JP2010056218A - Substrate processing apparatus, and substrate processing method - Google Patents

Abstract

To provide a substrate processing apparatus and a substrate processing method capable of processing a substrate with a processing liquid having a reduced oxygen concentration.
A substrate processing apparatus includes a spin chuck that holds a substrate and a substrate facing surface that faces the substrate held by the spin chuck. From the periphery of the substrate facing surface, the spin chuck is provided. And a first upper processing liquid supply pipe 35 for supplying a processing liquid to the substrate W held by the spin chuck 3. The chemical solution is supplied to the first upper processing liquid supply pipe 35 from the first in-pipe preparation unit 51 via the second upper processing liquid supply pipe 38. This chemical solution includes a chemical solution stock solution and an inert gas-dissolved water produced by degassing oxygen in pure water by the inert gas-dissolved water generating unit 50 and adding the inert gas to the pure water. It is prepared by mixing in one mixing unit 59.
[Selection] Figure 3

Description

  The present invention relates to a substrate processing apparatus and a substrate processing method for processing a substrate. Examples of substrates to be processed include semiconductor wafers, liquid crystal display substrates, plasma display substrates, FED (Field Emission Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, and photomasks. Substrate, ceramic substrate and the like.

  High integration and high speed of semiconductor integrated circuit elements are market demands. In order to meet this demand, lower resistance copper wiring has been used in place of the conventionally used aluminum wiring. If a multilayer wiring is formed by combining a copper wiring with a low dielectric constant insulating film (a so-called low-k film; an insulating film made of a material having a relative dielectric constant smaller than that of silicon oxide), an integrated circuit that operates at extremely high speed. A circuit element can be realized.

Connection between copper wirings of different layers is achieved by a copper plug embedded in a via formed in an interlayer insulating film. In order to form a fine wiring pattern, a via having a high aspect ratio is required. Therefore, a dry etching method represented by reactive ion etching is applied to the formation of the via.
However, in the dry etching method, not only the film to be processed but also the resist is corroded, and a part thereof is denatured and remains on the substrate surface as a polymer (resist residue). Since the wiring pattern is fine, this polymer must be surely removed from the substrate before the next step.

A substrate processing apparatus capable of performing a polymer removing process includes a spin chuck that holds and rotates a substrate to be processed, and a nozzle that supplies a processing liquid such as a polymer removing liquid to the upper surface of the substrate rotated by the spin chuck. (For example, refer to Patent Document 1).
JP 2004-158482 A JP 2004-22572 A

  However, in the configuration as described above, there is a problem that the polymer removing solution comes into contact with air and oxygen is dissolved in the polymer removing solution. When a polymer removal solution having a high oxygen concentration is supplied to the substrate, a metal film (such as a copper film) on the substrate may be oxidized by the dissolved oxygen in the polymer removal solution to produce a metal oxide. However, since the metal oxide is etched by the polymer removing solution, the metal film such as a wiring film on the substrate is reduced, and there is a possibility that the characteristics of a device formed from the substrate are deteriorated.

This problem is common to substrate processing apparatuses (wet etching processing apparatuses) that process substrates using chemicals that have an etching action on metal oxides. In addition to metal oxides, the same problem is generally encountered when a substrate is processed using a chemical having an etching action on oxides.
Accordingly, an object of the present invention is to provide a substrate processing apparatus and a substrate processing method capable of processing a substrate with a processing liquid having a reduced oxygen concentration.

  In order to achieve the above object, the invention according to claim 1 has a substrate holding mechanism (3) for holding the substrate (W) and a substrate facing surface (34) facing the substrate held by the substrate holding mechanism. And a blocking member (6) having a peripheral wall portion (32, 132, 232, 332) protruding from the periphery of the substrate facing surface toward the substrate holding mechanism, and a substrate held by the substrate holding mechanism. A treatment liquid nozzle (35) for supplying a treatment liquid, and an inert gas dissolved water generating unit for degassing oxygen in pure water and adding an inert gas to the pure water to generate an inert gas dissolved water (50) and an in-pipe preparation unit that mixes the chemical solution stock solution and the inert gas-dissolved water generated by the inert gas-dissolved water generation unit in the pipe (59) to prepare the chemical solution as the treatment liquid ( 51) and the in-pipe preparation unit Includes a treatment liquid supply path for guiding the treatment liquid (38) into the processing liquid nozzle, a substrate processing apparatus (1).

In addition, the alphanumeric characters in parentheses represent corresponding components in the embodiments described later. The same applies hereinafter.
According to this invention, the substrate can be processed by supplying the processing liquid from the processing liquid nozzle to the substrate held by the substrate holding means. The processing liquid supplied to the processing liquid nozzle is guided from the in-pipe preparation unit by the processing liquid supply path. In addition, the in-pipe preparation unit is an inert gas-dissolved water produced by degassing oxygen in pure water by a chemical stock solution and an inert gas-dissolved water generating unit, and adding an inert gas to the pure water. Can be mixed in a pipe to prepare a chemical solution as a processing solution. Further, since the chemical solution stock solution and the inert gas-dissolved water are mixed in the pipe, the chemical solution prepared by the in-pipe preparation unit is suppressed or prevented from increasing in oxygen concentration due to contact with air. Furthermore, since the inert gas is added to the inert gas-dissolved water contained in the prepared chemical solution, an increase in the oxygen concentration in the chemical solution is suppressed or prevented. Therefore, the chemical solution with a reduced oxygen concentration can be supplied from the in-pipe preparation unit to the treatment liquid nozzle, and the chemical solution with the reduced oxygen concentration can be discharged from the treatment liquid nozzle.

  Further, according to the present invention, the atmosphere on the substrate surface can be shielded from the external atmosphere by the shielding member having the substrate facing surface and the peripheral wall portion. Thereby, an increase in the oxygen concentration of the atmosphere on the substrate surface can be suppressed or prevented. Therefore, it is possible to suppress or prevent the processing liquid discharged from the processing liquid nozzle from reaching the substrate or touching the air on the substrate to increase the oxygen concentration. Therefore, the chemical solution from the treatment liquid nozzle can be supplied to the substrate while maintaining the state in which the oxygen concentration is reduced. Thereby, it can suppress or prevent that the oxidation reaction resulting from the dissolved oxygen in a chemical | medical solution arises on a board | substrate. As a result, even if the chemical solution supplied to the substrate has an etching action on the oxide, it is possible to suppress or prevent undesired etching from occurring on the substrate.

The “chemical solution stock” means a chemical solution before mixing with the inert gas-dissolved water. Examples of the chemical stock solution include hydrofluoric acid (HF), hydrochloric acid (HCL), a mixed solution of hydrofluoric acid and IPA (isopropyl alcohol), and ammonium fluoride (NH ₄ F). When hydrofluoric acid is used, dilute hydrofluoric acid (DHF) is generated by mixing (preparing) the hydrofluoric acid stock solution and the inert gas-dissolved water at a predetermined ratio.

The substrate may have a polymer residue (residue after dry etching or ashing) adhered to the surface. In this case, it is preferable that the said chemical | medical solution is a polymer removal liquid for removing the said polymer residue. Dilute hydrofluoric acid is an example of a polymer removal solution.
As the polymer removal liquid, at least one of a liquid containing an organic alkaline liquid, a liquid containing an organic acid, a liquid containing an inorganic acid, and a liquid containing an ammonium fluoride-based substance can be used. Among these, examples of the liquid containing an organic alkaline liquid include a liquid containing at least one of DMF (dimethylformamide), DMSO (dimethyl sulfoxide), hydroxylamine, and choline. Examples of the liquid containing an organic acid include a liquid containing at least one of citric acid, oxalic acid, iminodiacid, and oxalic acid. Examples of the liquid containing an inorganic acid include a liquid containing at least one of hydrofluoric acid and phosphoric acid. Other polymer removal solutions include 1-methyl-2pyrrolidone, tetrahydrothiophene 1.1-dioxide, isopropanolamine, monoethanolamine, 2- (2aminoethoxy) ethanol, catechol, N-methylpyrrolidone, aromatic diol, There is a liquid containing at least one of parkren (tetrachloroethylene), a liquid containing phenol, and more specifically, a mixture of 1-methyl-2pyrrolidone, tetrahydrothiophene 1.1-dioxide, and isopropanolamine. Liquid, a mixed liquid of dimethyl sulfoxide and monoethanolamine, a mixed liquid of 2- (2 aminoethoxy) ethanol, hydroxyamine and catechol, a mixed liquid of 2- (2 aminoethoxy) ethanol and N-methylpyrrolidone, A mixed solution of ethanol amine and water and aromatic diols include at least any one of a mixed solution of phenol and tetrachlorethylene (tetrachlorethylene). In addition, a liquid containing at least one of amines such as triethanolamine and pentamethyldiethylenetriamine, propylene glycol, dipropylene glycol monomethyl ether, and the like can be given.

In addition to the polymer removal solution, the present invention can be applied to substrate processing using other chemicals such as a selective etching solution for a high-k metal material.
The substrate may have a metal pattern exposed on the surface. The metal pattern may be a metal wiring. The metal pattern may be a single film of copper, tungsten, or other metal, or may be a multilayer film in which a plurality of metal films are stacked. As an example of the multilayer film, a laminated film in which a barrier metal film for preventing diffusion is formed on the surface of a copper film can be cited.

A typical example of the inert gas is nitrogen gas, but other inert gases such as argon gas and helium gas can also be used.
The processing liquid nozzle may have a discharge port (37) that faces (opposes) the substrate held by the substrate holding mechanism from the substrate facing surface.
The substrate processing apparatus further includes an inert gas supply means (36, 39, 40, 41) for supplying an inert gas to a space between the blocking member and the substrate held by the substrate holding mechanism. It is preferable. The inert gas supply means preferably has an inert gas discharge port (40) facing the substrate held by the substrate holding mechanism from the substrate facing surface of the blocking member.

The substrate holding mechanism may be a substrate holding and rotating mechanism (3) that holds and rotates the substrate. In this case, it is preferable that a blocking member rotation mechanism (43) for rotating the blocking member around an axis common to the rotation axis (L1) of the substrate by the substrate holding rotation mechanism is further provided.
The invention according to claim 2 is an inert gas-dissolved water supply means for supplying the inert gas-dissolved water generated by the inert gas-dissolved water generation unit as it is to the substrate as a processing liquid without mixing with the chemical liquid. 62. The substrate processing apparatus according to claim 1, further comprising 62, 86).

According to this invention, the inert gas-dissolved water can be supplied to the substrate held by the substrate holding means, and the substrate can be washed away with the inert gas-dissolved water. Therefore, for example, when a chemical solution is attached to the substrate, the chemical solution can be removed by washing the substrate.
As described above, the atmosphere on the substrate surface suppresses or prevents an increase in oxygen concentration. Further, the inert gas-dissolved water is obtained by degassing oxygen. Therefore, it is possible to supply the inert gas-dissolved water having a reduced oxygen concentration to the substrate. Thereby, it can suppress or prevent that the oxidation reaction resulting from the dissolved oxygen in the inert gas dissolved water occurs on the substrate W. Therefore, for example, even when the inert gas-dissolved water is supplied to the substrate after the chemical solution having an etching action on the oxide is supplied to the substrate, the oxide is caused by the chemical solution remaining on the substrate W. Etching can be suppressed or prevented. Thereby, it is possible to suppress or prevent undesired etching from occurring on the substrate W.

  The inert gas dissolved water supply means includes, for example, a chemical liquid valve (62) for switching supply / stop of the chemical liquid stock to the in-pipe preparation unit, and a valve control means (86) for controlling opening / closing of the chemical liquid valve. It may be a thing. In this case, by closing the chemical liquid valve by the valve control means, the inert gas dissolved water supplied to the in-pipe preparation unit is supplied from the processing liquid supply path to the processing liquid nozzle as it is without being mixed with the chemical raw material solution. And supplied from the processing liquid nozzle to the substrate.

Of course, the inert gas-dissolved water supply means may supply the inert gas-dissolved water to the substrate held by the substrate holding mechanism via a supply path different from the treatment liquid nozzle. .
A third aspect of the present invention is the substrate processing apparatus according to the first or second aspect, wherein the peripheral wall portion of the blocking member is formed so as to surround the entire circumference of the peripheral end surface of the substrate.

According to the present invention, the peripheral wall portion of the blocking member is formed in a cylindrical shape (for example, a cylindrical shape in the case of a circular substrate), and the cylindrical peripheral wall portion surrounds the entire peripheral end surface of the substrate. it can. Therefore, the atmosphere on the substrate surface can be reliably shielded from the surrounding atmosphere, and the atmosphere on the substrate surface can be further reliably shielded from the external atmosphere.
For example, the substrate facing surface may be formed in a plane parallel to the main surface of the substrate held by the substrate holding mechanism. The peripheral wall portion may have an inner wall surface (49, 149, 249) facing the peripheral end surface of the substrate, and the inner wall surface may be a surface parallel to the normal line (L2) of the substrate main surface. Further, it may be a surface inclined with respect to the normal line of the substrate main surface (preferably a surface inclined so as to approach the substrate holding mechanism as it goes outward of the substrate), or the substrate as it approaches the leading edge. It may be a surface in which the inclination angle with respect to the normal of the main surface gradually changes (a surface in which a cross section taken along a plane including the normal of the substrate main surface becomes a curve).

  According to a fourth aspect of the present invention, the substrate holding mechanism includes a holding base (8) having a surface (8a) facing the substrate facing surface of the blocking member, and the substrate processing apparatus includes the blocking member. It further includes a blocking member moving mechanism (42) that approaches / separates between a predetermined processing position and a retracted position with respect to the holding base, wherein the distal end edge of the peripheral wall portion of the blocking member is the processing position. The substrate processing apparatus according to claim 1, wherein the substrate processing apparatus is determined to be positioned closer to the holding base than the substrate held by the substrate holding mechanism.

  More specifically, a control means (86) for controlling the blocking member moving mechanism is provided, and the blocking member is made to approach / separate the holding base by the control of the control means. Also good. Further, it is preferable that the processing position is set such that a gap (G1) having a predetermined size is formed between the front end edge of the peripheral wall portion of the blocking member and the surface of the holding base. This distance is preferably equal to the distance between the substrate facing surface and the substrate or smaller than the distance between the substrate facing surface and the substrate.

  According to this invention, since the blocking member can be brought close to the holding base by the blocking member moving mechanism, the substrate facing surface of the blocking member can be brought close to the substrate held by the substrate holding means. Thereby, the space | interval of a board | substrate and a board | substrate opposing surface can be made small, and the atmosphere of a board | substrate surface can be more reliably interrupted | blocked from the external atmosphere. Further, at the processing position, the leading edge of the peripheral wall portion is closer to the holding base than the substrate held by the substrate holding mechanism, so that the blocking member is positioned at the processing position while the substrate is held by the substrate holding mechanism. Thereby, a surrounding wall part can be located in the circumference | surroundings of a board | substrate. As a result, the atmosphere on the substrate surface can be reliably shielded from the surrounding atmosphere. Further, when the processing position is set so that a predetermined gap is formed between the front edge of the peripheral wall portion of the blocking member and the surface of the holding base, the substrate and the substrate The atmosphere between the opposing surfaces can be exhausted from between the front end edge of the peripheral wall portion and the surface of the holding base.

The invention according to claim 5 is a chemical solution tank (71) for storing a chemical solution stock, an inert gas supply means (77, 78) for supplying an inert gas into the chemical solution tank, and a pipe from the chemical solution tank to the pipe. 5. The substrate processing apparatus according to claim 1, further comprising a chemical solution supply path (55, 56) for introducing the chemical solution stock solution to the preparation unit.
According to this invention, the inert gas can be filled into the chemical liquid tank by supplying the inert gas into the chemical liquid tank by the inert gas supply means. Thereby, it can suppress or prevent that the oxygen concentration in the chemical | medical solution stock solution stored by the chemical | medical solution tank rises. Therefore, it is possible to suppress or prevent the chemical solution stock having an increased oxygen concentration from being supplied from the chemical solution tank to the in-pipe preparation unit via the chemical solution supply path.

The invention described in claim 6 further includes a degassing unit (74) for degassing oxygen in the chemical solution stock solution so that the chemical solution stock deaerated by the degassing unit is supplied to the in-pipe preparation unit. It is a substrate processing apparatus as described in any one of Claims 1-5.
According to this invention, since the chemical solution stock solution from which oxygen in the chemical solution stock solution has been degassed by the degassing unit is supplied to the in-pipe preparation unit, the oxygen concentration in the chemical solution prepared by the in-pipe preparation unit is reduced. Can do. Therefore, the chemical solution with a reduced oxygen concentration can be supplied as a treatment liquid from the in-pipe preparation unit to the treatment liquid nozzle, and the chemical solution with the reduced oxygen concentration can be supplied to the substrate.

