JP2018101670A - Substrate processing method, solution sending method, and substrate processing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate processing method, a solution sending method and a substrate processing apparatus, which can inhibit cost increase and inhibit or prevent generation of a precipitate.SOLUTION: A substrate processing method comprises: performing a low-purity rinse solution supply process (carbonated water rinse treatment: S7) after performing a medicinal solution supply process (SC2 treatment: S5) of supplying an ion-containing medicinal solution (SC2) to a surface of a substrate; and performing a high-purity rinse solution supply process (DIW rinse treatment: S6) between the medicinal solution supply process and the low-purity rinse solution supply process. In the low-purity rinse solution supply process, the low-purity rinse solution (carbonated water) containing an impurity which forms a precipitate by interaction with ions contained in the medicinal solution is supplied to the surface of the substrate. In the high-purity rinse solution process, a high-purity rinse solution (DIW) containing less impurity than the low-purity rinse solution is supplied to the surface of the substrate.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate, and a liquid feeding method for feeding liquid to a nozzle used in the substrate processing apparatus. 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. Substrates such as substrates for substrates, ceramic substrates, and substrates for solar cells are included.

  In the substrate processing method described in Patent Document 1 below, after supplying a chemical solution to the substrate, carbonated water is supplied to the substrate in order to wash away the chemical solution adhering to the substrate.

JP 2001-358109 A

  If particles are generated on the substrate after the substrate processing, there is a possibility that an operation failure may occur in a process after the substrate processing (manufacture of a semiconductor device). Therefore, conventionally, preventive measures against the generation of particles have been taken by avoiding mixing of an acidic chemical solution and a basic chemical solution, or by filtering the chemical solution or the rinse solution with a filter. However, an operation failure may occur in a process (manufacturing a semiconductor device) after the substrate processing.

  The inventors of the present application have found that precipitates generated on the substrate after the chemical solution adhering to the surface of the substrate is washed away with a rinsing liquid are the cause of the malfunction of the process after the substrate treatment. Such precipitates are not detected as particles in the rinsing liquid before being supplied onto the substrate, and thus have not been focused on as a cause of a malfunction of the process after the substrate processing. Such precipitates can be generated not only on the substrate but also in the flow path through which the rinsing liquid and the chemical liquid pass.

In order to avoid the generation of precipitates, it is conceivable to perform substrate processing using a rinse solution having a relatively high purity. However, as the frequency of use of such a rinse solution increases, the cost required for substrate processing increases. To do.
Accordingly, an object of the present invention is to provide a substrate processing method, a liquid feeding method, and a substrate processing apparatus capable of suppressing an increase in cost and suppressing or preventing the generation of precipitates. .

In the substrate processing, the rinsing liquid and the chemical liquid are selected so that precipitates are not formed by the components originally contained in the chemical liquid and the components originally contained in the rinsing liquid. Nevertheless, precipitates are formed when the chemical solution on the substrate is washed away with the rinse solution.
Therefore, the inventors of the present application have detected that the diameter of the particle counter is not detected in the rinsing liquid or the chemical liquid even if the substance causing the precipitate is dissolved in the rinsing liquid or the chemical liquid. It was considered to be smaller than the limit (for example, 18 nm). The inventors of the present application have found that this precipitate is generated due to the interaction between impurities contained in the rinse liquid and ions contained in the chemical liquid.

  The present invention is performed after a chemical solution supply step for supplying a chemical solution containing ions to the surface of the substrate and the chemical solution supply step, and forms precipitates by interacting with the ions contained in the chemical solution. The amount of the impurities contained and contained between the low-purity rinsing liquid supply step for supplying the low-purity rinsing liquid containing impurities to the surface of the substrate, the chemical liquid supply step, and the low-purity rinsing liquid supply step There is provided a substrate processing method including a high-purity rinse liquid supply step of supplying a high-purity rinse liquid less than the low-purity rinse liquid to the surface of the substrate.

  According to this method, the high-purity rinsing process is executed between the chemical liquid supply process and the low-purity rinse liquid supply process. Therefore, the chemical liquid supplied on the substrate in the chemical liquid supply process includes a high-purity rinse liquid that contains less impurities than the low-purity rinse liquid, and a low-purity rinse liquid that is supplied onto the substrate after the high-purity rinse liquid. Washed away by. Therefore, the cost required for the substrate processing is reduced as compared with the substrate processing in which the chemical solution is washed away only with the high-purity rinse solution.

  Further, in the high-purity rinse liquid supply process executed before the low-purity rinse liquid supply process, part or all of the chemical solution on the substrate is replaced with the high-purity rinse liquid. Thereby, before the low-purity rinse liquid supply process is performed, the concentration of ions in the chemical solution on the substrate is diluted with the high-purity rinse liquid. Therefore, the interaction between the ions contained in the chemical liquid and the impurities contained in the low-purity rinse liquid is reduced. Therefore, the formation of precipitates in the low-purity rinsing liquid supply step is suppressed or prevented.

Therefore, an increase in cost can be suppressed and generation of precipitates can be suppressed or prevented.
In one Embodiment of this invention, the said chemical | medical solution contains acidic aqueous solution, and the said low-purity rinse liquid contains organic substance as said impurity.
According to this method, the chemical solution includes an acidic aqueous solution, and the low-purity rinse solution contains an organic substance as an impurity. Here, when an acidic aqueous solution and a rinse liquid containing an organic substance as an impurity are mixed, a precipitate may be formed. The formation of this precipitate is considered to be caused by salting out. Salting out refers to agglomerating organic substances dispersed in a solvent such as water using the action of salt. Specifically, water molecules are attracted to the anions in the acidic aqueous solution, and the water molecules become hydration water of the anions, whereby the water molecules hydrated to the organic matter are removed. As a result, water molecules necessary for hydration of the organic matter are insufficient, and the organic matter aggregates. Due to this aggregation, precipitates are generated. Examples of anions that cause salting out include chloride ions contained in hydrochloric acid. Examples of organic substances that cause salting out include proteins and organic compounds having a molecular weight smaller than that of proteins.

  However, in the high-purity rinse liquid supply process performed before the low-purity rinse liquid supply process, part or all of the acidic aqueous solution on the substrate is replaced with the high-purity rinse liquid. Thereby, before the low-purity rinse liquid supply process is performed, the concentration of anions in the acidic aqueous solution on the substrate is diluted with the high-purity rinse liquid. Therefore, the interaction between the anion and the organic substance contained in the low-purity rinse liquid is reduced. Therefore, the formation of precipitates in the low-purity rinsing liquid supply step is suppressed or prevented.

In one embodiment of the present invention, the low-purity rinse liquid may contain a carbonic acid-containing liquid containing carbon dioxide.
In one embodiment of the present invention, the substrate processing method is executed before the chemical solution supplying step, and a second low purity rinse solution supplying step for supplying the low purity rinse solution to the surface of the substrate, and the chemical solution A second high-purity rinse liquid supply process that is performed between the supply process and the second low-purity rinse liquid supply process and that supplies the high-purity rinse liquid to the surface of the substrate.

  According to this method, the second low-purity rinse liquid supply process is executed before the chemical liquid supply process, and the second high-purity rinse liquid supply is performed between the chemical liquid supply process and the second low-purity rinse liquid supply process. The process is executed. Therefore, in the substrate processing in which the surface of the substrate is washed with a rinsing liquid before the chemical solution supplying step, the surface of the substrate has a high-purity rinsing liquid that contains less impurities than the low-purity rinsing liquid, and after the high-purity rinsing liquid. The substrate is cleaned with a low-purity rinsing liquid supplied onto the substrate. Therefore, the cost required for the substrate processing is reduced as compared with the substrate processing in which the surface of the substrate is cleaned only with the high-purity rinse liquid.

  Further, in the second high-purity rinse liquid supply process executed before the chemical liquid supply process, part or all of the low-purity rinse liquid on the substrate is replaced with the high-purity rinse liquid. Thereby, the amount of impurities in the rinse liquid on the substrate is reduced before the chemical liquid supply step is executed. Therefore, the amount of precipitates formed by the interaction between ions contained in the chemical liquid and impurities contained in the low-purity rinse liquid is reduced. Alternatively, the formation of the precipitate can be prevented. Therefore, the formation of precipitates in the chemical solution supply process is suppressed or prevented.

Therefore, in the substrate processing in which the surface of the substrate is washed with the rinsing liquid before the chemical solution supplying step, it is possible to suppress an increase in cost and to suppress or prevent the generation of precipitates.
In one embodiment of the present invention, there is provided a liquid feeding method for feeding a liquid to a nozzle through a common flow path, a flow path chemical liquid supply step for supplying a chemical liquid containing ions to the common flow path, and the flow path A flow path low-purity rinse liquid supply process for supplying, to the common flow path, a low-purity rinse liquid containing impurities that form precipitates by interacting with the ions contained in the chemical liquid after the chemical liquid supply process. A high-purity rinse liquid that contains a smaller amount of the impurities than the low-purity rinse liquid is supplied to the common flow path between the flow path chemical liquid supply step and the flow path low-purity rinse liquid supply step. And a flow path high-purity rinsing liquid supply step.

