A preconditioning gas generating step of generating a preconditioning gas containing one substance; and the first processing liquid in the recovery tank before the first processing liquid supplied to the substrate is recovered in the first supply tank. 4. A pre-adjustment step of dissolving the pre-adjusted gas in a treatment liquid to adjust the dissolved oxygen concentration of the first treatment liquid in the recovery tank, further comprising: Substrate processing method.

According to this method, the first processing liquid supplied to the substrate from the first supply tank is recovered in the first supply tank via the recovery tank. The dissolved oxygen concentration of the first processing liquid supplied to the substrate has changed. Therefore, before the first treatment liquid is collected in the first supply tank, the preconditioning gas containing low oxygen gas is dissolved in the first treatment liquid in the collection tank. As a result, the dissolved oxygen concentration of the first treatment liquid in the recovery tank can be brought close to the dissolved oxygen concentration of the first treatment liquid in the first supply tank. Further, the preconditioned gas contains not only the low oxygen gas but also the first substance. Therefore, the dissolved oxygen concentration of the first processing liquid in the recovery tank can be adjusted while suppressing the decrease of the first processing liquid in the recovery tank.

In the invention according to claim 5, in the first final adjustment step, a gas supply step of causing the first adjusted gas to flow into the first supply tank, and a gas discharge step of discharging the gas in the first supply tank The substrate processing method includes a first cooling step of cooling the exhaust gas discharged from the first supply tank to liquefy the first substance contained in the exhaust gas, and the first cooling step. 5. The substrate processing method according to claim 1, further comprising a first recycling step of returning the first substance liquefied in the step to the first supply tank.

According to this method, the gas in the first supply tank is discharged from the first supply tank while causing the first adjusted gas to flow into the first supply tank. The exhaust gas discharged from the first supply tank contains vapor and mist of the first substance. When the exhaust gas is cooled, the vapor of the first substance changes into droplets of the first substance, or the droplets of the first substance contained in the mist of the first substance become large. The liquid of the first substance is returned to the first supply tank. As a result, it is possible to further reduce the reduction amount of the first processing liquid in the first supply tank.

In the invention according to claim 6, in the first cooling step, the exhaust gas in a first rising pipe extending upward from the first supply tank is cooled to remove the first substance contained in the exhaust gas. A first pipe cooling step of liquefying the inner surface of the first rising pipe is included, wherein the first recycling process includes the first rising pipe liquefied the first substance liquefied on the inner surface of the first rising pipe. 6. The substrate processing method according to claim 5, further comprising a first dropping step of dropping the first supply tank toward the first supply tank along the inner peripheral surface of the substrate.

According to this method, the exhaust gas containing the first substance is cooled in the first rising pipe extending upward from the first supply tank. Part of the first substance contained in the exhaust gas is liquefied in the first rising pipe and adheres to the inner peripheral surface of the first rising pipe. When the droplets of the first substance become large to some extent, they flow toward the first supply tank along the inner peripheral surface of the first ascending pipe by their own weight, and fall into the first processing liquid in the first supply tank. As a result, the first substance contained in the exhaust gas can be returned to the first supply tank.

The first ascending pipe may be vertical or may be inclined with respect to the horizontal plane as long as it extends upward from the first supply tank. Further, the first rising pipe may have any of a straight line shape, a broken line shape, and a curved shape. That is, if the liquid in the first rising pipe travels along the inner peripheral surface of the first rising pipe and drops into the first processing liquid in the first supply tank, what shape does the first rising pipe have? Good.

In the invention according to claim 7, the preliminary adjustment step includes a gas supply step of causing the preliminary adjustment gas to flow into the recovery tank, and a gas discharge step of discharging the gas in the recovery tank, In the substrate processing method, the exhaust gas discharged from the recovery tank is cooled to liquefy the first substance contained in the exhaust gas, and the first liquefied gas in the second cooling step is liquefied. The substrate processing method according to claim 4, further comprising a second recycling step of returning the substance to the recovery tank.

According to this method, the gas in the recovery tank is discharged from the recovery tank while allowing the preconditioned gas to flow into the recovery tank. The exhaust gas discharged from the recovery tank contains the vapor and mist of the first substance. When the exhaust gas is cooled, the vapor of the first substance changes into droplets of the first substance, or the droplets of the first substance contained in the mist of the first substance become large. The liquid of the first substance is returned to the recovery tank. This makes it possible to further reduce the reduction amount of the first processing liquid in the recovery tank.

In the invention according to claim 8, in the second cooling step, the exhaust gas in a second ascending pipe extending upward from the recovery tank is cooled, and the first substance contained in the exhaust gas is removed from the first substance. 2 A second pipe inside cooling step of liquefying on the inner peripheral surface of the ascending pipe, wherein the second recycling step is performed inside the second ascending pipe by liquefying the first substance liquefied on the inner peripheral surface of the second ascending pipe. The substrate processing method according to claim 7, further comprising a second dropping step of dropping along the peripheral surface toward the recovery tank.

According to this method, the exhaust gas containing the first substance is cooled in the second ascending pipe extending upward from the recovery tank. Part of the first substance contained in the exhaust gas is liquefied in the second rising pipe and adheres to the inner peripheral surface of the second rising pipe. When the droplets of the first substance become large to some extent, the droplets of the first substance flow toward the recovery tank along the inner peripheral surface of the second ascending pipe by their own weight, and fall into the first treatment liquid in the recovery tank. As a result, the first substance contained in the exhaust gas can be returned to the recovery tank.

The second ascending pipe may be vertical or may be inclined with respect to the horizontal plane as long as it extends upward from the recovery tank. Further, the second ascending pipe may have any of a linear shape, a broken line shape, and a curved shape. That is, as long as the liquid in the second rising pipe travels along the inner peripheral surface of the second rising pipe and drops into the first processing liquid in the recovery tank, the second rising pipe may have any shape. ..

According to a ninth aspect of the present invention, in the substrate processing method, the low oxygen gas is supplied into a second gas generation tank that stores a second liquid containing a second substance, and the low oxygen gas in the second gas generation tank A second gas generation step of forming bubbles of the low oxygen gas in the second liquid and generating a second adjusted gas containing the low oxygen gas and the second substance; and storing in a second supply tank. A second final adjustment step of adjusting the dissolved oxygen concentration of the second treatment liquid in the second supply tank by dissolving the second adjustment gas in the second treatment liquid containing the second substance. A mixing step immediately before mixing the first processing liquid and the second processing liquid outside the first supply tank and the second supply tank before the first processing liquid and the second processing liquid are supplied to the substrate; A mixing ratio changing step of changing a mixing ratio of the first processing liquid and the second processing liquid mixed in the immediately preceding mixing step, wherein the processing liquid supply step includes the first mixing step performed in the immediately preceding mixing step. The substrate processing method according to claim 1, further comprising a mixed liquid supply step of supplying a processing liquid and a second processing liquid to the substrate.

According to this method, the mixed liquid of the first processing liquid and the second processing liquid is supplied to the substrate. The first processing liquid and the second processing liquid are mixed not in the tank but immediately before being supplied to the substrate. Therefore, the mixing ratio of the first processing liquid and the second processing liquid can be changed according to the required quality of the substrate. Further, the second treatment liquid in the second supply tank has the dissolved oxygen concentration adjusted similarly to the first treatment liquid in the first supply tank. The second adjusted gas supplied to the second supply tank contains not only the low oxygen gas but also the second substance contained in the second processing liquid. Therefore, it is possible to supply the mixed liquid of the first processing liquid and the second processing liquid to the substrate while reducing the decrease amount of the second processing liquid in the second supply tank.

According to a tenth aspect of the present invention, the first treatment liquid is a liquid containing a second substance in addition to the first substance, and the first gas generation step includes the first substance and the second substance. And supplying the low oxygen gas into the first gas generation tank that stores the first liquid, and forming bubbles of the low oxygen gas in the first liquid in the first gas generation tank. A plurality-containing gas producing step of producing a plurality-containing gas containing the low oxygen gas, the first substance, and the second substance; and including one of the first substance and the second substance, The low oxygen gas is supplied into a second gas generation tank that stores a second liquid that does not include the other of the two substances, and bubbles of the low oxygen gas are generated in the second liquid in the second gas generation tank. A part-containing gas generating step of forming a part-containing gas containing one of the first substance and the second substance and the low oxygen gas and not containing the other of the first substance and the second substance, In the first final adjusting step, the plurality of contained gases corresponding to the first adjusting gas are dissolved in the first processing liquid in the first supply tank, and the first processing gas in the first supply tank is dissolved. 1 main adjusting step of adjusting the dissolved oxygen concentration of the treatment liquid, and dissolving the part-containing gas in the first treatment liquid in the first supply tank, the first treatment liquid in the first supply tank 9. The substrate processing method according to claim 1, further comprising: a sub-adjustment step of adjusting the dissolved oxygen concentration.

According to this method, the first processing liquid containing the first substance and the second substance is supplied to the substrate from the first supply tank. Since the vapor pressures of the first substance and the second substance are different, the concentration of the first processing liquid in the first supply tank changes with the passage of time. If the difference in vapor pressure between the first substance and the second substance is small, the amount of change in the concentration of the first treatment liquid is small, but if the difference in vapor pressure between the first substance and the second substance is large, the first treatment is performed. The concentration of the liquid changes drastically.

The plural-containing gas and the partially-containing gas are separately supplied to the first supply tank. Both the plural-containing gas and the partially-containing gas include low oxygen gas. Therefore, the dissolved oxygen concentration of the first treatment liquid in the first supply tank can be adjusted by supplying either the plural-containing gas or the partially-containing gas to the first supply tank. On the other hand, the plural-containing gas contains both the first substance and the second substance, and the partially-containing gas contains only one of the first substance and the second substance.

For example, when the second substance has a higher vapor pressure than the first substance and is more easily vaporized than the first substance, the concentration of the first substance in the first treatment liquid increases with time. In such a case, if a partially-containing gas containing the second substance but not the first substance is supplied to the first supply tank, the first substance can be reduced while reducing the decrease amount of the second substance from the first treatment liquid. Material can be reduced from the first process liquid. Thereby, the concentration of the first treatment liquid can be brought close to the initial concentration, and the change in the quality of the substrate over time can be suppressed.

The invention according to claim 11 includes a first gas generation tank that stores a first liquid containing a first substance, and low oxygen having an oxygen concentration lower than an oxygen concentration in air in the first gas generation tank. A gas is supplied to form bubbles of the low oxygen gas in the first liquid in the first gas generation tank to generate a first adjusted gas containing the low oxygen gas and the first substance; A first supply tank that stores a first processing liquid containing the first substance; and a first adjusting gas dissolved in the first processing liquid in the first supply tank, Substrate processing, including first final adjusting means for adjusting the dissolved oxygen concentration of the first processing liquid in the first supply tank, and a processing liquid nozzle for supplying the first processing liquid in the first supply tank to the substrate. It is a device. With this configuration, it is possible to achieve the same effects as the effects described regarding the substrate processing method described above.

According to a twelfth aspect of the present invention, the first gas generation means generates the first adjusted gas in which the concentration of the first substance is higher than that of the low oxygen gas before being supplied to the first gas generation tank. The substrate processing apparatus according to claim 11, which is a means for performing. With this configuration, it is possible to achieve the same effects as the effects described regarding the substrate processing method described above.
The invention according to claim 13 is the substrate processing apparatus according to claim 11 or 12, wherein the first gas generation tank is a tank for storing the first processing liquid. With this configuration, it is possible to achieve the same effects as the effects described regarding the substrate processing method described above.

The invention according to claim 14 includes a recovery tank that stores the first processing liquid after being supplied to the substrate, wherein the first processing liquid supplied to the substrate is transferred to the substrate via the recovery tank. A preliminarily gas generation tank that stores a preliminarily adjusted liquid containing the first substance, and a recovery unit that collects the first oxygen in the first supply tank. Preconditioning gas generating means for forming bubbles of the low oxygen gas in the preconditioning liquid in the gas generating tank to generate a preconditioning gas containing the low oxygen gas and the first substance, and the substrate. Before the supplied first processing liquid is recovered in the first supply tank, the preconditioning gas is dissolved in the first processing liquid in the recovery tank to remove the first processing liquid in the recovery tank. The substrate processing apparatus according to claim 11, further comprising a pre-adjustment unit that adjusts a dissolved oxygen concentration of the processing liquid. With this configuration, it is possible to achieve the same effects as the effects described regarding the substrate processing method described above.

According to a fifteenth aspect of the present invention, the first final adjustment means includes a gas supply pipe for flowing the first adjusted gas into the first supply tank, and a gas discharge for discharging the gas in the first supply tank. The substrate processing apparatus further includes a pipe, and the substrate processing apparatus cools the exhaust gas discharged from the first supply tank to liquefy the first substance contained in the exhaust gas, and the first cooler. 15. The substrate processing apparatus according to claim 11, further comprising: a first recycle pipe for returning the liquefied first substance to the first supply tank. With this configuration, it is possible to achieve the same effects as the effects described regarding the substrate processing method described above.

In the invention according to claim 16, the gas exhaust pipe includes a first rising pipe extending upward from the first supply tank, and the first cooler cools the exhaust gas in the first rising pipe. 16. The substrate processing apparatus according to claim 15, further comprising a first in-pipe cooler that liquefies the first substance contained in the exhaust gas on the inner peripheral surface of the first rising pipe. With this configuration, it is possible to achieve the same effects as the effects described regarding the substrate processing method described above.

In the invention according to claim 17, the pre-adjustment means further includes a gas supply pipe for introducing the pre-adjusted gas into the recovery tank, and a gas exhaust pipe for exhausting gas in the recovery tank. The substrate processing apparatus cools the exhaust gas discharged from the recovery tank to liquefy the first substance contained in the exhaust gas, and the first cooler liquefied by the second cooler. 15. The substrate processing apparatus according to claim 14, further comprising a second recycle pipe for returning a substance to the recovery tank. With this configuration, it is possible to achieve the same effects as the effects described regarding the substrate processing method described above.

In the invention according to claim 18, the gas exhaust pipe includes a second ascending pipe extending upward from the recovery tank, and the second cooler cools the exhaust gas in the second ascending pipe, 18. The substrate processing apparatus according to claim 17, further comprising a second in-pipe cooler that liquefies the first substance contained in the exhaust gas on an inner peripheral surface of the second ascending pipe. With this configuration, it is possible to achieve the same effects as the effects described regarding the substrate processing method described above.

In the invention according to claim 19, the substrate processing apparatus includes a second gas generation tank that stores a second liquid containing a second substance, and supplies the low oxygen gas into the second gas generation tank. A second gas generating means for forming bubbles of the low oxygen gas in the second liquid in the second gas generation tank and generating a second adjusted gas containing the low oxygen gas and the second substance; A second supply tank for storing a second processing liquid containing the second substance, wherein the second adjusted gas is dissolved in the second processing liquid in the second supply tank, Second final adjusting means for adjusting the dissolved oxygen concentration of the second processing liquid, and the first processing liquid and the second processing liquid before the first processing liquid and the second processing liquid are supplied to the substrate. A mixing means for mixing immediately outside the first supply tank and the second supply tank, and a mixing ratio changing valve for changing the mixing ratio of the first processing liquid and the second processing liquid mixed by the immediately preceding mixing means. 19. The method according to claim 11, wherein the processing liquid nozzle further includes a mixed liquid nozzle that supplies a mixed liquid of the first processing liquid and the second processing liquid mixed by the immediately preceding mixing means to the substrate. The substrate processing apparatus according to any one of claims 1 to 5. With this configuration, it is possible to achieve the same effects as the effects described regarding the substrate processing method described above.

