Substrate processing apparatus and substrate processing method

Abstract

This substrate processing apparatus comprises a substrate holding part, a substrate rotating part, a first nozzle, and a second nozzle. The substrate holding part horizontally holds a substrate. The substrate rotating part rotates the substrate and the substrate holding part integrally. The first nozzle discharges an etching solution toward the substrate which is being held by the substrate holding part while the substrate rotates. The second nozzle discharges a rinse solution toward the substrate which is being held by the substrate holding part while the substrate rotates, to remove the etching solution from the substrate. The etching solution contains an organic solvent and a chemical solution. The rinse solution contains an organic dissolving agent and water. The organic dissolving agent has a higher affinity for the organic solvent than water has.

Description

Substrate processing apparatus and substrate processing method

[0001] The present invention relates to a substrate processing apparatus and a substrate processing method.

[0002] Patent Document 1 discloses a single-wafer substrate processing apparatus that etches a substrate having a pattern formed on its upper surface. The substrate processing apparatus of Patent Document 1 supplies an etching solution to the upper surface of the substrate to remove a native oxide film from the substrate, and then supplies a rinse solution to the upper surface of the substrate to remove the etching solution from the substrate. The substrate processing apparatus of Patent Document 1 supplies hydrofluoric acid (HF) to the substrate as the etching solution and deionized water (DIW) to the substrate as the rinse solution.

[0003] Japanese Patent Application Laid-Open No. 2023-136723

[0004] However, in recent years, the patterns formed on substrates have become increasingly finer, and therefore further improvements are needed to ensure stable penetration of the etching solution deep into the fine patterns.

[0005] An object of the present invention is to provide a substrate processing apparatus and a substrate processing method that can stably penetrate an etching solution deep into a pattern.

[0006] According to one aspect of the present invention, a substrate processing apparatus includes a substrate holding unit, a substrate rotating unit, a first nozzle, and a second nozzle. The substrate holding unit holds a substrate horizontally. The substrate rotating unit rotates the substrate and the substrate holding unit together. The first nozzle ejects an etching solution toward the rotating substrate held by the substrate holding unit. The second nozzle ejects a rinse solution toward the rotating substrate held by the substrate holding unit to remove the etching solution from the substrate. The etching solution contains an organic solvent and a chemical solution. The rinse solution contains an organic solvent and water. The organic solvent has a higher affinity for the organic solvent than the water.

[0007] In certain embodiments, the organic solvent is non-water soluble.

[0008] In one embodiment, the organic solvent has a smaller relative dielectric constant than the chemical solution.

[0009] In one embodiment, the etching solution contains, as the organic solvent, a first organic solvent and a second organic solvent different from the first organic solvent, the first organic solvent and the second organic solvent having different dielectric constants.

[0010] In one embodiment, the etching solution further contains a surfactant.

[0011] In one embodiment, the etching solution further contains an additive that increases the hydrogen ion concentration of the etching solution.

[0012] In one embodiment, the chemical solution is an acidic chemical solution.

[0013] In one embodiment, the etching solution contains a first chemical liquid and a second chemical liquid different from the first chemical liquid, and both the first chemical liquid and the second chemical liquid are acidic chemical liquids.

[0014] In one embodiment, the concentration of the organic solvent in the rinse liquid is 25% or more.

[0015] In one embodiment, the substrate processing apparatus further includes a first liquid piping section, a second liquid piping section, a third liquid piping section, a flow rate adjustment valve, and a controller. The first liquid piping section supplies the rinse liquid to the second nozzle. The second liquid piping section supplies the water to the first liquid piping section. The third liquid piping section supplies the organic solvent to the first liquid piping section. The flow rate adjustment valve is provided in the third liquid piping section. The flow rate adjustment valve adjusts the flow rate of the organic solvent supplied from the third liquid piping section to the first liquid piping section. The controller controls the flow rate adjustment valve to adjust the concentration of the organic solvent in the rinse liquid. The controller controls the flow rate adjustment valve so that the concentration of the organic solvent at the end of discharge of the rinse liquid from the second nozzle is lower than the concentration of the organic solvent at the start of discharge of the rinse liquid from the second nozzle.

[0016] In one embodiment, the controller controls the flow rate adjustment valve so that the concentration of the organic solvent decreases stepwise or gradually during the discharge of the rinse liquid.

[0017] In one embodiment, the substrate processing apparatus further includes an on-off valve. The on-off valve is provided in the third liquid piping section. The on-off valve controls supply and stop of the organic solvent from the third liquid piping section to the first liquid piping section. The controller controls the on-off valve to stop the supply of the organic solvent while the rinse liquid is being discharged.

[0018] According to one aspect of the present invention, a substrate processing method includes a substrate holding step of holding a substrate horizontally, a substrate rotation step of rotating the substrate, an etching step of discharging an etching solution from a first nozzle toward the rotating substrate, and a rinsing step of discharging a rinse solution from a second nozzle toward the rotating substrate to remove the etching solution from the substrate. The etching solution contains an organic solvent and a chemical solution. The rinse solution contains an organic solvent and water. The organic solvent has a higher affinity for the organic solvent than the water.

[0019] In one embodiment, the rinsing step includes a step of supplying the water to a liquid piping section that supplies the rinse liquid to the second nozzle; a step of supplying the organic solvent to the liquid piping section; and a concentration adjusting step of adjusting a flow rate of the organic solvent supplied to the liquid piping section so that the concentration of the organic solvent at the end of discharge of the rinse liquid from the second nozzle is lower than the concentration of the organic solvent at the start of discharge of the rinse liquid from the second nozzle.

[0020] In one embodiment, in the concentration adjusting step, the flow rate of the organic solvent is adjusted so that the concentration of the organic solvent decreases stepwise or gradually while the rinse liquid is being discharged.

[0021] In one embodiment, the substrate processing method further includes the step of stopping the supply of the organic solvent to the liquid piping section while the rinsing liquid is being discharged.

[0022] According to at least one aspect of the present invention, the etching solution can be stably penetrated deep into the pattern.