  According to this method, the flow path high-purity rinsing process is executed between the flow path chemical liquid supply process and the flow path low-purity rinse liquid supply process. Therefore, the chemical liquid supplied to the common flow path in the flow path chemical liquid supply process includes a high-purity rinse liquid that contains less impurities than the low-purity rinse liquid, and a low-pressure liquid that is supplied to the common flow path after the high-purity rinse liquid. Wash away with a pure rinse. Therefore, the required cost is reduced as compared with the liquid feeding method in which the chemical liquid is washed away with only the high-purity rinse liquid.

  Moreover, a part or all of the chemical | medical solution in a common flow path is substituted by the high purity rinse liquid by the flow path high purity rinse liquid supply process performed before a flow path low purity rinse liquid supply process. Thereby, before the flow path low-purity rinse liquid supply step is executed, the concentration of ions in the chemical liquid in the common flow path is diluted by the high-purity rinse liquid. Therefore, the interaction between the ions contained in the chemical liquid and the impurities contained in the low-purity rinse liquid is reduced. Therefore, the formation of precipitates in the flow path low-purity rinse liquid supply step is suppressed or prevented.

Therefore, an increase in cost can be suppressed and generation of precipitates can be suppressed or prevented.
In one Embodiment of this invention, the said chemical | medical solution contains acidic aqueous solution, and the said low-purity rinse liquid contains organic substance as said impurity.
According to this method, the chemical solution includes an acidic aqueous solution, and the low-purity rinse solution contains an organic substance as an impurity. In the flow path high-purity rinse liquid supply process that is executed before the flow path low-purity rinse liquid supply process, part or all of the acidic aqueous solution in the common flow path is replaced with the high-purity rinse liquid. Thereby, before the flow path low-purity rinse liquid supply step is executed, the concentration of anions in the acidic aqueous solution on the substrate is diluted with the high-purity rinse liquid. Therefore, the interaction between the anion and the organic substance contained in the low-purity rinse liquid is reduced. Therefore, the formation of precipitates in the flow path low-purity rinse liquid supply step is suppressed or prevented.

In one embodiment of the present invention, the low-purity rinse liquid may contain a carbonic acid-containing liquid containing carbon dioxide.
In one embodiment of the present invention, the liquid feeding method is executed before the flow path chemical liquid supply step, and a second flow path low purity rinse liquid supply step for supplying the low purity rinse liquid to the common flow path. And a second flow path high-purity rinse liquid that is executed between the flow path chemical liquid supply process and the second flow path low-purity rinse liquid supply process and supplies the high-purity rinse liquid to the common flow path. Supply step.

  According to this method, the second flow path low-purity rinse liquid supply process is executed before the flow path chemical liquid supply process, and between the flow path chemical liquid supply process and the second flow path low-purity rinse liquid supply process. A 2nd flow path high-purity rinse liquid supply process is performed. Therefore, in the method in which the common flow path is washed with the rinsing liquid before the flow path chemical liquid supply step, the common flow path includes a high-purity rinse liquid that contains less impurities than a low-purity rinse liquid, and a high-purity rinse liquid. Thereafter, the substrate is cleaned with a low-purity rinsing liquid supplied onto the substrate. Therefore, the required cost is reduced as compared with the liquid feeding method in which the common flow path is washed only with the high-purity rinse liquid.

  In the second flow path high-purity rinse liquid supply process executed before the flow path chemical liquid supply process, part or all of the low-purity rinse liquid in the common flow path is replaced with the high-purity rinse liquid. Thereby, before the flow path chemical liquid supply step is executed, the amount of impurities in the rinse liquid in the common flow path is reduced. Therefore, the amount of precipitates formed by the interaction between ions contained in the chemical liquid and impurities contained in the low-purity rinse liquid is reduced. Alternatively, the formation of the precipitate can be prevented. Therefore, the formation of precipitates in the flow path chemical solution supply step is suppressed or prevented.

Therefore, in the method in which the common flow path is washed with the rinsing liquid before the flow path chemical liquid supply step, it is possible to suppress an increase in cost and to suppress or prevent the generation of precipitates.
In one embodiment of the present invention, a chemical solution supply unit that supplies a chemical solution containing ions to the surface of the substrate, and a low amount of impurities that can form precipitates by interacting with the ions contained in the chemical solution. A low purity rinsing liquid supply unit that supplies a purity rinsing liquid to the surface of the substrate, and a high purity that supplies a high purity rinsing liquid that contains less impurities than the low purity rinsing liquid to the surface of the substrate. Provided is a substrate processing apparatus including a rinsing liquid supply unit, and a controller that controls the chemical liquid supply unit, the rinsing liquid supply unit, and the high-purity rinsing liquid supply unit.

The control device includes a chemical solution supply step for supplying the chemical solution to the surface of the substrate, a low purity rinse solution supply step for supplying the low purity rinse solution to the surface of the substrate after the chemical solution supply step, and the chemical solution supply. A high-purity rinsing liquid supply step for supplying the high-purity rinsing liquid to the surface of the substrate is performed between the step and the low-purity rinsing liquid supply step.
According to this structure, a high purity rinse process is performed between a chemical | medical solution supply process and a low purity rinse liquid supply process. Therefore, the chemical liquid supplied on the substrate in the chemical liquid supply process includes a high-purity rinse liquid that contains less impurities than the low-purity rinse liquid, and a low-purity rinse liquid that is supplied onto the substrate after the high-purity rinse liquid. Washed away by. Therefore, the cost required for the substrate processing is reduced as compared with the substrate processing in which the chemical solution is washed away only with the high-purity rinse solution.

  Further, in the high-purity rinse liquid supply process executed before the low-purity rinse liquid supply process, part or all of the chemical solution on the substrate is replaced with the high-purity rinse liquid. Thereby, before the low-purity rinse liquid supply process is performed, the concentration of ions in the chemical solution on the substrate is diluted with the high-purity rinse liquid. Therefore, the interaction between the ions contained in the chemical liquid and the impurities contained in the low-purity rinse liquid is reduced. Therefore, the formation of precipitates in the low-purity rinsing liquid supply step is suppressed or prevented.

Therefore, an increase in cost can be suppressed and generation of precipitates can be suppressed or prevented.
In one embodiment of the present invention, the chemical solution supply unit includes an acidic aqueous solution supply unit that supplies an acidic aqueous solution to the surface of the substrate, and the low-purity rinse liquid contains an organic substance as the impurity.

  According to this configuration, the chemical solution supply unit includes the acidic aqueous solution supply unit that supplies an acidic aqueous solution to the surface of the substrate, and the low-purity rinse solution contains an organic substance as an impurity. In the high-purity rinse liquid supply process performed before the low-purity rinse liquid supply process, part or all of the acidic aqueous solution on the substrate is replaced with the high-purity rinse liquid. Thereby, before the low-purity rinse liquid supply process is performed, the concentration of anions in the acidic aqueous solution on the substrate is diluted with the high-purity rinse liquid. Therefore, the interaction between the anion and the organic substance contained in the low-purity rinse liquid is reduced. Therefore, the formation of precipitates in the low-purity rinsing liquid supply step is suppressed or prevented.

In one embodiment of the present invention, the low-purity rinsing liquid supply unit may include a carbonic acid-containing liquid supply unit that supplies a carbonic acid-containing liquid containing carbon dioxide to the surface of the substrate.
In one embodiment of the present invention, the control device includes a second low-purity rinse liquid supply process for supplying the low-purity rinse liquid to the surface of the substrate before the chemical liquid supply process, the chemical liquid supply process, and the A second high-purity rinse liquid supply step for supplying the high-purity rinse liquid to the surface of the substrate is performed between the second low-purity rinse liquid supply step.

  According to this configuration, the second low-purity rinse liquid supply process is executed before the chemical liquid supply process, and the second high-purity rinse liquid supply is performed between the chemical liquid supply process and the second low-purity rinse liquid supply process. The process is executed. Therefore, in the substrate processing in which the surface of the substrate is washed with a rinsing liquid before the chemical solution supplying step, the surface of the substrate has a high-purity rinsing liquid that contains less impurities than the low-purity rinsing liquid, and after the high-purity rinsing liquid. The substrate is cleaned with a low-purity rinsing liquid supplied onto the substrate. Therefore, the cost required for the substrate processing is reduced as compared with the substrate processing in which the surface of the substrate is cleaned only with the high-purity rinse liquid.

  Further, in the second high-purity rinse liquid supply process executed before the chemical liquid supply process, part or all of the low-purity rinse liquid on the substrate is replaced with the high-purity rinse liquid. Thus, the amount of impurities in the rinse liquid on the substrate is reduced before the chemical liquid supply step is executed. Therefore, the amount of precipitates formed by the interaction between ions contained in the chemical liquid and impurities contained in the low-purity rinse liquid is reduced. Alternatively, the formation of the precipitate can be prevented. Therefore, the formation of precipitates in the chemical solution supply process is suppressed or prevented.