The invention according to claim 20 is that the first treatment liquid is a liquid containing a second substance in addition to the first substance, and the first gas generating means is the first substance and the second substance. And supplying the low oxygen gas into the first gas generation tank that stores the first liquid, and forming bubbles of the low oxygen gas in the first liquid in the first gas generation tank. A plurality of contained gas generating means for generating a plurality of contained gas containing the low oxygen gas, the first substance and the second substance; and one of the first substance and the second substance, A second gas generation tank that stores a second liquid that does not include the other of the two substances, and supplies the low oxygen gas into the second gas generation tank to supply the second liquid in the second gas generation tank. A bubble of the low oxygen gas is formed therein, and a partially-containing gas containing one of the first substance and the second substance and the low oxygen gas and not containing the other of the first substance and the second substance is generated. And a part-containing gas generating means, wherein the first final adjusting means dissolves the plurality of containing gases corresponding to the first adjusted gas in the first processing liquid in the first supply tank, Main adjusting means for adjusting the dissolved oxygen concentration of the first treatment liquid in the first supply tank, and the part-containing gas is dissolved in the first treatment liquid in the first supply tank to obtain the first treatment liquid. The substrate processing apparatus according to claim 11, further comprising: a sub adjusting unit that adjusts a dissolved oxygen concentration of the first processing liquid in the supply tank. With this configuration, it is possible to achieve the same effects as the effects described regarding the substrate processing method described above.

It is the schematic diagram which looked at the substrate processing apparatus which concerns on 1st Embodiment of this invention from the top. It is the schematic diagram which looked at the substrate processing apparatus from the side. It is the schematic diagram which looked at the inside of the processing unit with which the substrate processing device was equipped horizontally. It is an enlarged view which expanded a part of FIG. It is a block diagram which shows the hardware of a control apparatus. FIG. 7 is a process diagram for describing an example of substrate processing performed by the substrate processing apparatus. It is a schematic diagram which shows a chemical solution supply unit, a chemical solution recovery unit, a concentration measurement unit, and a dissolved oxygen concentration change unit. It is the schematic diagram which looked at the external appearance of the 1st cooler attached to the 1st rise piping horizontally. It is a schematic diagram which shows the vertical cross section of a 1st rising piping and a 1st supply tank. It is a flow chart which shows an example of the flow from supplying new chemicals to the 1st supply tank until discharging the chemicals in the 1st supply tank. It is a schematic diagram which shows the chemical|medical solution supply unit and gas dissolving apparatus which concern on 2nd Embodiment. It is a schematic diagram which shows the chemical|medical solution supply unit and gas dissolving apparatus which concern on 3rd Embodiment.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a schematic view of a substrate processing apparatus 1 according to the first embodiment of the present invention viewed from above. FIG. 2 is a schematic view of the substrate processing apparatus 1 viewed from the side.
As shown in FIG. 1, the substrate processing apparatus 1 is a single-wafer processing apparatus that processes disk-shaped substrates W such as semiconductor wafers one by one. The substrate processing apparatus 1 includes a load port LP that holds a carrier CA that accommodates a substrate W, and a plurality of processes that processes the substrate W transported from the carrier CA on the load port LP with a processing fluid such as a processing liquid or a processing gas. The unit 2 includes a carrier robot that carries the substrate W between the carrier CA on the load port LP and the processing unit 2, and a controller 3 that controls the substrate processing apparatus 1.

The transfer robot includes an indexer robot IR for loading and unloading the substrate W with respect to the carrier CA on the load port LP, and a center robot CR for loading and unloading the substrate W with respect to the plurality of processing units 2. The indexer robot IR transfers the substrate W between the load port LP and the center robot CR, and the center robot CR transfers the substrate W between the indexer robot IR and the processing unit 2. The center robot CR includes a hand H1 that supports the substrate W, and the indexer robot IR includes a hand H2 that supports the substrate W.

The substrate processing apparatus 1 includes a plurality of (for example, four) fluid boxes FB that accommodate fluid devices such as valves. A chemical liquid cabinet CC that accommodates a chemical liquid tank and the like is arranged outside the outer wall 1 a of the substrate processing apparatus 1. The chemical liquid cabinet CC may be arranged beside the outer wall 1a of the substrate processing apparatus 1, or may be arranged below (underground) a clean room in which the substrate processing apparatus 1 is installed.

The plurality of processing units 2 form a plurality of towers arranged around the central robot CR in a plan view. FIG. 1 shows an example in which four towers are formed. As shown in FIG. 2, each tower includes a plurality of (for example, three) processing units 2 stacked one above the other. The four fluid boxes FB correspond to four towers, respectively. The chemical liquid in the chemical liquid cabinet CC is supplied to all the processing units 2 included in the tower corresponding to the fluid box FB via any of the fluid boxes FB.

FIG. 3 is a schematic view in which the inside of the processing unit 2 provided in the substrate processing apparatus 1 is viewed horizontally. FIG. 4 is an enlarged view in which a part of FIG. 3 is enlarged. FIG. 3 shows a state where the elevating frame 32 and the blocking member 33 are located at the lower position, and FIG. 4 shows a state where the elevating frame 32 and the blocking member 33 are located at the upper position.
The processing unit 2 includes a box-shaped chamber 4 having an internal space, and a spin chuck 10 that holds a single substrate W horizontally in the chamber 4 and rotates the substrate W around a vertical rotation axis A1 passing through the central portion of the substrate W. And a cylindrical processing cup 23 that surrounds the spin chuck 10 around the rotation axis A1.

The chamber 4 includes a box-shaped partition wall 6 provided with a loading/unloading port 6b through which the substrate W passes, and a shutter 7 for opening/closing the loading/unloading port 6b. The chamber 4 further includes a rectifying plate 8 arranged below the blower opening 6a that opens on the ceiling surface of the partition wall 6. The FFU 5 (fan filter unit) for sending clean air (air filtered by the filter) is arranged above the air outlet 6a. The exhaust duct 9 for discharging the gas in the chamber 4 is connected to the processing cup 23. The blower port 6 a is provided at the upper end of the chamber 4, and the exhaust duct 9 is arranged at the lower end of the chamber 4. A part of the exhaust duct 9 is arranged outside the chamber 4.

The current plate 8 partitions the internal space of the partition wall 6 into an upper space Su above the current plate 8 and a lower space SL below the current plate 8. The upper space Su between the ceiling surface of the partition wall 6 and the upper surface of the current plate 8 is a diffusion space in which clean air diffuses. The lower space SL between the lower surface of the current plate 8 and the floor surface of the partition wall 6 is a processing space in which the substrate W is processed. The spin chuck 10 and the processing cup 23 are arranged in the lower space SL. The vertical distance from the floor surface of the partition wall 6 to the lower surface of the flow straightening plate 8 is longer than the vertical distance from the upper surface of the flow straightening plate 8 to the ceiling surface of the partition wall 6.

The FFU 5 sends clean air to the upper space Su through the blower opening 6a. The clean air supplied to the upper space Su hits the current plate 8 and diffuses in the upper space Su. The clean air in the upper space Su passes through a plurality of through holes vertically penetrating the straightening vane 8 and flows downward from the entire area of the straightening vane 8. The clean air supplied to the lower space SL is sucked into the processing cup 23 and discharged from the lower end of the chamber 4 through the exhaust duct 9. As a result, a uniform downward flow (downflow) of clean air flowing downward from the current plate 8 is formed in the lower space SL. The processing of the substrate W is performed in a state where the downflow of clean air is formed.

The spin chuck 10 includes a disk-shaped spin base 12 held in a horizontal posture, a plurality of chuck pins 11 holding the substrate W in a horizontal posture above the spin base 12, and a central portion of the spin base 12. A spin shaft 13 extending downward and a spin motor 14 for rotating the spin base 12 and the plurality of chuck pins 11 by rotating the spin shaft 13 are included. The spin chuck 10 is not limited to a sandwich type chuck in which the plurality of chuck pins 11 are brought into contact with the outer peripheral surface of the substrate W, but the back surface (lower surface) of the substrate W, which is a non-device forming surface, is attracted to the upper surface 12u of the spin base 12. It may be a vacuum chuck that holds the substrate W horizontally.

The spin base 12 includes an upper surface 12u arranged below the substrate W. The upper surface 12u of the spin base 12 is parallel to the lower surface of the substrate W. The upper surface 12u of the spin base 12 is a facing surface that faces the lower surface of the substrate W. The upper surface 12u of the spin base 12 has a ring shape surrounding the rotation axis A1. The outer diameter of the upper surface 12u of the spin base 12 is larger than the outer diameter of the substrate W. The chuck pin 11 projects upward from the outer peripheral portion of the upper surface 12u of the spin base 12. The chuck pin 11 is held by the spin base 12. The substrate W is held by the plurality of chuck pins 11 with the lower surface of the substrate W separated from the upper surface 12u of the spin base 12.

The processing unit 2 includes a lower surface nozzle 15 that discharges the processing liquid toward the central portion of the lower surface of the substrate W. The lower surface nozzle 15 includes a nozzle disk portion arranged between the upper surface 12u of the spin base 12 and the lower surface of the substrate W, and a nozzle tubular portion extending downward from the nozzle disk portion. The liquid ejection port 15p of the lower surface nozzle 15 is open at the center of the upper surface of the nozzle disk portion. When the substrate W is held by the spin chuck 10, the liquid ejection port 15p of the lower surface nozzle 15 vertically opposes the central portion of the lower surface of the substrate W.

The substrate processing apparatus 1 includes a lower rinse liquid pipe 16 for guiding the rinse liquid to the lower surface nozzle 15, and a lower rinse liquid valve 17 interposed in the lower rinse liquid pipe 16. When the lower rinse liquid valve 17 is opened, the rinse liquid guided by the lower rinse liquid pipe 16 is discharged upward from the lower surface nozzle 15 and supplied to the central portion of the lower surface of the substrate W. The rinse liquid supplied to the bottom surface nozzle 15 is pure water (deionized water: DIW (Deionized Water)). The rinse liquid supplied to the lower surface nozzle 15 is not limited to pure water, but IPA (isopropyl alcohol), carbonated water, electrolytic ionic water, hydrogen water, ozone water, and hydrochloric acid water having a dilution concentration (for example, about 1 to 100 ppm). It may be either.

Although not shown, the lower rinse liquid valve 17 includes a valve body provided with an internal flow passage through which the liquid flows and an annular valve seat surrounding the internal flow passage, a valve body movable with respect to the valve seat, and a valve. And an actuator that moves the valve body between a closed position in which the body contacts the valve seat and an open position in which the valve body is spaced from the valve seat. The same applies to other valves. The actuator may be a pneumatic actuator or an electric actuator, or may be an actuator other than these. The control device 3 controls the actuator to open and close the lower rinse liquid valve 17.

An outer peripheral surface of the lower surface nozzle 15 and an inner peripheral surface of the spin base 12 form a lower tubular passage 19 extending vertically. The lower cylindrical passage 19 includes a lower central opening 18 that opens at the central portion of the upper surface 12u of the spin base 12. The lower central opening 18 is arranged below the nozzle disk portion of the lower surface nozzle 15. The substrate processing apparatus 1 includes a lower gas pipe 20 for guiding an inert gas supplied to the lower central opening 18 via a lower tubular passage 19, a lower gas valve 21 interposed in the lower gas pipe 20, and a lower gas. A lower gas flow rate adjusting valve 22 that changes the flow rate of the inert gas supplied from the pipe 20 to the lower tubular passage 19 is provided.

The inert gas supplied from the lower gas pipe 20 to the lower cylindrical passage 19 is nitrogen gas. Nitrogen gas does not contain oxygen or contains very little oxygen. The inert gas is not limited to nitrogen gas, and may be other inert gas such as helium gas or argon gas. These inert gases are gases having an oxygen concentration lower than the oxygen concentration in air (about 21 vol %).

When the lower gas valve 21 is opened, the nitrogen gas supplied from the lower gas pipe 20 to the lower tubular passage 19 is discharged upward from the lower central opening 18 at a flow rate corresponding to the opening degree of the lower gas flow rate adjusting valve 22. It After that, the nitrogen gas radially flows between the lower surface of the substrate W and the upper surface 12u of the spin base 12 in all directions. As a result, the space between the substrate W and the spin base 12 is filled with nitrogen gas, and the oxygen concentration in the atmosphere is reduced. The oxygen concentration in the space between the substrate W and the spin base 12 is changed according to the opening degrees of the lower gas valve 21 and the lower gas flow rate adjusting valve 22.

The processing cup 23 includes a plurality of guards 25 for receiving the liquid discharged outward from the substrate W, a plurality of cups 26 for receiving the liquid guided downward by the plurality of guards 25, a plurality of guards 25 and a plurality of cups. 26 and a cylindrical outer wall member 24 surrounding the same. FIG. 3 shows an example in which two guards 25 and two cups 26 are provided.
The guard 25 includes a cylindrical guard tubular portion 25b that surrounds the spin chuck 10, and an annular guard ceiling portion 25a that extends obliquely upward from the upper end portion of the guard tubular portion 25b toward the rotation axis A1. The plurality of guard ceiling portions 25a are vertically stacked, and the plurality of guard tubular portions 25b are arranged concentrically. The plurality of cups 26 are arranged below the plurality of guard tubular portions 25b, respectively. The cup 26 has an annular liquid receiving groove that opens upward.

The processing unit 2 includes a guard lifting unit 27 that lifts and lowers the plurality of guards 25 individually. The guard lifting unit 27 positions the guard 25 at any position from the upper position to the lower position. The upper position is a position where the upper end 25u of the guard 25 is arranged above the holding position where the substrate W held by the spin chuck 10 is arranged. The lower position is a position where the upper end 25u of the guard 25 is arranged below the holding position. The annular upper end of the guard ceiling portion 25a corresponds to the upper end 25u of the guard 25. The upper end 25u of the guard 25 surrounds the substrate W and the spin base 12 in a plan view.

When the processing liquid is supplied to the substrate W while the spin chuck 10 is rotating the substrate W, the processing liquid is shaken off from the substrate W. When the processing liquid is supplied to the substrate W, the upper end 25u of at least one guard 25 is arranged above the substrate W. Therefore, the processing liquid such as the chemical liquid and the rinse liquid discharged from the substrate W is received by one of the guards 25 and guided to the cup 26 corresponding to the guard 25.

As shown in FIG. 4, the processing unit 2 includes an elevating frame 32 arranged above the spin chuck 10, a blocking member 33 suspended from the elevating frame 32, and a central nozzle 45 inserted in the blocking member 33. And a blocking member lifting unit 31 that lifts the blocking member 33 and the central nozzle 45 by lifting the lifting frame 32. The elevating frame 32, the blocking member 33, and the central nozzle 45 are arranged below the straightening vane 8.

The blocking member 33 includes a disc portion 36 arranged above the spin chuck 10 and a cylindrical portion 37 extending downward from the outer peripheral portion of the disc portion 36. The blocking member 33 includes a cup-shaped inner surface that is recessed upward. The inner surface of the blocking member 33 includes the lower surface 36L of the disc portion 36 and the inner peripheral surface 37i of the tubular portion 37. Below, the lower surface 36L of the disk portion 36 may be referred to as the lower surface 36L of the blocking member 33.

The lower surface 36L of the disc portion 36 is a facing surface that faces the upper surface of the substrate W. The lower surface 36L of the disc portion 36 is parallel to the upper surface of the substrate W. The inner peripheral surface 37i of the tubular portion 37 extends downward from the outer peripheral edge of the lower surface 36L of the disc portion 36. The inner diameter of the tubular portion 37 increases as it approaches the lower end of the inner peripheral surface 37i of the tubular portion 37. The inner diameter of the lower end of the inner peripheral surface 37i of the tubular portion 37 is larger than the diameter of the substrate W. The inner diameter of the lower end of the inner peripheral surface 37i of the tubular portion 37 may be larger than the outer diameter of the spin base 12. When the blocking member 33 is arranged at a lower position (position shown in FIG. 3) described later, the substrate W is surrounded by the inner peripheral surface 37i of the tubular portion 37.