[0023] FIG. 1 is a schematic diagram of a substrate processing apparatus according to an embodiment of the present invention; FIG. 2 is a cross-sectional view schematically showing the configuration of a substrate processing unit included in the substrate processing apparatus according to an embodiment of the present invention; FIG. 3 is a diagram showing a part of the configuration of a substrate processing apparatus according to an embodiment of the present invention; FIG. 4 is a diagram showing another example of a part of the configuration of a substrate processing apparatus according to an embodiment of the present invention; FIG. 5 is a diagram showing another part of the configuration of a substrate processing apparatus according to an embodiment of the present invention; FIG. 6 is a flowchart showing a substrate processing method according to an embodiment of the present invention; FIG. 7 is a flowchart showing an example of a rinsing process; FIG. 8 is a diagram showing an example of a flow rate of a rinsing liquid; and FIG. 9 is a diagram showing another example of the flow rate of a rinsing liquid.

[0024] Hereinafter, embodiments of a substrate processing apparatus and a substrate processing method according to the present invention will be described with reference to the drawings (FIGS. 1 to 9). However, the present invention is not limited to the following embodiments, and can be implemented in various forms without departing from the spirit of the present invention. Note that where explanations are redundant, they may be omitted as appropriate. Furthermore, in the drawings, identical or corresponding parts are designated by the same reference numerals, and explanations thereof will not be repeated.

[0025] The "substrate" to be processed in the substrate processing apparatus and substrate processing method according to the present invention can be a semiconductor wafer, a glass substrate for a photomask, a glass substrate for a liquid crystal display, a glass substrate for a plasma display, a substrate for an FED (Field Emission Display), a substrate for an optical disk, a substrate for a magnetic disk, or a substrate for a magneto-optical disk. The following description of the embodiment of the present invention will be primarily focused on a case where a disk-shaped semiconductor wafer is the substrate to be processed. However, the substrate processing apparatus and substrate processing method according to the present invention can be similarly applied to various substrates other than the semiconductor wafers described above. Furthermore, the shape of the substrate is not limited to a disk shape, and the substrate processing apparatus and substrate processing method according to the present invention can be applied to substrates of various shapes.

[0026] Fig. 1 is a schematic diagram of a substrate processing apparatus 100 according to this embodiment. More specifically, Fig. 1 is a schematic plan view of the substrate processing apparatus 100 according to this embodiment. The substrate processing apparatus 100 is a single-wafer processing apparatus that processes substrates W one by one. More specifically, the substrate processing apparatus 100 is an etching apparatus that etches substrates W one by one.

[0027] As shown in FIG. 1, the substrate processing apparatus 100 includes a plurality of substrate processing units 2, a fluid cabinet 100A, a plurality of fluid boxes 100B, a plurality of load ports LP, an indexer robot IR, a center robot CR, and a controller 10.

[0028] A cassette CA is placed on each load port LP. The cassette CA accommodates a stack of substrates W. The cassette CA is, for example, a front opening unified pod (FOUP), a standard mechanical interface (SMIF) pod, or an open cassette (OC).

[0029] The indexer robot IR transports substrates W between the cassettes CA and the center robot CR. The center robot CR transports substrates W between the indexer robot IR and a plurality of substrate processing units 2. Note that a placement stage (path) on which substrates W are temporarily placed may be provided between the indexer robot IR and the center robot CR, and the device may be configured so that substrates W are indirectly transferred between the indexer robot IR and the center robot CR via the placement stage.

[0030] The substrate processing units 2 form a plurality of towers TW (four towers TW in FIG. 1 ). The towers TW are arranged to surround the center robot CR in a plan view. Each tower TW includes a plurality of substrate processing units 2 (three substrate processing units 2 in FIG. 1 ) stacked one above the other.

[0031] The fluid cabinet 100A contains a processing liquid, which includes an etching liquid and components of a rinse liquid. The etching liquid contains at least a chemical liquid and an organic solvent.

[0032] Specifically, the chemical solution may be an acidic chemical solution. The chemical solution may be, for example, a chemical solution containing hydrogen fluoride. For example, the chemical solution may be hydrofluoric acid (HF) or diluted hydrofluoric acid (DHF). Dilute hydrofluoric acid refers to hydrofluoric acid with a diluted concentration (for example, about 0.01% by weight). The etching solution may contain two or more types of chemical solutions. For example, the etching solution may contain a first chemical solution and a second chemical solution different from the first chemical solution. Both the first chemical solution and the second chemical solution may be acidic chemical solutions. For example, the etching solution may contain dilute hydrofluoric acid and hydrochloric acid (HCl) as chemical solutions.

[0033] The organic solvent may be, for example, water-insoluble. The dielectric constant of the organic solvent is preferably smaller than that of the chemical solution. The organic solvent may be, for example, PGMEA (propylene glycol monomethyl ether acetate). PGMEA is an example of a water-insoluble organic solvent. PGMEA is also an example of an organic solvent having a dielectric constant smaller than that of the chemical solution. The dielectric constant of PGMEA is 8.3.

[0034] The etching solution may contain two or more types of organic solvents. For example, the etching solution may contain, as organic solvents, a first organic solvent and a second organic solvent different from the first organic solvent. The first organic solvent and the second organic solvent may have different relative dielectric constants. For example, the etching solution may contain, as organic solvents, PGMEA and PGME (propylene glycol monomethyl ether).

[0035] The etching solution may further contain a surfactant or an additive that increases the hydrogen ion concentration of the etching solution. The surfactant may be, for example, IPA (isopropyl alcohol). The additive may be, for example, perchloric acid (HClO), hydrogen iodide (HI), hydrogen bromide (HBr), hydrogen chloride (HCl), sulfuric acid (HSO), nitric acid (HNO), hydronium (H2O), or the like. + ), oxalic acid (HO2C2O2H), sulfurous acid (H2SO3), hydrogen sulfate ion (HSO4 -), or phosphoric acid (H3PO4).

[0036] The rinse liquid contains water and an organic solvent as its components.