The invention according to claim 7 is characterized in that the processing liquid supply path includes an inner pipe (80) through which the processing liquid flows and an outer pipe (81) surrounding the processing liquid pipe. The substrate processing apparatus according to any one of claims 1 to 6, further comprising an inert gas filling means (82, 83) for filling an inert gas therebetween.
According to this invention, the inner pipe can be surrounded by the inert gas by filling the inert gas between the inner pipe and the outer pipe by the inert gas filling means. Therefore, even if the inner pipe is made of, for example, an oxygen permeable material, the amount of oxygen that enters the inner pipe through the inner pipe can be reduced. Thereby, it can suppress or prevent that oxygen melt | dissolves in the process liquid which distribute | circulates the inside piping, and the oxygen concentration in the said process liquid rises.

The inner pipe and the outer pipe may be made of, for example, a fluororesin (more specifically, a PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer) pipe.
The invention according to claim 8 further includes a control means (86) for controlling the in-pipe preparation unit, and the control means uses the inert gas dissolved water generated by the inert gas dissolved water generating unit as a chemical solution stock solution. The inert gas-dissolved water supply step for supplying the treatment liquid nozzle to the treatment liquid nozzle through the treatment liquid supply path without mixing with the chemical liquid stock solution and the inert gas-dissolved water is performed by the in-pipe preparation unit. Are mixed in a pipe to prepare a chemical solution, and a chemical solution supplying step of supplying the chemical solution to the processing solution nozzle through a processing solution supply path is executed. The substrate processing apparatus according to claim 1.

  According to this invention, the inert gas dissolved water produced | generated by the inert gas dissolved water production | generation unit is supplied to a process liquid nozzle via the in-pipe preparation unit and a process liquid supply path, Then, in an in-pipe preparation unit The prepared chemical liquid is supplied to the processing liquid nozzle via the processing liquid supply path. Therefore, for example, when the processing liquid remains in the processing liquid supply path, after removing the residual processing liquid with the inert gas dissolved water, the chemical liquid prepared by the in-pipe preparation unit is passed through the processing liquid supply path. The treatment liquid nozzle can be supplied. Thereby, even when the oxygen concentration in the processing liquid remaining in the processing liquid supply path is increased, it is possible to suppress or prevent the chemical liquid from being supplied to the substrate together with such a processing liquid. it can. Therefore, it is possible to suppress or prevent the occurrence of an oxidation reaction due to dissolved oxygen in the chemical solution on the substrate.

In a ninth aspect of the present invention, the control means continues the inert gas-dissolved water supplying step until the oxygen concentration in the processing liquid discharged from the processing liquid nozzle becomes 20 ppb or less. This is a substrate processing apparatus.
According to this invention, in the chemical solution supply step performed after the inert gas dissolved water supply step, a low oxygen concentration chemical solution (chemical solution having an oxygen concentration of 20 ppb or less) that can reliably suppress or prevent the oxidation reaction of the substrate. The treatment liquid nozzle can be supplied. Therefore, by supplying such a chemical solution having a low oxygen concentration to the substrate, it is possible to reliably suppress or prevent the occurrence of the oxidation reaction of the substrate.

  The invention according to claim 10 further includes inert gas supply means (36, 39, 40, 41) for supplying an inert gas to a space between the blocking member and the substrate held by the substrate holding mechanism. The control means further controls the inert gas supply means to execute an atmosphere replacement step of replacing the atmosphere near the surface of the substrate with an inert gas prior to the chemical solution supply step. 10. A substrate processing apparatus according to claim 8 or 9.

  According to this invention, prior to the chemical solution supplying step, the inert gas is supplied to the space between the blocking member and the substrate held by the substrate holding mechanism, and the atmosphere near the surface of the substrate is an inert gas. Replaced. Therefore, it is possible to more reliably suppress or prevent the chemical liquid discharged from the treatment liquid nozzle from reaching the substrate or touching the air on the substrate to increase the oxygen concentration in the chemical liquid. Thereby, the chemical solution from the processing solution nozzle can be supplied to the substrate while maintaining the state in which the oxygen concentration is reduced. Therefore, it is possible to suppress or prevent the occurrence of an oxidation reaction due to dissolved oxygen in the chemical solution on the substrate.

  The invention described in claim 11 is a substrate processing method for processing a substrate by supplying a processing solution from a processing solution nozzle to the substrate, wherein the oxygen in the pure water is degassed and inert in the pure water. Inert gas dissolved water generation step of adding gas to generate inert gas dissolved water, chemical solution stock solution and inert gas dissolved water are mixed in the pipe to prepare the chemical solution, and this chemical solution is supplied to the processing liquid A chemical solution supplying step (S14, S24, S34) for supplying the processing solution nozzle through the path, and an atmosphere replacement step for replacing the atmosphere near the surface of the substrate with an inert gas, prior to the chemical solution supplying step. (S11, S21, S31) and the inert gas-dissolved water generated by the inert gas-dissolved water generation step, which is performed prior to the chemical solution supply step (more preferably after the start of the atmosphere replacement step). Do not mix with chemical stock solution The treatment liquid inert gas dissolved water supply step of supplying to the processing liquid nozzle through the supply channel (S13, S23, S33) and a, a substrate processing method.

  According to the present invention, in the inert gas dissolved water generation step, oxygen in pure water is degassed, and the inert gas is added to the pure water to generate inert gas dissolved water. And this inert gas dissolved water is mixed with a chemical | medical solution undiluted solution in piping in a chemical | medical solution supply process, and the chemical | medical solution as a process liquid is prepared. Further, the prepared chemical liquid is supplied to the processing liquid nozzle via the processing liquid supply path. Thereby, the chemical | medical solution as a process liquid can be supplied to a board | substrate, and the said board | substrate can be processed.

  Moreover, according to this invention, an atmosphere replacement | exchange process and an inert gas dissolved water supply process are performed prior to a chemical | medical solution supply process. That is, prior to the chemical supply step, the atmosphere near the surface of the substrate is replaced with an inert gas. Further, the inert gas dissolved water generated by the inert gas dissolved water generating step is supplied to the processing liquid nozzle through the processing liquid supply path without being mixed with the chemical solution stock solution, and the processing liquid supply The inside of the passage and the inside of the treatment liquid nozzle are washed away by the inert gas dissolved water. Therefore, it is possible to suppress or prevent the chemical liquid discharged from the processing liquid nozzle in the chemical liquid supply process from increasing until the oxygen concentration reaches the substrate or touches the air on the substrate. Furthermore, even if a processing liquid having an increased oxygen concentration remains in the processing liquid supply path and the processing liquid nozzle, it is possible to suppress or prevent the chemical liquid from being supplied to the substrate together with such a processing liquid. Can do. Thereby, a board | substrate can be processed with the chemical | medical solution by which oxygen concentration was reduced. Therefore, it is possible to suppress or prevent the occurrence of an oxidation reaction due to dissolved oxygen in the chemical solution on the substrate. As a result, even if the chemical solution supplied to the substrate has an etching action on the oxide, it is possible to suppress or prevent undesired etching from occurring on the substrate.

  Further, since the chemical solution stock solution and the inert gas-dissolved water are mixed in the pipe in the chemical solution supply step, the prepared chemical solution is suppressed or prevented from increasing in oxygen concentration due to contact with air. Furthermore, since the inert gas is added to the inert gas-dissolved water contained in the prepared chemical solution, an increase in the oxygen concentration in the chemical solution is suppressed or prevented. Thereby, the chemical | medical solution in which oxygen concentration was further reduced can be supplied to a process liquid nozzle via a process liquid supply path.

The atmosphere replacement step includes a step (S11, S21, S31) of supplying an inert gas to a space between the blocking member and the substrate in a state where the substrate facing surface of the blocking member is opposed to the surface of the substrate. It is preferable.
More specifically, as in the invention described in claim 12, in the atmosphere replacement step, the substrate facing surface of the blocking member is opposed to the surface of the substrate, and the substrate is formed by a peripheral wall portion protruding from the periphery of the substrate facing surface. It is preferable to include a step (S11, S21, S31) of supplying an inert gas to a space between the blocking member and the substrate in a state of surrounding the substrate.

  By making the substrate-facing surface of the blocking member face the surface of the substrate, the atmosphere on the substrate surface can be blocked from the external atmosphere. Further, the substrate facing surface of the blocking member is opposed to the surface of the substrate, and the periphery of the substrate is surrounded by a peripheral wall portion protruding from the periphery of the substrate facing surface, so that the atmosphere on the surface of the substrate is further increased from the external atmosphere. It can be reliably shut off. Therefore, the increase in the oxygen concentration of the atmosphere on the substrate surface can be suppressed or prevented by making the substrate facing surface of the blocking member face the surface of the substrate. Furthermore, by supplying an inert gas to the space between the blocking member and the substrate, the atmosphere on the substrate surface can be changed to an inert gas atmosphere. Therefore, it is possible to suppress or prevent the chemical liquid discharged from the processing liquid nozzle from reaching the substrate or touching the air on the substrate to increase the oxygen concentration in the chemical liquid. Thereby, the chemical solution from the processing solution nozzle can be supplied to the substrate while maintaining the state in which the oxygen concentration is reduced. As a result, it is possible to suppress or prevent the occurrence of an oxidation reaction due to dissolved oxygen in the chemical solution on the substrate.

The blocking member may have a peripheral wall as in the invention described in claim 12 or may not have a peripheral wall.
According to a thirteenth aspect of the present invention, the atmosphere replacement step includes a step of holding the substrate by a holding base having a surface facing the substrate facing surface of the blocking member, and a tip edge of the peripheral wall portion of the blocking member from the substrate. The substrate processing method according to claim 12, further comprising a step of bringing the surface close to the surface of the holding base.

According to this invention, the periphery of the substrate can be surely surrounded by the peripheral wall portion by bringing the tip edge of the peripheral wall portion of the blocking member closer to the surface of the holding base than the substrate. As a result, the atmosphere on the substrate surface can be reliably shielded from the surrounding atmosphere, and the atmosphere on the substrate surface can be further reliably shielded from the external atmosphere.
In the invention described in claim 14, the inert gas dissolved water supply step is continued until the oxygen concentration in the treatment liquid discharged from the treatment liquid nozzle becomes 20 ppb or less, and then the chemical solution supply step is executed. The substrate processing method according to claim 11.

  According to this invention, in the chemical solution supply step performed after the inert gas dissolved water supply step, a low oxygen concentration chemical solution (chemical solution having an oxygen concentration of 20 ppb or less) that can reliably suppress or prevent the oxidation reaction of the substrate. The treatment liquid nozzle can be supplied. Therefore, by supplying such a chemical solution having a low oxygen concentration to the substrate, it is possible to reliably suppress or prevent the occurrence of the oxidation reaction of the substrate.

The invention according to claim 15 is a rinsing step of supplying the substrate with the inert gas dissolved water generated by the inert gas dissolved water generating step after the chemical solution supplying step, and rinsing the chemical on the surface of the substrate ( The substrate processing method according to any one of claims 11 to 14, further including S15, S25, and S35).
According to this invention, since the inert gas dissolved water generated by the inert gas dissolved water generating step is supplied to the substrate after the chemical solution supplying step, the chemical solution adhering to the substrate is removed from the substrate. can do. In addition, since the inert gas-dissolved water from which oxygen has been degassed is supplied to the substrate, the oxidation reaction of the substrate can be suppressed or prevented. Thereby, it can suppress or prevent that the oxide on a board | substrate is etched by the chemical | medical solution which remains on the board | substrate W. FIG. Therefore, undesired etching on the substrate W can be suppressed or prevented.

The invention described in claim 16 further includes a step of supplying an inert gas into a chemical tank storing the chemical stock solution, and the chemical solution is prepared using the chemical stock solution pumped from the chemical tank in the chemical solution supply step. The substrate processing method according to claim 1.
According to this invention, the inert gas can be filled in the chemical tank by supplying the inert gas into the chemical tank. Thereby, it can suppress or prevent that the oxygen concentration in the chemical | medical solution stock solution stored by the chemical | medical solution tank rises. Therefore, it is possible to suppress or prevent the chemical solution stock having an increased oxygen concentration from being pumped out and the chemical solution being prepared using this chemical solution stock solution in the chemical solution supply step.

The invention according to claim 17 further includes a step of degassing the chemical solution stock solution, and in the chemical solution supply step, a chemical solution is prepared using the degassed chemical solution stock solution. The substrate processing method according to one item.
According to this invention, since the chemical solution is prepared using the chemical solution stock from which oxygen has been degassed, the oxygen concentration in the chemical solution can be further reduced. Thereby, the chemical | medical solution in which oxygen concentration was further reduced can be supplied to a board | substrate.

According to an eighteenth aspect of the present invention, the processing liquid supply path includes an inner pipe through which the processing liquid flows and an outer pipe surrounding the processing liquid pipe, and there is no gap between the inner pipe and the outer pipe. The substrate processing method according to any one of claims 11 to 17, further comprising an inert gas filling step of filling the active gas.
According to this invention, the inert gas is filled between the inner pipe and the outer pipe, and the inner pipe is surrounded by the inert gas. Therefore, even if the inner pipe is made of, for example, an oxygen permeable material, the amount of oxygen that enters the inner pipe through the inner pipe can be reduced. Thereby, it can suppress or prevent that oxygen melt | dissolves in the process liquid which distribute | circulates the inside piping, and the oxygen concentration in the said process liquid rises.

The invention according to claim 19 is the substrate according to any one of claims 11 to 18, wherein the substrate has a polymer residue attached to a surface thereof, and the chemical solution is a polymer removal solution for removing the polymer residue. The substrate processing method according to the item.
According to this invention, the polymer residue can be removed from the surface of the substrate while supplying or removing the polymer removal liquid with a reduced oxygen concentration to the substrate while suppressing or preventing the oxidation reaction of the substrate.

The invention according to claim 20 is the substrate processing method according to any one of claims 11 to 19, wherein the substrate has a metal pattern exposed on a surface thereof.
According to the present invention, since the treatment liquid having a reduced oxygen concentration can be supplied to the substrate surface, the substrate surface can be treated while suppressing or preventing the oxidation reaction of the metal pattern on the substrate surface.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is an illustrative view for explaining the configuration of a substrate processing apparatus 1 according to an embodiment of the present invention.
The substrate processing apparatus 1 is a single wafer processing apparatus that processes substrates W one by one. In this embodiment, the substrate W is a circular substrate such as a semiconductor wafer. The substrate processing apparatus 1 includes a processing module M1 for processing the substrate W. The processing module M1 is held by a spin chuck 3 (substrate holding mechanism, substrate holding rotating mechanism) that holds and rotates one substrate W horizontally in a processing chamber 2 partitioned by a partition, and the spin chuck 3. A two-fluid nozzle 4 for supplying a droplet of processing liquid to the upper surface of the substrate W, a processing liquid nozzle 5 for supplying processing liquid to the upper surface of the substrate W held on the spin chuck 3, and the spin chuck 3. And a blocking plate 6 (blocking member) disposed above.

  The spin chuck 3 includes a rotating shaft 7 extending in a vertical direction, a disc-shaped spin base 8 (holding base) attached horizontally to the upper end of the rotating shaft 7, and a plurality of spin chucks 8 disposed on the spin base 8. A clamping member 9 and a chuck rotation driving mechanism 10 coupled to the rotary shaft 7 are provided. The spin base 8 is a disk-shaped member having a diameter larger than that of the substrate W, for example. The upper surface 8a of the spin base 8 (the surface of the holding base) is a circular plane having a diameter larger than that of the substrate W.

  The plurality of holding members 9 are arranged at appropriate intervals on the circumference corresponding to the outer peripheral shape of the substrate W at the peripheral portion of the upper surface 8 a of the spin base 8. The plurality of holding members 9 can hold (hold) one substrate W in a horizontal posture in cooperation with each other. In a state where the substrate W is held by the plurality of sandwiching members 9, the driving force of the chuck rotation driving mechanism 10 is input to the rotating shaft 7, whereby the held substrate W passes through the center of the vertical rotation axis L1. Rotated around.

  The rotating shaft 7 is a hollow shaft. A first lower processing liquid supply pipe 11 is inserted into the rotary shaft 7 in a non-contact state. A lower surface nozzle 12 that discharges the processing liquid toward the center of the lower surface of the substrate W is provided at the upper end of the first lower processing liquid supply pipe 11. The lower surface nozzle 12 is disposed so that the discharge port 12a is close to the center of the lower surface of the substrate W held by the plurality of clamping members 9.

  A second lower processing liquid supply pipe 13 is connected to the first lower processing liquid supply pipe 11. The first lower processing liquid supply pipe 11 is selectively supplied with a chemical liquid and a rinsing liquid as the processing liquid via the second lower processing liquid supply pipe 13. As a result, the processing liquid can be supplied from the first lower processing liquid supply pipe 11 to the lower surface nozzle 12, and the processing liquid can be discharged from the discharge port 12 a of the lower surface nozzle 12 toward the center of the lower surface of the substrate W.

  Further, a lower gas supply path 14 surrounding the first lower processing liquid supply pipe 11 is formed between the rotating shaft 7 and the first lower processing liquid supply pipe 11. The upper end of the lower gas supply path 14 is an annular lower gas discharge port 15 located at the same height as the upper surface 8 a of the spin base 8. A lower gas supply pipe 16 is connected to the lower gas supply path 14. An inert gas (for example, nitrogen gas) from a gas supply source (not shown) is supplied to the lower gas supply path 14 via a lower gas supply pipe 16. The inert gas supplied to the lower gas supply path 14 is discharged upward from the lower gas discharge port 15. The lower gas supply pipe 16 is provided with a lower gas valve 17 for switching between supply and stop of supply of the inert gas to the lower surface nozzle 12.