Therefore, in the substrate processing in which the surface of the substrate is washed with the rinsing liquid before the chemical solution supplying step, it is possible to suppress an increase in cost and to suppress or prevent the generation of precipitates.
In one embodiment of the present invention, the substrate processing apparatus further includes a nozzle and a common flow path for feeding liquid to the nozzle. The chemical liquid supply unit includes a chemical liquid valve that switches whether the chemical liquid is supplied to the common flow path. The low-purity rinse liquid supply unit includes a low-purity rinse liquid valve that switches whether the low-purity rinse liquid is supplied to the common flow path. The high-purity rinse liquid supply unit includes a high-purity rinse liquid valve that switches supply of the high-purity rinse liquid to the common flow path.

  And the said control apparatus controls the said chemical | medical solution valve | bulb, the said low purity rinse liquid valve, and the said high purity rinse liquid valve. A flow path chemical solution supplying process in which the control device supplies the chemical liquid to the common flow path, and a flow path low purity rinse liquid supply in which the low purity rinse liquid is supplied to the common flow path after the flow path chemical liquid supplying process. And a flow path high-purity rinse liquid supply process for supplying the high-purity rinse liquid to the common flow path between the step, the flow path chemical liquid supply process, and the flow path low-purity rinse liquid supply process.

  According to this configuration, the flow path high-purity rinsing process is executed between the flow path chemical liquid supply process and the flow path low-purity rinse liquid supply process. Therefore, the chemical liquid supplied to the common flow path in the flow path chemical liquid supply process includes a high-purity rinse liquid that contains less impurities than the low-purity rinse liquid, and a low-pressure liquid that is supplied to the common flow path after the high-purity rinse liquid. Wash away with a pure rinse. Therefore, the required cost is reduced as compared with the liquid feeding method in which the chemical liquid is washed away with only the high-purity rinse liquid.

  Moreover, a part or all of the chemical | medical solution in a common flow path is substituted by the high purity rinse liquid by the flow path high purity rinse liquid supply process performed before a flow path low purity rinse liquid supply process. Thereby, before the flow path low-purity rinse liquid supply step is executed, the concentration of ions in the chemical liquid in the common flow path is diluted by the high-purity rinse liquid. Therefore, the interaction between the ions contained in the chemical liquid and the impurities contained in the low-purity rinse liquid is reduced. Therefore, the formation of precipitates in the flow path low-purity rinse liquid supply step is suppressed or prevented.

  Therefore, an increase in cost can be suppressed and generation of precipitates can be suppressed or prevented.

FIG. 1 is an illustrative plan view for explaining the internal layout of the substrate processing apparatus according to the first embodiment of the present invention. FIG. 2 is a schematic longitudinal sectional view for explaining a configuration example of the processing unit provided in the substrate processing apparatus. FIG. 3 is a block diagram for explaining an electrical configuration of a main part of the substrate processing apparatus. FIG. 4 is a flowchart for explaining an example of substrate processing by the substrate processing apparatus. FIG. 5A is a schematic view of the periphery of the substrate in the carbonated water rinse treatment (S3 in FIG. 4). FIG. 5B is a schematic view of the periphery of the substrate in the DIW rinse process (S4 in FIG. 4). FIG. 5C is a schematic diagram of the periphery of the substrate in the SC2 process (S5 in FIG. 4). FIG. 5D is a schematic view of the periphery of the substrate in the DIW rinse process (S6 in FIG. 4). FIG. 5E is a schematic view of the periphery of the substrate in the carbonated water rinsing process (S7 in FIG. 4). FIG. 6A is a schematic diagram of the periphery of the mixing valve unit in the carbonated water rinsing process (S3 in FIG. 4). FIG. 6B is a schematic diagram of the periphery of the mixing valve unit in the DIW rinse process (S4 in FIG. 4). FIG. 6C is a schematic diagram of the periphery of the mixing valve unit in the SC2 process (S5 in FIG. 4). FIG. 6D is a schematic diagram of the periphery of the mixing valve unit in the DIW rinse process (S6 in FIG. 4). FIG. 6E is a schematic diagram of the periphery of the mixing valve unit in the carbonated water rinse treatment (S7 in FIG. 4). FIG. 7 is a flowchart for explaining another example of the substrate processing by the substrate processing apparatus. FIG. 8 is a flowchart for explaining still another example of the substrate processing by the substrate processing apparatus.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
<First Embodiment>
FIG. 1 is an illustrative plan view for explaining the internal layout of the substrate processing apparatus 1 according to the first embodiment of the present invention. The substrate processing apparatus 1 is a single wafer processing apparatus that processes substrates W such as silicon wafers one by one. In this embodiment, the substrate W is a circular substrate.

  The substrate processing apparatus 1 includes a plurality of processing units 2 that process a substrate W, a plurality of load ports LP that respectively hold carriers C that store a plurality of substrates W processed by the processing unit 2, a load port LP, A transfer robot IR and CR that transfer the substrate W to and from the processing unit 2 and a control device 3 that controls the substrate processing apparatus 1 are included. The transfer robot IR transfers the substrate W between the carrier C and the transfer robot CR. The transfer robot CR transfers the substrate W between the transfer robot IR and the processing unit 2.

The plurality of processing units 2 have the same configuration, for example. The processing unit 2 includes a chamber 14 that accommodates the substrate W in order to process the substrate W with the processing liquid, and pipes that supply a fluid such as a processing liquid or gas used in the chamber 14 for processing the substrate W. And a fluid box 15 containing
The treatment liquid is, for example, a chemical liquid or a rinse liquid. The chemical liquid is, for example, a liquid that removes a thin film formed on the surface of the substrate W from the surface of the substrate W, or removes particles, metal contamination, and the like attached to the surface of the substrate W from the surface of the substrate W. . The rinsing liquid is deionized water (DIW) that rinses away the chemical liquid from the surface of the substrate W or the like.

Although not shown, the chamber 14 is formed with an entrance for carrying the substrate W into the chamber 14 and carrying the substrate W out of the chamber 14. The chamber 14 is provided with a shutter unit that opens and closes the entrance / exit.
FIG. 2 is a schematic longitudinal sectional view for explaining a configuration example of the processing unit 2.
The processing unit 2 includes a spin chuck 5 that rotates the substrate W around a vertical rotation axis A <b> 1 that passes through the center of the substrate W while holding a single substrate W in a horizontal posture, and a cylindrical shape that surrounds the spin chuck 5. And a first nozzle 11 and a second nozzle 12 for supplying fluid to the upper surface (surface) of the substrate W.

The spin chuck 5 is an example of a substrate holding and rotating unit that rotates a horizontally held substrate W around a predetermined rotation axis A1 along the vertical direction. The spin chuck 5 includes a chuck pin 20, a spin base 21, a rotary shaft 22 coupled to the center of the lower surface of the spin base 21, and an electric motor 23 that applies a rotational force to the rotary shaft 22.
The rotation shaft 22 extends in the vertical direction along the rotation axis A1. A spin base 21 is coupled to the upper end of the rotating shaft 22. The spin base 21 has a disk shape along the horizontal direction. A plurality of chuck pins 20 are arranged at intervals in the circumferential direction on the peripheral edge of the upper surface of the spin base 21. When the rotating shaft 22 is rotated by the electric motor 23, the substrate W is rotated around the rotating axis A1.

  The first nozzle 11 has a discharge port 11 a that faces the upper surface of the substrate W. The first nozzle 11 is moved in the horizontal direction and the vertical direction by the first nozzle moving mechanism 24. The first nozzle 11 can move in the horizontal direction between a center position facing the rotation center of the upper surface of the substrate W and a home position (retreat position) not facing the upper surface of the substrate W. The home position is a position outside the spin base 21 in a plan view, and more specifically, may be a position outside the cup 8. The first nozzle 11 need not be a moving nozzle moved by the first nozzle moving mechanism 24, and may be a fixed nozzle whose position is fixed.

  The second nozzle 12 has a discharge port 12 a that faces the upper surface of the substrate W. The second nozzle 12 is moved in the horizontal direction and the vertical direction by the second nozzle moving mechanism 25. The second nozzle 12 can move in the horizontal direction between a center position facing the rotation center of the upper surface of the substrate W and a home position (retreat position) not facing the upper surface of the substrate W. The home position is a position outside the spin base 21 in a plan view, and more specifically, may be a position outside the cup 8. The second nozzle 12 does not have to be a moving nozzle moved by the second nozzle moving mechanism 25, and may be a fixed nozzle whose position is fixed.

  A first processing liquid supply path P61 is coupled to the first nozzle 11. A second processing liquid supply path P62 is coupled to the second nozzle 12. Both the first processing liquid supply path P61 and the second processing liquid supply path P62 are, for example, pipes. The first processing liquid supply path P61 and the second processing liquid supply path P62 are connected to the mixing valve unit 6. The first processing liquid supply path P61 and the second processing liquid supply path P62 receive the processing liquid supplied from the mixing valve unit 6.

  The mixing valve unit 6 includes a common flow path 60 that supplies liquid to the nozzles 11 and 12, a plurality of valves V61 and V62 on the outflow side, a plurality of valves V63 to V67 on the inflow side, and a drain valve V68. The plurality of valves V61 to V68 are all on-off valves. The first processing liquid supply path P61 is coupled to the common flow path 60. The first processing liquid supply path P61 is provided with a first processing liquid valve V61 among the plurality of valves V61 and V62 on the outflow side. The second processing liquid supply path P62 is provided with a second processing liquid valve V62 among the plurality of valves V61, V62 on the outflow side. In the second processing liquid supply path P62, a filter 45 may be interposed between the second processing liquid valve V62 and the common flow path 60.