The lower surface 36L of the disc portion 36 is an annular shape that surrounds the rotation axis A1. An inner peripheral edge of the lower surface 36L of the disc portion 36 forms an upper central opening 38 that opens at the central portion of the lower surface 36L of the disc portion 36. The inner peripheral surface of the blocking member 33 forms a through hole extending upward from the upper central opening 38. The through hole of the blocking member 33 vertically penetrates the blocking member 33. The central nozzle 45 is inserted into the through hole of the blocking member 33. The outer diameter of the lower end of the central nozzle 45 is smaller than the diameter of the upper central opening 38.

The inner peripheral surface of the blocking member 33 is coaxial with the outer peripheral surface of the central nozzle 45. The inner peripheral surface of the blocking member 33 surrounds the outer peripheral surface of the central nozzle 45 at intervals in the radial direction (direction orthogonal to the rotation axis A1). The inner peripheral surface of the blocking member 33 and the outer peripheral surface of the central nozzle 45 form an upper cylindrical passage 39 extending vertically. The central nozzle 45 projects upward from the elevating frame 32 and the blocking member 33. When the blocking member 33 is suspended from the elevating frame 32, the lower end of the central nozzle 45 is disposed above the lower surface 36L of the disc portion 36. A processing liquid such as a chemical liquid or a rinse liquid is discharged downward from the lower end of the central nozzle 45.

The blocking member 33 includes a tubular connecting portion 35 extending upward from the disc portion 36, and an annular flange portion 34 extending outward from the upper end portion of the connecting portion 35. The flange portion 34 is arranged above the disc portion 36 and the tubular portion 37 of the blocking member 33. The flange portion 34 is parallel to the disc portion 36. The outer diameter of the flange portion 34 is smaller than the outer diameter of the tubular portion 37. The flange portion 34 is supported by a lower plate 32L of the elevating frame 32, which will be described later.

The elevating frame 32 includes an upper plate 32u located above the flange portion 34 of the blocking member 33, a side ring 32s that extends downward from the upper plate 32u, and surrounds the flange portion 34, and an inner side from a lower end portion of the side ring 32s. And an annular lower plate 32L that extends downwardly and that is located below the flange portion 34 of the blocking member 33. The outer peripheral portion of the flange portion 34 is arranged between the upper plate 32u and the lower plate 32L. The outer peripheral portion of the flange portion 34 is vertically movable between the upper plate 32u and the lower plate 32L.

The elevating frame 32 and the blocking member 33 are positioned to restrict relative movement of the elevating frame 32 and the blocking member 33 in the circumferential direction (direction around the rotation axis A1) in a state where the blocking member 33 is supported by the elevating frame 32. It includes a protrusion 41 and a positioning hole 42. FIG. 3 shows an example in which a plurality of positioning protrusions 41 are provided in the lower plate 32L and a plurality of positioning holes 42 are provided in the flange portion 34. The positioning protrusion 41 may be provided on the flange portion 34, and the positioning hole 42 may be provided on the lower plate 32L.

The plurality of positioning protrusions 41 are arranged on a circle having a center arranged on the rotation axis A1. Similarly, the plurality of positioning holes 42 are arranged on a circle having a center arranged on the rotation axis A1. The plurality of positioning holes 42 are arranged in the circumferential direction with the same regularity as the plurality of positioning protrusions 41. The positioning protrusion 41 protruding upward from the upper surface of the lower plate 32L is inserted into the positioning hole 42 extending upward from the lower surface of the flange portion 34. This restricts the movement of the blocking member 33 in the circumferential direction with respect to the elevating frame 32.

The blocking member 33 includes a plurality of upper support portions 43 protruding downward from the inner surface of the blocking member 33. The spin chuck 10 includes a plurality of lower support portions 44 that respectively support the plurality of upper support portions 43. The plurality of upper support portions 43 are surrounded by the tubular portion 37 of the blocking member 33. The lower end of the upper support portion 43 is arranged above the lower end of the tubular portion 37. The radial distance from the rotation axis A1 to the upper support portion 43 is larger than the radius of the substrate W. Similarly, the radial distance from the rotation axis A1 to the lower support portion 44 is larger than the radius of the substrate W. The lower support portion 44 projects upward from the upper surface 12u of the spin base 12. The lower support portion 44 is arranged outside the chuck pin 11.

The plurality of upper support portions 43 are arranged on a circle having a center arranged on the rotation axis A1. Similarly, the plurality of lower support portions 44 are arranged on a circle having a center arranged on the rotation axis A1. The plurality of lower support portions 44 are arranged in the circumferential direction with the same regularity as the plurality of upper support portions 43. The plurality of lower support portions 44 rotate together with the spin base 12 about the rotation axis A1. The rotation angle of the spin base 12 is changed by the spin motor 14. When the spin base 12 is arranged at the reference rotation angle, the plurality of upper support portions 43 respectively overlap the plurality of lower support portions 44 in plan view.

The blocking member lifting unit 31 is connected to the lifting frame 32. When the blocking member elevating unit 31 lowers the elevating frame 32 while the flange portion 34 of the blocking member 33 is supported by the lower plate 32L of the elevating frame 32, the blocking member 33 also lowers. When the blocking member elevating unit 31 lowers the blocking member 33 in a state where the spin base 12 is arranged at a reference rotation angle where the plurality of upper supporting portions 43 overlap with the plurality of lower supporting portions 44 in a plan view, the upper supporting portions 43 are supported. The lower end of the portion 43 contacts the upper end of the lower support portion 44. As a result, the plurality of upper support portions 43 are respectively supported by the plurality of lower support portions 44.

When the blocking member elevating unit 31 lowers the elevating frame 32 after the upper support portion 43 of the blocking member 33 contacts the lower support portion 44 of the spin chuck 10, the lower plate 32L of the elevating frame 32 causes the lower plate 32L of the blocking member 33 to have a flange portion. Move downward with respect to 34. As a result, the lower plate 32L separates from the flange portion 34, and the positioning protrusion 41 comes out of the positioning hole 42. Furthermore, since the elevating frame 32 and the central nozzle 45 move downward with respect to the blocking member 33, the height difference between the lower end of the central nozzle 45 and the lower surface 36L of the disc portion 36 of the blocking member 33 decreases. At this time, the elevating frame 32 is arranged at a height (a lower position described later) where the flange portion 34 of the blocking member 33 does not contact the upper plate 32u of the elevating frame 32.

The blocking member lifting/lowering unit 31 positions the lifting/lowering frame 32 at an arbitrary position from the upper position (the position shown in FIG. 4) to the lower position (the position shown in FIG. 3). The upper position is a position where the positioning protrusion 41 is inserted into the positioning hole 42 and the flange portion 34 of the blocking member 33 is in contact with the lower plate 32L of the elevating frame 32. That is, the upper position is the position where the blocking member 33 is suspended from the elevating frame 32. The lower position is a position where the lower plate 32L is separated from the flange portion 34 and the positioning protrusion 41 is pulled out from the positioning hole 42. That is, the lower position is a position where the connection between the elevating frame 32 and the blocking member 33 is released and the blocking member 33 does not contact any part of the elevating frame 32.

When the elevating frame 32 and the blocking member 33 are moved to the lower position, the lower end of the tubular portion 37 of the blocking member 33 is arranged below the lower surface of the substrate W, and the upper surface of the substrate W and the lower surface 36L of the blocking member 33 are separated from each other. The space therebetween is surrounded by the tubular portion 37 of the blocking member 33. Therefore, the space between the upper surface of the substrate W and the lower surface 36L of the blocking member 33 is shielded not only from the atmosphere above the blocking member 33 but also from the atmosphere around the blocking member 33. As a result, the degree of airtightness of the space between the upper surface of the substrate W and the lower surface 36L of the blocking member 33 can be increased.

Further, when the elevating frame 32 and the blocking member 33 are arranged in the lower position, the blocking member 33 does not collide with the elevating frame 32 even if the blocking member 33 is rotated around the rotation axis A1 with respect to the elevating frame 32. When the upper support part 43 of the blocking member 33 is supported by the lower support part 44 of the spin chuck 10, the upper support part 43 and the lower support part 44 mesh with each other, and the relative positions of the upper support part 43 and the lower support part 44 in the circumferential direction. Movement is restricted. When the spin motor 14 rotates in this state, the torque of the spin motor 14 is transmitted to the blocking member 33 via the upper support portion 43 and the lower support portion 44. As a result, the blocking member 33 rotates in the same direction as the spin base 12 at the same speed while the elevating frame 32 and the central nozzle 45 are stationary.

The central nozzle 45 includes a plurality of liquid ejection ports that eject liquid and a gas ejection port that ejects gas. The plurality of liquid discharge ports include a first chemical liquid discharge port 46 that discharges the first chemical liquid, a second chemical liquid discharge port 47 that discharges the second chemical liquid, and an upper rinse liquid discharge port 48 that discharges the rinse liquid. The gas discharge port is the upper gas discharge port 49 that discharges the inert gas. The first chemical liquid discharge port 46, the second chemical liquid discharge port 47, and the upper rinse liquid discharge port 48 are open at the lower end of the center nozzle 45. The upper gas discharge port 49 opens on the outer peripheral surface of the central nozzle 45.

The first chemical solution and the second chemical solution are, for example, sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, aqueous ammonia, hydrogen peroxide solution, organic acids (eg citric acid, oxalic acid, etc.), organic alkalis (eg TMAH: A liquid containing at least one of tetramethylammonium hydroxide), an inorganic alkali (eg, NaOH: sodium hydroxide), a surfactant, and a corrosion inhibitor. Sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, aqueous ammonia, hydrogen peroxide solution, citric acid, oxalic acid, inorganic alkali and TMAH are etching solutions.

The first chemical liquid and the second chemical liquid may be the same chemical liquid or different chemical liquids from each other. FIG. 3 and the like show an example in which the first chemical liquid is DHF (dilute hydrofluoric acid) and the second chemical liquid is TMAH. 3 and the like show an example in which the rinse liquid supplied to the central nozzle 45 is pure water and the inert gas supplied to the central nozzle 45 is nitrogen gas. Strictly speaking, TMAH is an aqueous solution of TMAH, but hereinafter, an aqueous solution of TMAH is referred to as TMAH unless otherwise specified. The dissolved oxygen concentration of TMAH is adjusted in advance. The dissolved oxygen concentration of DHF is also adjusted in advance. The rinse liquid supplied to the central nozzle 45 may be a rinse liquid other than pure water. The inert gas supplied to the central nozzle 45 may be an inert gas other than nitrogen gas.

The substrate processing apparatus 1 guides a first chemical liquid to the central nozzle 45, a first chemical liquid pipe 50, a first chemical liquid valve 51 interposed in the first chemical liquid pipe 50, and a second chemical liquid to the central nozzle 45. The second chemical liquid pipe 52, the second chemical liquid valve 53 interposed in the second chemical liquid pipe 52, the upper rinse liquid pipe 54 for guiding the rinse liquid to the central nozzle 45, and the upper rinse liquid pipe 54. An upper rinse liquid valve 55 is provided. The substrate processing apparatus 1 further includes an upper gas pipe 56 for guiding the gas to the central nozzle 45, an upper gas valve 57 interposed in the upper gas pipe 56, and a gas supplied from the upper gas pipe 56 to the central nozzle 45. An upper gas flow rate adjusting valve 58 for changing the flow rate is provided.

When the first chemical liquid valve 51 is opened, the first chemical liquid is supplied to the center nozzle 45 and is discharged downward from the first chemical liquid discharge port 46 that opens at the lower end of the center nozzle 45. When the second chemical liquid valve 53 is opened, the second chemical liquid is supplied to the central nozzle 45 and is discharged downward from the second chemical liquid discharge port 47 that opens at the lower end of the central nozzle 45. When the upper rinse liquid valve 55 is opened, the rinse liquid is supplied to the central nozzle 45 and is discharged downward from the upper rinse liquid discharge port 48 that opens at the lower end of the central nozzle 45. As a result, the chemical liquid or the rinse liquid is supplied to the upper surface of the substrate W.

When the upper gas valve 57 is opened, the nitrogen gas guided by the upper gas pipe 56 is supplied to the central nozzle 45 at a flow rate corresponding to the opening degree of the upper gas flow rate adjusting valve 58, and is opened on the outer peripheral surface of the central nozzle 45. The gas is discharged obliquely downward from the upper gas discharge port 49. Then, the nitrogen gas flows downward in the upper tubular passage 39 while flowing in the upper tubular passage 39 in the circumferential direction. The nitrogen gas reaching the lower end of the upper tubular passage 39 flows out downward from the lower end of the upper tubular passage 39. After that, the nitrogen gas radially flows in all directions in the space between the upper surface of the substrate W and the lower surface 36L of the blocking member 33. As a result, the space between the substrate W and the blocking member 33 is filled with nitrogen gas, and the oxygen concentration in the atmosphere is reduced. The oxygen concentration in the space between the substrate W and the blocking member 33 is changed according to the opening degrees of the upper gas valve 57 and the upper gas flow rate adjusting valve 58.

FIG. 5 is a block diagram showing the hardware of the control device 3.
The control device 3 is a computer including a computer main body 61 and a peripheral device 64 connected to the computer main body 61. The computer main body 61 includes a CPU 62 (central processing unit) that executes various instructions and a main storage device 63 that stores information. The peripheral device 64 includes an auxiliary storage device 65 that stores information such as the program P, a reading device 66 that reads information from the removable medium M, and a communication device 67 that communicates with other devices such as a host computer.

The control device 3 is connected to the input device 68 and the display device 69. The input device 68 is operated when an operator such as a user or a person in charge of maintenance inputs information to the substrate processing apparatus 1. The information is displayed on the screen of the display device 69. The input device 68 may be any one of a keyboard, a pointing device, and a touch panel, or may be a device other than these. A touch panel display that also serves as the input device 68 and the display device 69 may be provided in the substrate processing apparatus 1.

The CPU 62 executes the program P stored in the auxiliary storage device 65. The program P in the auxiliary storage device 65 may be installed in the control device 3 in advance, or may be sent from the removable medium M to the auxiliary storage device 65 through the reading device 66, It may be sent from an external device such as a host computer to the auxiliary storage device 65 through the communication device 67.

The auxiliary storage device 65 and the removable medium M are non-volatile memories that retain storage even when power is not supplied. The auxiliary storage device 65 is, for example, a magnetic storage device such as a hard disk drive. The removable medium M is, for example, an optical disk such as a compact disk or a semiconductor memory such as a memory card. The removable medium M is an example of a computer-readable recording medium in which the program P is recorded. The removable medium M is a non-temporary tangible recording medium.

The auxiliary storage device 65 stores a plurality of recipes. The recipe is information that defines the processing content of the substrate W, the processing conditions, and the processing procedure. The plurality of recipes differ from each other in at least one of the processing content of the substrate W, the processing conditions, and the processing procedure. The controller 3 controls the substrate processing apparatus 1 so that the substrate W is processed according to the recipe specified by the host computer. The following steps are executed by the control device 3 controlling the substrate processing apparatus 1. In other words, the controller 3 is programmed to execute the following steps.

FIG. 6 is a process chart for explaining an example of the processing of the substrate W performed by the substrate processing apparatus 1.
A specific example of the treatment of the substrate W is an etching treatment in which TMAH, which is an example of an etching solution, is supplied to the surface of the substrate W (silicon wafer) where the polysilicon film is exposed to etch the polysilicon film. In the following, reference is made to FIGS. 1 to 4 and 6.