[0037] Specifically, the water may be deionized water (DIW). Deionized water is a type of so-called "ultrapure water." However, the water is not limited to deionized water. For example, the water may be carbonated water, electrolytic ionized water, hydrogen water, ozone water, ammonia water, or hydrochloric acid water with a diluted concentration (for example, about 0.001% by weight to about 0.01% by weight).

[0038] The organic solvent used has a higher affinity for the organic solvent of the etching solution than water. Specifically, the organic solvent may be an organic compound having a polar group. For example, the organic solvent may be isopropyl alcohol (IPA). Alternatively, the organic solvent may be ethanol, methanol, or acetone. The concentration of the organic solvent in the rinse solution is preferably 25% or more.

[0039] Each fluid box 100B corresponds to one of the multiple towers TW. The processing liquid in the fluid cabinet 100A is supplied to all of the substrate processing units 2 included in the corresponding tower TW via one of the fluid boxes 100B.

[0040] Each of the substrate processing units 2 processes one substrate W at a time. Specifically, each of the substrate processing units 2 performs etching, rinsing, and drying processes on the substrate W.

[0041] The controller 10 is configured or programmed to control the operation of each part of the substrate processing apparatus 100. For example, the controller 10 controls the substrate processing unit 2, the load port LP, the indexer robot IR, and the center robot CR. The controller 10 includes a control unit 11 and a memory unit 12.

[0042] The control unit 11 controls the operation of each unit of the substrate processing apparatus 100 based on various information stored in the storage unit 12. The control unit 11 has, for example, a processor. The control unit 11 may have a CPU (Central Processing Unit) or an MPU (Micro Processing Unit) as the processor. Alternatively, the control unit 11 may have a general-purpose computing device or a dedicated computing device.

[0043] The memory unit 12 stores various types of information for controlling the operation of the substrate processing apparatus 100. For example, the memory unit 12 stores various types of data and various computer programs. The various types of data include recipe data. The recipe data indicates a recipe that defines the processing content, processing conditions, and processing procedure for the substrate W. Various setting values ​​are set in the recipe as processing conditions.

[0044] The storage unit 12 includes a main storage device. The main storage device includes, for example, a semiconductor memory. The storage unit 12 may further include an auxiliary storage device. The auxiliary storage device includes, for example, at least one of a semiconductor memory and a hard disk drive. The storage unit 12 may also include removable media.

[0045] Next, the substrate processing apparatus 100 of this embodiment will be described with reference to Fig. 2. Fig. 2 is a cross-sectional view schematically showing the configuration of the substrate processing section 2 included in the substrate processing apparatus 100 of this embodiment.

[0046] 2 , the substrate processing unit 2 includes a chamber 2 a, a substrate holding unit 3, a substrate rotating unit 4, a first nozzle 5, a first nozzle moving unit 6, a second nozzle 7, a second nozzle moving unit 8, a liquid receiving unit 9, and a liquid receiving lifting unit 91. The substrate processing apparatus 100 further includes an etching liquid piping unit 101, an etching liquid on / off valve 102, a first rinse liquid piping unit 201, and a first rinse liquid on / off valve 221.

[0047] The chamber 2a has a generally box-like shape and accommodates the substrate holder 3, the substrate rotation unit 4, the first nozzle 5, the first nozzle movement unit 6, the second nozzle 7, the second nozzle movement unit 8, the liquid receiver 9, a portion of the etching liquid piping unit 101, and a portion of the first rinsing liquid piping unit 201. The remaining portion of the etching liquid piping unit 101 is accommodated in the fluid box 100B described with reference to FIG. 1. Similarly, the remaining portion of the first rinsing liquid piping unit 201 is accommodated in the fluid box 100B described with reference to FIG. 1.

[0048] The substrate W is carried into the chamber 2a by the center robot CR described with reference to Fig. 1. Therefore, the chamber 2a accommodates the substrate W. After being processed in the chamber 2a, the substrate W is carried out of the chamber 2a by the center robot CR described with reference to Fig. 1.

[0049] The substrate holding unit 3 is a substrate holder that holds the substrate W in a horizontal position. As shown in Fig. 2, the substrate holding unit 3 may have a spin base 31 and a plurality of chuck members 32. The spin base 31 is substantially disk-shaped and supports the plurality of chuck members 32 in a horizontal position. The plurality of chuck members 32 are arranged on the periphery of the spin base 31. The plurality of chuck members 32 clamp the periphery of the substrate W. The plurality of chuck members 32 hold the substrate W in a horizontal position. The operation of the plurality of chuck members 32 is controlled by a controller 10 (control unit 11).

[0050] The substrate rotation unit 4 is a substrate rotator that rotates the substrate holder 3 and the substrate W together around a first rotation axis AX1 that extends vertically. The controller 10 (control unit 11) controls the rotation of the substrate W by the substrate rotation unit 4. More specifically, the first rotation axis AX1 passes through the center of the spin base 31. The multiple chuck members 32 are arranged so that the center of the substrate W faces the center of the spin base 31. Therefore, the substrate W rotates around the center of the substrate W as the center of rotation.

[0051] 2, the substrate rotating unit 4 may have a shaft 41 and a motor main body 42. The shaft 41 is coupled to the center of the spin base 31 and protrudes downward from the spin base 31 along a first rotation axis AX1. The motor main body 42 rotates the shaft 41. As a result, the spin base 31 rotates. The operation of the motor main body 42 is controlled by the controller 10 (control unit 11).

[0052] The first nozzle 5 ejects the etching liquid toward the rotating substrate W held by the substrate holder 3. Specifically, the first nozzle 5 ejects the etching liquid from above the substrate W toward the upper surface of the rotating substrate W. As the etching liquid is ejected onto the upper surface of the rotating substrate W, a liquid film of the etching liquid is formed on the upper surface of the substrate W. As a result, the upper surface of the substrate W is treated with the etching liquid.

[0053] More specifically, a pattern is formed on the upper surface of the substrate W. For example, the pattern is formed on the upper surface of the substrate W by dry etching. The pattern includes a nitride film and an oxide film. The oxide film includes a native oxide film. In this embodiment, the etching solution etches the oxide film of the pattern. However, the nitride film is also slightly etched by the etching solution. In other words, the etching rate of the nitride film is smaller than the etching rate of the oxide film.