  The two-fluid nozzle 4 is, for example, an external mixing type that generates a droplet of the processing liquid by mixing the processing liquid and gas outside the casing. The two-fluid nozzle 4 can cause the droplets of the processing liquid to collide with the upper surface of the substrate W held by the spin chuck 3 to separate the foreign matter from the upper surface of the substrate W. The two-fluid nozzle 4 is attached to the tip of a nozzle arm 19 that extends horizontally. The two-fluid nozzle 4 is disposed above the spin chuck 3 with its discharge port directed downward.

  A treatment liquid supply pipe 20 and a gas supply pipe 21 are connected to the two-fluid nozzle 4. The two-fluid nozzle 4 is supplied with a processing liquid (for example, carbonated water) and a gas (for example, nitrogen gas) through a processing liquid supply pipe 20 and a gas supply pipe 21, respectively. The two-fluid nozzle 4 can mix the supplied processing liquid and gas to generate droplets of the processing liquid. The processing liquid supply pipe 20 is provided with a processing liquid valve 22 for switching between supply and stop of supply of the processing liquid to the two-fluid nozzle 4. The gas supply pipe 21 is provided with a gas valve 23 for switching between supply and stop of gas supply to the two-fluid nozzle 4.

  A support shaft 24 extending along the vertical direction is coupled to the nozzle arm 19. The support shaft 24 can swing around its central axis. The support shaft 24 is coupled to a nozzle swing drive mechanism 25 configured by, for example, a motor. When the driving force of the nozzle swing drive mechanism 25 is input to the support shaft 24, the two-fluid nozzle 4 and the nozzle arm 19 are horizontally moved integrally around the central axis of the support shaft 24. Thereby, the two-fluid nozzle 4 can be disposed above the substrate W held on the spin chuck 3, or the two-fluid nozzle 4 can be retracted from above the spin chuck 3. Further, while the substrate W is rotated by the spin chuck 3, the two-fluid nozzle 4 is swung within a predetermined angle range while supplying the droplet of the processing liquid from the two-fluid nozzle 4 to the upper surface of the substrate W. Thus, the droplet collision position (supply position) on the upper surface of the substrate W can be moved.

  Specifically, for example, the collision position of the droplet on the upper surface of the substrate W moves between the rotation center and the peripheral portion while drawing an arc-shaped locus in the upper surface, or an arc shape passing through the rotation center. The two-fluid nozzle 4 can be moved horizontally so as to move from the peripheral part to the peripheral part while drawing the locus. Accordingly, the upper surface of the substrate W can be scanned with the droplets of the processing liquid, and the droplets of the processing liquid can be directly collided with the entire upper surface.

The processing liquid nozzle 5 is, for example, a straight nozzle that discharges the processing liquid in a continuous flow state. The treatment liquid nozzle 5 is attached to the tip of a nozzle arm 26 that extends horizontally. The treatment liquid nozzle 5 is disposed above the spin chuck 3 with its discharge port directed downward.
Two treatment liquid supply pipes 27 a and 27 b are connected to the treatment liquid nozzle 5. A processing liquid (for example, carbonated water) from a processing liquid supply source (not shown) is supplied to the processing liquid nozzle 5 through a processing liquid supply pipe 27a. The processing liquid nozzle 5 is supplied with a processing liquid (for example, pure water (deionized water)) from a processing liquid supply source (not shown) via the processing liquid supply pipe 27b. A treatment liquid valve 28 a for switching between supply and stop of supply of the treatment liquid to the treatment liquid nozzle 5 is interposed in the treatment liquid supply pipe 27 a. Further, the processing liquid supply pipe 27b is provided with a processing liquid valve 28b for switching between supply and stop of supply of the processing liquid to the processing liquid nozzle 5.

  The nozzle arm 26 is coupled to a support shaft 29 extending along the vertical direction. The support shaft 29 can swing around its central axis. The support shaft 29 is coupled with a nozzle swing drive mechanism 30 formed of, for example, a motor. When the driving force of the nozzle swing driving mechanism 30 is input to the support shaft 29, the processing liquid nozzle 5 and the nozzle arm 26 are horizontally moved integrally around the central axis of the support shaft 29. Thereby, the processing liquid nozzle 5 can be disposed above the substrate W held on the spin chuck 3, and the processing liquid nozzle 5 can be retracted from above the spin chuck 3. Further, in a state where the substrate W is rotated by the spin chuck 3, the processing liquid nozzle 5 is swung within a predetermined angle range while discharging the processing liquid from the processing liquid nozzle 5 toward the upper surface of the substrate W. As a result, the position where the processing liquid is deposited on the upper surface of the substrate W can be moved. Thereby, the upper surface of the substrate W can be scanned with the processing liquid, and the processing liquid can be deposited over the entire upper surface.

The blocking plate 6 is a disk-shaped member having a substantially constant thickness. The diameter of the blocking plate 6 is larger than that of the substrate W. The blocking plate 6 is connected to the lower end of a support shaft 31 disposed on the same axis as the rotation shaft 7 of the spin chuck 3. The blocking plate 6 is horizontally disposed above the spin chuck 3 so that the central axis thereof is located on the common axis with the rotation shaft 7.
The outer peripheral portion of the blocking plate 6 is bent downward over the entire circumference. The outer peripheral portion of the blocking plate 6 forms a cylindrical peripheral wall portion 32. A portion inside the peripheral wall portion 32 of the blocking plate 6 forms a flat plate portion 33 having a circular shape. The lower surface of the flat plate portion 33 is formed in a plane and is parallel to the upper surface of the substrate W held by the spin chuck 3. The lower surface of the flat plate portion 33 is a substrate facing surface 34 that faces the substrate W held by the spin chuck 3. The substrate facing surface 34 faces the substrate W held by the spin chuck 3 and faces the upper surface 8 a of the spin base 8. The peripheral wall portion 32 protrudes from the periphery of the substrate facing surface 34 toward the spin chuck 3.

  In addition, a through-hole penetrating the shielding plate 6 in the vertical direction is formed in the central portion of the shielding plate 6. The lower end of the through hole is an opening located at the center of the lower surface of the blocking plate 6. The support shaft 31 is a hollow shaft, and its internal space communicates with the through hole. A first upper processing liquid supply pipe 35 (processing liquid nozzle) is inserted through the support shaft 31 in a non-contact state. The lower end of the first upper processing liquid supply pipe 35 reaches the through hole.

A cylindrical gas flow passage 36 through which an inert gas flows is formed around the first upper processing liquid supply pipe 35. Further, an upper processing liquid discharge port 37 (discharge port) for discharging the processing liquid is formed at the lower end of the first upper processing liquid supply pipe 35. The upper processing liquid discharge port 37 faces the substrate W held by the spin chuck 3 from the substrate facing surface 34.
A second upper processing liquid supply pipe 38 (processing liquid supply path) is connected to the first upper processing liquid supply pipe 35. The first upper processing liquid supply pipe 35 is selectively supplied with a chemical liquid and a rinsing liquid as a processing liquid via a second upper processing liquid supply pipe 38. Thereby, the processing liquid can be discharged from the upper processing liquid discharge port 37 formed at the lower end of the first upper processing liquid supply pipe 35 toward the center of the upper surface of the substrate W held by the spin chuck 3.

  An upper gas supply pipe 39 is connected to the upper end portion of the support shaft 31. Nitrogen gas, which is an example of an inert gas, is supplied to the gas flow passage 36 from an upper gas supply pipe 39. The inert gas supplied to the gas flow passage 36 flows downward through the gas flow passage 36, and the inner peripheral surface (surface that defines the through hole) of the blocking plate 6 and the lower end of the first upper processing liquid supply pipe 35. The liquid is discharged downward from between the outer peripheral surfaces of the parts. An upper gas discharge port 40 (not fixed) between the inner peripheral surface of the blocking plate 6 and the outer peripheral surface of the lower end portion of the first upper processing liquid supply pipe 35 faces the substrate W held by the spin chuck 3 from the substrate facing surface 34. Active gas discharge port). By discharging the inert gas from the upper gas discharge port 40, the inert gas can be supplied to the space between the blocking plate 6 and the substrate W held by the spin chuck 3. The upper gas supply pipe 39 includes an upper gas valve 41 for switching between supply and stop of supply of the inert gas to the gas flow passage 36 and a gas flow rate adjustment valve for adjusting the supply flow rate of the inert gas to the gas flow passage 36. 18 is interposed.

  Further, the support shaft 31 is coupled with a blocking plate lifting / lowering driving mechanism 42 (blocking member moving mechanism) and a blocking plate rotation driving mechanism 43 (blocking member rotating mechanism). By inputting the driving force of the shield plate lifting / lowering drive mechanism 42 to the support shaft 31, the support shaft 31 and the shield plate 6 are moved to the processing position where the substrate facing surface 34 approaches the upper surface 8 a of the spin base 8 and the spin base 8. It can be moved up and down integrally with the retreat position that is far away from the upper surface 8a. In FIG. 1, the state where the blocking plate 6 is located at the processing position is indicated by a two-dot chain line, and the state where the blocking plate 6 is positioned at the retracted position is indicated by a solid line. Further, by inputting the driving force of the shield plate rotation drive mechanism 43 to the support shaft 31, the support shaft 31 and the shield plate 6 can be integrally rotated about the common axis (rotation axis L <b> 1) with the substrate W. it can. Thereby, for example, the support shaft 31 and the blocking plate 6 can be rotated almost in synchronization with the rotation of the substrate W by the spin chuck 3 (or with a slightly different rotational speed).

  Further, the processing module M1 is provided with a cleaning nozzle 44 for cleaning the blocking plate 6. The cleaning nozzle 44 is, for example, a straight nozzle that discharges the cleaning liquid in a continuous flow state. The cleaning nozzle 44 is attached to the tip of a nozzle arm 45 that extends horizontally. The cleaning nozzle 44 is disposed above the spin chuck 3 with its discharge port directed obliquely upward. The cleaning nozzle 44 is located below the retracted position of the blocking plate 6.

A cleaning liquid supply pipe 46 is connected to the cleaning nozzle 44. A cleaning liquid (for example, pure water) from a cleaning liquid supply source (not shown) is supplied to the cleaning nozzle 44 via a cleaning liquid supply pipe 46. The cleaning liquid supply pipe 46 is provided with a cleaning liquid valve 47 for switching between supply and stop of supply of the cleaning liquid to the cleaning nozzle 44.
A nozzle moving mechanism 48 is coupled to the nozzle arm 45. The nozzle moving mechanism 48 can horizontally move the cleaning nozzle 44 and the nozzle arm 45 integrally. By integrally moving the cleaning nozzle 44 and the nozzle arm 45 horizontally by the nozzle moving mechanism 48, the cleaning nozzle 44 can be disposed above the spin chuck 3 or retracted from above the spin chuck 3. Therefore, the cleaning nozzle 44 can be moved below the blocking plate 6 by moving the cleaning nozzle 44 above the spin chuck 3 with the blocking plate 6 positioned at the retracted position.

  The blocking plate 6 can be cleaned by discharging the cleaning liquid from the cleaning nozzle 44 with the cleaning nozzle 44 positioned below the blocking plate 6. Specifically, with the cleaning nozzle 44 positioned below the blocking plate 6, the blocking plate 6 is rotated by the blocking plate rotation drive mechanism 43, and the cleaning liquid is discharged from the cleaning nozzle 44. Is moved horizontally, the position of the cleaning liquid landing on the blocking plate 6 is moved, and the cleaning liquid can be supplied to the entire area of the substrate facing surface 34 and the inner wall surface 49 of the peripheral wall portion 32. Thereby, the entire region of the substrate facing surface 34 and the inner wall surface 49 can be cleaned. Accordingly, it is possible to suppress or prevent foreign substances such as particles adhering to the substrate facing surface 34 and the inner wall surface 49 from moving to the substrate W held by the spin chuck 3 and contaminating the substrate W. .

FIG. 2 is a schematic side view of the spin chuck 3 and the blocking plate 6 and configurations related thereto. FIG. 2 shows a state where the blocking plate 6 is located at the processing position.
As described above, the blocking plate 6 includes the circular flat plate portion 33 and the cylindrical peripheral wall portion 32. The flat plate portion 33 has a diameter larger than that of the substrate W held by the spin chuck 3. Therefore, the diameter of the substrate facing surface 34 is larger than that of the substrate W held by the spin chuck 3. The blocking plate 6 can cover the entire upper surface of the substrate W held by the spin chuck 3 with the substrate facing surface 34. Moreover, although the upper surface side edge part of the disk-shaped spin base 8 is chamfered, it does not need to be chamfered.

  The peripheral wall portion 32 extends downward from the outer peripheral edge of the flat plate portion 33. The upper end part (connection part with the flat plate part 33) of the surrounding wall part 32 is formed in the curve shape. The peripheral wall portion 32 is inclined so as to expand downward. The peripheral wall portion 32 has a frustoconical inner wall surface 49 whose diameter increases toward the lower side. The inner wall surface 49 is a surface inclined with respect to the normal line L2 of the upper surface of the substrate W.

  The inner wall surface 49 approaches the spin base 8 toward the outside of the substrate W (in the direction away from the rotation axis L1). Further, the vicinity of the upper end of the inner wall surface 49 is a surface (a plane including the normal line L2) in which the inclination angle with respect to the normal line L2 of the upper surface of the substrate W gradually changes toward the leading edge (lower edge in FIG. 2). The cross section becomes a curved surface). The diameter of the inner wall surface 49 is larger than the diameter of the substrate W at all points from the upper end to the lower end. Therefore, the blocking plate 6 can surround the entire circumference of the peripheral end surface of the substrate W by the inner wall surface 49.

  As shown in FIG. 2, when the blocking plate 6 is positioned at the processing position while the substrate W is held on the spin chuck 3, the substrate facing surface 34 approaches the upper surface of the substrate W, and the entire upper surface of the substrate W is Is covered by the substrate facing surface 34. Further, the tip edge of the peripheral wall portion 32 is closer to the spin base 8 than the substrate W, and the entire peripheral end surface of the substrate W is surrounded by the inner wall surface 49. Further, a gap (interval) smaller than the interval between the substrate facing surface 34 and the upper surface of the substrate W is formed between the tip edge of the peripheral wall portion 32 and the upper surface 8 a of the spin base 8. Therefore, when the blocking plate 6 is positioned at the processing position while the substrate W is held on the spin chuck 3, a substantially sealed narrow space extending in the horizontal direction is formed above the substrate W.

In this embodiment, the processing position is such that the substrate facing surface 34 approaches the upper surface of the substrate W held by the spin chuck 3, and the tip edge of the peripheral wall portion 32 is positioned closer to the spin base 8 than the substrate W. The distance between the tip edge of the peripheral wall portion 32 and the upper surface 8a of the spin base 8 is set to be smaller than the distance between the substrate facing surface 34 and the upper surface of the substrate W.
When the positional relationship among the substrate W, the spin base 8 and the blocking plate 6 in a state where the blocking plate 6 is located at the processing position is shown by specific numerical values, the leading edge of the peripheral wall portion 32 and the upper surface 8a of the spin base 8 A gap G1 in the vertical direction is set to 4 mm or less, for example. Further, when the substrate W is held on the spin chuck 3, the vertical gap G2 between the upper surface of the substrate W and the upper surface 8a of the spin base 8 is set to 10 mm, for example. Therefore, when the blocking plate 6 is positioned at the processing position while the substrate W is held on the spin chuck 3, the leading edge of the peripheral wall portion 32 is positioned 6 mm or more below the upper surface of the substrate W. As a result, the entire circumference of the peripheral end surface of the substrate W is surrounded by the inner wall surface 49. The vertical distance G3 between the upper surface of the substrate W and the substrate facing surface 34 is, for example, 8 mm when the vertical distance between the tip edge of the peripheral wall portion 32 and the upper surface 8a of the spin base 8 is 4 mm. It is set to be 5 mm.

  When the blocking plate 6 is positioned at the processing position while the substrate W is held on the spin chuck 3, and the inert gas is discharged from the upper gas discharge port 40 located at the center of the substrate facing surface 34, the upper gas is discharged. The inert gas discharged from the discharge port 40 spreads outward (in the direction away from the rotation axis L1) in the space between the upper surface of the substrate W held by the spin chuck 3 and the substrate facing surface 34. . Therefore, the air existing in the space between the upper surface of the substrate W and the substrate facing surface 34 is pushed outward by the inert gas, and is formed between the tip edge of the peripheral wall portion 32 and the upper surface 8 a of the spin base 8. It is discharged from the gap. Thereby, the atmosphere between the upper surface of the substrate W and the substrate facing surface 34 can be replaced with an inert gas.