When the substrate W is processed by the substrate processing apparatus 1, a loading process of loading the substrate W into the chamber 4 is performed (step S1 in FIG. 6).
Specifically, the center robot CR supports the substrate W with the hand H1 while the elevating frame 32 and the blocking member 33 are located at the upper position and all the guards 25 are located at the lower position. , The hand H1 enters the chamber 4. Then, the center robot CR places the substrate W on the hand H1 on the plurality of chuck pins 11 with the surface of the substrate W facing upward. Then, the plurality of chuck pins 11 are pressed against the outer peripheral surface of the substrate W, and the substrate W is gripped. The central robot CR puts the substrate W on the spin chuck 10 and then retracts the hand H1 from the inside of the chamber 4.

Next, the upper gas valve 57 and the lower gas valve 21 are opened, and the upper central opening 38 of the blocking member 33 and the lower central opening 18 of the spin base 12 start discharging nitrogen gas. As a result, the oxygen concentration in the atmosphere in contact with the substrate W is reduced. Further, the blocking member elevating unit 31 lowers the elevating frame 32 from the upper position to the lower position, and the guard elevating unit 27 raises one of the guards 25 from the lower position to the upper position. At this time, the spin base 12 is held at the reference rotation angle at which the plurality of upper support portions 43 overlap the plurality of lower support portions 44 in plan view. Therefore, the upper support portion 43 of the blocking member 33 is supported by the lower support portion 44 of the spin base 12, and the blocking member 33 separates from the elevating frame 32. Then, the spin motor 14 is driven and the rotation of the substrate W is started (step S2 in FIG. 6).

Next, a first chemical liquid supply step of supplying DHF, which is an example of the first chemical liquid, to the upper surface of the substrate W is performed (step S3 in FIG. 6).
Specifically, the first chemical liquid valve 51 is opened while the blocking member 33 is located at the lower position, and the central nozzle 45 starts discharging DHF. The DHF discharged from the central nozzle 45, after landing on the central portion of the upper surface of the substrate W, flows outward along the upper surface of the rotating substrate W. As a result, a DHF liquid film covering the entire upper surface of the substrate W is formed, and DHF is supplied to the entire upper surface of the substrate W. When a predetermined time has passed since the first chemical liquid valve 51 was opened, the first chemical liquid valve 51 is closed and the discharge of DHF is stopped.

Next, a first rinse liquid supply step of supplying pure water, which is an example of the rinse liquid, to the upper surface of the substrate W is performed (step S4 in FIG. 6).
Specifically, the upper rinse liquid valve 55 is opened with the blocking member 33 located at the lower position, and the central nozzle 45 starts discharging pure water. The pure water that has landed on the central portion of the upper surface of the substrate W flows outward along the upper surface of the rotating substrate W. The DHF on the substrate W is washed away by the pure water discharged from the central nozzle 45. As a result, a pure water liquid film covering the entire upper surface of the substrate W is formed. When a predetermined time has passed since the upper rinse liquid valve 55 was opened, the upper rinse liquid valve 55 is closed and the discharge of pure water is stopped.

Next, a second chemical liquid supply step of supplying TMAH, which is an example of the second chemical liquid, to the upper surface of the substrate W is performed (step S5 in FIG. 6).
Specifically, the second chemical liquid valve 53 is opened with the blocking member 33 positioned at the lower position, and the central nozzle 45 starts discharging TMAH. Before the ejection of TMAH is started, the guard elevating unit 27 may move at least one guard 25 vertically in order to switch the guard 25 that receives the liquid discharged from the substrate W. The TMAH that has landed on the central portion of the upper surface of the substrate W flows outward along the upper surface of the rotating substrate W. Pure water on the substrate W is replaced with TMAH discharged from the central nozzle 45. As a result, a TMAH liquid film covering the entire upper surface of the substrate W is formed. When a predetermined time has passed since the second chemical liquid valve 53 was opened, the second chemical liquid valve 53 is closed and the discharge of TMAH is stopped.

Next, a second rinse liquid supply step of supplying pure water, which is an example of the rinse liquid, to the upper surface of the substrate W is performed (step S6 in FIG. 6).
Specifically, the upper rinse liquid valve 55 is opened with the blocking member 33 located at the lower position, and the central nozzle 45 starts discharging pure water. The pure water that has landed on the central portion of the upper surface of the substrate W flows outward along the upper surface of the rotating substrate W. The TMAH on the substrate W is washed away by the pure water discharged from the central nozzle 45. As a result, a pure water liquid film covering the entire upper surface of the substrate W is formed. When a predetermined time has passed since the upper rinse liquid valve 55 was opened, the upper rinse liquid valve 55 is closed and the discharge of pure water is stopped.

Next, a drying process of drying the substrate W by rotating the substrate W is performed (step S7 in FIG. 6).
Specifically, the spin motor 14 accelerates the substrate W in the rotation direction while the blocking member 33 is in the lower position, and the substrate W in the period from the first chemical liquid supply process to the second rinse liquid supply process is increased. The substrate W is rotated at a high rotation speed (for example, several thousand rpm) higher than the rotation speed. As a result, the liquid is removed from the substrate W and the substrate W is dried. When a predetermined time has passed since the high speed rotation of the substrate W was started, the spin motor 14 stops rotating. At this time, the spin motor 14 stops the spin base 12 at the reference rotation angle. As a result, the rotation of the substrate W is stopped (step S8 in FIG. 6).

Next, an unloading step of unloading the substrate W from the chamber 4 is performed (step S9 in FIG. 6).
Specifically, the blocking member elevating unit 31 raises the elevating frame 32 to the upper position, and the guard elevating unit 27 lowers all the guards 25 to the lower position. Further, the upper gas valve 57 and the lower gas valve 21 are closed, and the upper central opening 38 of the blocking member 33 and the lower central opening 18 of the spin base 12 stop the discharge of nitrogen gas. After that, the center robot CR causes the hand H1 to enter the chamber 4. The center robot CR supports the substrate W on the spin chuck 10 with the hand H1 after the plurality of chuck pins 11 release the grip of the substrate W. After that, the central robot CR retracts the hand H1 from the inside of the chamber 4 while supporting the substrate W with the hand H1. As a result, the processed substrate W is unloaded from the chamber 4.

FIG. 7 is a schematic diagram showing the chemical solution supply unit 71, the chemical solution recovery unit 81, the concentration measurement unit 95, and the dissolved oxygen concentration changing unit. In FIG. 7, the liquid medicine cabinet CC is shown by a one-dot chain line. The members arranged in the area surrounded by the alternate long and short dash line in FIG. 7 are arranged in the liquid medicine cabinet CC. In the following description, the second chemical liquid is simply referred to as a chemical liquid. An example of the second chemical liquid is TMAH.

The substrate processing apparatus 1 includes a chemical liquid supply unit 71 that supplies the chemical liquid to the substrate W, and a chemical liquid recovery unit 81 that recovers the chemical liquid supplied to the substrate W to the chemical liquid supply unit 71. The central nozzle 45, the second chemical liquid pipe 52, and the second chemical liquid valve 53 are included in the chemical liquid supply unit 71. The substrate processing apparatus 1 further includes a concentration measuring unit 95 for measuring the concentration of the gas dissolved in the chemical liquid, and a dissolved oxygen concentration changing unit for changing the dissolved oxygen concentration of the chemical liquid.

The chemical solution supply unit 71 includes a first supply tank 72A that stores a chemical solution (TMAH in this example) to be supplied to the substrate W, and a first liquid level sensor 73A that detects the amount of the chemical solution in the first supply tank 72A. including. The chemical liquid supply unit 71 further includes a first circulation pipe 74A that forms an annular circulation path for circulating the chemical liquid in the first supply tank 72A, and a first circulation pipe 74A that sends the chemical liquid in the first supply tank 72A to the first circulation pipe 74A. It includes one pump 75A and a first filter 76A for removing foreign matters such as particles from the chemical liquid flowing through the circulation path.

The upstream end and the downstream end of the first circulation pipe 74A are connected to the first supply tank 72A. The first pump 75A and the first filter 76A are provided in the first circulation pipe 74A. The chemical liquid is sent from the first supply tank 72A to the upstream end of the first circulation pipe 74A by the first pump 75A, and returns to the first supply tank 72A from the downstream end of the first circulation pipe 74A. As a result, the chemical liquid in the first supply tank 72A circulates in the circulation path. The upstream end of the second chemical liquid pipe 52 is connected to the first circulation pipe 74A. When the second chemical liquid valve 53 is opened, a part of the chemical liquid flowing in the first circulation pipe 74A is supplied to the central nozzle 45 via the second chemical liquid pipe 52.

The chemical liquid supply unit 71 measures the temperature of the chemical liquid whose temperature is adjusted by the first temperature controller 77A that changes the temperature of the chemical liquid in the first supply tank 72A by heating or cooling the chemical liquid, and the temperature of the chemical liquid adjusted by the first temperature controller 77A. The first thermometer 78A may be included. The first temperature controller 77A and the first thermometer 78A are installed in the first circulation pipe 74A. The temperature of the first temperature controller 77A is changed based on the measurement value of the first thermometer 78A. As a result, the temperature of the chemical liquid in the first supply tank 72A is maintained at the set temperature.

FIG. 7 is a heater in which the first temperature controller 77A heats the liquid at a temperature higher than room temperature (for example, 20 to 30° C.), and the first thermometer 78A measures the temperature of the chemical liquid in the first circulation pipe 74A. An example is shown. The first temperature controller 77A may be a cooler that cools the liquid at a temperature lower than room temperature, or may have both heating and cooling functions. In addition, the first temperature controller 77A may be arranged in the first supply tank 72A. The first thermometer 78A may measure the temperature of the chemical liquid in the first supply tank 72A.

The chemical liquid recovery unit 81 includes an upstream recovery tank 84 that stores the chemical liquid recovered from the processing unit 2 and a downstream recovery tank 89 that stores the chemical liquid recovered from the upstream recovery tank 84. The chemical liquid recovery unit 81 further includes an upstream pipe 82 that guides the chemical liquid from the processing unit 2 to the upstream recovery tank 84, an intermediate pipe 87 that guides the chemical liquid from the upstream recovery tank 84 to the downstream recovery tank 89, and a first recovery pipe 89 from the downstream recovery tank 89. And a downstream pipe 90 for guiding the chemical liquid to the supply tank 72A. The upstream recovery tank 84 and the downstream recovery tank 89 are recovery tanks that temporarily store the chemical liquid recovered from the processing unit 2 to the first supply tank 72A.

FIG. 7 shows an example in which the upstream recovery tank 84 is disposed below the processing unit 2 and the downstream recovery tank 89 is disposed in the chemical liquid cabinet CC. The upstream recovery tank 84 may be arranged inside the outer wall 1a of the substrate processing apparatus 1 (see FIG. 1), or may be arranged outside the outer wall 1a of the substrate processing apparatus 1. The upstream recovery tank 84 may be connected to the plurality of processing units 2 via the upstream pipe 82, or may be connected to only one processing unit 2 via the upstream pipe 82. In the former case, the upstream recovery tank 84 may be connected only to all the processing units 2 included in the same tower, or may be connected to all the processing units 2 included in the substrate processing apparatus 1.

The upstream end of the upstream pipe 82 is connected to one of the processing cups 26. The downstream end of the upstream pipe 82 is connected to the upstream recovery tank 84. The upstream end of the intermediate pipe 87 is connected to the upstream recovery tank 84. The downstream end of the intermediate pipe 87 is connected to the downstream recovery tank 89. The chemical liquid recovery unit 81 includes an upstream valve 83 that opens and closes the inside of the upstream pipe 82, and an upstream pump 88 that sends the chemical liquid in the upstream recovery tank 84 to the downstream recovery tank 89 through the intermediate pipe 87.

The chemical liquid supplied to the substrate W flows from the cup 26 connected to the upstream pipe 82 to the upstream pipe 82. When the upstream valve 83 is closed, the chemical liquid flowing from the cup 26 into the upstream pipe 82 is blocked by the upstream valve 83. When the upstream valve 83 is opened, the chemical liquid in the cup 26 flows into the upstream recovery tank 84 through the upstream pipe 82. At this time, the gas in the upstream recovery tank 84 is discharged to the breather pipe 86.

The chemical liquid in the upstream recovery tank 84 is sent from the upstream recovery tank 84 to the intermediate pipe 87 by the upstream pump 88 and flows into the downstream recovery tank 89. As a result, the chemical liquid in the upstream recovery tank 84 is recovered in the downstream recovery tank 89 through the intermediate pipe 87. When the chemical liquid in the upstream recovery tank 84 is sent to the intermediate pipe 87 by the upstream pump 88, air flows into the upstream recovery tank 84 via the breather pipe 86.

The downstream recovery tank 89 is connected to the upstream end of the downstream pipe 90. The downstream end of the downstream pipe 90 is connected to the first supply tank 72A. The chemical liquid recovery unit 81 includes a downstream valve 93 that opens and closes the inside of the downstream pipe 90. The chemical liquid recovery unit 81 further includes a downstream pump 91 that sends the chemical liquid in the downstream recovery tank 89 to the first supply tank 72A through the downstream pipe 90, a downstream filter 92 that removes foreign matters from the chemical liquid that flows in the downstream pipe 90, and a downstream. A return pipe 94 for guiding the chemical liquid in the pipe 90 to the downstream recovery tank 89 is included.

The downstream pump 91 and the downstream filter 92 are provided in the downstream pipe 90. The upstream end of the return pipe 94 is connected to the downstream pipe 90. The downstream end of the return pipe 94 is connected to the downstream recovery tank 89. The downstream pump 91 and the downstream filter 92 are arranged upstream of the downstream valve 93. Similarly, the upstream end of the return pipe 94 is arranged upstream of the downstream valve 93. The upstream end of the return pipe 94 is arranged downstream of the downstream pump 91.

When the downstream valve 93 is opened, a part of the chemical liquid sent from the downstream recovery tank 89 to the downstream pipe 90 by the downstream pump 91 is supplied to the first supply tank 72A through the downstream pipe 90, and the remaining chemical liquid is supplied. Return to the downstream recovery tank 89 through the return pipe 94. When the downstream valve 93 is closed, all of the chemical liquid sent from the downstream recovery tank 89 to the downstream pipe 90 by the downstream pump 91 returns to the downstream recovery tank 89 through the return pipe 94. Therefore, when the downstream valve 93 is closed, the chemical liquid in the downstream recovery tank 89 circulates in the annular circulation path formed by the downstream pipe 90 and the return pipe 94.

The concentration measuring unit 95 includes a first oxygen concentration meter 96 for measuring the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A and a second oxygen concentration meter 98 for measuring the dissolved oxygen concentration of the chemical liquid in the downstream recovery tank 89. including. FIG. 7 shows an example in which the first oxygen concentration meter 96 and the second oxygen concentration meter 98 measure the dissolved oxygen concentration of the chemical liquid outside the first supply tank 72A and the downstream recovery tank 89. In this example, the concentration measurement unit 95 includes a first measurement pipe 97 for guiding the chemical liquid sent from the first supply tank 72A and a second measurement pipe 99 for guiding the chemical liquid sent from the downstream recovery tank 89. . The first oxygen concentration meter 96 may measure the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A. Similarly, the second oxygen concentration meter 98 may measure the dissolved oxygen concentration of the chemical liquid in the downstream recovery tank 89.

The first oxygen concentration meter 96 is provided in the first measurement pipe 97. The second oxygen concentration meter 98 is provided in the second measurement pipe 99. The first oxygen concentration meter 96 and the second oxygen concentration meter 98 may be installed in the first circulation pipe 74A and the downstream pipe 90, respectively. In this case, the first measurement pipe 97 and the second measurement pipe 99 may be omitted. The upstream end of the first measurement pipe 97 is connected to the first filter 76A. The upstream end of the second measurement pipe 99 is connected to the downstream pipe 90 at a position upstream of the downstream valve 93. The downstream ends of the first measurement pipe 97 and the second measurement pipe 99 are connected to the drain tank 100. The upstream end of the first measurement pipe 97 may be connected to the first circulation pipe 74A. The upstream end of the second measurement pipe 99 may be connected to the downstream filter 92.