[0054] As already described, in this embodiment, the etching solution contains a chemical solution and an organic solvent. Therefore, the wettability of the etching solution is improved compared to when the etching solution does not contain an organic solvent. As a result, even when a fine pattern is formed on the substrate W, the etching solution can be stably penetrated deep into the pattern. Therefore, the oxide film can be stably removed from the entire pattern. Furthermore, since the oxide film can be stably removed from the entire pattern, the electrical characteristics of the device manufactured from the substrate W can be improved compared to when the etching solution does not contain an organic solvent.

[0055] As already explained, in this embodiment, the dielectric constant of the organic solvent is smaller than that of the chemical solution. As a result, etching (peeling) of the nitride film is suppressed compared to when the etching solution does not contain an organic solvent with a low dielectric constant. Therefore, the selectivity can be improved.

[0056] The etching liquid pipe 101 supplies the etching liquid to the first nozzle 5. The etching liquid pipe 101 is a tube-shaped member through which the liquid flows.

[0057] The etching solution on-off valve 102 is provided in the etching solution piping section 101. The etching solution on-off valve 102 is housed in the fluid box 100B described with reference to FIG. 1. The etching solution on-off valve 102 is switchable between an open state and a closed state. The controller 10 (control section 11) controls the opening and closing operation of the etching solution on-off valve 102. The actuator of the etching solution on-off valve 102 is, for example, an electric actuator or a pneumatic actuator.

[0058] The etching liquid on-off valve 102 controls the flow and stop of the flow of the etching liquid through the etching liquid piping part 101. In other words, the etching liquid on-off valve 102 controls the supply and stop of the supply of the etching liquid to the first nozzle 5.

[0059] The controller 10 (control unit 11) opens the etching liquid on-off valve 102 when discharging the etching liquid from the first nozzle 5. As a result, the etching liquid flows through the etching liquid piping unit 101 toward the first nozzle 5, and the etching liquid is discharged from the first nozzle 5 toward the substrate W.

[0060] The controller 10 (control unit 11) closes the etching liquid on-off valve 102 when stopping the discharge of the etching liquid from the first nozzle 5. As a result, the flow of the etching liquid through the etching liquid piping unit 101 is stopped, and the discharge of the etching liquid from the first nozzle 5 is stopped.

[0061] The first nozzle moving unit 6 moves the first nozzle 5 in the vertical and horizontal directions. The first nozzle moving unit 6 is controlled by a controller 10 (control unit 11). As shown in FIG. 2 , the first nozzle moving unit 6 may include a first nozzle arm 61, a first nozzle base 62, and a first nozzle moving mechanism 63.

[0062] The first nozzle base 62 extends in the vertical direction. The base end of the first nozzle arm 61 is connected to the first nozzle base 62. The first nozzle arm 61 extends in the horizontal direction from the first nozzle base 62. The first nozzle arm 61 supports the first nozzle 5. The first nozzle 5 protrudes vertically downward from the first nozzle arm 61.

[0063] The first nozzle moving mechanism 63 moves the first nozzle arm 61 in the vertical and horizontal directions. As a result, the first nozzle 5 moves in the vertical and horizontal directions. The first nozzle moving mechanism 63 is controlled by the controller 10 (control unit 11). Specifically, the first nozzle moving mechanism 63 has a rotation mechanism and a lifting mechanism.

[0064] The rotation mechanism of the first nozzle movement mechanism 63 rotates the first nozzle base 62 in both forward and reverse directions about a second rotation axis AX2 extending in the vertical direction. As a result, the first nozzle 5 moves along a horizontal plane. The lifting mechanism of the first nozzle movement mechanism 63 raises and lowers the first nozzle base 62 in the vertical direction. As a result, the first nozzle 5 moves in the vertical direction. The actuator of the rotation mechanism may include, for example, a servo motor such as a stepping motor and a reducer. The actuator of the lifting mechanism may include, for example, a ball screw and an electric motor that can rotate forward and backward.

[0065] More specifically, the first nozzle moving unit 6 moves the first nozzle 5 between a first retracted position and a processing position. The first retracted position is a position outside the liquid receiving unit 9. In this embodiment, the processing position is a position opposite the center of the substrate W. The first nozzle 5 ejects the etching liquid from the processing position toward the top surface of the substrate W.

[0066] After the discharge of the etching liquid from the first nozzle 5 has stopped, the second nozzle 7 discharges the rinse liquid toward the rotating substrate W held by the substrate holder 3, thereby removing the etching liquid from the substrate W. Specifically, the second nozzle 7 discharges the rinse liquid from above the substrate W toward the upper surface of the rotating substrate W. By discharging the rinse liquid onto the upper surface of the rotating substrate W, the etching liquid is removed from the upper surface of the substrate W, and a liquid film of the rinse liquid is formed. In other words, the liquid film on the substrate W is replaced with the liquid film of the etching liquid by the liquid film of the rinse liquid.

[0067] As already explained, the rinse liquid contains an organic solvent and water. The organic solvent in the rinse liquid has a higher affinity for the organic solvent in the etching liquid than the water in the rinse liquid. Therefore, the organic solvent in the etching liquid can be more stably removed from the substrate W than when the rinse liquid does not contain an organic solvent. This makes it less likely that residues of the organic solvent in the etching liquid will remain on the substrate W. In particular, when the organic solvent in the etching liquid is water-insoluble, using only water as the rinse liquid makes it more likely that residues of the organic solvent in the etching liquid will remain on the substrate W. In contrast, in this embodiment, the rinse liquid contains an organic solvent that has a high affinity for the organic solvent in the etching liquid. Therefore, even if the organic solvent in the etching liquid is water-insoluble, the organic solvent in the etching liquid can be more stably removed from the substrate W.