  A plurality of fluid supply paths P63 to P67 for supplying fluid to the common flow path 60 are coupled to the common flow path 60. Each of the plurality of fluid supply paths P63 to P67 is, for example, a pipe. A plurality of inflow valves V63 to V67 are interposed in each of the plurality of fluid supply paths P63 to P67. By opening or closing the valves V63 to V67, the presence or absence of supply of the processing liquid to the common flow path 60 is switched.

The plurality of fluid supply paths P63 to P67 include a first fluid supply path P63, a second fluid supply path P64, a third fluid supply path P65, a fourth fluid supply path P66, and a fifth fluid supply path P67. The plurality of valves V63 to 67 includes a first fluid valve V63, a second fluid valve V64, a third fluid valve V65, a fourth fluid valve V66, and a fifth fluid valve V67.
In the present embodiment, the first fluid supply path P63 is connected to the carbonated water supply source 70. The second fluid supply path P64 is connected to the DIW supply source 71. The third fluid supply path P65 is connected to an ammonia water supply source 72 (NH ₄ OH supply source). The fourth fluid supply path P66 is connected to a hydrogen peroxide solution supply source 73 (H ₂ O ₂ supply source). The fifth fluid supply path P67 is connected to a hydrochloric acid supply source 74 (HCl supply source). The carbonated water of the carbonated water supply source 70 may be carbonated water prepared by dissolving carbon dioxide gas in DIW supplied from the DIW supply source 71.

A drainage channel P68 is coupled to the common channel 60. The drainage path P68 is, for example, a pipe. A drain valve V68 is interposed in the drain path P68. The drainage path P68 is connected to the suction mechanism 80. The suction mechanism 80 is, for example, a vacuum pump.
A gas supply path 30 is coupled to the first nozzle 11 in addition to the first processing liquid supply path P61. A gas valve 40 is interposed in the gas supply path 30. A gas supply source 75 is connected to the gas supply path 30. A gas such as nitrogen (N ₂ ) gas is supplied from the gas supply source 75 to the first nozzle 11 via the gas supply path 30. In the present embodiment, the first nozzle 11 is a two-fluid nozzle that can discharge a fluid obtained by mixing a treatment liquid and a gas onto the upper surface of the substrate W.

  As the gas supplied from the gas supply source 75 to the first nozzle 11, it is preferable to use an inert gas such as nitrogen gas. The inert gas is a gas that is inert with respect to the upper surface of the substrate W. In addition to nitrogen gas, the inert gas includes, for example, argon rare gas. The gas valve 40 is accommodated in the fluid box 15 together with the mixing valve unit 6. The gas supply source 75 is disposed outside the fluid box 15 together with the fluid supply sources 70 to 74 and the suction mechanism 80.

The first nozzle 11 and the second nozzle 12 can be supplied with any one type of processing liquid flowing into the common flow path 60 and mixed with any two types of processing liquid flowing into the common flow path 60 Treatment liquid can be supplied.
One type of treatment liquid may be a rinse liquid such as carbonated water or DIW. As the rinse liquid, in addition to carbonated water and DIW, electrolytic ion water, ozone water, diluted hydrochloric acid water (for example, about 1 to 100 ppm), reduced water (hydrogen water), ammonia water, and the like can be used. .

  In the present embodiment, DIW and carbonated water can be supplied to each of the first nozzle 11 and the second nozzle 12 as a rinse liquid. As the rinsing liquid, a solution obtained by dissolving carbon dioxide gas in a mixed liquid of a liquid other than DIW such as an organic solvent and DIW can be used instead of carbonated water. Such a mixed solution containing carbon dioxide gas and carbonated water are collectively referred to as a carbonate-containing solution.

  As the mixed treatment liquid, a chemical solution such as SC1 (ammonia hydrogen peroxide solution mixture) or SC2 (hydrochloric acid hydrogen peroxide solution mixture) can be used. SC1 is a mixed solution of ammonia water, hydrogen peroxide solution, and DIW, and is a basic aqueous solution. SC2 is a mixed solution of hydrochloric acid and hydrogen peroxide solution, and is an acidic aqueous solution. SC2 is an example of a hydrochloric acid-containing liquid containing hydrochloric acid. In the present embodiment, SC1 and SC2 can be supplied as chemical solutions to the first nozzle 11 and the second nozzle 12, respectively.

  The rinse liquid may contain impurities. For example, organic substances constituting the first fluid supply path P63, the common flow path 60, the first process liquid supply path P61, and the second process liquid supply path P62 may dissolve in carbonated water. Thereby, the carbonated water supplied to the first nozzle 11 or the second nozzle 12 contains an organic substance as an impurity. Examples of this organic substance include proteins and organic compounds having a lower molecular weight than proteins.

  As another example, in the case where carbon dioxide water is generated by dissolving carbon dioxide gas in DIW supplied from the DIW supply source 71, impurities such as organic substances contained in the carbon dioxide gas are mixed with carbon dioxide in the DIW. May melt. Also in this case, the carbonated water supplied to the first nozzle 11 or the second nozzle 12 contains an organic substance as an impurity.

  Thus, in this embodiment, carbonated water may contain a large amount of impurities as compared with DIW. The purity of the rinsing liquid is higher as the amount of impurities is smaller, and is lower as the amount of impurities is larger. Therefore, in this embodiment, carbonated water is a low-purity rinse liquid. DIW is a high-purity rinsing liquid that contains less impurities than carbonated water. The content of impurities in the rinse liquid is large when the number of moles of impurities present in the rinse liquid per unit volume is large, and is small when the number of moles of impurities present in the rinse liquid per unit volume is small.

  When the rinse liquid containing impurities and the chemical liquid containing predetermined ions are mixed, precipitates (precipitates) may be generated due to the interaction between the ions and the impurities. Impurities that cause this precipitate are dissolved in the rinsing liquid, or even if they are not dissolved in the rinsing liquid, the diameter is larger than the detection limit of the particle counter (not shown) (for example, 18 nm). small. Therefore, this impurity cannot be detected by the particle counter. This impurity becomes a precipitate having a size that can be detected by the particle counter due to the interaction with the ions. When the impurity is an organic substance, this precipitate is considered to be caused by salting out.

  Salting out refers to aggregating organic substances dispersed in a solvent such as water using the action of salt. Specifically, water molecules are attracted to predetermined ions in the chemical solution and the water molecules become hydrated water of the predetermined ions, thereby removing water molecules hydrated to the organic matter. As a result, water molecules necessary for hydration of the organic matter are insufficient, and the organic matter aggregates. Due to this aggregation, precipitates are generated.

  Predetermined ions that cause salting-out include citrate ions, tartrate ions, sulfate ions, chloride ions, bromide ions, iodide ions, carbonate ions, acetate ions, nitrate ions, ammonium ions, Cations such as potassium ion, sodium ion, calcium ion and magnesium ion can be mentioned. Examples of the acidic aqueous solution (chemical solution) containing sulfate ions include SPM (sulfuric acid / hydrogen peroxide mixture). The lower the concentration of these ions in the solvent, the less likely salting out occurs. In other words, the closer the pH of the solvent is to 7, the less salting out occurs.

  FIG. 3 is a block diagram for explaining the electrical configuration of the main part of the substrate processing apparatus 1. The control device 3 includes a microcomputer, and controls a control target provided in the substrate processing apparatus 1 according to a predetermined control program. More specifically, the control device 3 includes a processor (CPU) 3A and a memory 3B in which a control program is stored. The processor 3A executes the control program to perform various controls for substrate processing. Is configured to run. In particular, the control device 3 controls operations of the transport robots IR and CR, the electric motor 23, the nozzle moving mechanisms 24 and 25, the valves 40, V61 to V68, and the like.

4 to 6 below, an example of a substrate processing method and a liquid feeding method that can suppress or prevent the formation of precipitates caused by mixing of carbonated water and SC2 will be described.
FIG. 4 is a flowchart for explaining an example of substrate processing by the substrate processing apparatus 1. FIG. 4 mainly shows processing realized by the control device 3 executing the operation program.

In the substrate processing by the substrate processing apparatus 1, for example, as shown in FIG. 4, substrate loading (S1), SC1 processing (S2), carbonated water rinsing processing (S3), DIW rinsing processing (S4), and SC2 processing (S5). The DIW rinse process (S6), the carbonated water rinse process (S7), the drying (S8), and the substrate unloading (S9) are executed in this order.
In the substrate processing of the present embodiment, SC1 is supplied from the first nozzle 11, and SC2 as an acidic aqueous solution, DIW as a high-purity rinsing liquid, and carbonated water as a low-purity rinsing liquid are supplied from the second nozzle 12. Supplied.

That is, in the present embodiment, the second nozzle 12, the second processing liquid supply path P62, the second processing liquid valve V62, the second fluid supply path P64, the second fluid valve V64, and the common flow path 60 are made of a high-purity rinse liquid. It constitutes a supply unit. The second fluid valve V64 is an example of a high-purity rinse liquid valve that switches the supply of the high-purity rinse liquid to the common flow path 60.
The second nozzle 12, the second processing liquid supply path P62, the second processing liquid valve V62, the first fluid supply path P63, the first fluid valve V63, and the common flow path 60 are combined with a carbonic acid-containing liquid supply unit (low-purity rinse). Liquid supply unit). The first fluid valve V63 is an example of a low-purity rinse liquid valve that switches the supply of the low-purity rinse liquid to the common flow path 60.