  Further, since the inner wall surface 49 of the peripheral wall portion 32 is inclined with respect to the normal line L2 of the upper surface of the substrate W, when air is discharged from the space between the upper surface of the substrate W and the substrate facing surface 34. The air can be guided smoothly by the inner wall surface 49 and moved smoothly. Thus, the atmosphere between the upper surface of the substrate W and the substrate facing surface 34 can be smoothly replaced with an inert gas atmosphere without causing air to stay in the space between the upper surface of the substrate W and the substrate facing surface 34. Can do.

  Further, when the blocking plate 6 is positioned at the processing position while the substrate W is held on the spin chuck 3, the space between the upper surface of the substrate W and the substrate facing surface 34 can be surrounded by the peripheral wall portion 32. It is possible to suppress or prevent the surrounding air from entering the outer peripheral portion of the space. Thereby, after the atmosphere between the upper surface of the substrate W and the substrate facing surface 34 is replaced with an inert gas atmosphere, air enters the space between the upper surface of the substrate W and the substrate facing surface 34, and An increase in the oxygen concentration in the space can be suppressed or prevented.

FIG. 3 is a schematic diagram of a configuration for supplying the processing liquid to the processing module M1.
The substrate processing apparatus 1 degass oxygen in pure water, adds an inert gas to the pure water, and generates an inert gas-dissolved water, and a processing module M1. A processing liquid supply module M2 for supplying a processing liquid is further provided.
The inert gas dissolved water production | generation unit 50 can produce | generate inert gas dissolved water from the pure water supplied from the pure water supply source which is not shown in figure. The inert gas dissolved water generated by the inert gas dissolved water generating unit 50 is supplied to the treatment liquid supply module M2. The inert gas dissolved water generation unit 50 performs degassing of oxygen from pure water and addition of the inert gas to pure water through, for example, a hollow fiber separation membrane having gas permeability and liquid impermeability. Is. A specific configuration of the inert gas-dissolved water generating unit 50 is shown in Patent Document 2, for example.

  The inert gas dissolved water generation unit 50 degass oxygen until the oxygen concentration in the supplied pure water becomes, for example, 20 ppb or less. Moreover, the inert gas dissolved water production | generation unit 50 adds nitrogen gas with high purity (concentration of nitrogen gas is 99.999% to 99.99999999999%, for example) to pure water, and the nitrogen concentration is For example, 7 ppm to 24 ppm of inert gas dissolved water is generated. By setting the nitrogen concentration in the inert gas-dissolved water to a value within this range, it is possible to suppress or prevent the oxygen concentration in the inert gas-dissolved water from increasing with time.

  The processing liquid supply module M2 can supply the processing liquid to a configuration for discharging the processing liquid such as the two-fluid nozzle 4 and the processing liquid nozzle 5. In FIG. 3, only the configuration for supplying the processing liquid to the first upper processing liquid supply pipe 35 and the first lower processing liquid supply pipe 11 is illustrated. The treatment liquid supply module M2 mixes the chemical solution stock solution and the inert gas-dissolved water to prepare a chemical solution as a treatment liquid (a first in-pipe preparation unit 51 and a second in-pipe preparation unit 52). ), And a chemical solution supply unit 53 that supplies the chemical solution stock solution to the first and second in-pipe preparation units 51 and 52.

The “chemical solution stock” means a chemical solution before mixing with the inert gas-dissolved water. Examples of the chemical stock solution include hydrofluoric acid (HF), hydrochloric acid (HCL), a mixed solution of hydrofluoric acid and IPA (isopropyl alcohol), and ammonium fluoride (NH ₄ F). When hydrofluoric acid is used as the chemical solution stock solution, hydrofluoric acid and inert gas-dissolved water are mixed (prepared) at a predetermined ratio in the first and second in-pipe preparation units 51 and 52, and diluted hydrofluoric acid ( DHF) is generated.

  The first in-pipe preparation unit 51 is connected to the inert gas dissolved water generation unit 50 via the first supply pipe 54. The inert gas-dissolved water is supplied from the inert gas-dissolved water generation unit 50 to the first in-pipe preparation unit 51 via the first supply pipe 54. The first in-pipe preparation unit 51 is connected to the chemical solution supply unit 53 via a first branch pipe 56 that is branched and connected to the chemical solution supply pipe 55. The chemical solution stock solution is supplied from the chemical solution supply unit 53 to the first in-pipe preparation unit 51 via the chemical solution supply pipe 55 and the first branch pipe 56. In this embodiment, a chemical solution supply path is constituted by the chemical solution supply pipe 55 and the first branch pipe 56. The first in-pipe preparation unit 51 mixes the chemical solution supplied from the chemical supply unit 53 and the inert gas dissolved water supplied from the inert gas dissolved water generation unit 50 to prepare a chemical as a treatment liquid. can do.

  The second in-pipe preparation unit 52 is connected to the inert gas dissolved water generation unit 50 via the second supply pipe 57. The inert gas-dissolved water is supplied from the inert gas-dissolved water generation unit 50 to the second in-pipe preparation unit 52 via the second supply pipe 57. The second in-pipe preparation unit 52 is connected to the chemical solution supply unit 53 via a second branch pipe 58 that is branched and connected to the chemical solution supply pipe 55. The chemical solution stock solution is supplied from the chemical solution supply unit 53 to the second in-pipe preparation unit 52 via the chemical solution supply pipe 55 and the second branch pipe 58. The second pipe preparation unit 52 mixes the chemical solution supplied from the chemical supply unit 53 and the inert gas dissolved water supplied from the inert gas dissolved water generation unit 50 to prepare the chemical as the treatment liquid. can do.

  The first in-pipe preparation unit 51 is connected to the second upper process liquid supply pipe 38, and a chemical solution as a process liquid is supplied to the first upper process liquid supply pipe 35 via the second upper process liquid supply pipe 38. Can be supplied. Further, the first in-pipe preparation unit 51 does not mix the chemical stock solution with the inert gas dissolved water supplied from the inert gas dissolved water generation unit 50, and uses the inert gas dissolved water as the rinse liquid as it is. It can be supplied to the upper processing liquid supply pipe 35. Thereby, the chemical liquid and the rinse liquid can be selectively supplied to the first upper processing liquid supply pipe 35.

  The second in-pipe preparation unit 52 is connected to the second lower processing liquid supply pipe 13, and passes through the second lower processing liquid supply pipe 13 to the first lower processing liquid supply pipe 11 as a processing liquid. The chemical solution can be supplied. Further, the second in-pipe preparation unit 52 does not mix the chemical solution stock with the inert gas dissolved water supplied from the inert gas dissolved water generation unit 50, and the second inert gas dissolved water is used as the rinse liquid as it is. It can be supplied to the lower processing liquid supply pipe 13. Thereby, a chemical | medical solution and a rinse liquid can be selectively supplied to the 1st lower side process liquid supply pipe | tube 11. As shown in FIG.

  The first in-pipe preparation unit 51 was interposed between a first mixing part 59 (manifold) as a pipe capable of mixing the chemical stock solution and the inert gas-dissolved water, and a first supply pipe 54. A first valve 60 and a first flow rate adjustment valve 61, a first chemical solution valve 62 (chemical solution valve) and a first chemical solution flow rate adjustment valve 63 interposed in the first branch pipe 56 are provided. The first supply pipe 54 and the first branch pipe 56 are each connected to a first mixing unit 59.

  By opening the first valve 60, it is possible to supply a predetermined flow rate of inert gas dissolved water adjusted by the first flow rate adjustment valve 61 to the first mixing unit 59, and by opening the first chemical liquid valve 62, A chemical solution stock solution having a predetermined flow rate adjusted by the first chemical solution flow rate adjustment valve 63 can be supplied to the first mixing unit 59. With the first valve 60 opened, the first chemical valve 62 is opened, thereby injecting (injecting) the chemical solution into the inert gas dissolved water flowing through the first mixing unit 59, Inert gas-dissolved water can be mixed. Therefore, the chemical | medical solution prepared by the predetermined | prescribed ratio can be produced | generated by adjusting the supply amount of the chemical | medical solution stock solution with respect to the 1st mixing part 59, and the supply amount of inert gas dissolved water. Further, only the inert gas-dissolved water can be supplied to the first mixing unit 59 by opening only the first valve 60 without opening the first chemical liquid valve 62. As a result, the inert gas-dissolved water can be supplied as it is to the first upper treatment liquid supply pipe 35 without being mixed with the inert gas-dissolved water as a rinsing liquid.

  On the other hand, the second in-pipe preparation unit 52 includes a second mixing part 64 (manifold) capable of mixing the chemical solution stock and the inert gas-dissolved water therein, and a second supply pipe 57. 2 valve 65 and second flow rate adjustment valve 66, and second chemical solution valve 67 and second chemical solution flow rate adjustment valve 68 interposed in second branch pipe 58 are provided. The second supply pipe 57 and the second branch pipe 58 are each connected to the second mixing unit 64. About these structures of the 2nd in-pipe preparation unit 52, since it is the same as that of the 1st in-pipe preparation unit 51, the description is abbreviate | omitted. Below, a different point from the 1st in-pipe preparation unit 51 is demonstrated.

  A drainage pipe 70 in which a drainage valve 69 is interposed is connected to the second mixing unit 64. By opening the drain valve 69, the processing liquid can be drained from the second mixing unit 64. By draining the processing liquid from the second mixing unit 64, the processing liquid remaining in the lower surface nozzle 12 is moved to the first lower processing liquid supply pipe 11 side, and the processing liquid is discharged from the lower surface nozzle 12. It can be liquidated. Thereby, the processing liquid can be removed from the lower surface nozzle 12.

  The chemical solution supply unit 53 includes a chemical solution tank 71 that stores the chemical solution stock solution, and a chemical solution supply pipe 55 that guides the chemical solution stock solution from the chemical solution tank 71 to the first and second in-pipe preparation units 51 and 52. The chemical liquid tank 71 is a sealed container, and the internal space of the chemical liquid tank 71 is blocked from the external space. One end of the chemical solution supply pipe 55 is connected to the chemical solution tank 71. A pump 72, a filter 73, and a deaeration unit 74 are interposed in the chemical solution supply pipe 55 in this order from the chemical solution tank 71 side. The deaeration unit 74 has the same configuration as the inert gas dissolved water generation unit 50, and does not add an inert gas.

  Further, a chemical liquid supply pipe 75 is connected to the chemical liquid tank 71. The chemical solution stock 71 is supplied from a chemical solution supply source (not shown) to the chemical solution tank 71 via the chemical solution supply pipe 75. The chemical solution supply pipe 75 is provided with a chemical solution valve 76 for switching between supply and stop of supply of the chemical solution to the chemical solution tank 71. For example, when the amount of liquid in the chemical liquid tank 71 becomes a predetermined amount or less, the unused chemical liquid stock solution is supplied to the chemical liquid tank 71. Thus, the unused chemical solution stock solution can be replenished to the chemical solution tank 71.

  An inert gas supply pipe 77 is connected to the chemical tank 71. The chemical tank 71 is supplied with an inert gas from an inert gas supply source (not shown) via an inert gas supply pipe 77. The inert gas supply pipe 77 is provided with an inert gas valve 78 for switching between supply and stop of supply of the inert gas to the chemical tank 71. For example, an inert gas is constantly supplied to the chemical tank 71. In this embodiment, the inert gas supply pipe 77 and the inert gas valve 78 constitute an inert gas supply means.

  By supplying an inert gas to the chemical liquid tank 71, air can be expelled from the chemical liquid tank 71. Therefore, it is possible to suppress or prevent the oxygen contained in the air in the chemical solution tank 71 from being dissolved in the chemical solution stock stored in the chemical solution tank 71 and increasing the amount of dissolved oxygen in the chemical solution stock. Further, by pressurizing the chemical liquid tank 71 with the inert gas, the chemical liquid stock solution stored in the chemical liquid tank 71 can be pumped to the chemical liquid supply pipe 55.

  The chemical solution stock solution in the chemical solution tank 71 is pumped out of the chemical solution tank 71 by the pressure of the inert gas or the suction force by the pump 72. And the chemical | medical solution stock solution pumped out is pressurized by the pump 72, passes the filter 73, and a foreign material is removed. Furthermore, the chemical solution stock that has passed through the filter 73 is degassed by the degassing unit 74, and the amount of dissolved oxygen is reduced. Thereafter, the chemical stock solution in which the amount of dissolved oxygen is reduced is sent to the first and second branch pipes 56 and 58. Thereby, a chemical | medical solution stock solution can be supplied and supplied to the 1st and 2nd in-pipe preparation units 51 and 52. FIG.

FIG. 4 is an illustrative view of a pipe 79 provided in the substrate processing apparatus 1.
All the pipes for circulating the processing liquid such as the second upper processing liquid supply pipe 38 have the structure shown in FIG. Hereinafter, all the pipes for circulating the processing liquid such as the second upper processing liquid supply pipe 38 are collectively referred to as “pipe 79”.
The pipe 79 has a double structure, and has an inner pipe 80 through which the processing liquid flows and an outer pipe 81 that surrounds the inner pipe 80. The inner pipe 80 is supported inside the outer pipe 81 by a support member (not shown) interposed between the inner pipe 80 and the outer pipe 81. The inner pipe 80 is supported in a non-contact state with respect to the outer pipe 81. A cylindrical space is formed between the inner pipe 80 and the outer pipe 81. The inner pipe 80 and the outer pipe 81 are made of, for example, a fluororesin (more specifically, PFA (perfluoro-alkylvinyl-ether-tetrafluoro-ethlene-copolymer) excellent in chemical resistance and heat resistance. PFA is It can permeate oxygen.

  Further, an inert gas supply pipe 83 provided with an inert gas valve 82 and an exhaust pipe 85 provided with an exhaust valve 84 are connected to the outer pipe 81. By opening the inert gas valve 82, an inert gas from an inert gas supply source (not shown) (for example, nitrogen gas) can be supplied into the outer pipe 81 through the inert gas supply pipe 83. Thereby, an inert gas can be filled between the inner pipe 80 and the outer pipe 81. In this embodiment, the inert gas filling means is constituted by the inert gas valve 82 and the inert gas supply pipe 83. Further, by opening the exhaust valve 84, gas can be exhausted from between the inner pipe 80 and the outer pipe 81.

  By opening the inert gas valve 82 with the exhaust valve 84 open, air can be expelled from between the inner pipe 80 and the outer pipe 81, and the atmosphere in the meantime can be replaced with an inert gas atmosphere. Thereby, the inner pipe 80 can be surrounded by the inert gas. Then, after the atmosphere between the inner pipe 80 and the outer pipe 81 is replaced with the inert gas atmosphere, the inner pipe 80 is surrounded by the inert gas by closing the inert gas valve 82 and the exhaust valve 84. Can be maintained.

By enclosing the inner pipe 80 with an inert gas, the amount of oxygen entering the inside of the inner pipe 80 via the inner pipe 80 can be reduced. Thereby, it can suppress or prevent that oxygen melt | dissolves in the process liquid which distribute | circulates the inside piping 80, and the oxygen concentration in the said process liquid rises.
FIG. 5 is a block diagram for explaining the electrical configuration of the substrate processing apparatus 1.

  The substrate processing apparatus 1 includes a control unit 86 (valve control means, control means). The control unit 86 controls operations of the chuck rotation driving mechanism 10, the nozzle swing driving mechanisms 25 and 30, the blocking plate lifting / lowering driving mechanism 42, the nozzle moving mechanism 48, the blocking plate rotation driving mechanism 43, and the like. Further, the controller 86 controls the opening and closing of the valves provided in the substrate processing apparatus 1 and the adjustment of the opening degree of the flow rate adjusting valve.

FIG. 6 is a cross-sectional view for explaining an example of the surface state of the substrate W processed by the substrate processing apparatus 1.
As will be described below, the substrate W processed by the substrate processing apparatus 1 has, for example, a polymer residue (residue after dry etching or ashing) attached to the surface and an exposed metal pattern. The metal pattern may be a single film of copper, tungsten, or other metal, or may be a multilayer film in which a plurality of metal films are stacked. As an example of the multilayer film, a laminated film in which a barrier metal film for preventing diffusion is formed on the surface of a copper film can be cited.

  As shown in FIG. 6, an interlayer insulating film 87 is formed on the surface of the substrate W. In the interlayer insulating film 87, a lower wiring groove 88 is formed by digging from the upper surface. A copper wiring 89 is embedded in the lower wiring groove 88. On the interlayer insulating film 87, a low dielectric constant insulating film 91 as an example of a film to be processed is laminated via an etch stopper film 90. An upper wiring groove 92 is formed in the low dielectric constant insulating film 91 by digging from the upper surface. Further, a via hole 93 reaching the surface of the copper wiring 89 from the bottom surface of the upper wiring groove 92 is formed in the low dielectric constant insulating film 91. Copper is buried in the upper wiring trench 92 and the via hole 93 in a lump.