[0068] Furthermore, in this embodiment, since the rinse liquid contains an organic solvent, the wettability of the rinse liquid is improved compared to when the rinse liquid does not contain an organic solvent. As a result, even when a fine pattern is formed on the substrate W, the rinse liquid can be stably penetrated deep into the pattern. Therefore, the etching liquid can be stably removed from inside the pattern.

[0069] The first rinse liquid piping section 201 supplies the rinse liquid to the second nozzle 7. The first rinse liquid on / off valve 221 is provided in the first rinse liquid piping section 201. The first rinse liquid on / off valve 221 is housed in the fluid box 100B described with reference to FIG. 1 . The controller 10 (control section 11) opens the first rinse liquid on / off valve 221 when discharging the rinse liquid from the second nozzle 7. The controller 10 (control section 11) closes the first rinse liquid on / off valve 221 when stopping the discharge of the rinse liquid from the second nozzle 7. The configurations of the first rinse liquid piping section 201 and the first rinse liquid on / off valve 221 are substantially the same as the configurations of the etching liquid piping section 101 and the etching liquid on / off valve 102, respectively, and therefore detailed description thereof will be omitted.

[0070] The second nozzle moving unit 8 is controlled by the controller 10 (control unit 11) to move the second nozzle 7 in the vertical and horizontal directions. As shown in FIG. 2 , the second nozzle moving unit 8 may include a second nozzle arm 81, a second nozzle base 82, and a second nozzle moving mechanism 83. Similar to the first nozzle moving mechanism 63, the second nozzle moving mechanism 83 includes a rotation mechanism and an elevation mechanism. The rotation mechanism of the second nozzle moving mechanism 83 rotates the second nozzle base 82 in both forward and reverse directions about a third rotation axis AX3 extending vertically. The configurations of the second nozzle arm 81, the second nozzle base 82, and the second nozzle moving mechanism 83 are substantially the same as the configurations of the first nozzle arm 61, the first nozzle base 62, and the first nozzle moving mechanism 63, respectively, and therefore detailed description thereof will be omitted.

[0071] The second nozzle moving unit 8 moves the second nozzle 7 between a second retracted position and a processing position. The second retracted position is a position outside the liquid receiving unit 9 that is different from the first retracted position of the first nozzle 5. Like the first nozzle 5, the second nozzle 7 ejects the rinse liquid toward the top surface of the substrate W from a position (processing position) facing the center of the top surface of the substrate W.

[0072] The liquid receiving unit 9 surrounds the substrate holding unit 3 and the substrate rotating unit 4. The liquid receiving unit 9 receives the etching liquid and rinsing liquid discharged from the rotating substrate W. Specifically, the liquid receiving lifting unit 91 is controlled by the controller 10 (control unit 11) to raise and lower the liquid receiving unit 9 between an upper position and a lower position. The liquid receiving lifting unit 91 includes, for example, an electric motor that can rotate in both forward and reverse directions and a ball screw mechanism. The upper position is a position above the lower position. When the liquid receiving unit 9 is located at the upper position, it surrounds the substrate W held by the substrate holding unit 3. When the substrate W is being processed, the liquid receiving unit 9 is located at the upper position to receive the etching liquid and rinsing liquid discharged from the rotating substrate W.

[0073] When the liquid receiving part 9 is in the lower position, the upper end of the liquid receiving part 9 is located below the substrate W held by the substrate holder 3. The liquid receiving part 9 is located in the lower position when the center robot CR described with reference to Fig. 1 carries the substrate W into the chamber 2a. The liquid receiving part 9 is also located in the lower position when the center robot CR described with reference to Fig. 1 carries the substrate W out of the chamber 2a.

[0074] The liquid receiving lifting unit 91 may be housed inside the chamber 2a or may be disposed outside the chamber 2a.

[0075] Next, the substrate processing apparatus 100 of this embodiment will be described with reference to FIG. 3 . FIG. 3 is a diagram showing a portion of the configuration of the substrate processing apparatus 100 of this embodiment. As shown in FIG. 3 , the substrate processing apparatus 100 of this embodiment further includes a storage tank 103, a circulation piping unit 104, a circulation pump 105, a circulation filter 106, a first component piping unit 121, a first component on-off valve 131, a second component piping unit 122, and a second component on-off valve 132. The storage tank 103, a portion of the circulation piping unit 104, the circulation pump 105, the circulation filter 106, the first component piping unit 121, the first component on-off valve 131, the second component piping unit 122, and the second component on-off valve 132 are housed in the fluid cabinet 100A described with reference to FIG. 1 . The other portion of the circulation piping unit 104 is housed in the fluid box 100B described with reference to FIG. 1 .

[0076] The storage tank 103 stores an etching solution. Specifically, a chemical solution supplied from a first component supply source 111 is stored in the storage tank 103 via a first component piping section 121. An organic solvent supplied from a second component supply source 112 is stored in the storage tank 103 via a second component piping section 122. As a result, the chemical solution and the organic solvent are mixed in the storage tank 103 to generate an etching solution. The first component supply source 111 may be a facility in a factory in which the substrate processing apparatus 100 is installed. Similarly, the second component supply source 112 may be a facility in a factory in which the substrate processing apparatus 100 is installed. However, the substrate processing apparatus 100 may include at least one of the first component supply source 111 and the second component supply source 112. The same applies to a third component supply source 113, which will be described later with reference to FIG. 4 .

[0077] Specifically, first component piping section 121 is a tubular member through which liquid flows, and allows the chemical solution supplied from first component supply source 111 to flow to storage tank 103. First component on-off valve 131 is provided in first component piping section 121. Controller 10 (controller 11) opens first component on-off valve 131 when supplying the chemical solution to storage tank 103. Controller 10 (controller 11) closes first component on-off valve 131 when stopping the supply of the chemical solution to storage tank 103.

[0078] Second component piping section 122 is a tubular member through which a liquid flows, and allows the organic solvent supplied from second component supply source 112 to flow to storage tank 103. Second component on-off valve 132 is provided in second component piping section 122. Controller 10 (control section 11) opens second component on-off valve 132 when supplying organic solvent to storage tank 103. Controller 10 (control section 11) closes second component on-off valve 132 when stopping the supply of organic solvent to storage tank 103.