The second nozzle 12, the second processing liquid supply path P62, the fluid valves V66, V67, the fluid supply paths P66, P67, and the common flow path 60 serve as a hydrochloric acid-containing liquid supply unit (an acidic aqueous solution supply unit, a chemical liquid supply unit). It is composed. In the present embodiment, the fluid valves V66 and V67 are an example of a chemical valve that switches supply of the chemical liquid to the common flow path 60.
The substrate processing S1 to S9 by the substrate processing apparatus 1 will be described in detail.

First, an unprocessed substrate W is carried into the processing unit 2 from the carrier C by the transfer robots IR and CR, and transferred to the spin chuck 5 (S1). Thereafter, the substrate W is horizontally held by the chuck pins 20 with an interval upward from the upper surface of the spin base 21 until it is carried out by the transfer robot CR (substrate holding step).
The electric motor 23 rotates the substrate W together with the spin base 21 (substrate rotation process). The substrate rotation process at this rotation speed may be continued until the start of the drying process (S8) described later. In the substrate processing, the liquid supplied onto the rotating substrate W is scattered outward from the periphery of the substrate W by centrifugal force and is received by the cup 8.

Then, an SC1 process (S2) is performed in which the upper surface of the substrate W held by the chuck pins 20 is processed by SC1.
Specifically, the first nozzle moving mechanism 24 arranges the first nozzle 11 at the processing position above the substrate W. The processing position may be a position where the chemical liquid discharged from the first nozzle 11 is supplied to the rotation center of the upper surface of the substrate W. SC1 is supplied from the first nozzle 11 toward the upper surface of the rotating substrate W. SC1 supplied to the upper surface of the rotating substrate W flows radially outward along the upper surface of the substrate W by centrifugal force. As a result, the cleaning liquid spreads over the entire top surface of the substrate W. The gas valve 40 may be opened simultaneously with the start of the supply of SC1, or after the start of the supply of SC1. Thereby, the fluid in which SC1 and nitrogen gas are mixed is discharged toward the upper surface of the substrate W.

Next, after the SC1 process (S2) for a predetermined time, a carbonated water rinse process (S3) is performed in which SC1 on the upper surface of the substrate W is washed with carbonated water. FIG. 5A is a schematic view of the periphery of the substrate W in the carbonated water rinsing process (S3 in FIG. 4).
Specifically, the second nozzle moving mechanism 25 arranges the second nozzle 12 at a processing position above the substrate W. The processing position may be a position where carbonated water discharged from the second nozzle 12 is supplied to the rotation center of the upper surface of the substrate W. Then, carbonated water is supplied from the second nozzle 12 toward the upper surface of the rotating substrate W (second low-purity rinse liquid supply step). On the other hand, the supply of SC1 from the first nozzle 11 is stopped. The first nozzle moving mechanism 24 retracts the first nozzle 11 to the retracted position. Centrifugal force acts on the carbonated water that has landed on the upper surface of the rotating substrate W. Accordingly, the carbonated water that has landed on the upper surface of the substrate W flows on the upper surface of the substrate W toward the outer periphery of the substrate W. Thereby, SC1 on the substrate W is replaced with carbonated water. By supplying carbonated water to the upper surfaces of the second nozzle 12 and the substrate W, static electricity on the upper surfaces of the second nozzle 12 and the substrate W can be removed.

Next, after a fixed time carbonated water rinse treatment (S3), a DIW rinse treatment (S4) is performed in which carbonated water on the upper surface of the substrate W is washed away with DIW. FIG. 5B is a schematic diagram of the periphery of the substrate W in the DIW rinse process (S4 in FIG. 4).
Specifically, the second nozzle 12 is maintained in a state where it is disposed at a processing position above the substrate W. Then, DIW is supplied from the second nozzle 12 toward the upper surface of the rotating substrate W (second high-purity rinsing liquid supply step). Centrifugal force acts on DIW that has landed on the upper surface of the rotating substrate W. As a result, DIW deposited on the upper surface of the substrate W flows on the upper surface of the substrate W toward the outer periphery of the substrate W. Thereby, carbonated water on the substrate W is replaced by DIW. At this time, the carbonated water on the substrate W does not necessarily need to be completely replaced by DIW. The period during which DIW is supplied may be a period in which a portion of carbonated water on the substrate W is replaced by DIW.

Next, after a DIW rinse process (S4) for a predetermined time, an SC2 process (S5) is performed in which the upper surface of the substrate W is processed by the SC2. FIG. 5C is a schematic diagram of the periphery of the substrate W in the SC2 process (S5 in FIG. 4).
Specifically, the second nozzle 12 is maintained in a state where it is disposed at a processing position above the substrate W. Then, SC2 is supplied from the second nozzle 12 toward the upper surface of the rotating substrate W (chemical solution supply step, acidic aqueous solution supply step, hydrochloric acid-containing solution supply step). Centrifugal force acts on SC2 that has landed on the upper surface of the rotating substrate W. As a result, SC2 that has landed on the upper surface of the substrate W flows on the upper surface of the substrate W toward the outer periphery of the substrate W. Thereby, the DIW on the substrate W is replaced by SC2.

If carbonated water remains on the substrate W immediately after the DIW rinse process (S4), the mixed solution of DIW and carbonated water on the substrate W is replaced by SC2. After the DIW on the substrate W is replaced by SC2, the supply of SC2 to the upper surface of the substrate W is continued to remove metal contamination on the upper surface of the substrate W.
In this substrate process, the second low-purity rinse liquid supply process in the carbonated water rinse process (S3) is performed before the chemical liquid supply process in the SC2 process (S5). In this substrate process, the second high-purity rinse supply process in the DIW rinse process (S4) includes the second low-purity rinse liquid supply process in the carbonated water rinse process (S3) and the chemical solution supply process in the SC2 process (S5). Running between.

Next, after the SC2 process (S5) for a predetermined time, a DIW rinse process (S6) is performed to wash off SC2 on the upper surface of the substrate W with DIW. FIG. 5D is a schematic diagram of the periphery of the substrate W in the DIW rinse process (S6 in FIG. 4).
Specifically, the second nozzle 12 is maintained in a state where it is disposed at a processing position above the substrate W. Then, DIW is supplied from the second nozzle 12 toward the upper surface of the rotating substrate W (high purity rinsing liquid supply step). Centrifugal force acts on DIW that has landed on the upper surface of the rotating substrate W. As a result, DIW deposited on the upper surface of the substrate W flows on the upper surface of the substrate W toward the outer periphery of the substrate W. Thereby, SC2 on the substrate W is replaced by DIW. At this time, the carbonated water on the substrate W does not necessarily need to be completely replaced by DIW. The period during which DIW is supplied may be a period in which a part of SC2 on the substrate W is replaced by DIW.

Next, after the DIW rinsing process (S6) for a predetermined time, a carbonated water rinsing process (S7) is performed in which DIW on the upper surface of the substrate W is washed with carbonated water. FIG. 5E is a schematic view of the periphery of the substrate W in the carbonated water rinsing process (S7 in FIG. 4).
Specifically, the second nozzle 12 is maintained in a state where it is disposed at a processing position above the substrate W. Then, carbonated water is supplied from the second nozzle 12 toward the upper surface of the rotating substrate W (low-purity rinse liquid supply step). Centrifugal force acts on the carbonated water that has landed on the upper surface of the rotating substrate W. Accordingly, the carbonated water that has landed on the upper surface of the substrate W flows on the upper surface of the substrate W toward the outer periphery of the substrate W. Thereby, DIW on the substrate W is replaced with carbonated water. If SC2 remains on the substrate W immediately after the DIW rinse process (S6), the mixed solution of DIW and SC2 on the substrate W is replaced with carbonated water.

In this substrate processing, the high-purity rinse liquid supply process in the DIW rinse process (S6) is executed between the chemical liquid supply process in the SC2 process (S5) and the low-purity rinse liquid supply process in the carbonated water rinse process (S7). Has been.
Next, a drying process (S8) for drying the substrate W is performed.
Specifically, the supply of carbonated water from the second nozzle 12 is stopped. The second nozzle moving mechanism 25 retracts the second nozzle 12 to the retracted position. The electric motor 23 rotates the substrate W at a high rotation speed (for example, 500 to 3000 rpm) faster than the rotation speed of the substrate W in the SC1 process (S2) to the carbonated water process (S7). Thereby, a large centrifugal force acts on the carbonated water on the substrate W, and the carbonated water on the substrate W is shaken off around the substrate W. In this way, carbonated water is removed from the substrate W, and the substrate W is dried. Then, when a predetermined time elapses after the high-speed rotation of the substrate W is started, the control device 3 stops the rotation of the substrate W by the spin base 21.

Thereafter, the transfer robot CR enters the processing unit 2, picks up the processed substrate W from the spin chuck 5, and carries it out of the processing unit 2 (S 9). The substrate W is transferred from the transfer robot CR to the transfer robot IR, and is stored in the carrier C by the transfer robot IR.
Next, a liquid feeding method for feeding the liquid to the second nozzle 12 through the common channel 60 in the above-described substrate processing will be described.