The dissolved oxygen concentration changing unit includes a gas dissolving device 101 that dissolves a regulated gas having an oxygen concentration lower than that of air into a chemical solution. The conditioning gas includes a low oxygen gas having an oxygen concentration lower than the oxygen concentration in air. The low oxygen gas may be an inert gas such as nitrogen gas, or may be a mixed gas of an inert gas and another gas. The adjustment gas contains a substance contained in the chemical liquid in addition to the low oxygen gas. The following describes an example in which both of TMAH (anhydride) and water _(H 2 O) is included in the conditioning gas. Therefore, the adjustment gas contains two substances (TMAH and H ₂ O) in addition to the low oxygen gas.

The gas dissolving apparatus 101 includes a first gas generation tank 122 that stores a chemical solution (TMAH in this example), a first upstream gas supply pipe 123 that supplies low oxygen gas into the first gas generation tank 122, and a first gas generation tank 123. A first downstream gas supply pipe 121 for supplying the adjusted gas generated in the gas generation tank 122 to the first supply tank 72A is included. The gas dissolving device 101 may include a first check valve 124 provided in the first upstream gas supply pipe 123. In this case, the reverse flow of gas in the first upstream gas supply pipe 123 (the flow of gas in the direction away from the gas discharge port 123p of the first upstream gas supply pipe 123) is prevented by the first check valve 124.

The gas discharge port 123p of the first upstream gas supply pipe 123 is arranged in the chemical liquid in the first gas generation tank 122. When the low oxygen gas is discharged from the gas discharge port 123p of the first upstream gas supply pipe 123, the low oxygen gas forms many bubbles in the chemical liquid in the first gas generation tank 122. After that, the low oxygen gas floats in the chemical liquid to the liquid surface of the chemical liquid and mixes with the gas on the liquid surface of the chemical liquid. In the process up to this point, the chemical vapor and mist are dispersed in the low oxygen gas. Thereby, the adjusted gas containing the low oxygen gas and the chemical liquid is generated in the first gas generation tank 122.

The adjusted gas in the first gas generation tank 122 flows into the upstream end of the first downstream gas supply pipe 121 provided with a gas inlet. The upstream end of the first downstream gas supply pipe 121 is connected to the first gas generation tank 122. The upstream end of the first downstream gas supply pipe 121 is arranged above the liquid level of the chemical liquid in the first gas generation tank 122. If the gas in the first gas generation tank 122 flows into the first downstream gas supply pipe 121, the upstream end of the first downstream gas supply pipe 121 may be arranged in the first gas generation tank 122. Alternatively, it may be arranged on the surface of the first gas generation tank 122.

The gas discharge port 121p of the first downstream gas supply pipe 121 is arranged in the chemical liquid in the first supply tank 72A. If the regulated gas discharged from the gas discharge port 121p of the first downstream gas supply pipe 121 is supplied into the first supply tank 72A, the gas discharge port 121p of the first downstream gas supply pipe 121 receives the first supply. It may be arranged above the liquid surface of the chemical liquid in the tank 72A. The adjustment gas discharged from the gas discharge port 121p of the first downstream gas supply pipe 121 forms a large number of bubbles in the chemical liquid in the first supply tank 72A. After that, the adjusted gas floats in the chemical liquid to the liquid surface of the chemical liquid and mixes with the gas on the liquid surface of the chemical liquid.

A part of the adjustment gas supplied into the first supply tank 72A dissolves in the chemical liquid in the first supply tank 72A. Dissolved gas such as dissolved oxygen is discharged from the chemical liquid in the first supply tank 72A by dissolving the adjusted gas. The adjustment gas is a gas whose main component is a low oxygen gas whose oxygen concentration is lower than that of air. Therefore, the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A decreases due to the dissolution of the adjusted gas. As a result, the chemical liquid having a low dissolved oxygen concentration is supplied from the first supply tank 72A to the central nozzle 45.

The gas dissolving apparatus 101 includes a second gas generation tank 132 that stores a chemical liquid (TMAH in this example), a second upstream gas supply pipe 133 that supplies low oxygen gas into the second gas generation tank 132, and a second gas generation tank 133. The second downstream gas supply pipe 131 for supplying the regulated gas generated in the gas generation tank 132 to the downstream recovery tank 89. The gas dissolving device 101 may include a second check valve 134 interposed in the second upstream gas supply pipe 133. In this case, the reverse flow of gas in the second upstream gas supply pipe 133 (the flow of gas in the direction away from the gas discharge port 133p of the second upstream gas supply pipe 133) is prevented by the second check valve 134.

The gas discharge port 133p of the second upstream gas supply pipe 133 is arranged in the chemical liquid in the second gas generation tank 132. When the low oxygen gas is discharged from the gas discharge port 133p of the second upstream gas supply pipe 133, the low oxygen gas forms a large number of bubbles in the chemical liquid in the second gas generation tank 132. After that, the low oxygen gas floats in the chemical liquid to the liquid surface of the chemical liquid and mixes with the gas on the liquid surface of the chemical liquid. In the process up to this point, the chemical vapor and mist are dispersed in the low oxygen gas. As a result, the adjusted gas containing the low oxygen gas and the chemical liquid is generated in the second gas generation tank 132.

The adjusted gas in the second gas generation tank 132 flows into the upstream end of the second downstream gas supply pipe 131 provided with a gas inlet. The upstream end of the second downstream gas supply pipe 131 is connected to the second gas generation tank 132. The upstream end of the second downstream gas supply pipe 131 is arranged above the liquid surface of the chemical liquid in the second gas generation tank 132. If the gas in the second gas generation tank 132 flows into the second downstream gas supply pipe 131, even if the upstream end of the second downstream gas supply pipe 131 is arranged in the second gas generation tank 132. It may be arranged on the surface of the second gas generation tank 132.

The gas discharge port 131 p of the second downstream gas supply pipe 131 is arranged in the chemical liquid in the downstream recovery tank 89. If the adjusted gas discharged from the gas discharge port 131p of the second downstream gas supply pipe 131 is supplied into the downstream recovery tank 89, the gas discharge port 131p of the second downstream gas supply pipe 131 will be connected to the downstream recovery tank 89. It may be arranged above the liquid surface of the drug solution inside. The adjustment gas discharged from the gas discharge port 131p of the second downstream gas supply pipe 131 forms a large number of bubbles in the chemical liquid in the downstream recovery tank 89. After that, the adjusted gas floats in the chemical liquid to the liquid surface of the chemical liquid and mixes with the gas on the liquid surface of the chemical liquid.

A part of the adjusted gas supplied into the downstream recovery tank 89 dissolves in the chemical liquid in the downstream recovery tank 89. Dissolved gas such as dissolved oxygen is discharged from the chemical liquid in the downstream recovery tank 89 by dissolving the adjusted gas. The adjustment gas is a gas whose main component is a low oxygen gas whose oxygen concentration is lower than that of air. Therefore, the dissolved oxygen concentration of the chemical solution in the downstream recovery tank 89 decreases due to the dissolution of the adjusted gas. As a result, the chemical liquid having a low dissolved oxygen concentration is supplied from the downstream recovery tank 89 to the first supply tank 72A.

The first gas generation tank 122 and the first upstream gas supply pipe 123 are included in the first gas generator that generates the first adjusted gas. The second gas generation tank 132 and the second upstream gas supply pipe 133 are included in the second gas generator that generates the second adjusted gas. In this embodiment, the second gas generation tank 132 corresponds to the preliminary gas generation tank. Therefore, the chemical liquid in the second gas generation tank 132 corresponds to the preconditioned liquid, and the regulated gas generated in the second gas generation tank 132 corresponds to the preconditioned gas.

In the gas dissolving device 101, a first inert gas pipe 103 that guides the inert gas to the first upstream gas supply pipe 123, and the inert gas flows from the first inert gas pipe 103 to the first upstream gas supply pipe 123. A first inert gas valve 104 that opens and closes between an open state and a closed state in which the inert gas is blocked by the first inert gas pipe 103; and a supply from the first inert gas pipe 103 to the first upstream gas supply pipe 123. And a first inert gas flow rate adjusting valve 105 for changing the flow rate of the inert gas.

Similarly, the gas dissolving apparatus 101 includes a second inert gas pipe 110 that guides an inert gas to the second upstream gas supply pipe 133, and an inert gas from the second inert gas pipe 110 to the second upstream gas supply pipe 133. A second inert gas valve 111 that opens and closes between an open state in which gas flows and a closed state in which inert gas is blocked by the second inert gas pipe 110, and a second upstream gas supply pipe from the second inert gas pipe 110. And a second inert gas flow rate adjusting valve 112 for changing the flow rate of the inert gas supplied to 133.

The gas dissolving device 101 includes, in addition to the first inert gas pipe 103 and the like, a first oxygen-containing gas pipe 106 that guides an oxygen-containing gas containing oxygen such as clean air to the first upstream gas supply pipe 123; A first oxygen-containing gas valve 107 that opens and closes between an open state in which the oxygen-containing gas flows from the oxygen-containing gas pipe 106 to the first upstream gas supply pipe 123 and a closed state in which the oxygen-containing gas is dammed by the first oxygen-containing gas pipe 106. And a first oxygen-containing gas flow rate adjusting valve 108 that changes the flow rate of the oxygen-containing gas supplied from the first oxygen-containing gas pipe 106 to the first upstream gas supply pipe 123.

Similarly, the gas dissolving apparatus 101 includes, in addition to the second inert gas pipe 110 and the like, a second oxygen-containing gas pipe 113 for guiding an oxygen-containing gas containing oxygen such as clean air to the second upstream gas supply pipe 133. Second oxygen that is opened and closed between an open state in which the oxygen-containing gas flows from the second oxygen-containing gas pipe 113 to the second upstream gas supply pipe 133 and a closed state in which the oxygen-containing gas is dammed by the second oxygen-containing gas pipe 113. It may include a containing gas valve 114 and a second oxygen containing gas flow rate adjusting valve 115 for changing the flow rate of the oxygen containing gas supplied from the second oxygen containing gas pipe 113 to the second upstream gas supply pipe 133.

When the first inert gas valve 104 is opened, that is, when the first inert gas valve 104 is switched from the closed state to the open state, the nitrogen gas, which is an example of the inert gas, changes the first inert gas flow rate adjusting valve 105. The gas is supplied from the first inert gas pipe 103 to the first upstream gas supply pipe 123 at a flow rate corresponding to the opening degree. Similarly, when the first oxygen-containing gas valve 107 is opened, air, which is an example of the oxygen-containing gas, flows through the first oxygen-containing gas pipe 106 from the first oxygen-containing gas pipe 106 at a flow rate corresponding to the opening of the first oxygen-containing gas flow rate adjustment valve 108. 1 is supplied to the upstream gas supply pipe 123. When both the first inert gas valve 104 and the first oxygen-containing gas valve 107 are opened, the mixed gas of nitrogen gas and air is supplied to the first upstream gas supply pipe 123.

The first gas generation tank 122 is a sealed tank. When the gas is supplied from the first upstream gas supply pipe 123 to the first gas generation tank 122, the same amount of gas as the gas supplied to the first gas generation tank 122 is discharged from the first gas generation tank 122 to the first downstream side. It is discharged to the gas supply pipe 121. Therefore, by adjusting the opening degrees of the first inert gas flow rate adjusting valve 105 and the first oxygen-containing gas flow rate adjusting valve 108, the flow rate of the adjusting gas supplied into the first supply tank 72A can be precisely controlled. Thereby, the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A can be precisely controlled.

Like the first gas generation tank 122, the second gas generation tank 132 is a sealed tank. When the second inert gas valve 111 is opened, nitrogen gas is supplied from the second inert gas pipe 110 to the second upstream gas supply pipe 133 at a flow rate corresponding to the opening degree of the second inert gas flow rate adjusting valve 112. It When the second oxygen-containing gas valve 114 is opened, air is supplied from the second oxygen-containing gas pipe 113 to the second upstream gas supply pipe 133 at a flow rate corresponding to the opening degree of the second oxygen-containing gas flow rate adjusting valve 115. . Therefore, by adjusting the openings of the second inert gas flow rate adjusting valve 112 and the second oxygen-containing gas flow rate adjusting valve 115, the flow rate of the adjusting gas supplied into the downstream recovery tank 89 can be precisely controlled.

The control device 3 may constantly supply the adjusted gas into the first supply tank 72A, or may supply the adjusted gas into the first supply tank 72A only when necessary. Similarly, the control device 3 may constantly supply the adjusted gas into the downstream recovery tank 89, or may supply the adjusted gas into the downstream recovery tank 89 only when necessary. The control device 3 maintains the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A within the final concentration range by changing the flow rate and composition of the adjusted gas based on the measurement value of the first oxygen concentration meter 96. To do. The control device 3 maintains the dissolved oxygen concentration of the chemical solution in the downstream recovery tank 89 at a value within the intermediate concentration range by changing the flow rate and composition of the adjusted gas based on the measurement value of the second oxygen concentration meter 98. You may.

The gas dissolving device 101 includes a first gas discharge pipe 125 that discharges the gas in the first supply tank 72A. The upstream end of the first gas discharge pipe 125 provided with a gas inlet is connected to the first supply tank 72A. The downstream end of the first gas discharge pipe 125 provided with a gas outlet is arranged in a space maintained at atmospheric pressure. Therefore, the atmospheric pressure in the first supply tank 72A is maintained at or near atmospheric pressure. The gas dissolving device 101 may include a relief valve that discharges the gas in the first supply tank 72A to the first gas discharge pipe 125 only when the atmospheric pressure in the first supply tank 72A is equal to or higher than the set pressure.

The gas dissolving device 101 includes a second gas discharge pipe 135 that discharges the gas in the downstream recovery tank 89. The upstream end of the second gas discharge pipe 135 provided with the gas inlet is connected to the downstream recovery tank 89. The downstream end of the second gas discharge pipe 135 provided with a gas outlet is arranged in a space maintained at atmospheric pressure. Therefore, the atmospheric pressure in the downstream recovery tank 89 is maintained at a value at or near atmospheric pressure. The gas dissolving device 101 may include a relief valve that discharges the gas in the downstream recovery tank 89 to the second gas exhaust pipe 135 only when the atmospheric pressure in the downstream recovery tank 89 is equal to or higher than the set pressure.

The first gas discharge pipe 125 includes a first rising pipe 126 extending upward from the first supply tank 72A. Similarly, the second gas discharge pipe 135 includes a second ascending pipe 136 extending upward from the downstream recovery tank 89. As long as it extends upward from the first supply tank 72A, the first rising pipe 126 may be vertical or may be inclined with respect to the horizontal plane. Further, the first rising pipe 126 may have any of a linear shape, a broken line shape, and a curved shape. The same applies to the second rising pipe 136. The upstream end of the first ascending pipe 126 corresponds to the uppermost end of the first ascending pipe 126. The upstream end of the second ascending pipe 136 corresponds to the uppermost end of the second ascending pipe 136.

The substrate processing apparatus 1 includes a first cooler 127 that cools the exhaust gas discharged from the first supply tank 72A to the first gas discharge pipe 125, and an exhaust gas discharged from the downstream recovery tank 89 to the second gas discharge pipe 135. And a second cooler 137 for cooling the. FIG. 7 shows an example in which the first cooler 127 is attached to the first ascending pipe 126 and the second cooler 137 is attached to the second ascending pipe 136. In this example, the exhaust gas in the first rising pipe 126 is cooled by the first cooler 127, and the exhaust gas in the second rising pipe 136 is cooled by the second cooler 137.

FIG. 8A is a schematic horizontal view of the outer appearance of the first cooler 127 attached to the first ascending pipe 126. FIG. 8B is a schematic diagram showing a vertical cross section of the first rising pipe 126 and the first supply tank 72A. The second cooler 137 has the same configuration as the first cooler 127. The positional relationship between the second cooler 137 and the second rising pipe 136 is the same as the positional relationship between the first cooler 127 and the first rising pipe 126. Therefore, hereinafter, the first cooler 127 will be described and the description of the second cooler 137 will be omitted.