[0079] Specifically, the controller 10 (control unit 11) controls the first component on-off valve 131 and the second component on-off valve 132 so that the ratio of the chemical solution to the organic solvent is a predetermined ratio. Note that the configurations of the first component on-off valve 131 and the second component on-off valve 132 are substantially the same as those of the etching solution on-off valve 102 described with reference to FIG. 2, and therefore detailed description thereof will be omitted.

[0080] The circulation pipe 104 is a tubular member through which a liquid flows. One end (upstream end) and the other end (downstream end) of the circulation pipe 104 are connected to the storage tank 103.

[0081] The circulation pump 105 is provided in the circulation piping section 104. The circulation pump 105 pumps the etching liquid so that the etching liquid flows through the circulation piping section 104 from one end (upstream end) to the other end (downstream end) of the circulation piping section 104. As a result, the etching liquid circulates through the circulation piping section 104 via the storage tank 103. The circulation pump 105 is controlled by the controller 10 (control section 11).

[0082] The circulation filter 106 is provided in the circulation piping section 104. The circulation filter 106 removes foreign matter from the etching liquid flowing through the circulation piping section 104.

[0083] 3 , one end (downstream end) of the etching liquid piping section 101 is connected to the first nozzle 5, and the other end (upstream end) of the etching liquid piping section 101 is connected to the circulation piping section 104. When the etching liquid on-off valve 102 is opened, the etching liquid that has flowed from the circulation piping section 104 into the etching liquid piping section 101 is supplied to the first nozzle 5 via the etching liquid piping section 101. As a result, the etching liquid is discharged from the first nozzle 5.

[0084] Here, an example of the chemical solution and the organic solvent will be described. The present inventors observed whether or not the chemical solution and the organic solvent separate under conditions 1 to 3 shown in Table 1 below. If the chemical solution and the organic solvent separate, for example, there is a possibility that the chemical solution will not penetrate deep into the pattern.

[0085]

[0086] In the experiment under Condition 1, hydrofluoric acid (49% HF) with a concentration of 49% and PGMEA were prepared. Deionized water was used as the solvent for the hydrofluoric acid. Then, the 49% HF and PGMEA were mixed in a beaker at a ratio of 49% HF:PGMEA = 1:15. The total amount of 49% HF and PGMEA was 100 ml. As a result, the 49% HF and PGMEA did not separate in the beaker. In other words, liquid separation did not occur.

[0087] In the experiment under condition 2, dilute hydrofluoric acid (DHF) and PGMEA were prepared. Hydrofluoric acid diluted with deionized water (DIW) was used for the dilute hydrofluoric acid. The ratio of hydrofluoric acid to deionized water was "HF:DIW = 1:100." Then, DHF and PGMEA were mixed in a beaker at a ratio of "DHF:PGMEA = 1:300." The total amount of DHF and PGMEA was 100 ml. As a result, DHF and PGMEA separated in the beaker. In other words, liquid separation occurred.

[0088] In the experiment under condition 3, DHF and PGMEA were prepared as in condition 2. Then, DHF and PGMEA were mixed in a beaker at a ratio of "DHF:PGMEA = 1:399". The total amount of DHF and PGMEA was 100 ml. As a result, DHF and PGMEA separated in the beaker. In other words, liquid separation occurred.

[0089] From the experiments under conditions 1 to 3, it was confirmed that liquid separation is more likely to occur when the hydrogen ion concentration of the etching solution is low.

[0090] Next, the inventors of the present invention observed whether or not liquid separation occurs when the mixing ratio (proportion) of 49% HF (chemical liquid) and PGMEA (organic solvent) is changed. Specifically, the inventors of the present invention observed whether or not separation occurs between 49% HF (chemical liquid) and PGMEA (organic solvent) under conditions 4 and 5 shown in Table 2 below.

[0091]

[0092] In the experiment under condition 4, 49% HF and PGMEA were mixed in a beaker at a ratio of 49% HF:PGMEA = 1:300. The total amount of 49% HF and PGMEA was 100 ml. As a result, no liquid separation occurred.

[0093] In the experiment under condition 5, 49% HF and PGMEA were mixed in a beaker at a ratio of 49% HF:PGMEA = 1:399. The total amount of 49% HF and PGMEA was 100 ml. As a result, no liquid separation occurred.

[0094] From the experiments under conditions 1, 4, and 5, it was confirmed that by increasing the hydrogen ion concentration of the etching solution, liquid separation is less likely to occur even when the mixing ratio (proportion) of the chemical solution and the organic solvent is changed.

[0095] Next, another example of the substrate processing apparatus 100 of this embodiment will be described with reference to Fig. 4. Fig. 4 is a diagram showing another example of a portion of the configuration of the substrate processing apparatus 100 of this embodiment. As shown in Fig. 4, the substrate processing apparatus 100 of this embodiment may further include a third component piping section 123 and a third component on-off valve 133.

[0096] In the example shown in FIG. 4 , the first component supply source 111 supplies a first chemical liquid. The third component supply source 113 supplies a second chemical liquid. For example, the first and second chemical liquids may both be acidic chemical liquids. For example, the first chemical liquid may be a chemical liquid containing hydrogen fluoride. Specifically, the first chemical liquid may be hydrofluoric acid (HF) or dilute hydrofluoric acid (DHF). The second chemical liquid may be hydrochloric acid (HCl). Note that the second component supply source 112 supplies an organic solvent. Therefore, in the example shown in FIG. 4 , the first chemical liquid, the second chemical liquid, and the organic solvent are mixed in the storage tank 103 to generate an etching solution. In other words, the etching solution contains the first chemical liquid, the second chemical liquid, and the organic solvent.

[0097] The second chemical liquid is supplied to third component piping section 123 from third component supply source 113. Third component piping section 123 is a tubular member through which a liquid flows, and distributes the second chemical liquid to storage tank 103. Third component on / off valve 133 is provided in third component piping section 123. Third component on / off valve 133 controls the distribution of the second chemical liquid through third component piping section 123 and the stop of this distribution.