6A is a schematic diagram of the periphery of the mixing valve unit 6 in the carbonated water rinsing process (S3 in FIG. 4). In FIG. 6A, supply paths P61 to P67 through which a fluid flows are illustrated using thick lines (the same applies to FIGS. 6B to 6E described later). In the carbonated water rinsing process (S <b> 3), carbonated water is supplied to the second nozzle 12 via the common channel 60.
In the carbonated water rinsing process (S3), first, the supply of SC1 to the substrate W is stopped as described above. In order to stop the supply of SC1 to the substrate W, in the mixing valve unit 6, the first processing liquid valve V61 is closed. Then, the second fluid valve V64, the third fluid valve V65, and the fourth fluid valve V66 are closed. As a result, the supply of DIW, ammonia water and hydrogen peroxide solution to the common flow path 60 is stopped, so that the supply of SC1 to the first nozzle 11 and the substrate W is also stopped.

  Then, as described above, the supply of carbonated water to the substrate W is started. In order to start the supply of carbonated water to the substrate W, in the mixing valve unit 6, the first fluid valve V63 is opened. Thereby, the supply of carbonated water to the common flow path 60 via the first fluid supply path P63 is started (second flow path low-purity rinse liquid supply step). Then, by maintaining the state in which the second processing liquid valve V62 is opened, carbonated water is supplied from the common flow path 60 to the second nozzle 12 through the second processing liquid supply path P62. As a result, supply of carbonated water to the substrate W is also started.

Before carbonated water is supplied from the common channel 60 to the second nozzle 12, SC1 remaining in the common channel 60 may be replaced with carbonated water.
Specifically, when the fluid supplied to the common flow path 60 is switched from SC1 to carbonated water, the second treatment liquid valve V62 is not opened, but the drainage valve V68 is opened. Thereby, SC1 remaining in the common flow path 60 is washed away with carbonated water. After SC1 in the common channel 60 is replaced with carbonated water, the drain valve V68 is closed, and the second processing liquid valve V62 is opened as described above. Thereby, carbonated water is sent to the 2nd nozzle 12 from the common flow path 60 via the 2nd process liquid supply path P62.

FIG. 6B is a schematic diagram of the periphery of the mixing valve unit 6 in the DIW rinse process (S4 in FIG. 4). In the DIW rinse process (S4), DIW is supplied to the second nozzle 12 via the common flow path 60.
In the DIW rinse process (S4), first, the supply of carbonated water to the substrate W is stopped as described above. In order to stop the supply of carbonated water to the substrate W, in the mixing valve unit 6, the first fluid valve V63 is closed. As a result, the supply of carbonated water to the common flow path 60 is stopped, so the supply of carbonated water to the second nozzle 12 and the substrate W is also stopped.

  Then, as described above, supply of DIW to the substrate W is started. In order to start the supply of DIW to the substrate W, the second fluid valve V64 is opened in the mixing valve unit 6. Thereby, the supply of DIW to the common flow path 60 via the second fluid supply path P64 is started (second flow path high-purity rinse liquid supply process). Then, by maintaining the state where the second processing liquid valve V62 is opened, DIW is supplied from the common flow path 60 to the second nozzle 12 via the second processing liquid supply path P62. As a result, supply of DIW to the substrate W is also started.

At this time, the carbonated water in the common channel 60 does not necessarily need to be completely replaced by DIW. The period during which DIW is supplied may be a period in which a portion of the carbonated water in the common channel 60 is replaced by DIW.
Conversely, before supplying DIW to the second nozzle 12, the carbonated water remaining in the common flow path 60 may be completely replaced by DIW. Specifically, when the fluid supplied to the common flow path 60 is switched from carbonated water to DIW, the second processing liquid valve V62 is not maintained, but the second processing liquid valve V62 is once opened. It is closed and the drainage valve V68 is opened. Thereby, carbonated water remaining in the common flow path 60 is washed away with DIW. After the carbonated water in the common channel 60 is replaced by DIW, the drain valve V68 is closed and the second treatment liquid valve V62 is opened again. Thereby, DIW is supplied to the 2nd nozzle 12 from the common flow path 60 via the 2nd process liquid supply path P62.

FIG. 6C is a schematic diagram of the periphery of the mixing valve unit 6 in the SC2 process (S5 in FIG. 4). In the SC2 process (S5), SC2 is supplied to the second nozzle 12 through the common flow path 60.
In the SC2 process (S5), first, the supply of DIW to the substrate W is stopped as described above. In order to stop the supply of DIW to the substrate W, in the mixing valve unit 6, the second fluid valve V64 is closed. Thereby, the supply of DIW to the common flow path 60 is stopped, and the supply of DIW to the second nozzle 12 and the substrate W is also stopped.

  Then, as described above, supply of SC2 to the substrate W is started. In order to start the supply of SC2 to the substrate W, in the mixing valve unit 6, the fourth fluid valve V66 and the fifth fluid valve V67 are opened. As a result, the hydrogen peroxide solution is supplied to the common flow path 60 via the fourth fluid supply path P66, and the hydrochloric acid is supplied to the common flow path 60 via the fifth fluid supply path P67. Hydrogen peroxide solution and hydrochloric acid are mixed in the common channel 60. As a result, SC2 is supplied to the common channel 60 (channel chemical solution supply step, channel acidic aqueous solution supply step, channel hydrochloric acid-containing solution supply step). And SC2 is supplied to the 2nd nozzle 12 from the common flow path 60 via the 2nd process liquid supply path P62 by maintaining the state where the 2nd process liquid valve V62 was opened. As a result, supply of SC2 to the substrate W is started.

Similar to the DIW rinse process (S4), the drain valve V68 is opened, so that the DIW remaining in the common flow path 60 may be replaced by SC2 before SC2 is supplied to the second nozzle 12. .
FIG. 6D is a schematic diagram of the periphery of the mixing valve unit 6 in the DIW rinse process (S6 in FIG. 4). In the DIW rinse process (S6), DIW is supplied to the second nozzle 12 via the common flow path 60.

  In the DIW rinse process (S6), first, the supply of SC2 to the substrate W is stopped as described above. In order to stop the supply of SC2 to the substrate W, in the mixing valve unit 6, the fourth fluid valve V66 and the fifth fluid valve V67 are closed. As a result, the supply of the hydrogen peroxide solution and hydrochloric acid to the common channel 60 is stopped, so the supply of SC2 to the second nozzle 12 and the substrate W is also stopped.

  Then, as described above, supply of DIW to the substrate W is started. In order to start the supply of DIW to the substrate W, the second fluid valve V64 is opened in the mixing valve unit 6. Thereby, the supply of DIW to the common flow path 60 via the second fluid supply path P64 is started (flow path high-purity rinse liquid supply process). Then, by maintaining the state where the second processing liquid valve V62 is opened, DIW is supplied from the common flow path 60 to the second nozzle 12 via the second processing liquid supply path P62. As a result, supply of DIW to the substrate W is also started.

At this time, SC2 in the common flow path 60 does not necessarily need to be completely replaced by DIW. The period during which DIW is supplied may be a period in which a part of SC2 in the common channel 60 is replaced by DIW.
Conversely, as with the DIW rinse process (S4), the SC2 remaining in the common flow path 60 is completely replaced by DIW before the DIW is supplied to the second nozzle 12 by opening the drain valve V68. May be.

FIG. 6E is a schematic view of the periphery of the mixing valve unit 6 in the carbonated water rinsing process (S7 in FIG. 4). In the carbonated water rinsing process (S <b> 7), carbonated water is supplied to the second nozzle 12 through the common channel 60.
In the carbonated water rinsing process (S7), first, the supply of DIW to the substrate W is stopped as described above. In order to stop the supply of DIW to the substrate W, in the mixing valve unit 6, the second fluid valve V64 is closed. Thereby, the supply of DIW to the common flow path 60 is stopped, and the supply of DIW to the second nozzle 12 and the substrate W is also stopped.

  Then, as described above, the supply of carbonated water to the substrate W is started. At that time, in the mixing valve unit 6, the first fluid valve V63 is opened. Thereby, the supply of carbonated water to the common flow path 60 via the first fluid supply path P63 is started (flow path low-purity rinse liquid supply process). Then, when the second processing liquid valve V62 is opened, carbonated water is supplied from the common flow path 60 to the second nozzle 12 via the second processing liquid supply path P62. As a result, supply of carbonated water to the substrate W is also started.

Similar to the DIW rinse process (S4), the drain valve V68 is opened, so that the DIW remaining in the common flow path 60 is replaced with carbonated water before the carbonated water is supplied to the second nozzle 12. Good.
According to this embodiment, the high-purity rinsing process is executed between the chemical liquid supply process and the low-purity rinse liquid supply process. Therefore, the chemical liquid (SC2) supplied onto the substrate W in the chemical liquid supply process includes a high-purity rinse liquid (DIW) containing less impurities (organic matter) than a low-purity rinse liquid (carbonated water) and a high-purity rinse. After the liquid, it is washed away with a low-purity rinse liquid (carbonated water) supplied onto the substrate W. Therefore, the cost required for the substrate processing is reduced as compared with the substrate processing in which the chemical solution is washed away only with the high-purity rinse solution.