  The upper wiring trench 92 and the via hole 93 are subjected to a dry etching process after a hard mask is formed on the low dielectric constant insulating film 91, and a portion exposed from the hard mask in the low dielectric constant insulating film 91 is removed. Is formed. After the formation of the upper wiring trench 92 and the via hole 93, an ashing process is performed, and the unnecessary hard mask is removed from the low dielectric constant insulating film 91. At the time of dry etching and ashing, the reaction product including the components of the low dielectric constant insulating film 91 and the hard mask becomes a polymer residue, and the surface of the low dielectric constant insulating film 91 (the inner surfaces of the upper wiring trench 92 and the via hole 93). ). Therefore, after ashing, a process for removing the polymer residue from the surface of the low dielectric constant insulating film 91 is performed by supplying a polymer removing liquid to the surface of the substrate W.

Below, the process example for removing a polymer residue from the surface of such a board | substrate W using the substrate processing apparatus 1 is demonstrated.
FIG. 7 is a process diagram for explaining a first processing example of the substrate W by the substrate processing apparatus 1.
Below, with reference to FIG.1, FIG.3 and FIG.5, the 1st example of a process of the board | substrate W by the substrate processing apparatus 1 is demonstrated.

  The unprocessed substrate W is carried into the processing chamber 2 by a transfer robot (not shown), and is transferred to the spin chuck 3 with the surface, which is a device formation surface, facing up. Then, the control plate 86 controls the shield plate lifting / lowering drive mechanism 42, and the shield plate 6 is lowered to the processing position (step S11). As a result, the substrate facing surface 34 approaches the upper surface (front surface) of the substrate W held by the spin chuck 3, and the entire upper surface of the substrate W is covered by the substrate facing surface 34. Further, the tip edge of the peripheral wall portion 32 is closer to the spin base 8 than the substrate W, and the entire peripheral end surface of the substrate W is surrounded by the inner wall surface 49. Therefore, a substantially sealed narrow space extending in the horizontal direction is formed above the substrate W (see FIG. 2).

  Next, an inert gas purge process is performed in which air is expelled from the space between the upper surface of the substrate W and the substrate facing surface 34 and the atmosphere in the space is replaced with an inert gas atmosphere (step S12). Specifically, the upper gas valve 41 is opened by the controller 86 with the blocking plate 6 positioned at the processing position, and nitrogen gas as an inert gas is spin-chucked from the upper gas discharge port 40 at a predetermined discharge flow rate. 3 is discharged toward the center of the upper surface of the substrate W held on the substrate 3. Further, the lower gas valve 17 is opened by the control unit 86, and nitrogen gas as an inert gas is directed upward from the lower gas discharge port 15 at a predetermined discharge flow rate (for example, 10 L / min to 50 L / min). Discharged. At this time, the substrate W and the blocking plate 6 held by the spin chuck 3 may be rotated or rotated by the controller 86 controlling the chuck rotation driving mechanism 10 and the blocking plate rotation driving mechanism 43. Instead, it may be in a non-rotating state. When the substrate W is in a rotating state, the blocking plate 6 may be rotated almost in synchronization with the rotation of the substrate W by the spin chuck 3 (or at a slightly different rotational speed), or only the substrate W is rotated. The blocking plate 6 may be in a non-rotating state.

  The nitrogen gas discharged from the upper gas discharge port 40 spreads outward (in the direction away from the rotation axis L1) in the space between the upper surface of the substrate W held by the spin chuck 3 and the substrate facing surface 34. Go. Therefore, the air existing in the space between the upper surface of the substrate W and the substrate facing surface 34 is pushed outward by the nitrogen gas, and is formed between the tip edge of the peripheral wall portion 32 and the upper surface 8 a of the spin base 8. It is discharged from the gap. As a result, the atmosphere near the surface of the substrate W is replaced with nitrogen gas as an inert gas, and air is expelled from the space between the upper surface of the substrate W and the substrate facing surface 34 by the inert gas, and the atmosphere of the space An inert gas purge process is performed to replace the gas with an inert gas atmosphere.

  On the other hand, the nitrogen gas discharged from the lower gas discharge port 15 outwards in the space between the lower surface of the substrate W held by the spin chuck 3 and the upper surface 8a of the spin base 8 (in a direction away from the rotation axis L1). It spreads toward. Therefore, air and nitrogen gas existing in the space between the lower surface of the substrate W and the upper surface 8a of the spin base 8 are pushed outward by the subsequent nitrogen gas and discharged from the space.

  The inert gas purge process is continued until the oxygen concentration in the space between the upper surface of the substrate W and the substrate facing surface 34 becomes, for example, 100 ppm or less. Specifically, for example, an oxygen concentration sensor (not shown) is provided to detect the oxygen concentration in the space between the upper surface of the substrate W and the substrate facing surface 34, or the discharge flow rate of nitrogen gas from the upper gas discharge port 40 and By controlling the discharge time, the inert gas purging process is continued until the oxygen concentration in the space between the upper surface of the substrate W and the substrate facing surface 34 becomes 100 ppm or less.

  When the specific numerical value in the case of controlling the discharge flow rate and discharge time of nitrogen gas from the upper gas discharge port 40 is given, the discharge flow rate of nitrogen gas from the upper gas discharge port 40 is, for example, 50 L / min to 300 L / min. The discharge time is, for example, 10 sec to 60 sec, preferably 30 sec. Thus, by controlling the discharge flow rate and discharge time from the upper gas discharge port 40, the oxygen concentration in the space between the upper surface of the substrate W and the substrate facing surface 34 can be reduced to 10 ppm.

  After the inert gas purge process is performed for a predetermined time, a pre-dispensing process is performed to drain the inert gas dissolved water remaining in the first and second upper process liquid supply pipes 35 and 38 (steps). S13). Specifically, the chuck rotation driving mechanism 10 and the blocking plate rotation driving mechanism 43 are controlled by the control unit 86 with the blocking plate 6 positioned at the processing position, and the substrate W and the blocking plate held by the spin chuck 3 are controlled. 6 is rotated at a predetermined rotation speed (for example, 10 rpm to 500 rpm, preferably 500 rpm). Then, the opening degree of the gas flow rate adjusting valve 18 is adjusted by the control unit 86, and the discharge flow rate of nitrogen gas from the upper gas discharge port 40 is reduced as compared with the inert gas purge process. Specifically, the discharge flow rate of nitrogen gas from the upper gas discharge port 40 is changed to, for example, 10 L / min to 50 L / min, preferably 10 L / min to 20 L / min. At this time, nitrogen gas is continuously discharged from the lower gas discharge port 15 at the predetermined discharge flow rate.

  Next, in a state where the first chemical liquid valve 62 of the first in-pipe preparation unit 51 is closed, the first valve 60 is opened by the control unit 86 and the inert gas dissolved water is supplied to the first mixing unit 59. The Thereby, the inert gas dissolved water is supplied to the first and second upper process liquid supply pipes 35 and 38, and the inert gas dissolved water remaining in the first and second upper process liquid supply pipes 35 and 38 is supplied. Is discharged from the upper processing liquid discharge port 37. In this way, the pre-dispensing process for draining the processing liquid remaining in the first and second upper processing liquid supply pipes 35 and 38 is performed.

  Before the pre-dispensing process is performed, the inert gas dissolved water remaining in the first and second upper process liquid supply pipes 35 and 38 is, for example, from the upper process liquid discharge port 37 to the first and second upper process liquids. Oxygen in the air that has entered the processing liquid supply pipes 35 and 38 may be dissolved. Therefore, the oxygen concentration of the inert gas dissolved water remaining in the first and second upper treatment liquid supply pipes 35 and 38 is higher than that generated when the inert gas dissolved water generation unit 50 generates the oxygen concentration. There is a case. Therefore, if the pre-dispensing process is not performed, a chemical solution having a high oxygen concentration or an inert gas-dissolved water may be supplied to the substrate W. Therefore, by performing the pre-dispensing process, it is possible to suppress or prevent the chemical liquid having a high oxygen concentration or the inert gas-dissolved water from being supplied to the substrate W.

  In the pre-dispensing process, the oxygen concentration in the inert gas dissolved water discharged from the upper process liquid discharge port 37 is, for example, a value generated by the inert gas dissolved water generating unit 50, that is, 20 ppb or less in this processing example. Continue until Specifically, for example, an oxygen concentration sensor (not shown) is provided to detect the oxygen concentration of the inert gas dissolved water discharged from the upper processing liquid discharge port 37 or the inert gas dissolved from the upper processing liquid discharge port 37. The pre-dispensing process is continued until the oxygen concentration of the inert gas dissolved water discharged from the upper process liquid discharge port 37 becomes 20 ppb or less by controlling the discharge flow rate and discharge time of water.

To give specific numerical values for controlling the discharge flow rate and discharge time of the inert gas dissolved water from the upper process liquid discharge port 37, the discharge flow rate of the inert gas dissolved water from the upper process liquid discharge port 37 is: For example, 0.5 L / min to 3 L / min, preferably 2 L / min, and the discharge time is, for example, 5 sec to 300 sec, preferably 10 sec.
After the pre-dispensing process is performed for a predetermined time, a chemical process for removing the polymer residue from the surface of the substrate W is performed on the upper surface of the substrate W (step S14). Specifically, the first in-pipe preparation unit 51 is controlled by the control unit 86 in a state where the blocking plate 6 is located at the processing position, and dilute hydrofluoric acid as a chemical solution is discharged at a predetermined discharge flow rate (0.5 L / min). -3 L / min, preferably 2 L / min) and discharged from the upper processing liquid discharge port 37 for a predetermined time (for example, 5 sec to 90 sec, preferably 10 sec). That is, the controller 86 controls the opening and closing of the first chemical liquid valve 62 and the first valve 60, and the state where the first chemical liquid valve 62 and the first valve 60 are open is maintained for the predetermined time. Further, the opening degree of the first flow rate adjusting valve 61 and the first chemical liquid flow rate adjusting valve 63 is adjusted by the control unit 86 so that the discharge flow rate of the diluted hydrofluoric acid becomes the predetermined discharge flow rate. Dilute hydrofluoric acid is an example of a chemical solution and an example of a polymer removal solution. The diluted hydrofluoric acid is prepared, for example, so that the ratio of hydrofluoric acid to pure water is 1:10 to 1: 1800, preferably 1:10 to 1: 800.

  By opening the first chemical liquid valve 62 and the first valve 60, the first mixing section 59 is supplied with hydrofluoric acid as the chemical liquid stock solution and inert gas-dissolved water. As a result, hydrofluoric acid is injected into the inert gas-dissolved water flowing through the first mixing unit 59, and dilute hydrofluoric acid prepared at the above-described ratio is generated. The generated dilute hydrofluoric acid is supplied to the first and second upper processing liquid supply pipes 35 and 38 and is directed from the upper processing liquid discharge port 37 toward the center of the upper surface of the substrate W held by the spin chuck 3. Discharged. At this time, the substrate W and the blocking plate 6 are rotated at the predetermined rotation speed, and nitrogen gas is continuously discharged from the upper gas discharge port 40 and the lower gas discharge port 15 at the predetermined discharge flow rate. .

  The diluted hydrofluoric acid discharged from the upper processing liquid discharge port 37 is deposited on the center of the upper surface of the substrate W, receives a centrifugal force due to the rotation of the substrate W, and instantaneously moves from the center of the upper surface of the substrate W toward the peripheral portion. To spread. Accordingly, the diluted hydrofluoric acid discharged from the upper processing liquid discharge port 37 is supplied to the entire upper surface of the substrate W. When dilute hydrofluoric acid is supplied to the upper surface of the substrate W, the flow rate of dilute hydrofluoric acid from the upper processing liquid discharge port 37 is such that the space between the upper surface of the substrate W and the substrate facing surface 34 is liquid-tight. It is set not to be.

  By supplying dilute hydrofluoric acid to the entire upper surface of the substrate W, the polymer residue is removed from the entire upper surface of the substrate W. Thereby, a chemical treatment for removing the polymer residue from the surface of the substrate W is performed. As for the dilute hydrofluoric acid as the chemical liquid supplied from the upper processing liquid discharge port 37 to the upper surface of the substrate W, the hydrofluoric acid as the chemical liquid stock solution that has passed through the degassing unit 74 is generated by the inert gas dissolved water generation unit 50. Diluted with inert gas dissolved water. In other words, dilute hydrofluoric acid supplied to the upper surface of the substrate W from the upper processing liquid discharge port 37 is dehydrated by the degassing unit 74 and deoxygenated by the inert gas dissolved water generating unit 50. Diluted with purified water. Moreover, the inert gas dissolved water produced | generated by the inert gas dissolved water production | generation unit 50 is suppressed or prevented that oxygen concentration raises with progress of time by addition of nitrogen gas. Accordingly, dilute hydrofluoric acid with a sufficiently reduced oxygen concentration is discharged from the upper processing liquid discharge port 37.

  Further, when the chemical treatment is performed, a narrow space substantially sealed by the blocking plate 6 is formed above the substrate W. Further, the atmosphere in the space between the upper surface of the substrate W and the substrate facing surface 34 is replaced with the nitrogen gas atmosphere by the nitrogen gas discharged from the upper gas discharge port 40. Furthermore, since the entire peripheral end surface of the substrate W is surrounded by the peripheral wall portion 32 of the blocking plate 6, the surrounding air is caught between the upper surface peripheral portion of the substrate W and the peripheral portion of the substrate facing surface 34. An increase in oxygen concentration in the space between the upper surface of the substrate W and the substrate facing surface 34 is suppressed or prevented. Therefore, it is possible to suppress or prevent the oxygen in the atmosphere from being dissolved in the diluted hydrofluoric acid discharged from the upper processing liquid discharge port 37 and the oxygen concentration in the diluted hydrofluoric acid from increasing. In other words, the oxygen concentration of the diluted hydrofluoric acid discharged from the upper processing liquid discharge port 37 can be maintained in a reduced state. Accordingly, dilute hydrofluoric acid with a sufficiently reduced oxygen concentration can be supplied to the upper surface of the substrate W. Thereby, it is possible to suppress or prevent the occurrence of an oxidation reaction due to dissolved oxygen in dilute hydrofluoric acid on the substrate W. As a result, even if the chemical solution supplied to the substrate W has an etching action on the oxide, such as dilute hydrofluoric acid, it is possible to suppress or prevent undesired etching on the substrate W. it can.

  After the chemical processing is performed for a predetermined time, a rinsing process for washing the chemical from the upper surface of the substrate W is performed on the upper surface of the substrate W (step S15). Specifically, the first chemical liquid valve 62 of the first in-pipe preparation unit 51 is closed and the first valve 60 is opened by the controller 86 with the blocking plate 6 positioned at the processing position. . At this time, the substrate W and the blocking plate 6 are rotated at the predetermined rotation speed. Further, nitrogen gas is continuously discharged from the upper gas discharge port 40 and the lower gas discharge port 15 at the predetermined discharge flow rate.

  Only the inert gas-dissolved water is supplied to the first mixing unit 59 by closing the first chemical liquid valve 62 and opening the first valve 60. Accordingly, the inert gas dissolved water is supplied to the first and second upper process liquid supply pipes 35 and 38, and the inert gas dissolved water as the rinse liquid is discharged from the upper process liquid discharge port 37. The discharged inert gas dissolved water is deposited on the center of the upper surface of the substrate W, receives a centrifugal force due to the rotation of the substrate W, and spreads instantaneously from the center of the upper surface of the substrate W toward the peripheral portion. Thereby, the inert gas dissolved water is supplied to the entire upper surface of the substrate W, and the chemical solution is washed away from the upper surface of the substrate W by the inert gas dissolved water. In this way, the rinsing process is performed on the upper surface of the substrate W.

  As described above, the inert gas-dissolved water discharged from the upper processing liquid discharge port 37 is degassed by the inert gas-dissolved water generating unit 50, and the amount of dissolved oxygen is sufficiently reduced. Further, the inert gas-dissolved water produced by the inert gas-dissolved water production unit 50 is suppressed or prevented from increasing in oxygen concentration over time due to the addition of nitrogen gas. Furthermore, the oxygen concentration in the atmosphere in the space between the upper surface of the substrate W and the substrate facing surface 34 is sufficiently reduced. Therefore, the inert gas-dissolved water having a sufficiently reduced oxygen concentration can be supplied to the upper surface of the substrate W, and an oxidation reaction caused by the dissolved oxygen in the inert gas-dissolved water occurs on the substrate W. This can be suppressed or prevented. Accordingly, it is possible to suppress or prevent the oxide from being etched by the diluted hydrofluoric acid remaining on the substrate W and causing unwanted etching on the substrate W.

The rinsing process is continued until the residual amount of fluorine ions in the space between the upper surface of the substrate W and the substrate facing surface 34 becomes 0.15 ng / cm ² or less, for example. Specifically, for example, a fluorine ion detection sensor (not shown) is provided to detect the residual amount of fluorine ions in the space between the upper surface of the substrate W and the substrate facing surface 34, or from the upper processing liquid discharge port 37. By controlling the discharge flow rate and discharge time of the inert gas-dissolved water, the residual amount of fluorine ions in the space between the upper surface of the substrate W and the substrate facing surface 34 becomes 0.15 ng / cm ² or less. The rinse process is continued.