[0098] Specifically, controller 10 (controller 11) controls the opening and closing operations of first component on-off valve 131, second component on-off valve 132, and third component on-off valve 133 so that the ratio of the first chemical liquid, the second chemical liquid, and the organic solvent is a predetermined ratio. Note that the configuration of third component on-off valve 133 is substantially the same as that of etching solution on-off valve 102 described with reference to FIG. 2, and therefore a detailed description thereof will be omitted.

[0099] Here, an example of the first chemical liquid, the second chemical liquid, and the organic solvent will be described. The inventors of the present invention observed whether liquid separation occurred under conditions 6 to 8 shown in Table 3 below.

[0100]

[0101] In the experiment under condition 6, 49% HF, HCl, and PGMEA were prepared. Then, 49% HF, HCl, and PGMEA were mixed in a beaker in a ratio of 49% HF:HCl:PGMEA = 1:1:14. The total amount of 49% HF, HCl, and PGMEA was 100 ml. As a result, no liquid separation occurred.

[0102] In the experiment under condition 7, DHF, HCl, and PGMEA were prepared. Then, DHF, HCl, and PGMEA were mixed in a beaker at a ratio of "DHF:HCl:PGMEA = 1:1:300." The total amount of DHF, HCl, and PGMEA was 100 ml. As a result, unlike the experiment under condition 2, no liquid separation occurred.

[0103] In the experiment under condition 8, DHF, HCl, and PGMEA were prepared as in condition 7. Then, DHF, HCl, and PGMEA were mixed in a beaker at a ratio of "DHF:HCl:PGMEA = 1:1:398". The total amount of DHF, HCl, and PGMEA was 100 ml. As a result, unlike the experiment under condition 3, no liquid separation occurred.

[0104] From the experiments under conditions 6 to 8, it was confirmed that when the hydrogen ion concentration of the etching solution is high, liquid separation is unlikely to occur even if the mixing ratio (proportion) of the chemical solution and the organic solvent is changed.

[0105] In the example shown in FIG. 4 , the etching solution is generated by mixing the first chemical solution, the second chemical solution, and an organic solvent. However, the substrate processing apparatus 100 may be configured to generate the etching solution by mixing a chemical solution, an organic solvent, and a surfactant. Alternatively, the substrate processing apparatus 100 may be configured to generate the etching solution by mixing two or more types of chemical solutions, an organic solvent, and a surfactant. The surfactant may be supplied to the storage tank 103, for example, in the same manner as the second chemical solution. The surfactant may be, for example, IPA. By including a surfactant in the etching solution, the penetration of the etching solution into the depth of the pattern can be further improved.

[0106] The substrate processing apparatus 100 may further include a configuration for adding an additive to the etching solution. The additive may be supplied to the storage tank 103 in the same manner as the second chemical solution, for example. The additive includes an additive for increasing the hydrogen ion concentration of the etching solution. The additive may be, for example, perchloric acid (HClO), hydrogen iodide (HI), hydrogen bromide (HBr), hydrogen chloride (HCl), sulfuric acid (HSO), nitric acid (HNO), hydronium (H2O), or the like. + ), oxalic acid (HO2C2O2H), sulfurous acid (H2SO3), hydrogen sulfate ion (HSO4 -), or phosphoric acid (H3PO4). As described with reference to Tables 1 to 3, increasing the hydrogen ion concentration of the etching solution makes it less likely that liquid separation will occur. Therefore, adding an additive can further improve the penetration of the etching solution into the depths of the pattern. Furthermore, if the hydrogen ion concentration is increased by increasing the hydrogen fluoride concentration to avoid liquid separation, the etching amount may be greater than the intended target amount. In contrast, when an additive is used, the hydrogen ion concentration can be increased without increasing the hydrogen fluoride concentration, making it less likely that the etching amount will be greater than the intended target amount.

[0107] Next, the substrate processing apparatus 100 of this embodiment will be described with reference to Fig. 5. Fig. 5 is a diagram showing another portion of the configuration of the substrate processing apparatus 100 of this embodiment. As shown in Fig. 5, the substrate processing apparatus 100 of this embodiment further includes a second rinse liquid piping section 202, a third rinse liquid piping section 203, a second rinse liquid on / off valve 222, a third rinse liquid on / off valve 223, a first flow rate adjustment valve 232, and a second flow rate adjustment valve 233. A portion of the second rinse liquid piping section 202, a portion of the third rinse liquid piping section 203, the second rinse liquid on / off valve 222, the third rinse liquid on / off valve 223, the first flow rate adjustment valve 232, and the second flow rate adjustment valve 233 are accommodated in the fluid box 100B described with reference to Fig. 1.

[0108] 5 , one end (downstream end) of the first rinse liquid piping section 201 is connected to the second nozzle 7. The other end (upstream end) of the first rinse liquid piping section 201 is connected to one end (downstream end) of the second rinse liquid piping section 202 and one end (downstream end) of the third rinse liquid piping section 203. Hereinafter, the point at which the first rinse liquid piping section 201, the second rinse liquid piping section 202, and the third rinse liquid piping section 203 are connected may be referred to as a "connection point P."

[0109] The second rinse liquid piping section 202 supplies water to the first rinse liquid piping section 201. In the present embodiment, the first rinse liquid piping section 201 is an example of a "first liquid piping section" and a "liquid piping section," and the second rinse liquid piping section 202 is an example of a "second liquid piping section." Specifically, the second rinse liquid piping section 202 is a tubular member through which a liquid flows. The second rinse liquid piping section 202 flows water supplied from the fourth component supply source 211 to a connection point P. As a result, water is supplied to the first rinse liquid piping section 201.

[0110] The third rinse liquid piping section 203 supplies the organic solvent to the first rinse liquid piping section 201. In the present embodiment, the third rinse liquid piping section 203 is an example of a "third liquid piping section." Specifically, the third rinse liquid piping section 203 is a tubular member through which a liquid flows. The third rinse liquid piping section 203 flows the organic solvent supplied from the fifth component supply source 212 to the connection point P. As a result, the organic solvent is supplied to the first rinse liquid piping section 201.