As shown in FIG. 8A, the first cooler 127 includes a first cooling pipe 128 that guides a cooling fluid having a temperature lower than room temperature. The first cooling pipe 128 is spirally wound around the first rising pipe 126. The first cooling pipe 128 is in contact with the outer peripheral surface of the first rising pipe 126. The cooling fluid constantly flows in the first rising pipe 126, and cools the first rising pipe 126 via the first cooling pipe 128. The cooling fluid may be a cooling liquid such as cooling water or a cooling gas.

The exhaust gas discharged from the first supply tank 72A to the first ascending pipe 126 contains not only low oxygen gas, but also vapor of chemical liquid and mist. When the exhaust gas in the first ascending pipe 126 is cooled, the vapor of the chemical solution changes into droplets or the droplets contained in the mist of the chemical solution become large. Therefore, as shown in FIG. 8B, the liquid droplets of the chemical liquid adhere to the inner peripheral surface of the first rising pipe 126. Similarly, in the second ascending pipe 136, liquid drops of the chemical liquid adhere to the inner peripheral surface of the second ascending pipe 136.

The first ascending pipe 126 is an example of a first recycling pipe that returns the liquid droplets of the chemical liquid to the first supply tank 72A. The second ascending pipe 136 is an example of a second recycle pipe for returning the liquid drops of the chemical liquid to the downstream recovery tank 89. As shown in FIG. 8B, when the liquid drop of the chemical liquid becomes large to some extent, it flows toward the first supply tank 72A along the inner peripheral surface of the first rising pipe 126 by its own weight, and drops into the chemical liquid in the first supply tank 72A. To do. Similarly, when the liquid droplets of the chemical liquid become large to some extent, they drop into the chemical liquid in the downstream recovery tank 89. As a result, it is possible to reduce the reduction amount of the chemical liquid in the first supply tank 72A and the downstream recovery tank 89.

FIG. 9 is a flowchart showing an example of a flow from supplying a new chemical liquid to the first supply tank 72A to discharging the chemical liquid in the first supply tank 72A. The operations described below are executed by the control device 3 controlling the substrate processing apparatus 1. In other words, the control device 3 is programmed to execute the following operations and the like. In the following, reference is made to FIGS. 7 and 9.

When the processing of the substrate W shown in FIG. 6 is started by the substrate processing apparatus 1, the chemical solution (TMAH which is an example of the second chemical solution) whose dissolved oxygen concentration is not adjusted is the first supply tank 72A and the upstream recovery tank. It is supplied to 84, the 1st gas production tank 122, and the 2nd gas production tank 132 (Step S11 of Drawing 9).
When the liquid amount in the first supply tank 72A exceeds the lower limit value, the control device 3 opens the first inert gas valve 104 and starts the supply of nitrogen gas to the first gas generation tank 122. Similarly, the control device 3 opens the second inert gas valve 111 and starts the supply of nitrogen gas to the second gas generation tank 132. Thereby, the bubbling of the chemical liquid is started in the first gas generation tank 122 and the second gas generation tank 132. Along with that, the generation of the adjusted gas containing the nitrogen gas and the chemical liquid is started in the first gas generation tank 122 and the second gas generation tank 132 (step S12 in FIG. 9).

The adjusted gas generated in the first gas generation tank 122 is supplied to the first supply tank 72A. The adjusted gas generated in the second gas generation tank 132 is supplied to the downstream recovery tank 89. Therefore, when the supply of the nitrogen gas to the first gas generation tank 122 and the second gas generation tank 132 is started, the supply of the adjusted gas to the first supply tank 72A and the downstream recovery tank 89 is started. Thereby, the bubbling of the chemical liquid is started in the first supply tank 72A and the downstream recovery tank 89 (step S13 in FIG. 9).

When the supply of the regulated gas to the first supply tank 72A is started, the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A decreases with the passage of time. Similarly, when the supply of the regulated gas to the downstream recovery tank 89 is started, the dissolved oxygen concentration of the chemical solution in the downstream recovery tank 89 decreases with the passage of time. When a predetermined time has passed since the adjustment of the dissolved oxygen concentration was started, the control device 3 determines that the dissolved oxygen concentration of the chemical solution in the first supply tank 72A is in the final concentration range based on the measurement value of the first oxygen concentration meter 96. It is confirmed whether or not it is within (step S14 of FIG. 9).

When the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A is not within the final concentration range (No in step S14 in FIG. 9), the control device 3 again stores the first supply tank 72A in the first supply tank 72A after a predetermined time has elapsed. Check whether the dissolved oxygen concentration of the chemical solution is within the final concentration range. Before confirming the dissolved oxygen concentration of the chemical liquid again, the control device 3 changes the flow rate of the nitrogen gas supplied to the first gas generation tank 122 or changes the mixed gas of nitrogen gas and air to the first gas generation tank 122. It may be supplied to.

When the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A is within the final concentration range (Yes in step S14 of FIG. 9), the control device 3 opens the second chemical liquid valve 53 to start the first supply tank 72A. The supply of the chemical liquid to the central nozzle 45 is started (step S15 in FIG. 9). When a predetermined time has passed since the second chemical liquid valve 53 was opened, the control device 3 closes the second chemical liquid valve 53 and stops the supply of the chemical liquid to the central nozzle 45. As a result, the second chemical liquid supply step of supplying TMAH, which is an example of the second chemical liquid, to the upper surface of the substrate W is performed (step S5 in FIG. 6).

While the central nozzle 45 is discharging the chemical liquid, the chemical liquid discharged from the substrate W is supplied to the upstream recovery tank 84 via the guard 25, the cup 26, and the upstream pipe 82. The chemical liquid in the upstream recovery tank 84 is supplied to the downstream recovery tank 89 through the intermediate pipe 87. As a result, the chemical liquid discharged from the substrate W is recovered in the downstream recovery tank 89, and the dissolved oxygen concentration is adjusted in the downstream recovery tank 89. The chemical liquid in the downstream recovery tank 89 is supplied to the first supply tank 72A as needed.

After the supply of the chemical liquid to one substrate W is completed, the control device 3 determines whether the chemical liquid in the first supply tank 72A should be replaced with a new chemical liquid (step S16 in FIG. 9). Whether or not the chemical solution is replaced may be determined based on at least one of the usage time of the chemical solution and the number of processed substrates W, or may be determined based on other criteria. Alternatively, the chemical liquid in the first supply tank 72A may be exchanged when the user of the substrate processing apparatus 1 inputs a chemical liquid exchange command to the input device 68 (see FIG. 5).

When it is not necessary to replace the chemical liquid in the first supply tank 72A with a new chemical liquid (No in step S16 of FIG. 9), the control device 3 again determines that the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A is the final value. It is confirmed whether or not it is within the concentration range (step S14 in FIG. 9). If the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A is within the final concentration range (Yes in step S14 of FIG. 9), the control device 3 opens the second chemical liquid valve 53 to start the first supply tank 72A. The supply of the chemical liquid to the central nozzle 45 is started (step S16 in FIG. 9). As a result, TMAH, which is an example of the second chemical liquid, is supplied to another substrate W.

When the chemical liquid in the first supply tank 72A is to be replaced with a new chemical liquid (Yes in step S16 of FIG. 9 ), the control device 3 closes the first inert gas valve 104, and the nitrogen gas to the first gas generation tank 122 is closed. Stop the gas supply. Similarly, the control device 3 closes the second inert gas valve 111 to stop the supply of the nitrogen gas to the second gas generation tank 132. When at least one of the first oxygen-containing gas valve 107 and the second oxygen-containing gas valve 114 is open, the control device 3 also controls the opened valve (at least one of the first oxygen-containing gas valve 107 and the second oxygen-containing gas valve 114). close. Thereby, the bubbling of the chemical liquid in the first gas generation tank 122 and the second gas generation tank 132 is stopped (step S17 in FIG. 9). Therefore, the production of the adjusted gas in the first gas production tank 122 and the second gas production tank 132 is stopped.

When the production of the adjusted gas in the first gas production tank 122 is stopped, the supply of the adjusted gas to the first supply tank 72A is also stopped. Similarly, when the production of the adjusted gas in the second gas production tank 132 is stopped, the supply of the adjusted gas to the downstream recovery tank 89 is also stopped. Therefore, when the supply of the nitrogen gas to the first gas generation tank 122 and the second gas generation tank 132 is stopped, the supply of the adjustment gas to the first supply tank 72A and the downstream recovery tank 89 is stopped. Thereby, the bubbling of the chemical liquid in the first supply tank 72A and the downstream recovery tank 89 is stopped (step S18 in FIG. 9).

After the supply of the nitrogen gas to the first gas generation tank 122 and the second gas generation tank 132 is stopped, the chemical solution in the first gas generation tank 122 and the second gas generation tank 132 is discharged (see FIG. 9). Step S19). Similarly, the chemical liquid in the first supply tank 72A and the downstream recovery tank 89 is discharged (step S19 in FIG. 9). After that, the chemical solution whose dissolved oxygen concentration is not adjusted is again supplied to the first supply tank 72A, the upstream recovery tank 84, the first gas generation tank 122, and the second gas generation tank 132 (step S11 in FIG. 9). . As a result, the existing drug solution is replaced with a new drug solution.

In this way, the first supply tank 72A is supplied with not only the low oxygen gas but also the adjusted gas containing a trace amount of the chemical liquid. The exhaust gas exhausted from the first supply tank 72A to the first gas exhaust pipe 125 also contains a small amount of the chemical liquid. The chemical liquid contained in the adjusted gas dissolves in the chemical liquid in the first supply tank 72A. Further, the concentration of the chemical liquid in the adjusted gas is equal to or approximately the same as the concentration of the chemical liquid in the exhaust gas. Therefore, the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A can be adjusted while suppressing the decrease of the chemical liquid in the first supply tank 72A.

Similarly, the downstream recovery tank 89 is supplied with not only the low oxygen gas but also the adjusted gas containing a trace amount of the chemical liquid. The exhaust gas discharged from the downstream recovery tank 89 to the second gas exhaust pipe 135 also contains a small amount of the chemical liquid. The chemical liquid contained in the adjusted gas dissolves in the chemical liquid in the downstream recovery tank 89. Further, the concentration of the chemical liquid in the adjusted gas is equal to or approximately the same as the concentration of the chemical liquid in the exhaust gas. Therefore, the dissolved oxygen concentration of the chemical liquid in the downstream recovery tank 89 can be adjusted while suppressing the decrease of the chemical liquid in the downstream recovery tank 89.

On the other hand, since only the low oxygen gas is supplied to the first gas generation tank 122, if the bubbling of the chemical liquid is continued, the chemical liquid in the first gas generation tank 122 gradually decreases. The amount of the new chemical liquid supplied to the first gas generation tank 122 decreases between the time when the new chemical liquid is supplied to the first supply tank 72A and the use of this chemical liquid is stopped. It is preferable that the amount is larger than the amount of the drug solution. In this case, it is not necessary to replenish the first gas generation tank 122 with a new chemical solution between the time when the new chemical solution is supplied to the first supply tank 72A and the use of this chemical solution is stopped.

Similarly, since only low oxygen gas is supplied to the second gas generation tank 132, if bubbling of the chemical liquid is continued, the chemical liquid in the second gas generation tank 132 gradually decreases. The amount of the new chemical liquid supplied to the second gas generation tank 132 decreases between the time when the new chemical liquid is supplied to the downstream recovery tank 89 and the use of this chemical liquid is stopped. It is preferable that the amount is larger than the amount. In this case, it is not necessary to replenish the second gas generation tank 132 with a new chemical solution between the time when the new chemical solution is supplied to the downstream recovery tank 89 and the use of this chemical solution is stopped.

As described above, in the first embodiment, the low oxygen gas having the oxygen concentration lower than the oxygen concentration in the air is supplied into the first gas generation tank 122. The first gas generation tank 122 stores a chemical liquid corresponding to the first liquid. The low oxygen gas is dispersed in the chemical liquid in the first gas generation tank 122 to form a large number of bubbles. After that, the low oxygen gas floats in the chemical liquid to the liquid surface of the chemical liquid and mixes with the gas on the liquid surface of the chemical liquid. In the process up to this point, the vapor and mist of the chemical solution are dispersed in the low oxygen gas. Thereby, the adjusted gas containing the low oxygen gas and the chemical liquid is generated.

The adjusted gas is supplied to the first supply tank 72A that stores the chemical liquid corresponding to the first processing liquid, and is dissolved in the chemical liquid in the first supply tank 72A. The adjusted gas contains low oxygen gas. Therefore, by dissolving the adjusted gas, oxygen in the chemical liquid is discharged, and the dissolved oxygen concentration of the chemical liquid decreases. As a result, the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A is adjusted.
Further, since the same substance (TMAH (anhydrous) and water (H ₂ O)) is contained in both the adjusted gas and the chemical solution, even if the adjusted gas is continuously supplied to the first supply tank 72A, It is difficult for the chemical solution in the first supply tank 72A to decrease. As a result, the frequency of supplying new chemical liquid to the first supply tank 72A can be reduced. Further, it is possible to suppress a change in the concentration of the chemical solution. Accordingly, it is possible to suppress the change in the quality of the substrate W with the passage of time.

In the present embodiment, the low oxygen gas containing no chemical liquid is supplied into the first gas generation tank 122. As described above, the low oxygen gas forms a large number of bubbles in the chemical liquid in the first gas generation tank 122 and floats in the chemical liquid to the liquid surface of the chemical liquid. As a result, a regulated gas having a high concentration of the chemical liquid (for example, a regulated gas having a concentration of the chemical liquid at or near the saturated concentration) is generated. Then, the adjustment gas having a high concentration of the chemical liquid is supplied to the first supply tank 72A. As a result, the reduction amount of the chemical liquid in the first supply tank 72A can be effectively reduced.

In the present embodiment, the chemical liquid is stored not only in the first supply tank 72A but also in the first gas generation tank 122. Therefore, the adjusted gas containing the chemical liquid is generated in the first gas generation tank 122 and supplied to the first supply tank 72A. Even if the liquid component of the adjusted gas dissolves in the chemical liquid, the concentration of the chemical liquid in the first supply tank 72A does not change or hardly changes. Accordingly, it is possible to suppress the change in the concentration of the chemical liquid in the first supply tank 72A.

In the present embodiment, the chemical liquid supplied to the substrate W from the first supply tank 72A is recovered in the first supply tank 72A via the downstream recovery tank 89. The dissolved oxygen concentration of the chemical liquid supplied to the substrate W has changed. Therefore, before the chemical solution is collected in the first supply tank 72A, the adjusted gas containing the low oxygen gas is dissolved in the chemical solution in the downstream recovery tank 89. Thereby, the dissolved oxygen concentration of the chemical liquid in the downstream recovery tank 89 can be brought close to the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A. Further, the regulated gas contains not only low oxygen gas but also chemical liquid. Therefore, the dissolved oxygen concentration of the chemical liquid in the downstream recovery tank 89 can be adjusted while suppressing the decrease of the chemical liquid in the downstream recovery tank 89.

In the present embodiment, the adjusted gas is allowed to flow into the first supply tank 72A while the gas inside the first supply tank 72A is discharged from the first supply tank 72A. The exhaust gas discharged from the first supply tank 72A contains vapor of chemical liquid and mist. The exhaust gas is cooled in the first ascending pipe 126 extending upward from the first supply tank 72A. A part of the chemical liquid contained in the exhaust gas adheres to the inner peripheral surface of the first rising pipe 126. When the droplet of the chemical liquid becomes large to some extent, the droplet of the chemical liquid flows toward the first supply tank 72A along the inner peripheral surface of the first rising pipe 126 by its own weight, and drops into the chemical liquid in the first supply tank 72A. .. Thereby, the chemical liquid contained in the exhaust gas can be returned to the first supply tank 72A.