  Further, in the high-purity rinse liquid supply process executed before the low-purity rinse liquid supply process, part or all of the chemical solution on the substrate W is replaced with the high-purity rinse liquid. Thereby, before the low-purity rinse liquid supply process is executed, the concentration of ions (chloride ions) in the chemical liquid (SC2) on the substrate W is diluted by the high-purity rinse liquid. Therefore, the interaction between the ions contained in the chemical liquid and the impurities contained in the low-purity rinse liquid is reduced. Therefore, the formation of precipitates in the low-purity rinsing liquid supply step is suppressed or prevented.

Therefore, an increase in cost can be suppressed and generation of precipitates can be suppressed or prevented.
According to this embodiment, the second low-purity rinse liquid supply process is executed before the chemical liquid supply process, and the second high-purity rinse liquid is supplied between the chemical liquid supply process and the second low-purity rinse liquid supply process. A rinse liquid supply process is performed. Therefore, in the substrate processing in which the upper surface of the substrate W is washed with the rinsing liquid before the chemical solution supplying step, the upper surface of the substrate W is a high-purity rinse that contains less impurities (organic matter) than the low-purity rinsing liquid (carbonated water). Cleaning is performed with the liquid (DIW) and the low-purity rinse liquid supplied onto the substrate W after the high-purity rinse liquid. Therefore, the cost required for the substrate processing is reduced as compared with the substrate processing in which the upper surface of the substrate W is cleaned only with the high-purity rinse liquid.

  Further, in the second high-purity rinse liquid supply process executed before the chemical liquid supply process, part or all of the low-purity rinse liquid (carbonated water) on the substrate W is replaced with the high-purity rinse liquid. As a result, the amount of impurities (organic matter) in the rinse liquid on the substrate W is reduced before the chemical liquid supply step is executed. Therefore, the amount of precipitates formed by the interaction between ions (chloride ions) contained in the chemical solution (SC2) and impurities contained in the low-purity rinse solution (carbonated water) is reduced. Alternatively, the formation of the precipitate can be prevented. Therefore, the formation of precipitates in the chemical solution supply process is suppressed or prevented.

Therefore, in the substrate processing in which the upper surface of the substrate W is washed with the rinsing liquid before the chemical solution supply step, it is possible to suppress an increase in cost and to suppress or prevent the generation of precipitates.
Further, according to this embodiment, the flow path high-purity rinsing process is executed between the flow path chemical liquid supply process and the flow path low-purity rinse liquid supply process. Therefore, the chemical liquid (SC2) supplied to the common flow path 60 in the flow path chemical liquid supply step is a high-purity rinse liquid (DIW) that contains less impurities (organic matter) than the low-purity rinse liquid (carbonated water). After the high-purity rinse liquid, the low-purity rinse liquid (carbonated water) supplied to the common channel 60 is washed away. Therefore, the required cost is reduced as compared with the liquid feeding method in which the chemical liquid is washed away with only the high-purity rinse liquid.

  In addition, a part or all of the chemical solution (SC2) in the common flow path 60 is obtained by the high purity rinse liquid (DIW) by the flow path high purity rinse liquid supply process executed before the flow path low purity rinse liquid supply process. Replaced. Thereby, before the flow path low-purity rinse liquid supply step is executed, the concentration of ions (chloride ions) in the chemical liquid (SC2) on the substrate W is diluted with the high-purity rinse liquid (DIW). Therefore, the interaction between the ions contained in the chemical liquid and the impurities (organic substances) contained in the low-purity rinse liquid is reduced. Therefore, the formation of precipitates in the flow path low-purity rinse liquid supply step is suppressed or prevented.

Therefore, an increase in cost can be suppressed, and generation of precipitates due to mixing of the chemical liquid and the rinse liquid can be suppressed or prevented.
In addition, according to this embodiment, the second flow path low-purity rinse liquid supply process is executed before the flow path chemical liquid supply process, and the flow path chemical liquid supply process and the second flow path low-purity rinse liquid supply process are performed. In the meantime, the second flow path high-purity rinse liquid supply step is executed. Therefore, in the method in which the common flow path 60 is washed with the rinse liquid before the flow path chemical liquid supply step, the common flow path 60 has a lower content of impurities (organic matter) than the low-purity rinse liquid (carbonated water). Cleaning is performed with a purity rinse liquid (DIW) and a low purity rinse liquid supplied onto the substrate W after the high purity rinse liquid. Therefore, the necessary cost is reduced as compared with the liquid feeding method in which the common flow path 60 is washed only with the high-purity rinse liquid.

  In the second flow path high-purity rinse liquid supply process executed before the flow path chemical liquid supply process, part or all of the low-purity rinse liquid (carbonated water) in the common flow path 60 is a high-purity rinse liquid. Replaced by (DIW). Thereby, before the flow path chemical liquid supply step is executed, the amount of impurities (organic substances) in the rinse liquid of the common flow path 60 is reduced. Therefore, the amount of precipitates formed by the interaction between ions (chloride ions) contained in the chemical liquid (SC2) and impurities contained in the low-purity rinse liquid is reduced. Alternatively, the formation of the precipitate can be prevented. Therefore, the formation of precipitates in the flow path chemical solution supply step is suppressed or prevented.

Therefore, in the method in which the common flow path is cleaned with the rinsing liquid before the flow path chemical supply step, the increase in cost is suppressed and the generation of precipitates due to the mixing of the chemical and the rinsing liquid is suppressed or prevented. Can do.
The present invention is not limited to the embodiments described above, and can be implemented in other forms.

  For example, in the substrate processing in the above-described embodiment, SC1 is supplied from the first nozzle 11, and SC2, DIW, and carbonated water are supplied from the second nozzle 12. The nozzles 11 and 12 may be configured to be supplied to the substrate W. These processing liquids may be configured to be supplied to the substrate W from nozzles provided separately from the nozzles 11 and 12.

In the substrate processing in the above-described embodiment, it is assumed that carbonated water is a low-purity rinse liquid and DIW is a high-purity rinse liquid. However, unlike the substrate processing in the above-described embodiment, DIW containing impurities may be used as the low-purity rinsing liquid, and DIW containing less impurities than the DIW may be used as the high-purity rinsing liquid. .
In this case, instead of the carbonated water rinsing process (S3) in FIG. 4, a DIW rinsing process for replacing SC1 on the substrate W is performed by DIW (low-purity rinsing liquid). Then, instead of the carbonated water rinsing process (S7) in FIG. 4, a DIW rinsing process for replacing DIW (high purity rinsing liquid) on the substrate W by DIW (low purity rinsing liquid) is executed.

Further, unlike the substrate processing in the above-described embodiment, carbonated water containing impurities is used as the low-purity rinse liquid, and carbonated water containing less impurities than the carbonated water is used as the high-purity rinse liquid. May be.
In this case, instead of the DIW rinse process (S4) in FIG. 4, a carbonated water rinse process is performed in which carbonated water (low purity rinse liquid) is replaced with carbonated water (high purity rinse liquid). Then, instead of the DIW rinse process (S6) of FIG. 4, a carbonated water rinse process is performed in which SC2 (chemical solution) is replaced with carbonated water (high-purity rinse liquid).

Further, unlike the substrate processing in the above-described embodiment, DIW containing impurities may be used as the low-purity rinsing liquid, and carbonated water containing less impurities than DIW may be used as the high-purity rinsing liquid. Good.
In this case, instead of the carbonated water rinsing process (S3) in FIG. 4, a DIW rinsing process for replacing SC1 on the substrate W is performed by DIW (low-purity rinsing liquid). Then, instead of the DIW rinse process (S4) of FIG. 4, a carbonated water rinse process is performed in which DIW (low purity rinse liquid) is replaced with carbonated water (high purity rinse liquid). Then, instead of the DIW rinse process (S6) of FIG. 4, a carbonated water rinse process is performed in which SC2 (chemical solution) is replaced with carbonated water (high-purity rinse liquid). Then, instead of the carbonated water rinsing process (S7) of FIG. 4, DIW rinsing process for replacing carbonated water (high purity rinsing liquid) on the substrate W by DIW (low purity rinsing liquid) is executed.

Unlike the substrate processing in the above-described embodiment, a type of rinse liquid different from DIW or carbonated water (the rinse liquid listed in the above-described embodiment) may be used as the low-purity rinse liquid or the high-purity rinse liquid.
When the SC1 process (S2) is not performed in the substrate process (see FIG. 4) in the above-described embodiment, the subsequent carbonated water rinse process (S3) and DIW rinse process (S4) are not performed as shown in FIG. May be. That is, SC2 process (S5) may be performed after board | substrate carrying in (S1). In this case, at the start of the SC2 process (S5), the supply of DIW and carbonated water to the substrate W is stopped, and the supply of DIW and carbonated water to the common channel 60 is also stopped.