To give specific numerical values for controlling the discharge flow rate and discharge time of the inert gas dissolved water from the upper process liquid discharge port 37, the discharge flow rate of the inert gas dissolved water from the upper process liquid discharge port 37 is: For example, 0.5 L / min to 3 L / min, preferably 2 L / min, and the discharge time is, for example, 5 sec to 300 sec, preferably 20 sec.
After the rinsing process is performed on the upper surface of the substrate W, a drying process (spin drying) for drying the substrate W is performed (step S16). Specifically, the chuck rotation driving mechanism 10 is controlled by the controller 86 in a state where the blocking plate 6 is located at the processing position, and the substrate W held on the spin chuck 3 has a high rotation speed (for example, 2000 rpm or more). It is rotated by. Further, the opening degree of the gas flow rate adjusting valve 18 is adjusted by the control unit 86, and the discharge flow rate of nitrogen gas from the upper gas discharge port 40 is increased as compared with the rinse process. Specifically, the discharge flow rate of nitrogen gas from the upper gas discharge port 40 is changed to, for example, 150 L / min to 200 L / min. At this time, the blocking plate 6 is rotated almost in synchronization with the rotation of the substrate W by the spin chuck 3 (or at a slightly different rotational speed), and from the lower gas discharge port 15 at the predetermined discharge flow rate. Nitrogen gas continues to be discharged.

When the substrate W is rotated at a high rotational speed, the rinsing liquid adhering to the substrate W receives a centrifugal force due to the rotation of the substrate W and is shaken off around the substrate W. Thereby, the rinse liquid is drained from the substrate W, and the substrate W is dried. In this way, a drying process (spin drying) for drying the substrate W is performed.
After the high-speed rotation of the substrate W is continued for a predetermined time, the controller 86 controls the chuck rotation driving mechanism 10 and the blocking plate rotation driving mechanism 43, and the rotation of the substrate W and the blocking plate 6 is stopped. Then, the control plate 86 controls the shield plate lifting / lowering drive mechanism 42 to raise the shield plate 6 to the retracted position. Thereafter, the processed substrate W is received by a transfer robot (not shown), and the substrate W is unloaded from the processing chamber 2.

FIG. 8 is a process diagram for explaining a second processing example of the substrate W by the substrate processing apparatus 1.
The difference between the second processing example and the first processing example is that not only the upper surface of the substrate W but also the lower surface of the substrate W is processed by the processing liquid. More specifically, in the second processing example, when the chemical treatment is performed on the upper surface of the substrate W, the lower surface of the substrate W is rinsed, and the upper surface of the substrate W is rinsed. Sometimes, a rinsing process is performed on the lower surface of the substrate W. Below, with reference to FIG.1, FIG3 and FIG.8, the 2nd example of a process of the board | substrate W by the substrate processing apparatus 1 is demonstrated.

  The unprocessed substrate W is carried into the processing chamber 2 by a transfer robot (not shown), and is transferred to the spin chuck 3 with the surface, which is a device formation surface, facing up. Then, the control plate 86 controls the shield plate raising / lowering drive mechanism 42, and the shield plate 6 is lowered to the processing position (step S21). As a result, the substrate facing surface 34 approaches the upper surface (front surface) of the substrate W held by the spin chuck 3, and the entire upper surface of the substrate W is covered by the substrate facing surface 34. Further, the tip edge of the peripheral wall portion 32 is closer to the spin base 8 than the substrate W, and the entire peripheral end surface of the substrate W is surrounded by the inner wall surface 49. Therefore, a substantially sealed narrow space extending in the horizontal direction is formed above the substrate W (see FIG. 2).

  Next, an inert gas purge process is performed in which air is expelled from the space between the upper surface of the substrate W and the substrate facing surface 34 and the atmosphere in the space is replaced with an inert gas atmosphere (step S22). Specifically, the upper gas valve 41 is opened by the controller 86 with the blocking plate 6 positioned at the processing position, and nitrogen gas as an inert gas is spin-chucked from the upper gas discharge port 40 at a predetermined discharge flow rate. 3 is discharged toward the center of the upper surface of the substrate W held on the substrate 3. Further, the lower gas valve 17 is opened by the control unit 86, and nitrogen gas as an inert gas is directed upward from the lower gas discharge port 15 at a predetermined discharge flow rate (for example, 10 L / min to 50 L / min). Discharged. At this time, the substrate W and the blocking plate 6 held by the spin chuck 3 may be rotated or rotated by the controller 86 controlling the chuck rotation driving mechanism 10 and the blocking plate rotation driving mechanism 43. Instead, it may be in a non-rotating state. When the substrate W is in a rotating state, the blocking plate 6 may be rotated almost in synchronization with the rotation of the substrate W by the spin chuck 3 (or at a slightly different rotational speed), or only the substrate W is rotated. The blocking plate 6 may be in a non-rotating state.

  The nitrogen gas discharged from the upper gas discharge port 40 spreads outward (in the direction away from the rotation axis L1) in the space between the upper surface of the substrate W held by the spin chuck 3 and the substrate facing surface 34. Go. Therefore, the air existing in the space between the upper surface of the substrate W and the substrate facing surface 34 is pushed outward by the nitrogen gas, and is formed between the tip edge of the peripheral wall portion 32 and the upper surface 8 a of the spin base 8. It is discharged from the gap. As a result, the atmosphere near the surface of the substrate W is replaced with nitrogen gas as an inert gas, and air is expelled from the space between the upper surface of the substrate W and the substrate facing surface 34 by the inert gas, and the atmosphere of the space An inert gas purge process is performed to replace the gas with an inert gas atmosphere. The inert gas purge process is continued until the oxygen concentration in the space between the upper surface of the substrate W and the substrate facing surface 34 becomes, for example, 100 ppm or less.

  On the other hand, the nitrogen gas discharged from the lower gas discharge port 15 outwards in the space between the lower surface of the substrate W held by the spin chuck 3 and the upper surface 8a of the spin base 8 (in a direction away from the rotation axis L1). It spreads toward. Therefore, air and nitrogen gas existing in the space between the lower surface of the substrate W and the upper surface 8a of the spin base 8 are pushed outward by the subsequent nitrogen gas and discharged from the space.

  After the inert gas purge process is performed for a predetermined time, a pre-dispensing process is performed to drain the inert gas dissolved water remaining in the first and second upper process liquid supply pipes 35 and 38 (steps). S23). Specifically, the chuck rotation driving mechanism 10 and the blocking plate rotation driving mechanism 43 are controlled by the control unit 86 with the blocking plate 6 positioned at the processing position, and the substrate W and the blocking plate held by the spin chuck 3 are controlled. 6 is rotated at a predetermined rotation speed (for example, 10 rpm to 500 rpm, preferably 500 rpm). Then, the opening degree of the gas flow rate adjusting valve 18 is adjusted by the control unit 86, and the discharge flow rate of nitrogen gas from the upper gas discharge port 40 is reduced as compared with the inert gas purge process. Specifically, the discharge flow rate of nitrogen gas from the upper gas discharge port 40 is changed to, for example, 10 L / min to 50 L / min, preferably 10 L / min to 20 L / min. At this time, nitrogen gas is continuously discharged from the lower gas discharge port 15 at the predetermined discharge flow rate.

  Next, in a state where the first chemical liquid valve 62 of the first in-pipe preparation unit 51 is closed, the first valve 60 is opened by the control unit 86 and the inert gas dissolved water is supplied to the first mixing unit 59. The Thereby, the inert gas dissolved water is supplied to the first and second upper process liquid supply pipes 35 and 38, and the inert gas dissolved water remaining in the first and second upper process liquid supply pipes 35 and 38 is supplied. Is discharged from the upper processing liquid discharge port 37. In this way, the pre-dispensing process for draining the processing liquid remaining in the first and second upper processing liquid supply pipes 35 and 38 is performed. In the pre-dispensing process, the oxygen concentration in the inert gas dissolved water discharged from the upper process liquid discharge port 37 is, for example, a value generated by the inert gas dissolved water generating unit 50, that is, 20 ppb or less in this processing example. Continue until

After the pre-dispensing process is performed for a predetermined time, a chemical process for removing the polymer residue from the surface of the substrate W is performed on the upper surface of the substrate W, and at the same time, the lower surface (back surface) of the substrate W is rinsed. A rinsing process for washing with the liquid is performed on the lower surface of the substrate W (step S24).
Specifically, the first in-pipe preparation unit 51 is controlled by the control unit 86 in a state where the blocking plate 6 is located at the processing position, and dilute hydrofluoric acid as a chemical solution is discharged at a predetermined discharge flow rate (0.5 L / min). -3 L / min, preferably 2 L / min) and discharged from the upper processing liquid discharge port 37 for a predetermined time (for example, 5 sec to 90 sec, preferably 10 sec). As a result, dilute hydrofluoric acid is supplied to the entire upper surface of the substrate W, and a chemical treatment for removing the polymer residue is performed on the upper surface of the substrate W.

  On the other hand, while the chemical treatment is performed on the upper surface of the substrate W, the control unit 86 controls the second in-pipe preparation unit 52 so that the inert gas dissolved water as the rinsing liquid is supplied at a predetermined discharge flow rate for a predetermined time. It is discharged from the discharge port 12a of the lower surface nozzle 12. Specifically, the second valve 65 is opened by the control unit 86 in a state where the second chemical valve 67 of the second in-pipe preparation unit 52 is closed, and the inert gas dissolved water is supplied to the second mixing unit 64. Supplied. Thereby, the inert gas dissolved water is supplied to the lower surface nozzle 12 through the first and second lower processing liquid supply pipes 11 and 13, and the inert gas dissolved water is discharged from the discharge port 12 a of the lower surface nozzle 12. .

  The inert gas-dissolved water discharged from the discharge port 12a of the lower surface nozzle 12 is deposited on the central portion of the lower surface of the substrate W, receives centrifugal force due to the rotation of the substrate W, and from the central portion along the lower surface of the substrate W. It spreads toward the periphery. As a result, the inert gas-dissolved water is supplied to the entire lower surface of the substrate W, and the rinsing process for rinsing the lower surface of the substrate W with the rinse liquid is performed on the lower surface of the substrate W. When the chemical treatment on the upper surface of the substrate W and the rinse treatment on the lower surface of the substrate W are performed, the substrate W and the blocking plate 6 are rotated at the predetermined rotational speed, and the upper gas discharge port 40 and the lower gas are rotated. Nitrogen gas continues to be discharged from the discharge port 15 at the predetermined discharge flow rate.

  In the second processing example, when the chemical treatment is performed on the upper surface of the substrate W, the inert gas-dissolved water is discharged from the lower surface nozzle 12 to perform the rinsing processing on the lower surface of the substrate W. As described above, the dilute hydrofluoric acid is discharged from the lower surface nozzle 12 in place of the inert gas-dissolved water, and simultaneously with the chemical solution treatment on the upper surface of the substrate W, the chemical solution treatment with the diluted hydrofluoric acid is performed on the lower surface of the substrate W. May be performed.

After the chemical treatment on the upper surface of the substrate W and the rinsing treatment on the lower surface of the substrate W are performed for a predetermined time, a rinsing treatment for washing the chemical solution from the upper surface of the substrate W is performed on the upper surface of the substrate W. A rinsing process for rinsing the lower surface of the substrate W with the rinse liquid is performed on the lower surface of the substrate W (step S25).
Specifically, the first chemical liquid valve 62 of the first in-pipe preparation unit 51 is closed and the first valve 60 is opened by the controller 86 with the blocking plate 6 positioned at the processing position. . At this time, the substrate W and the blocking plate 6 are rotated at the predetermined rotation speed. Further, nitrogen gas is continuously discharged from the upper gas discharge port 40 and the lower gas discharge port 15 at the predetermined discharge flow rate.

  Only the inert gas-dissolved water is supplied to the first mixing unit 59 by closing the first chemical liquid valve 62 and opening the first valve 60. Accordingly, the inert gas dissolved water is supplied to the first and second upper process liquid supply pipes 35 and 38, and the inert gas dissolved water as the rinse liquid is discharged from the upper process liquid discharge port 37. The discharged inert gas dissolved water is deposited on the center of the upper surface of the substrate W, receives a centrifugal force due to the rotation of the substrate W, and spreads instantaneously from the center of the upper surface of the substrate W toward the peripheral portion. Thereby, the inert gas dissolved water is supplied to the entire upper surface of the substrate W, and the chemical solution is washed away from the upper surface of the substrate W by the inert gas dissolved water. In this way, the rinsing process is performed on the upper surface of the substrate W.

On the other hand, while the rinsing process is performed on the upper surface of the substrate W, the second chemical liquid valve 67 of the second in-pipe preparation unit 52 is closed by the control unit 86 and the second valve 65 is opened. Thereby, only the inert gas dissolved water is supplied to the second mixing unit 64, and the inert gas is supplied from the second mixing unit 64 to the lower surface nozzle 12 via the first and second lower processing liquid supply pipes 11 and 13. Dissolved water is supplied. Accordingly, the inert gas dissolved water is discharged from the discharge port 12 a of the lower surface nozzle 12, and the discharged inert gas dissolved water is deposited on the center of the lower surface of the substrate W and receives a centrifugal force due to the rotation of the substrate W. Thus, the substrate W instantaneously spreads from the lower surface center portion toward the peripheral edge portion. Thereby, the inert gas dissolved water is supplied to the entire lower surface of the substrate W, and the lower surface of the substrate W is washed away by the inert gas dissolved water. In this way, the rinsing process is performed on the lower surface of the substrate W. The rinsing process for the upper surface and the lower surface of the substrate W is continued until the residual amount of fluorine ions in the space between the upper surface of the substrate W and the substrate facing surface 34 becomes 0.15 ng / cm ² or less, for example.

  After the rinsing process is performed on the upper and lower surfaces of the substrate W, a drying process (spin drying) for drying the substrate W is performed (step S26). Specifically, first, the drain valve 69 of the second in-pipe preparation unit 52 is opened by the control unit 86, and the inert gas dissolved water is drained from the second mixing unit 64. As a result, the inert gas dissolved water remaining in the lower surface nozzle 12 is drained from the lower surface nozzle 12, and the inert gas dissolved water is removed from the lower surface nozzle 12.

  Next, in a state where the blocking plate 6 is located at the processing position, the chuck rotation driving mechanism 10 is controlled by the controller 86, and the substrate W held on the spin chuck 3 is rotated at a high rotation speed (for example, 2000 rpm or more). Is done. Further, the opening degree of the gas flow rate adjusting valve 18 is adjusted by the control unit 86, and the discharge flow rate of nitrogen gas from the upper gas discharge port 40 is increased as compared with the rinse process. Specifically, the discharge flow rate of nitrogen gas from the upper gas discharge port 40 is changed to, for example, 150 L / min to 200 L / min. At this time, the blocking plate 6 is rotated almost in synchronization with the rotation of the substrate W by the spin chuck 3 (or at a slightly different rotational speed), and from the lower gas discharge port 15 at the predetermined discharge flow rate. Nitrogen gas continues to be discharged.

  When the substrate W is rotated at a high rotational speed, the rinsing liquid adhering to the substrate W receives a centrifugal force due to the rotation of the substrate W and is shaken off around the substrate W. Thereby, the rinse liquid is drained from the substrate W, and the substrate W is dried. At this time, since the inert gas dissolved water is drained from the lower surface nozzle 12 in advance, the inert gas dissolved water remaining in the lower surface nozzle 12 does not jump out and adhere to the lower surface of the substrate W. . Thereby, it can suppress or prevent that the inert gas dissolved water which jumped out from the lower surface nozzle 12 adheres to the lower surface of the board | substrate W, and the dry defect of the said board | substrate W arises.

  After the high-speed rotation of the substrate W is continued for a predetermined time, the controller 86 controls the chuck rotation driving mechanism 10 and the blocking plate rotation driving mechanism 43, and the rotation of the substrate W and the blocking plate 6 is stopped. Then, the control plate 86 controls the shield plate lifting / lowering drive mechanism 42 to raise the shield plate 6 to the retracted position. Thereafter, the processed substrate W is received by a transfer robot (not shown), and the substrate W is unloaded from the processing chamber 2.

FIG. 9 is a process diagram for explaining a third processing example of the substrate W by the substrate processing apparatus 1.
The main difference between the third processing example and the first processing example described above is that physical cleaning for cleaning the upper surface of the substrate W by causing a droplet of the processing liquid to collide with the upper surface of the substrate W is performed on the upper surface of the substrate W. There is to do with it. Below, with reference to FIG.1, FIG3 and FIG.9, the 3rd example of a process of the board | substrate W by the substrate processing apparatus 1 is demonstrated.

  The unprocessed substrate W is carried into the processing chamber 2 by a transfer robot (not shown), and is transferred to the spin chuck 3 with the surface, which is a device formation surface, facing up. Then, the controller 86 controls the shield plate lifting drive mechanism 42, and the shield plate 6 is lowered to the processing position (step S31). As a result, the substrate facing surface 34 approaches the upper surface (front surface) of the substrate W held by the spin chuck 3, and the entire upper surface of the substrate W is covered by the substrate facing surface 34. Further, the tip edge of the peripheral wall portion 32 is closer to the spin base 8 than the substrate W, and the entire peripheral end surface of the substrate W is surrounded by the inner wall surface 49. Therefore, a substantially sealed narrow space extending in the horizontal direction is formed above the substrate W (see FIG. 2).