In the present embodiment, the gas in the downstream recovery tank 89 is discharged from the downstream recovery tank 89 while allowing the adjusted gas to flow into the downstream recovery tank 89. The exhaust gas discharged from the downstream recovery tank 89 contains chemical vapor and mist. The exhaust gas is cooled in the second ascending pipe 136 extending upward from the downstream recovery tank 89. A part of the chemical liquid contained in the exhaust gas adheres to the inner peripheral surface of the second ascending pipe 136. When the liquid droplets of the chemical liquid become large to some extent, the liquid droplets of the chemical liquid flow toward the downstream recovery tank 89 along the inner peripheral surface of the second ascending pipe 136 by their own weight, and fall into the chemical liquid in the downstream recovery tank 89. As a result, the chemical liquid contained in the exhaust gas can be returned to the downstream recovery tank 89.

Second Embodiment Next, a second embodiment will be described. The main difference between the second embodiment and the first embodiment is that a plurality of supply tanks for storing the processing liquid supplied to the substrate W are provided, and the processing liquid in these supply tanks is applied to the substrate W. It is to be mixed before being supplied.
FIG. 10 is a schematic diagram showing the chemical liquid supply unit 71 and the gas dissolving device 101 according to the second embodiment. 10, configurations similar to those shown in FIGS. 1 to 9 are given the same reference numerals as those in FIG. 1 and the like, and description thereof is omitted.

As shown in FIG. 10, the chemical liquid supply unit 71 includes a second supply tank 72B in addition to the first supply tank 72A. In FIG. 10, “X” indicates the first treatment liquid and “Y” indicates the second treatment liquid. Therefore, the first processing liquid is stored in the first supply tank 72A and the first gas generation tank 122, and the second processing liquid is stored in the second supply tank 72B and the second gas generation tank 132. An example of the first treatment liquid is TMAH (an aqueous solution of TMAH), and an example of the second treatment liquid is water (H ₂ O). TMAH (anhydrous) is an example of the first substance, and water (H ₂ O) is an example of the second substance.

The adjusted gas generated in the first gas generation tank 122 is supplied to the first supply tank 72A. Thereby, the dissolved oxygen concentration of the first processing liquid in the first supply tank 72A is adjusted. Similarly, the adjusted gas generated in the second gas generation tank 132 is supplied to the second supply tank 72B. Thereby, the dissolved oxygen concentration of the second processing liquid in the second supply tank 72B is adjusted. The gas in the first supply tank 72A is discharged to the first gas discharge pipe 125, and the gas in the second supply tank 72B is discharged to the second gas discharge pipe 135.

The chemical liquid supply unit 71 forms a second liquid level sensor 73B that detects the amount of the second processing liquid in the second supply tank 72B and an annular circulation path that circulates the second processing liquid in the second supply tank 72B. A second circulation pipe 74B for performing the second treatment, a second pump 75B for sending the second treatment liquid in the second supply tank 72B to the second circulation pipe 74B, and a second treatment for removing foreign matters such as particles from the second treatment liquid flowing through the circulation path. 2 filter 76B.

The upstream end and the downstream end of the second circulation pipe 74B are connected to the second supply tank 72B. The second pump 75B and the second filter 76B are interposed in the second circulation pipe 74B. The second processing liquid is sent from the second supply tank 72B to the upstream end of the second circulation pipe 74B by the second pump 75B, and returns to the second supply tank 72B from the downstream end of the second circulation pipe 74B. As a result, the second processing liquid in the second supply tank 72B circulates in the circulation path.

The temperature of the chemical liquid supply unit 71 is adjusted by a second temperature controller 77B that changes the temperature of the second processing liquid in the second supply tank 72B by heating or cooling the second processing liquid, and a second temperature controller 77B. A second thermometer 78B for measuring the temperature of the second processing liquid may be included. The second temperature controller 77B and the second thermometer 78B are provided in the second circulation pipe 74B. The temperature of the second temperature controller 77B is changed based on the measurement value of the second thermometer 78B. As a result, the temperature of the second processing liquid in the second supply tank 72B is maintained at the set temperature.

The chemical liquid supply unit 71 includes a first individual pipe 70A that guides the first processing liquid in the first circulation pipe 74A to the second chemical liquid pipe 52, and a first individual pipe 70A that supplies the first chemical liquid to the second chemical liquid pipe 52 from the first individual pipe 70A. A first flow rate adjusting valve 79A for changing the flow rate of the processing liquid and a first opening/closing valve 80A interposed in the first individual pipe 70A are included. The chemical liquid supply unit 71 is further supplied to the second chemical liquid pipe 52 from the second individual pipe 70B that guides the second processing liquid in the second circulation pipe 74B to the second chemical liquid pipe 52, and the second individual pipe 70B. It includes a second flow rate adjusting valve 79B for changing the flow rate of the second processing liquid, and a second opening/closing valve 80B interposed in the second individual pipe 70B.

The first processing liquid in the first circulation pipe 74A is supplied to the second chemical liquid pipe 52 at a flow rate corresponding to the opening of the first flow rate adjusting valve 79A. Similarly, the second processing liquid in the second circulation pipe 74B is supplied to the second chemical liquid pipe 52 at a flow rate corresponding to the opening degree of the second flow rate adjusting valve 79B. The first treatment liquid and the second treatment liquid are mixed in the second chemical liquid pipe 52 corresponding to the collecting pipe, and discharged from the central nozzle 45. As a result, the mixed liquid of the first processing liquid and the second processing liquid is supplied to the substrate W.

The mixed liquid of the first treatment liquid and the second treatment liquid corresponds to the second chemical liquid. When the above-described second chemical liquid supply step (step S5 in FIG. 6) is performed, the mixed liquid of the first processing liquid and the second processing liquid is discharged from the central nozzle 45 and supplied to the substrate W. The mixing ratio of the first processing liquid and the second processing liquid is changed according to the opening degrees of the first flow rate adjusting valve 79A and the second flow rate adjusting valve 79B. Therefore, the control device 3 can change the concentration of the second chemical liquid supplied to the substrate W by changing the openings of the first flow rate adjusting valve 79A and the second flow rate adjusting valve 79B.

In the second embodiment, the following effects can be obtained in addition to the effects according to the first embodiment. Specifically, in the second embodiment, a mixed liquid of the first processing liquid and the second processing liquid is supplied to the substrate W. The first processing liquid and the second processing liquid are mixed not in the tank but immediately before being supplied to the substrate W. Therefore, the mixing ratio of the first processing liquid and the second processing liquid can be changed according to the required quality of the substrate W. Further, the second treatment liquid in the second supply tank 72B has the dissolved oxygen concentration adjusted similarly to the first treatment liquid in the first supply tank 72A. The adjustment gas supplied to the second supply tank 72B contains not only the low oxygen gas but also the second processing liquid. Therefore, the mixed liquid of the first processing liquid and the second processing liquid can be supplied to the substrate W while reducing the decrease amount of the second processing liquid in the second supply tank 72B.

Third Embodiment Next, a third embodiment will be described. The main difference between the third embodiment and the first embodiment is that not only the adjusted gas generated in the first gas generation tank 122 but also the adjusted gas generated in the second gas generation tank 132 is the first supply tank. Is to be supplied to 72A.
FIG. 11 is a schematic diagram showing the chemical liquid supply unit 71 and the gas dissolving device 101 according to the third embodiment. 11, the same components as those shown in FIGS. 1 to 10 are given the same reference numerals as those in FIG. 1 and the like, and the description thereof will be omitted.

In FIG. 11, “X” indicates the first treatment liquid and “Y” indicates the second treatment liquid. Therefore, in the third embodiment, the first processing liquid is stored in the first supply tank 72A and the first gas generation tank 122, and the second processing liquid is stored in the first gas generation tank 122. An example of the first treatment liquid is TMAH (an aqueous solution of TMAH), and an example of the second treatment liquid is water (H ₂ O). The first processing liquid corresponds to the second chemical liquid supplied to the substrate W in the above-mentioned second chemical liquid supply step (step S5 in FIG. 6).

In the first gas generation tank 122, the vapor and mist of the first treatment liquid are dispersed in the low oxygen gas, and the adjusted gas containing the low oxygen gas and the first treatment liquid is generated. In the second gas generation tank 132, the vapor and mist of the second processing liquid are dispersed in the low oxygen gas, and the adjusted gas containing the low oxygen gas and the second processing liquid is generated. Below, the adjustment gas containing low oxygen gas and 1st process liquid is called multiple containing gas, and the adjustment gas containing low oxygen gas and 2nd process liquid is called partial containing gas.

The control device 3 supplies the plural-containing gas generated in the first gas generation tank 122 to the first supply tank 72A to dissolve the plural-containing gas in the first processing liquid in the first supply tank 72A, The dissolved oxygen concentration of the first treatment liquid is adjusted. Further, the control device 3 generates a part of the contained gas in the second gas generation tank 132 and supplies it to the first supply tank 72A, if necessary. The controller 3 may supply both the plural-containing gas and the partially-containing gas into the first supply tank 72A, or may supply only the partially-containing gas into the first supply tank 72A. The supply of the partially-containing gas to the first supply tank 72A may be performed based on a detection value of a densitometer (not shown) that detects the concentration of the first processing liquid in the first supply tank 72A, It may be done on a regular basis.

In the third embodiment, the following effects can be obtained in addition to the effects according to the first embodiment. Specifically, in the third embodiment, the first treatment liquid (TMAH aqueous solution) in the first supply tank 72A includes TMAH (anhydrous) corresponding to the first substance and water (water) corresponding to the second substance. H ₂ O). TMAH (anhydrous) and water (H ₂ O) have different vapor pressures. Therefore, the concentration of the first processing liquid in the first supply tank 72A changes with the passage of time. If the difference in vapor pressure between the first substance and the second substance is small, the amount of change in the concentration of the first treatment liquid is small, but if the difference in vapor pressure between the first substance and the second substance is large, the first treatment is performed. The concentration of the liquid changes drastically.

The plural-containing gas and the partially-containing gas are separately supplied to the first supply tank 72A. Both the plural-containing gas and the partially-containing gas include low oxygen gas. Therefore, the dissolved oxygen concentration of the first treatment liquid in the first supply tank 72A can be adjusted by supplying either the plural-containing gas or the partially-containing gas to the first supply tank 72A. On the other hand, the plural-containing gas contains both the first substance and the second substance, and the partially-containing gas contains only the second substance.

For example, when the second substance has a higher vapor pressure than the first substance and is more easily vaporized than the first substance, the concentration of the first substance in the first treatment liquid increases with time. In such a case, if a partially containing gas containing the second substance but not the first substance is supplied to the first supply tank 72A, the reduction amount of the second substance from the first processing liquid is reduced and One substance can be reduced from the first processing liquid. As a result, the concentration of the first processing liquid can be brought close to the initial concentration, and the change in the quality of the substrate W over time can be suppressed.

Other Embodiments The present invention is not limited to the contents of the above-described embodiments, and various modifications can be made.
For example, an etching solution such as TMAH may be supplied to the lower surface of the substrate W instead of the upper surface of the substrate W. Alternatively, the etching liquid may be supplied to both the upper surface and the lower surface of the substrate W. In these cases, the etching liquid may be discharged to the lower surface nozzle 15.

The material etched by TMAH may be a material other than polysilicon. The etching liquid may be a liquid other than TMAH. Processing other than etching may be performed by the substrate processing apparatus 1. For example, polymer removal may be performed by supplying a polymer removing liquid to the surface of the substrate W where the metal such as copper is exposed to remove the polymer residue from the substrate W. DHF is an example of a polymer removing liquid.

At least one of the first cooler 127 and the second cooler 137 may be a cooler such as a Peltier element that does not use a cooling fluid. At least one of the first cooler 127 and the second cooler 137 may be omitted. That is, the exhaust gas discharged from the first supply tank 72A does not have to be cooled. Similarly, the exhaust gas discharged from the downstream recovery tank 89 may not be cooled.

The chemical liquid formed by cooling the exhaust gas may be returned to the first supply tank 72A or the downstream recovery tank 89 via a pipe other than the first gas exhaust pipe 125 and the second gas exhaust pipe 135. Specifically, a first recycle pipe for guiding the chemical liquid from the first cooler 127 to the first gas discharge pipe 125 may be provided. Similarly, a second recycle pipe for guiding the chemical liquid from the second cooler 137 to the second gas discharge pipe 135 may be provided.

At least one of the upstream recovery tank 84 and the downstream recovery tank 89 may be omitted. Alternatively, a recovery tank connected in series with the upstream recovery tank 84 and the downstream recovery tank 89 may be provided. That is, three or more recovery tanks connected in series may be arranged on the recovery path from the processing unit 2 to the first supply tank 72A.
The liquid in the first gas generation tank 122 may be different from the liquid in the first supply tank 72A. That is, the number of substances contained in the liquid in the first gas generation tank 122 may be different from the number of substances contained in the liquid in the first supply tank 72A. Similarly, the liquid in the second gas generation tank 132 may be different from the liquid in the downstream recovery tank 89. The liquid in the second gas generation tank 132 may be different from the liquid in the second supply tank 72B.

FIG. 10 shows an example in which the second processing liquid supplied from the second supply tank 72B is mixed with the first processing liquid supplied from the first supply tank 72A in the second chemical liquid pipe 52. The second processing liquid may be mixed in a nozzle such as the central nozzle 45.
The tubular portion 37 may be omitted from the blocking member 33. The upper support portion 43 and the lower support portion 44 may be omitted from the blocking member 33 and the spin chuck 10.

The blocking member 33 may be omitted from the processing unit 2. In this case, the processing unit 2 may be provided with a nozzle that discharges the processing liquid such as the first chemical liquid toward the substrate W. The nozzle may be a scan nozzle that can move horizontally in the chamber 4, or may be a fixed nozzle fixed to the partition wall 6 of the chamber 4. The nozzle may include a plurality of liquid ejection ports that supply the treatment liquid to the upper surface or the lower surface of the substrate W by simultaneously ejecting the treatment liquid toward a plurality of positions that are separated in the radial direction of the substrate W. In this case, at least one of the flow rate, temperature, and concentration of the processing liquid to be discharged may be changed for each liquid discharge port.

As shown by the chain double-dashed line in FIG. 7, the dissolved oxygen concentration changing unit may include, in addition to the gas dissolving device 101, a degassing device 85 for removing the dissolved gas of the chemical liquid. The deaerator 85 is, for example, an ultrasonic wave generator that generates ultrasonic vibrations. FIG. 7 shows an example in which the ultrasonic generator is arranged in the upstream recovery tank 84.
The ultrasonic generator is in contact with the chemical solution in the upstream recovery tank 84. When the ultrasonic generator generates ultrasonic vibrations, bubbles are generated in the chemical liquid in the upstream recovery tank 84. The bubbles are discharged from the surface (liquid surface) of the chemical liquid into the space inside the upstream recovery tank 84. As a result, the dissolved gas of the chemical liquid in the upstream recovery tank 84 is removed, and the total amount of gas dissolved in the chemical liquid is reduced. The gas released from the chemical solution in the upstream recovery tank 84 is discharged from the upstream recovery tank 84 through the breather pipe 86 connected to the upstream recovery tank 84.

Although FIG. 7 shows an example in which the ultrasonic wave generator is arranged in the upstream recovery tank 84, the ultrasonic wave generator may be arranged outside the upstream recovery tank 84. That is, the ultrasonic vibration generated by the ultrasonic generator may be transmitted to the chemical liquid in the upstream recovery tank 84 via the upstream recovery tank 84. In addition to or in place of the ultrasonic generator, the degassing device 85 includes a decompression device that reduces the atmospheric pressure in the upstream recovery tank 84, a stirring device that stirs the chemical liquid in the upstream recovery tank 84, and a At least one of a semi-permeable membrane that allows only unnecessary gas to pass therethrough may be provided.