As described above, salting out can also occur when the chemical solution is a basic aqueous solution containing a predetermined cation. When SC1 (basic aqueous solution) containing ammonium ions is used as in the substrate processing in the above embodiment, as shown in FIG. 8, DIW is provided between the SC1 processing (S2) and the carbonated water rinsing processing (S3). A rinse process (S10) may be performed.
In the DIW rinsing process (S10), DIW is supplied to the upper surface of the substrate W, whereby SC1 on the upper surface of the substrate W is replaced by DIW (high purity rinsing liquid supply step). At this time, DIW is supplied to the common flow path 60, whereby SC1 in the common flow path 60 is replaced by DIW (flow path high-purity rinse liquid supply step). In the carbonated water rinse process (S3) subsequent to the DIW rinse process (S10), carbonated water is supplied to the upper surface of the substrate W, and DIW on the upper surface of the substrate W or a mixed solution of DIW and SC1 is replaced with carbonated water. (Low-purity rinsing liquid supply step). At that time, carbonated water is supplied to the common flow path 60, whereby DIW in the common flow path 60 or a mixed liquid of DIW and SC1 is replaced by DIW (flow path low-purity rinse liquid supply step).

  Unlike the substrate processing in the above-described embodiment, a chemical solution other than SC2 or SC1 may be used as a chemical solution containing ions that form precipitates by interacting with impurities contained in the rinse solution. For example, SPM containing sulfate ions may be used as an acidic aqueous solution (chemical solution). In this case, for example, instead of the SC2 process (S5), after the DIW rinse process (S4) for a predetermined time, an SPM process is performed in which the upper surface of the substrate W is processed by the SPM by supplying the SPM to the upper surface of the substrate W. (Chemical solution supplying step, acidic aqueous solution supplying step). In this case, it is necessary to provide a sulfuric acid supply source instead of the hydrochloric acid supply source 74.

  In addition, various changes can be made within the scope described in the claims.

1: substrate processing device 3: control device 11: first nozzle (nozzle, chemical solution supply unit, low purity rinse solution supply unit, high purity rinse solution supply unit)
12: 2nd nozzle (nozzle, chemical solution supply unit, low purity rinse solution supply unit, high purity rinse solution supply unit)
60: Common flow path P61: 1st process liquid supply path (chemical solution supply unit, acidic aqueous solution supply unit, low-purity rinse liquid supply unit, carbonic acid-containing liquid supply unit, high-purity rinse liquid supply unit)
P62: Second treatment liquid supply path (chemical solution supply unit, acidic aqueous solution supply unit, low-purity rinse liquid supply unit, carbonic acid-containing liquid supply unit, high-purity rinse liquid supply unit)
P63: First fluid supply path (low-purity rinse liquid supply unit, carbonic acid-containing liquid supply unit)
P64: Second fluid supply path (high-purity rinse liquid supply unit)
P65: Third fluid supply path P66: Fourth fluid supply path (chemical solution supply unit, acidic aqueous solution supply unit)
P67: Fifth fluid supply path (chemical solution supply unit, acidic aqueous solution supply unit)
V61: First treatment liquid valve V62: Second treatment liquid valve (chemical solution supply unit, acidic aqueous solution supply unit, low purity rinse solution supply unit, carbonic acid-containing solution supply unit, high purity rinse solution supply unit)
V63: First fluid valve (low-purity rinse liquid supply unit, carbonate-containing liquid supply unit, low-purity rinse liquid valve)
V64: Second fluid valve (high purity rinse liquid supply unit, high purity rinse liquid valve)
V65: Third fluid valve V66: Fourth fluid valve (chemical solution supply unit, acidic aqueous solution supply unit, chemical solution valve)
V67: Fifth fluid valve (chemical solution supply unit, acidic aqueous solution supply unit, chemical solution valve)
W: Substrate

Claims (16)

A chemical solution supplying step of supplying a chemical solution containing ions to the surface of the substrate;
Low-purity rinse liquid supply that is performed after the chemical liquid supply step and supplies a low-purity rinse liquid containing impurities that form precipitates by interacting with the ions contained in the chemical liquid to the surface of the substrate Process,
A high-purity rinse that is performed between the chemical liquid supply step and the low-purity rinse liquid supply step, and supplies a high-purity rinse liquid that contains less impurities than the low-purity rinse liquid to the surface of the substrate. A substrate processing method including a liquid supply step. The chemical solution includes an acidic aqueous solution,
The substrate processing method according to claim 1, wherein the low-purity rinse liquid contains an organic substance as the impurity.   The substrate processing method according to claim 2, wherein the acidic aqueous solution contains hydrochloric acid.   The substrate processing method according to claim 1, wherein the low-purity rinsing liquid includes a carbonic acid-containing liquid containing carbon dioxide. A second low-purity rinse liquid supply step that is performed before the chemical liquid supply step and supplies the low-purity rinse liquid to the surface of the substrate;
And a second high-purity rinse liquid supply step that is performed between the chemical liquid supply step and the second low-purity rinse liquid supply step and supplies the high-purity rinse liquid to the surface of the substrate. The substrate processing method as described in any one of 1-4. A liquid feeding method for feeding liquid to a nozzle through a common flow path,
A flow path chemical liquid supply step for supplying a chemical liquid containing ions to the common flow path;
A flow path low-purity rinse for supplying a low-purity rinse liquid containing impurities that form precipitates by interacting with the ions contained in the chemical liquid to the common flow path after the flow path chemical liquid supply step A liquid supply process;
A flow for supplying a high-purity rinse liquid, which contains less impurities than the low-purity rinse liquid, to the common flow path between the flow path chemical liquid supply process and the flow path low-purity rinse liquid supply process. A liquid feeding method including a road high purity rinse liquid supply step. The chemical solution includes an acidic aqueous solution,
The liquid feeding method according to claim 6, wherein the low-purity rinsing liquid contains an organic substance as the impurity.   The liquid feeding method according to claim 7, wherein the acidic aqueous solution contains hydrochloric acid.   The liquid feeding method according to any one of claims 6 to 8, wherein the low-purity rinsing liquid includes a carbonic acid-containing liquid containing carbon dioxide. A second flow path low-purity rinse liquid supply process that is performed before the flow path chemical liquid supply process and supplies the low-purity rinse liquid to the common flow path;
A second flow path high-purity rinse liquid supply process that is performed between the flow path chemical liquid supply process and the second flow path low-purity rinse liquid supply process and supplies the high-purity rinse liquid to the common flow path. The liquid feeding method as described in any one of Claims 6-9 containing these. A chemical solution supply unit for supplying a chemical solution containing ions to the surface of the substrate;
A low-purity rinsing liquid supply unit that supplies a low-purity rinsing liquid that may contain impurities that form precipitates by interacting with ions contained in the chemical liquid, to the surface of the substrate;
A high-purity rinsing liquid supply unit that supplies a high-purity rinsing liquid that contains less impurities than the low-purity rinsing liquid to the surface of the substrate;
A control device for controlling the chemical liquid supply unit, the rinse liquid supply unit, and the high-purity rinse liquid supply unit;
The control device supplies a chemical solution to the surface of the substrate, a chemical solution supply step, a low-purity rinse solution supply step to supply the low-purity rinse solution to the surface of the substrate after the chemical solution supply step, and the chemical solution supply The substrate processing apparatus which performs the high purity rinse liquid supply process which supplies the said high purity rinse liquid to the surface of the said board | substrate between a process and the said low purity rinse liquid supply process. The chemical solution supply unit includes an acidic aqueous solution supply unit that supplies an acidic aqueous solution to the surface of the substrate,
The substrate processing apparatus according to claim 11, wherein the low-purity rinse liquid contains an organic substance as the impurity.   The substrate processing apparatus according to claim 12, wherein the acidic aqueous solution contains hydrochloric acid.   The substrate processing apparatus according to claim 11, wherein the low-purity rinsing liquid supply unit includes a carbonic acid-containing liquid supply unit that supplies a carbonic acid-containing liquid containing carbon dioxide to the surface of the substrate. .   A second low-purity rinsing liquid supplying step for supplying the low-purity rinsing liquid to the surface of the substrate before the chemical liquid supplying step; and the chemical liquid supplying step and the second low-purity rinsing liquid supply. The substrate processing apparatus as described in any one of Claims 11-14 which performs the 2nd high purity rinse liquid supply process which supplies the said high purity rinse liquid to the surface of the said board | substrate between processes. A nozzle and a common flow path for feeding the nozzle,
The chemical liquid supply unit includes a chemical liquid valve for switching presence / absence of supply of the chemical liquid to the common flow path,
The low-purity rinsing liquid supply unit includes a low-purity rinsing liquid valve that switches whether or not the low-purity rinsing liquid is supplied to the common flow path;
The high-purity rinse liquid supply unit includes a high-purity rinse liquid valve that switches supply of the supply of the high-purity rinse liquid to the common flow path;
The control device controls the chemical liquid valve, the low-purity rinse liquid valve, and the high-purity rinse liquid valve;
A flow path chemical solution supplying process in which the control device supplies the chemical liquid to the common flow path, and a flow path low purity rinse liquid supply in which the low purity rinse liquid is supplied to the common flow path after the flow path chemical liquid supplying process. And a flow path high-purity rinse liquid supply process for supplying the high-purity rinse liquid to the common flow path between the flow path chemical liquid supply process and the flow path low-purity rinse liquid supply process. Item 16. The substrate processing apparatus according to any one of Items 11 to 15.

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