  Next, an inert gas purge process is performed in which air is expelled from the space between the upper surface of the substrate W and the substrate facing surface 34 and the atmosphere in the space is replaced with an inert gas atmosphere (step S32). Specifically, the upper gas valve 41 is opened by the controller 86 with the blocking plate 6 positioned at the processing position, and nitrogen gas as an inert gas is spin-chucked from the upper gas discharge port 40 at a predetermined discharge flow rate. 3 is discharged toward the center of the upper surface of the substrate W held on the substrate 3. Further, the lower gas valve 17 is opened by the control unit 86, and nitrogen gas as an inert gas is directed upward from the lower gas discharge port 15 at a predetermined discharge flow rate (for example, 10 L / min to 50 L / min). Discharged. At this time, the substrate W and the blocking plate 6 held by the spin chuck 3 may be rotated or rotated by the controller 86 controlling the chuck rotation driving mechanism 10 and the blocking plate rotation driving mechanism 43. Instead, it may be in a non-rotating state. When the substrate W is in a rotating state, the blocking plate 6 may be rotated almost in synchronization with the rotation of the substrate W by the spin chuck 3 (or at a slightly different rotational speed), or only the substrate W is rotated. The blocking plate 6 may be in a non-rotating state.

  The nitrogen gas discharged from the upper gas discharge port 40 spreads outward (in the direction away from the rotation axis L1) in the space between the upper surface of the substrate W held by the spin chuck 3 and the substrate facing surface 34. Go. Therefore, the air existing in the space between the upper surface of the substrate W and the substrate facing surface 34 is pushed outward by the nitrogen gas, and is formed between the tip edge of the peripheral wall portion 32 and the upper surface 8 a of the spin base 8. It is discharged from the gap. As a result, the atmosphere near the surface of the substrate W is replaced with nitrogen gas as an inert gas, and air is expelled from the space between the upper surface of the substrate W and the substrate facing surface 34 by the inert gas, and the atmosphere of the space An inert gas purge process is performed to replace the gas with an inert gas atmosphere. The inert gas purge process is continued until the oxygen concentration in the space between the upper surface of the substrate W and the substrate facing surface 34 becomes, for example, 100 ppm or less.

  On the other hand, the nitrogen gas discharged from the lower gas discharge port 15 outwards in the space between the lower surface of the substrate W held by the spin chuck 3 and the upper surface 8a of the spin base 8 (in a direction away from the rotation axis L1). It spreads toward. Therefore, air and nitrogen gas existing in the space between the lower surface of the substrate W and the upper surface 8a of the spin base 8 are pushed outward by the subsequent nitrogen gas and discharged from the space.

  After the inert gas purge process is performed for a predetermined time, a pre-dispensing process is performed to drain the inert gas dissolved water remaining in the first and second upper process liquid supply pipes 35 and 38 (steps). S33). Specifically, the chuck rotation driving mechanism 10 and the blocking plate rotation driving mechanism 43 are controlled by the control unit 86 with the blocking plate 6 positioned at the processing position, and the substrate W and the blocking plate held by the spin chuck 3 are controlled. 6 is rotated at a predetermined rotation speed (for example, 10 rpm to 500 rpm, preferably 500 rpm). Then, the opening degree of the gas flow rate adjustment valve 18 is adjusted by the control unit 86, and the discharge flow rate of nitrogen gas from the upper gas discharge port 40 is reduced as compared with the inert gas purge process. Specifically, the discharge flow rate of nitrogen gas from the upper gas discharge port 40 is changed to, for example, 10 L / min to 50 L / min, preferably 10 L / min to 20 L / min. At this time, nitrogen gas is continuously discharged from the lower gas discharge port 15 at the predetermined discharge flow rate.

  Next, in a state where the first chemical liquid valve 62 of the first in-pipe preparation unit 51 is closed, the first valve 60 is opened by the control unit 86 and the inert gas dissolved water is supplied to the first mixing unit 59. The Thereby, the inert gas dissolved water is supplied to the first and second upper process liquid supply pipes 35 and 38, and the inert gas dissolved water remaining in the first and second upper process liquid supply pipes 35 and 38 is supplied. Is discharged from the upper processing liquid discharge port 37. In this way, the pre-dispensing process for draining the processing liquid remaining in the first and second upper processing liquid supply pipes 35 and 38 is performed. In the pre-dispensing process, the oxygen concentration in the inert gas dissolved water discharged from the upper process liquid discharge port 37 is, for example, a value generated by the inert gas dissolved water generating unit 50, that is, 20 ppb or less in this processing example. Continue until

  After the pre-dispensing process is performed for a predetermined time, a chemical process for removing the polymer residue from the surface of the substrate W is performed on the upper surface of the substrate W (step S34). Specifically, the first in-pipe preparation unit 51 is controlled by the control unit 86 in a state where the blocking plate 6 is located at the processing position, and dilute hydrofluoric acid as a chemical solution is discharged at a predetermined discharge flow rate (0.5 L / min). -3 L / min, preferably 2 L / min) and discharged from the upper processing liquid discharge port 37 for a predetermined time (for example, 5 sec to 90 sec, preferably 10 sec). Thereby, dilute hydrofluoric acid is supplied to the entire upper surface of the substrate W, and the polymer residue is removed from the entire upper surface of the substrate W. In this way, a chemical treatment for removing the polymer residue from the surface of the substrate W is performed.

  After the chemical treatment is performed for a predetermined time, a rinsing process for washing away the chemical from the upper surface of the substrate W is performed on the upper surface of the substrate W (step S35). Specifically, the first chemical liquid valve 62 of the first in-pipe preparation unit 51 is closed and the first valve 60 is opened by the controller 86 with the blocking plate 6 positioned at the processing position. . At this time, the substrate W and the blocking plate 6 are rotated at the predetermined rotation speed. Further, nitrogen gas is continuously discharged from the upper gas discharge port 40 and the lower gas discharge port 15 at the predetermined discharge flow rate.

Only the inert gas-dissolved water is supplied to the first mixing unit 59 by closing the first chemical liquid valve 62 and opening the first valve 60. Accordingly, the inert gas dissolved water is supplied to the first and second upper process liquid supply pipes 35 and 38, and the inert gas dissolved water as the rinse liquid is discharged from the upper process liquid discharge port 37. The discharged inert gas dissolved water is deposited on the center of the upper surface of the substrate W, receives a centrifugal force due to the rotation of the substrate W, and spreads instantaneously from the center of the upper surface of the substrate W toward the peripheral portion. Thereby, the inert gas dissolved water is supplied to the entire upper surface of the substrate W, and the chemical solution is washed away from the upper surface of the substrate W by the inert gas dissolved water. In this way, the rinsing process is performed on the upper surface of the substrate W. The rinsing process is continued until the residual amount of fluorine ions in the space between the upper surface of the substrate W and the substrate facing surface 34 becomes 0.15 ng / cm ² or less, for example.

  After the rinsing process is performed on the upper surface of the substrate W, physical cleaning is performed on the upper surface of the substrate W by causing a droplet of the processing liquid to collide with the upper surface of the substrate W to clean the upper surface of the substrate W (step). S36). Specifically, the control plate 86 controls the shield plate lifting / lowering drive mechanism 42 to raise the shield plate 6 to the retracted position. The control unit 86 controls the nozzle swing drive mechanisms 25 and 30 so that the two-fluid nozzle 4 and the treatment liquid nozzle 5 are disposed above the spin chuck 3. At this time, the substrate W is rotated at the predetermined rotation speed, and nitrogen gas is continuously discharged from the lower gas discharge port 15 at the predetermined discharge flow rate.

  Next, the processing liquid valve 28 a is opened by the controller 86, and carbonated water as a rinsing liquid is discharged from the processing liquid nozzle 5 toward the upper surface of the substrate W. The discharged carbonated water is deposited on the center of the upper surface of the substrate W, receives a centrifugal force due to the rotation of the substrate W, and spreads instantaneously from the center of the upper surface of the substrate W toward the peripheral edge. Thereby, carbonated water is supplied to the entire upper surface of the substrate W, and the entire upper surface of the substrate W is covered with the carbonated water. By supplying carbonated water to the upper surface of the substrate W, charging of the substrate W can be suppressed or prevented. Thereby, damage to the device formed on the substrate W can be suppressed or prevented.

Next, in a state where carbonated water is discharged from the treatment liquid nozzle 5, the treatment liquid valve 22 and the gas valve 23 are opened by the control unit 86, and carbonated water and nitrogen gas are supplied into the two-fluid nozzle 4. Thereby, carbonated water and nitrogen gas are discharged from the two-fluid nozzle 4. The discharged carbonated water is mixed with nitrogen gas to form carbonated water droplets that collide with the upper surface of the substrate W.
Foreign matter such as particles adhering to the upper surface of the substrate W is peeled off from the upper surface of the substrate W by the kinetic energy of the droplets. Then, the peeled foreign matter is washed away by the carbonated water supplied from the treatment liquid nozzle 5 and removed from the upper surface of the substrate W.

The carbonated water discharged from the treatment liquid nozzle 5 washes out foreign substances from the substrate W, and prevents the carbonated water droplets, etc., that bounced off the upper surface of the substrate W from adhering to the upper surface of the substrate W. Functions as a rinse solution.
While carbonated water and nitrogen gas are being discharged from the two-fluid nozzle 4, the two-fluid nozzle 4 is horizontally moved above the substrate W under the control of the nozzle swing drive mechanism 25 by the controller 86. Specifically, the collision position of the carbonated water droplet on the upper surface of the substrate W is reciprocated a plurality of times from the peripheral portion to the peripheral portion while drawing an arc-shaped trajectory passing through the rotation center in the upper surface. The two-fluid nozzle 4 is moved horizontally. Thereby, the upper surface of the substrate W is scanned by the carbonated water droplets, and the carbonated water droplets directly collide with the entire upper surface of the substrate W. As a result, foreign matters are reliably removed from the entire upper surface of the substrate W.

  After the physical process is performed on the upper surface of the substrate W, a rinsing process for washing the upper surface of the substrate W with a rinsing liquid is performed on the upper surface of the substrate W (step S37). Specifically, the processing liquid valve 28 b is opened by the control unit 86, and pure water as a rinsing liquid is discharged from the processing liquid nozzle 5 toward the upper surface of the substrate W. The discharged pure water is deposited on the center of the upper surface of the substrate W, receives a centrifugal force due to the rotation of the substrate W, and spreads instantaneously from the center of the upper surface of the substrate W toward the peripheral edge. Thereby, pure water is supplied to the entire upper surface of the substrate W, and the upper surface of the substrate W is washed away by the pure water. In this way, the rinsing process is performed on the upper surface of the substrate W.

  After the rinsing process is performed on the upper surface of the substrate W, a drying process (spin drying) for drying the substrate W is performed (step S38). Specifically, the chuck rotation drive mechanism 10 is controlled by the controller 86, and the substrate W held on the spin chuck 3 is rotated at a high rotation speed (for example, 2000 rpm or more). At this time, nitrogen gas is continuously discharged from the lower gas discharge port 15 at the predetermined discharge flow rate.

When the substrate W is rotated at a high rotation speed, the carbonated water adhering to the substrate W receives a centrifugal force due to the rotation of the substrate W and is shaken off around the substrate W. Thereby, carbonated water is drained from the substrate W, and the substrate W is dried. In this way, a drying process (spin drying) for drying the substrate W is performed.
After high-speed rotation of the substrate W is continued for a predetermined time, the chuck rotation driving mechanism 10 is controlled by the control unit 86, and the rotation of the substrate W is stopped. Thereafter, the processed substrate W is received by a transfer robot (not shown), and the substrate W is unloaded from the processing chamber 2.

  Although the three processing examples of the substrate W by the substrate processing apparatus 1 have been described above, the processing of the substrate W by the substrate processing apparatus 1 is not limited to the three processing examples described above. For example, in the above-described first to third processing examples, before the chemical liquid processing is performed, the pre-drain for discharging the inert gas dissolved water remaining in the first and second upper processing liquid supply pipes 35 and 38 is discharged. Although the case where the dispensing process is performed has been described, the chemical process may be performed following the inert gas purge process without performing the pre-dispensing process.

  That is, when the processing liquid is discharged from the upper processing liquid discharge port 37 without leaving a long interval (for example, at an interval of less than 2 minutes), for example, when processing a plurality of substrates W continuously. In some cases, the oxygen concentration of the inert gas dissolved water remaining in the first and second upper processing liquid supply pipes 35 and 38 hardly increases. Therefore, in such a case, the pre-dispensing process is not performed in the processing of all the substrates W, but a predetermined time or more has elapsed since the previous substrate W was processed, such as the first substrate W of the lot. Alternatively, the pre-dispensing process may be performed only in the processing of the substrate W to be processed.

  Further, in the first to third processing examples described above, continuous discharge processing (chemical solution processing and rinsing processing) is performed in which processing liquid is continuously supplied to the substrate W held on the spin chuck 3 to advance the processing. However, the present invention is not limited to this, but is not limited to this. Paddle processing (liquid deposition processing) is performed by performing liquid deposition on the upper surface of the substrate W with the processing liquid and holding the liquid film of the processing liquid on the upper surface of the substrate W. ) May be performed. For example, in the first and second processing examples described above, between the rinsing process and the drying process (spin drying) (in the second processing example, between the rinsing process and the drying process for the upper surface and the lower surface of the substrate W). Alternatively, paddle treatment with a rinsing liquid may be performed.

  Specifically, while the substrate W held on the spin chuck 3 is in a stopped state or a low-speed rotation state (for example, a state where the substrate W is rotated at a rotation speed of about 10 to 300 rpm), a rinse liquid is formed on the upper surface of the substrate W. Supply. The rinse liquid supplied to the upper surface of the substrate W may be an inert gas dissolved water discharged from the upper processing liquid discharge port 37 or pure water discharged from the processing liquid nozzle 5.

Since the rinse liquid supplied to the upper surface of the substrate W is in a stopped state or in a low-speed rotation state, there is almost no rinse liquid scattered around the substrate W due to the centrifugal force caused by the rotation of the substrate W. It accumulates on W. As a result, the rinsing liquid is deposited on the upper surface of the substrate W, and a liquid film of the rinsing liquid covering the entire upper surface of the substrate W is formed.
After the rinsing liquid film is formed, the supply of the rinsing liquid to the upper surface of the substrate W is stopped, and the state in which the rinsing liquid film is held on the upper surface of the substrate W is maintained for a predetermined time. As a result, paddle processing (liquid deposition processing) using the rinse liquid is performed on the upper surface of the substrate W. By performing the paddle process on the upper surface of the substrate W, even if the upper surface of the substrate W is hydrophobic, the upper surface can be reliably wetted with the rinse liquid. Then, the rinsing liquid is drained from the upper surface of the substrate W by spin drying, so that the chemical liquid and the foreign matter adhering to the upper surface of the substrate W can be removed from the upper surface of the substrate W together with the rinsing liquid.

  In the description of the paddle processing described above, the case where the rinsing liquid is the inert gas dissolved water discharged from the upper processing liquid discharge port 37 or the pure water discharged from the processing liquid nozzle 5 has been described. The treatment liquid used is not limited to this. For example, a low surface tension organic solvent having a lower surface tension than pure water such as IPA (isopropyl alcohol) and higher volatility than pure water may be used as the rinsing liquid.

Specifically, an IPA supply mechanism for supplying IPA may be newly provided, and IPA may be supplied from the IPA supply mechanism to the upper processing liquid discharge port 37 or the processing liquid nozzle 5. Thereby, paddle processing by IPA can be performed on the upper surface of the substrate W. In addition, the rinsing process using IPA can be performed on the upper surface of the substrate W.
As a specific processing example, in the first and second processing examples described above, paddle processing with inert gas-dissolved water or pure water is not performed on the upper surface of the substrate W between the rinsing processing and the drying processing. In addition, the paddle treatment by IPA may be performed on the upper surface of the substrate W, or after the paddle treatment by inert gas dissolved water or pure water is performed on the upper surface of the substrate W, the rinse treatment by IPA is performed. Then, the paddle processing by IPA may be performed on the upper surface of the substrate W.

  By performing the paddle treatment by IPA on the upper surface of the substrate W, even if the upper surface of the substrate W is hydrophobic, the upper surface of the substrate W is surely wetted, similarly to the paddle treatment by the inert gas-dissolved water or pure water. be able to. In addition, since IPA is a processing liquid having higher volatility than pure water, the substrate W is dried immediately after the treatment with IPA, so that the substrate is compared with that immediately after the treatment with the inert gas-dissolved water or pure water. W can be dried quickly.

  In the first to third processing examples described above, when the rinsing process and the drying process are performed (in the third processing example, when the first rinsing process is performed), the blocking plate 6 is positioned at the processing position. However, the rinsing process and the drying process may be performed in a state where the blocking plate 6 is located at the retracted position. Further, when the above-described paddle processing is performed on the upper surface of the substrate W, the blocking plate 6 may be disposed at the processing position or may be disposed at the retracted position.