The chemical liquid supplied to the substrate W in the processing unit 2 is recovered in the upstream recovery tank 84. When the chemical liquid is supplied to the substrate W, the chemical liquid and the atmosphere come into contact with each other. Therefore, the chemical liquid supplied to the substrate W is dissolved with a gas contained in the atmosphere, such as oxygen gas, and the dissolved oxygen concentration is increasing. The gas generated by the chemical reaction between the substrate W and the chemical solution may be dissolved in the chemical solution. For example, hydrogen gas is generated when etching silicon such as silicon single crystal, polysilicon, and amorphous silicon with an acidic or alkaline etching solution. In this case, the chemical solution having an increased dissolved hydrogen concentration is recovered in the upstream recovery tank 84.

The first oxygen concentration meter 96 and the second oxygen concentration meter 98 are diaphragm type oxygen concentration meters that measure the dissolved oxygen concentration by, for example, an electrochemical analysis method (diaphragm electrode method). The diaphragm-type oxygen concentration meter measures the dissolved oxygen concentration of the measurement target by detecting the concentration of oxygen that has passed through the diaphragm. Since the hydrogen molecules are smaller than the oxygen molecules, the hydrogen molecules dissolved in the chemical solution may pass through the diaphragm of the oximeter. Carbon dioxide may also penetrate the diaphragm. That is, molecules or atoms having a size equal to or smaller than that of oxygen molecules pass through the diaphragm of the oximeter. These molecules may reduce the detection accuracy of the first oximeter 96 and the second oximeter 98.

As described above, the deaerator 85 removes the dissolved gas of the chemical liquid stored in the upstream recovery tank 84. As a result, the unnecessary gas dissolved in the chemical liquid during the processing of the substrate W is removed from the chemical liquid. In the downstream recovery tank 89, the adjusted gas dissolves in the chemical liquid. Even if unnecessary gas remains in the chemical solution collected in the downstream recovery tank 89, this unnecessary gas is discharged from the chemical solution by dissolving the adjusted gas. Therefore, the chemical liquid having an extremely low concentration of unnecessary gas is collected in the first supply tank 72A. Therefore, the dissolved oxygen concentration of the chemical liquid in the first supply tank 72A can be detected with high accuracy.

The substrate processing apparatus 1 may be a batch type apparatus that collectively processes a plurality of substrates W. That is, the processing unit 2 includes an inner tank for storing the processing liquid, a nozzle for discharging the processing liquid stored in the inner tank, an outer tank for storing the processing liquid overflowing from the inner tank, and a plurality of substrates W. A lifter that moves up and down while simultaneously holding a plurality of substrates W between a lower position immersed in the processing liquid in the inner tank and an upper position where the plurality of substrates W are located above the processing liquid in the inner tank; May be provided. In this case, the second chemical liquid pipe 52 (see FIG. 7) may be connected to the nozzle, and the upstream pipe 82 (see FIG. 7) may be connected to the outer tank.

The substrate processing apparatus 1 is not limited to the apparatus that processes the disk-shaped substrate W, but may be an apparatus that processes the polygonal substrate W.
Two or more of all the configurations described above may be combined. Two or more of all of the above steps may be combined.
In addition, various design changes can be made within the scope of the matters described in the claims.

1: Substrate processing device 45: Central nozzle (processing liquid nozzle, mixed liquid nozzle)
52: Second chemical liquid pipe (immediately before mixing means)
70A: First individual pipe (immediately before mixing means)
70B: Second individual pipe (immediately before mixing means)
72A: First supply tank (first final adjusting means)
72B: Second supply tank (second final adjusting means)
79A: First flow rate adjusting valve (mixing ratio changing valve)
79B: Second flow rate adjusting valve (mixing ratio changing valve)
81: Chemical solution recovery unit (recovery means)
89: Downstream recovery tank (recovery tank)
121: First downstream gas supply pipe (main adjusting means)
122: First gas generation tank (first gas generation means, plural-containing gas generation means)
126: First rising pipe (first recycling pipe)
127: 1st cooler (cooler in 1st piping)
131: Second downstream gas supply pipe (sub-adjustment means)
132: Second gas generation tank (preliminary gas generation tank, preconditioning gas generation means, second gas generation means, partially contained gas generation means)
136: Second rising pipe (second recycling pipe)
137: Second cooler (second pipe cooler)
W: Substrate

Claims (20)

A low oxygen gas having an oxygen concentration lower than the oxygen concentration in the air is supplied into the first gas generation tank that stores the first liquid containing the first substance, and the first liquid in the first gas generation tank is supplied. A first gas generating step of forming bubbles of the low oxygen gas therein, and generating a first adjusted gas containing the low oxygen gas and the first substance;
A first adjusting gas is dissolved in a first treatment liquid containing the first substance stored in a first supply tank to adjust a dissolved oxygen concentration of the first treatment liquid in the first supply tank. The final adjustment process,
And a treatment liquid supplying step of supplying the first treatment liquid in the first supply tank to the substrate. The substrate processing method according to claim 1, wherein the concentration of the first substance in the first adjusted gas is higher than the concentration of the first substance in the low oxygen gas before being supplied to the first gas generation tank. .. The substrate processing method according to claim 1, wherein the first gas generation tank is a tank that stores the first processing liquid. A recovery step of recovering the first processing liquid after being supplied to the substrate to the first supply tank via a recovery tank;
The low oxygen gas is supplied into a pre-gas generation tank that stores a pre-conditioning liquid containing the first substance to form bubbles of the low oxygen gas in the pre-conditioning liquid in the pre-gas generation tank. And a preconditioned gas generating step of generating a preconditioned gas containing the low oxygen gas and the first substance,
Before the first processing liquid supplied to the substrate is recovered in the first supply tank, the preconditioning gas is dissolved in the first processing liquid in the recovery tank to recover the first processing liquid in the recovery tank. The substrate processing method according to claim 1, further comprising a preliminary adjustment step of adjusting a dissolved oxygen concentration of the first processing liquid. The first final adjusting step includes a gas supplying step of flowing the first adjusting gas into the first supply tank, and a gas discharging step of discharging gas in the first supply tank,
The substrate processing method includes a first cooling step of cooling the exhaust gas discharged from the first supply tank to liquefy the first substance contained in the exhaust gas, and the liquefied gas in the first cooling step. The substrate processing method according to claim 1, further comprising a first recycling step of returning a first substance to the first supply tank. In the first cooling step, the exhaust gas in a first ascending pipe extending upward from the first supply tank is cooled and the first substance contained in the exhaust gas is removed from the inner peripheral surface of the first ascending pipe. Including a first pipe cooling step of liquefying in
In the first recycling step, a first dropping step in which the first substance liquefied on the inner peripheral surface of the first rising pipe is dropped toward the first supply tank along the inner peripheral surface of the first rising pipe. The substrate processing method according to claim 5, further comprising: The preliminary adjustment step includes a gas supply step of flowing the preliminary adjustment gas into the recovery tank, and a gas discharge step of discharging the gas in the recovery tank,
In the substrate processing method, the exhaust gas discharged from the recovery tank is cooled to liquefy the first substance contained in the exhaust gas, and the first liquefied gas in the second cooling step is liquefied. The substrate processing method according to claim 4, further comprising a second recycling step of returning a substance to the recovery tank. In the second cooling step, the exhaust gas in the second ascending pipe extending upward from the recovery tank is cooled and the first substance contained in the exhaust gas is liquefied on the inner peripheral surface of the second ascending pipe. Including a second pipe cooling step to
The second recycling step includes a second dropping step of dropping the first substance liquefied on the inner peripheral surface of the second rising pipe toward the recovery tank along the inner peripheral surface of the second rising pipe. The substrate processing method according to claim 7. The substrate processing method,
The low oxygen gas is supplied into a second gas generation tank that stores a second liquid containing a second substance to form bubbles of the low oxygen gas in the second liquid in the second gas generation tank. A second gas generating step of generating a second adjusted gas containing the low oxygen gas and the second substance,
A second adjustment gas is dissolved in a second treatment liquid containing the second substance stored in a second supply tank to adjust the dissolved oxygen concentration of the second treatment liquid in the second supply tank. 2 final adjustment process,
A mixing step immediately before mixing the first processing liquid and the second processing liquid outside the first supply tank and the second supply tank before the first processing liquid and the second processing liquid are supplied to the substrate; ,
A mixing ratio changing step of changing a mixing ratio of the first processing liquid and the second processing liquid mixed in the immediately preceding mixing step,
9. The processing liquid supply step according to claim 1, wherein the processing liquid supply step includes a mixed liquid supply step of supplying the first processing liquid and the second processing liquid mixed in the immediately preceding mixing step to the substrate. Substrate processing method. The first treatment liquid is a liquid containing a second substance in addition to the first substance,
In the first gas generation step,
The low oxygen gas is supplied into the first gas generation tank that stores the first liquid containing the first substance and the second substance, and the low oxygen gas is supplied into the first liquid in the first gas generation tank. A plurality-containing gas generating step of forming bubbles of the low-oxygen gas and generating a plurality-containing gas containing the low-oxygen gas, the first substance, and the second substance;
The low oxygen gas is supplied into a second gas generation tank that stores a second liquid that includes one of the first substance and the second substance and does not include the other of the first substance and the second substance, A bubble of the low-oxygen gas is formed in the second liquid in the two-gas generation tank and includes one of the first substance and the second substance and the low-oxygen gas. A part-containing gas generating step of generating a part-containing gas that does not include the other,
The first final adjustment step,
Mainly adjusting the dissolved oxygen concentration of the first treatment liquid in the first supply tank by dissolving the plurality of contained gases corresponding to the first adjustment gas in the first treatment liquid in the first supply tank. Adjustment process,
A sub-adjustment step of dissolving the part-containing gas in the first processing liquid in the first supply tank to adjust the dissolved oxygen concentration of the first processing liquid in the first supply tank. The substrate processing method according to claim 1. A first gas generation tank for storing a first liquid containing a first substance is included, and a low oxygen gas having an oxygen concentration lower than an oxygen concentration in the air is supplied into the first gas generation tank to supply the first gas. First gas generation means for forming bubbles of the low oxygen gas in the first liquid in the gas generation tank to generate a first adjusted gas containing the low oxygen gas and the first substance;
A first supply tank for storing a first processing liquid containing the first substance, wherein the first adjusted gas is dissolved in the first processing liquid in the first supply tank, First final adjusting means for adjusting the dissolved oxygen concentration of the first treatment liquid;
A substrate processing apparatus, comprising: a processing liquid nozzle that supplies the first processing liquid in the first supply tank to a substrate. The said 1st gas production|generation means is a means which produces|generates the said 1st adjustment gas whose concentration of the said 1st substance is higher than the said low oxygen gas before being supplied to the said 1st gas production tank. The substrate processing apparatus described. The substrate processing apparatus according to claim 11, wherein the first gas generation tank is a tank that stores the first processing liquid. A recovery unit that includes a recovery tank that stores the first processing liquid after being supplied to the substrate, and that recovers the first processing liquid that has been supplied to the substrate to the first supply tank via the recovery tank. When,
A pre-gas generation tank for storing a pre-conditioning liquid containing the first substance, wherein the low oxygen gas is supplied into the pre-gas generating tank, and the pre-conditioning liquid in the pre-gas generating tank is supplied. Pre-conditioning gas generating means for forming bubbles of the low-oxygen gas, and generating a pre-conditioning gas containing the low-oxygen gas and the first substance,
Before the first processing liquid supplied to the substrate is recovered in the first supply tank, the preconditioning gas is dissolved in the first processing liquid in the recovery tank to recover the first processing liquid in the recovery tank. The substrate processing apparatus according to claim 11, further comprising a pre-adjustment unit that adjusts a dissolved oxygen concentration of the first processing liquid. The first final adjusting means further includes a gas supply pipe for introducing the first adjusted gas into the first supply tank, and a gas exhaust pipe for exhausting gas in the first supply tank.
The substrate processing apparatus cools the exhaust gas discharged from the first supply tank to liquefy the first substance contained in the exhaust gas, and the first cooler liquefied by the first cooler. The substrate processing apparatus according to claim 11, further comprising a first recycling pipe that returns one substance to the first supply tank. The gas discharge pipe includes a first rising pipe extending upward from the first supply tank,
The first cooler is a first pipe cooler that cools the exhaust gas in the first rising pipe to liquefy the first substance contained in the exhaust gas on an inner peripheral surface of the first rising pipe. The substrate processing apparatus according to claim 15, further comprising: The pre-adjustment means further includes a gas supply pipe for introducing the pre-adjusted gas into the recovery tank, and a gas exhaust pipe for exhausting gas in the recovery tank,
The substrate processing apparatus cools the exhaust gas discharged from the recovery tank to liquefy the first substance contained in the exhaust gas, and the first substance liquefied by the second cooler. 15. The substrate processing apparatus according to claim 14, further comprising a second recycling pipe that returns the gas to the recovery tank. The gas discharge pipe includes a second ascending pipe extending upward from the recovery tank,
The second cooler is a second pipe cooler that cools the exhaust gas in the second rising pipe and liquefies the first substance contained in the exhaust gas on an inner peripheral surface of the second rising pipe. The substrate processing apparatus according to claim 17, which comprises: The substrate processing apparatus,
A second gas generation tank that stores a second liquid containing a second substance is provided, and the low oxygen gas is supplied into the second gas generation tank, and the second liquid in the second gas generation tank is supplied with the low oxygen gas. Second gas generating means for forming bubbles of the low oxygen gas and generating a second adjusted gas containing the low oxygen gas and the second substance;
A second supply tank for storing a second processing liquid containing the second substance, wherein the second adjusted gas is dissolved in the second processing liquid in the second supply tank, Second final adjusting means for adjusting the dissolved oxygen concentration of the second treatment liquid;
A mixing means immediately before mixing the first processing liquid and the second processing liquid outside the first supply tank and the second supply tank before the first processing liquid and the second processing liquid are supplied to the substrate; ,
A mixing ratio changing valve for changing a mixing ratio of the first processing liquid and the second processing liquid mixed by the immediately preceding mixing means,
19. The processing liquid nozzle according to claim 11, wherein the processing liquid nozzle includes a mixed liquid nozzle that supplies a mixed liquid of the first processing liquid and the second processing liquid mixed by the immediately preceding mixing unit to the substrate. The substrate processing apparatus described. The first treatment liquid is a liquid containing a second substance in addition to the first substance,
The first gas generating means,
The low oxygen gas is supplied into the first gas generation tank that stores the first liquid containing the first substance and the second substance, and the low oxygen gas is supplied into the first liquid in the first gas generation tank. A plurality-containing gas generating means for forming bubbles of the low-oxygen gas and generating a plurality-containing gas containing the low-oxygen gas, the first substance and the second substance;
A second gas generation tank that stores a second liquid that contains one of the first substance and the second substance and does not contain the other of the first substance and the second substance, and stores the second liquid in the second gas generation tank. Supplying oxygen gas to form bubbles of the low oxygen gas in the second liquid in the second gas generation tank, and includes one of the first substance and the second substance and the low oxygen gas, And a part-containing gas generation unit that generates a part-containing gas that does not include the other of the first substance and the second substance,
The first final adjustment means,
Mainly adjusting the dissolved oxygen concentration of the first treatment liquid in the first supply tank by dissolving the plurality of contained gases corresponding to the first adjustment gas in the first treatment liquid in the first supply tank. Adjusting means,
A sub-adjusting unit that dissolves the part-containing gas in the first processing liquid in the first supply tank to adjust the dissolved oxygen concentration of the first processing liquid in the first supply tank. The substrate processing apparatus according to claim 11.

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