As a specific example of performing the rinsing process and the drying process on the upper surface of the substrate W with the blocking plate 6 positioned at the retracted position, for example, in the rinsing process of the first processing example described above, After the residual amount of fluorine ions in the space between the upper surface and the substrate facing surface 34 becomes 0.012 ng / cm ² or less, the blocking plate 6 is raised to the retracted position. Then, the processing liquid nozzle 5 is disposed above the substrate W held by the spin chuck 3, and pure water is discharged from the processing liquid nozzle 5 toward the upper surface of the substrate W, so that the rinsing process using pure water is performed on the substrate W. To the top surface of That is, the rinse treatment with the inert gas-dissolved water and the rinse treatment with pure water are performed continuously. Thereafter, the substrate W is rotated at a high speed by the spin chuck 3 with the blocking plate 6 positioned at the retracted position, and the substrate W is dried (spin dry). By rinsing and drying the upper surface of the substrate W with the blocking plate 6 positioned at the retracted position, for example, the transfer of fluorine ions attached to the blocking plate 6 to the substrate W is suppressed. Or it can be prevented.

Hereinafter, measurement results and the like obtained by processing the substrate W by the substrate processing apparatus 1 will be described.
FIG. 10 is a diagram showing the relationship between the oxygen concentration in the inert gas-dissolved water and the etching amount of copper.
FIG. 10 shows the measurement results of the etching amount (film reduction) of copper when a chemical solution treatment (polymer removal treatment) with dilute hydrofluoric acid is performed on the surface of the substrate W. The dilute hydrofluoric acid used was prepared with a ratio of hydrofluoric acid to pure water of 1: 100. As hydrofluoric acid contained in dilute hydrofluoric acid, oxygen that was not degassed was used. Since the dilute hydrofluoric acid used in this measurement has a very small proportion of hydrofluoric acid with respect to the pure water, the oxygen concentration in dilute hydrofluoric acid is the inertness used to prepare the dilute hydrofluoric acid It can be regarded as almost equal to the oxygen concentration in the gas dissolved water. The chemical treatment time is 60 seconds.

  In FIG. 10, the leftmost measured value (the leftmost ● value) is prepared by diluting hydrofluoric acid with an inert gas-dissolved water having an oxygen concentration of 12 ppb, and using this dilute hydrofluoric acid for chemical treatment. This is the amount of copper etching performed. The second measured value from the left (second value from the left) is prepared by dilute hydrofluoric acid with an inert gas-dissolved water having an oxygen concentration of 20 ppb, and chemical treatment is performed using this dilute hydrofluoric acid. This is the amount of copper etching. From the measurement results shown in FIG. 10, it is understood that the etching of copper can be reliably suppressed or prevented by performing chemical treatment using dilute hydrofluoric acid prepared with an inert gas-dissolved water having an oxygen concentration of 20 ppb or less. That is, it is understood that dilute hydrofluoric acid prepared with an inert gas-dissolved water having an oxygen concentration of 20 ppb or less can reliably suppress or prevent the formation of copper oxide.

FIG. 11 is a diagram showing the relationship between the oxygen concentration above the substrate W and the oxygen concentration in the pure water supplied to the upper surface of the substrate W.
In FIG. 11, inactive gas-dissolved water is discharged from the upper processing liquid discharge port 37 toward the upper surface of the substrate W held by the spin chuck 3 with the blocking plate 6 positioned at the processing position. It is the result of having measured the oxygen concentration of the inert gas dissolved water supplied to the upper surface of this. Inert gas dissolved water with an oxygen concentration adjusted to 10 ppb was discharged from the upper processing liquid discharge port 37.

  In FIG. 11, the measured value on the left side (value of the leftmost ■) is the inertness supplied to the upper surface of the substrate W when the oxygen concentration above the substrate W is 0.001% (10 ppm). It is the value of the oxygen concentration of the gas-dissolved water, and the oxygen concentration in the inert gas-dissolved water at this time was 12 ppb. The second measured value from the left (second value from the left) is the inert gas supplied to the upper surface of the substrate W when the oxygen concentration above the substrate W is 0.01% (100 ppm). This is the value of the dissolved water oxygen concentration, and the oxygen concentration in the inert gas dissolved water at this time was 20 ppb.

  From the measurement result shown in FIG. 11, when pure water whose oxygen concentration is adjusted to 10 ppb is discharged toward the upper surface of the substrate W, if the oxygen concentration above the substrate W is 100 ppm or less, the upper surface of the substrate W is It can be seen that the oxygen concentration of pure water supplied to the water can be maintained at 20 ppb or less. Therefore, in consideration of the measurement results shown in FIG. 10, if the oxygen concentration above the substrate W is 100 ppm or less and dilute hydrofluoric acid having an oxygen concentration of 10 ppb or less is discharged toward the upper surface of the substrate W, the oxygen concentration is 20 ppb. The following dilute hydrofluoric acid can be supplied to the upper surface of the substrate W to reliably suppress or prevent copper from being oxidized by dissolved oxygen in the dilute hydrofluoric acid.

FIG. 12 is a diagram showing the relationship between the oxygen concentration in pure water and the nitrogen concentration in pure water.
In FIG. 12, the value indicated by the alternate long and short dash line is a measured value of the oxygen concentration immediately after degassing oxygen from pure water, and the value indicated by the solid line indicates that oxygen has reached the value indicated by the alternate long and short dash line. This is a measured value of oxygen concentration after degassed pure water is opened to the atmosphere for 10 seconds or more. Moreover, the nitrogen concentration in the pure water when no nitrogen gas was added to the pure water was 3 ppm.

  From the measurement results shown in FIG. 12, when the nitrogen concentration in the pure water is less than 7 ppm, the oxygen concentration in the pure water increases with time. Therefore, it is possible to suppress or prevent the oxygen concentration in the pure water from increasing over time by adding nitrogen gas to the pure water so that the nitrogen concentration in the pure water is 7 ppm or more. Thereby, the oxygen concentration in the pure water from which oxygen has been deaerated can be maintained in a low state.

  Although the description of the embodiment of the present invention has been described above, the present invention is not limited to the contents of the above-described embodiment, and various modifications can be made within the scope of the claims. For example, in the above-described embodiment, the case where the peripheral wall portion 32 of the blocking plate 6 is inclined so as to expand downward is not limited to this, and the peripheral wall portion 32 of the blocking plate 6 is, for example, You may comprise the cylindrical shape extended straight from the outer periphery of the flat plate part 33, without inclining. In this case, the inner wall surface 49 of the peripheral wall portion 32 may be a surface parallel to the normal line L2 of the upper surface of the substrate W, such as the inner wall surface 149 of the peripheral wall portion 132 shown in FIG. A surface inclined with respect to the normal line L2 of the upper surface of the substrate W may be used like an inner wall surface 249 of the peripheral wall portion 232 shown.

Further, the peripheral wall portion 32 of the blocking plate 6 is formed in a cylindrical shape that is inclined so as to expand downward, for example, like a peripheral wall portion 332 shown in FIG. May be.
Furthermore, in the above-described embodiment, only the vicinity of the upper end of the inner wall surface 49 has been described as a surface in which the inclination angle with respect to the normal line L2 of the upper surface of the substrate W gradually changes toward the tip edge. The entire inner wall surface of the portion is formed on a surface in which the inclination angle with respect to the normal line L2 of the upper surface of the substrate W gradually changes toward the tip edge (a surface in which a cross section taken along a plane including the normal line L2 becomes a curve). May be.

  In the above-described embodiment, a case where the degassing unit 74 is provided for degassing oxygen from the chemical solution stock supplied from the chemical solution supply unit 53 to the first and second in-pipe preparation units 51 and 52. As explained above, for example, when the proportion of the chemical solution in the chemical solution is very small relative to the proportion of pure water, the oxygen concentration in the chemical solution hardly increases even if oxygen is not degassed from the chemical solution stock solution. In such a case, the deaeration unit 74 may not be provided.

In the above-described embodiment, the semiconductor wafer is taken up as the substrate W to be processed. However, the substrate is not limited to the semiconductor wafer, but is used for a liquid crystal display device substrate, a plasma display substrate, an FED substrate, an optical disk substrate, and a magnetic disk substrate. Other types of substrates such as a substrate, a magneto-optical disk substrate, and a photomask substrate may be processed.
In addition, various design changes can be made within the scope of matters described in the claims.

It is an illustration figure for demonstrating the structure of the substrate processing apparatus which concerns on one Embodiment of this invention. FIG. 3 is a schematic side view of a spin chuck and a blocking plate and configurations related to them. It is a schematic diagram of the structure for supplying a process liquid with respect to a process module. It is an illustration figure of piping provided in the substrate processing apparatus. It is a block diagram for demonstrating the electrical structure of a substrate processing apparatus. It is sectional drawing for demonstrating an example of the surface state of the board | substrate processed with a substrate processing apparatus. It is process drawing for demonstrating the 1st process example of the board | substrate by a substrate processing apparatus. It is process drawing for demonstrating the 2nd example of a process of the board | substrate by a substrate processing apparatus. It is process drawing for demonstrating the 3rd example of a process of the board | substrate by a substrate processing apparatus. It is a figure which shows the relationship between the oxygen concentration in inert gas dissolved water, and the etching amount of copper. It is a figure which shows the relationship between the oxygen concentration above a board | substrate, and the oxygen concentration in the pure water supplied to the upper surface of the board | substrate. It is a figure which shows the relationship between the oxygen concentration in a pure water, and the nitrogen concentration in a pure water. It is an illustrative side view for demonstrating the shape of the surrounding wall part which concerns on other embodiment of this invention. It is an illustrative side view for demonstrating the shape of the surrounding wall part which concerns on further another embodiment of this invention. It is an illustrative side view for demonstrating the shape of the surrounding wall part which concerns on further another embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate processing apparatus 3 Spin chuck 6 Blocking plate 8a (Spin base) upper surface 8 Spin base 32 Peripheral wall 34 Substrate facing surface 35 First upper processing liquid supply pipe 36 Gas flow path 37 Upper processing liquid discharge port 38 Second upper processing Liquid supply pipe 39 Upper gas supply pipe 40 Upper gas discharge port 41 Upper gas valve 42 Shutter plate lifting / lowering drive mechanism 43 Shutter plate rotation drive mechanism 49 Inner wall surface 50 Inert gas dissolved water generation unit 51 First pipe internal preparation unit 55 Chemical liquid supply pipe 56 First branch pipe 59 First mixing unit 62 First chemical liquid valve 71 Chemical liquid tank 74 Deaeration unit 77 Inert gas supply pipe 78 Inert gas valve 80 Inner pipe 81 Outer pipe 82 Inactive gas valve 83 Inert gas supply pipe 86 Control Part 132 peripheral wall part 149 inner wall surface 232 peripheral wall part 249 inner wall surface 332 peripheral wall part G1 interval L1 rotation axis L2 method Wire W substrate

Claims (20)

A substrate holding mechanism for holding the substrate;
A blocking member having a substrate facing surface facing the substrate held by the substrate holding mechanism, and having a peripheral wall portion protruding from the periphery of the substrate facing surface toward the substrate holding mechanism;
A processing liquid nozzle for supplying a processing liquid to the substrate held by the substrate holding mechanism;
An inert gas dissolved water generating unit for degassing oxygen in pure water and adding an inert gas to the pure water to generate an inert gas dissolved water;
An in-pipe preparation unit that mixes the chemical solution stock solution and the inert gas dissolved water generated by the inert gas dissolved water generation unit in the pipe to prepare the chemical solution as the treatment liquid;
A substrate processing apparatus, comprising: a processing liquid supply path for guiding a processing liquid from the in-pipe preparation unit to the processing liquid nozzle.   The inert gas dissolved water supply means which supplies the inert gas dissolved water produced | generated by the said inert gas dissolved water production | generation unit to a board | substrate as a process liquid as it is, without mixing with the said chemical | medical solution is further included. Substrate processing equipment.   The substrate processing apparatus according to claim 1, wherein the peripheral wall portion of the blocking member is formed so as to surround the entire periphery of the peripheral end surface of the substrate. The substrate holding mechanism includes a holding base having a surface facing the substrate facing surface of the blocking member,
The substrate processing apparatus further includes a blocking member moving mechanism that causes the blocking member to approach / separate the holding base between a predetermined processing position and a retracted position,
The said processing position is defined so that the front-end edge of the surrounding wall part of the said interruption | blocking member may be located near the said holding | maintenance base rather than the board | substrate hold | maintained at the said board | substrate holding mechanism. The substrate processing apparatus according to item. A chemical tank for storing the chemical stock solution,
An inert gas supply means for supplying an inert gas into the chemical liquid tank;
The substrate processing apparatus according to claim 1, further comprising a chemical solution supply path that guides the chemical solution stock from the chemical solution tank to the in-pipe preparation unit.   A degassing unit for degassing oxygen in the chemical solution stock solution is further included, and the chemical solution stock solution degassed by the degassing unit is supplied to the in-pipe preparation unit. The substrate processing apparatus according to claim 1. The processing liquid supply path includes an inner pipe through which the processing liquid flows, and an outer pipe surrounding the processing liquid pipe,
The substrate processing apparatus according to claim 1, further comprising an inert gas filling unit that fills an inert gas between the inner pipe and the outer pipe. Further comprising control means for controlling the in-pipe preparation unit,
This control means is for dissolving the inert gas dissolved water generated by the inert gas dissolved water generating unit through the processing liquid supply path to the processing liquid nozzle without mixing with the chemical liquid stock solution. A water supply step is performed, and thereafter, the chemical solution stock solution and the inert gas-dissolved water are mixed in the pipe by the in-pipe preparation unit to prepare a chemical solution, and the chemical solution is supplied to the processing solution through the processing solution supply path. The substrate processing apparatus as described in any one of Claims 1-7 which performs the chemical | medical solution supply process supplied to a nozzle.   The substrate processing apparatus according to claim 8, wherein the control means continues the inert gas dissolved water supply step until an oxygen concentration in the processing liquid discharged from the processing liquid nozzle becomes 20 ppb or less. An inert gas supply means for supplying an inert gas to a space between the blocking member and the substrate held by the substrate holding mechanism;
The control unit further performs an atmosphere replacement step of replacing the atmosphere near the surface of the substrate with an inert gas prior to the chemical solution supply step by controlling the inert gas supply unit. 10. The substrate processing apparatus according to claim 8 or 9. A substrate processing method for processing a substrate by supplying a processing liquid from a processing liquid nozzle to the substrate,
An inert gas-dissolved water generating step of degassing oxygen in pure water and adding an inert gas to the pure water to generate an inert gas-dissolved water;
A chemical solution supplying step of mixing a chemical solution stock solution and the inert gas-dissolved water in a pipe to prepare a chemical solution, and supplying the chemical solution to the processing solution nozzle through a processing solution supply path;
An atmosphere replacement step that is performed prior to the chemical solution supply step and replaces the atmosphere near the surface of the substrate with an inert gas;
Prior to the chemical liquid supply step, the inert gas dissolved water generated by the inert gas dissolved water generation step is passed through the processing liquid supply path to the processing liquid nozzle without mixing with the chemical liquid stock solution. A substrate processing method including an inert gas dissolved water supply step of supplying.   In the atmosphere replacement step, the substrate facing surface of the blocking member is opposed to the surface of the substrate, and the periphery of the substrate is surrounded by a peripheral wall portion protruding from the periphery of the substrate facing surface. The substrate processing method according to claim 11, further comprising a step of supplying an inert gas to the space.   The atmosphere replacement step includes a step of holding the substrate by a holding base having a surface facing the substrate facing surface of the blocking member, and a tip edge of the peripheral wall portion of the blocking member is brought closer to the surface of the holding base than the substrate. The substrate processing method according to claim 12, further comprising:   The inert gas dissolved water supply step is continued until the oxygen concentration in the treatment liquid discharged from the treatment liquid nozzle becomes 20 ppb or less, and then the chemical solution supply step is executed. The substrate processing method as described in any one of Claims.   15. The method further includes a rinsing step of supplying the inert gas dissolved water generated by the inert gas dissolved water generating step to the substrate and rinsing the chemical on the surface of the substrate after the chemical solution supplying step. The substrate processing method as described in any one of these. A step of supplying an inert gas into the chemical tank storing the chemical stock solution;
The substrate processing method according to claim 1, wherein in the chemical solution supply step, a chemical solution is prepared using a chemical solution stock pumped from the chemical solution tank. Further comprising degassing the stock solution.
The substrate processing method according to any one of claims 1 to 16, wherein in the chemical solution supply step, a chemical solution is prepared using the degassed chemical solution stock solution. The processing liquid supply path has an inner pipe through which the processing liquid flows and an outer pipe surrounding the processing liquid pipe.
The substrate processing method according to any one of claims 11 to 17, further comprising an inert gas filling step of filling an inert gas between the inner pipe and the outer pipe. The substrate has a polymer residue attached to the surface,
The said chemical | medical solution is a substrate removal method as described in any one of Claims 11-18 which is a polymer removal liquid for removing the said polymer residue.   The substrate processing method according to claim 11, wherein the substrate has a metal pattern exposed on a surface thereof.

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