[0111] The first rinse liquid piping section 201 and the second rinse liquid piping section 202 may be configured by a single tubular member. Alternatively, the first rinse liquid piping section 201 and the third rinse liquid piping section 203 may be configured by a single tubular member.

[0112] The fourth component supply source 211 may be a facility of a factory in which the substrate processing apparatus 100 is installed. Similarly, the fifth component supply source 212 may be a facility of a factory in which the substrate processing apparatus 100 is installed. However, the substrate processing apparatus 100 may include at least one of the fourth component supply source 211 and the fifth component supply source 212.

[0113] The second rinse liquid on-off valve 222 is provided in the second rinse liquid piping section 202. The second rinse liquid on-off valve 222 is controlled by the controller 10 (control section 11) to control the supply and stop of water from the second rinse liquid piping section 202 to the first rinse liquid piping section 201. Specifically, the second rinse liquid on-off valve 222 can be opened and closed. When the second rinse liquid on-off valve 222 is in an open state, water flows through the second rinse liquid piping section 202 and flows into the first rinse liquid piping section 201 from a connection point P.

[0114] The third rinse liquid on-off valve 223 is provided in the third rinse liquid piping section 203. The third rinse liquid on-off valve 223 is controlled by the controller 10 (control section 11) to control the supply and stop of the organic solvent from the third rinse liquid piping section 203 to the first rinse liquid piping section 201. Specifically, the third rinse liquid on-off valve 223 can be opened and closed. When the third rinse liquid on-off valve 223 is in an open state, the organic solvent flows through the third rinse liquid piping section 203 and flows into the first rinse liquid piping section 201 from the connection point P.

[0115] More specifically, when a rinse liquid containing water and an organic solvent is to be ejected from the second nozzle 7, the controller 10 (controller 11) opens the first rinse liquid on-off valve 221, the second rinse liquid on-off valve 222, and the third rinse liquid on-off valve 223. As a result, the water and the organic solvent flow into the first rinse liquid piping section 201 via the connection point P. The water and the organic solvent are then mixed in the first rinse liquid piping section 201 to generate a rinse liquid containing water and the organic solvent, which is then ejected from the second nozzle 7. Hereinafter, the rinse liquid containing water and an organic solvent may be referred to as a "mixed rinse liquid."

[0116] Furthermore, when stopping the discharge of the rinse liquid from the second nozzle 7, the controller 10 (control unit 11) closes the first rinse liquid on-off valve 221, the second rinse liquid on-off valve 222, and the third rinse liquid on-off valve 223.

[0117] In this embodiment, the controller 10 (controller 11) causes the mixed rinse liquid to be discharged from the second nozzle 7, and then causes a rinse liquid containing only water, out of water and an organic solvent, to be discharged from the second nozzle 7. Hereinafter, a rinse liquid containing only water, out of water and an organic solvent, may be referred to as a "water rinse liquid." When discharging the water rinse liquid from the second nozzle 7, the controller 10 (controller 11) opens the first rinse liquid on-off valve 221 and the second rinse liquid on-off valve 222 and closes the third rinse liquid on-off valve 223.

[0118] The configurations of the second rinse liquid on-off valve 222 and the third rinse liquid on-off valve 223 are substantially the same as the configuration of the etching liquid on-off valve 102 described with reference to FIG. 2, and therefore detailed description thereof will be omitted.

[0119] The first flow rate adjustment valve 232 is provided in the second rinse liquid piping section 202. The first flow rate adjustment valve 232 is controlled by the controller 10 (control section 11) to adjust the flow rate (flow rate per unit time) of water supplied from the second rinse liquid piping section 202 to the first rinse liquid piping section 201.

[0120] Specifically, the opening degree of the first flow rate adjustment valve 232 is adjustable. The controller 10 (control unit 11) adjusts the opening degree of the first flow rate adjustment valve 232 to adjust the flow rate of water flowing through the second rinse liquid piping unit 202. As a result, the flow rate of water supplied from the second rinse liquid piping unit 202 to the connection point P is adjusted. The first flow rate adjustment valve 232 may be, for example, a motor needle valve.

[0121] The second flow rate adjustment valve 233 is provided in the third rinse liquid piping section 203. The second flow rate adjustment valve 233 is controlled by the controller 10 (control section 11) to adjust the flow rate of the organic solvent supplied from the third rinse liquid piping section 203 to the first rinse liquid piping section 201. The configuration of the second flow rate adjustment valve 233 is substantially the same as that of the first flow rate adjustment valve 232, and therefore a detailed description thereof will be omitted.

[0122] The controller 10 (controller 11) adjusts the concentration of the organic solvent in the mixed rinse solution by controlling the second flow rate adjustment valve 233. Specifically, the controller 10 (controller 11) controls the first flow rate adjustment valve 232 and the second flow rate adjustment valve 233 so that the ratio of water to the organic solvent becomes a predetermined ratio.

[0123] Here, examples of etching solutions and rinse solutions will be described. The present inventors observed whether liquid separation occurred using the etching solutions under conditions 1, 4, and 5 described with reference to Tables 1 and 2, and the rinse solution shown in Table 4. If liquid separation occurs, for example, the etching solution may not be completely removed from the substrate W, leaving residual etching solution on the substrate W. Specifically, the present inventors observed whether liquid separation occurred using a rinse solution consisting solely of DIW (water rinse solution) as shown in Table 4 below. They also observed whether liquid separation occurred using a rinse solution (mixed rinse solution) containing a mixture of DIW and IPA. They also observed whether liquid separation occurred by varying the concentration of IPA. In all experiments, the etching solution and rinse solution were mixed in a beaker. The total volume of the etching solution and rinse solution was 100 ml.

[0124]

[0125] As shown in Table 4, in the case of the etching solution under condition 1 (49% HF:PGMEA = 1:15), liquid separation did not occur when the IPA concentration was 25% or higher. Similarly, in the case of the etching solution under condition 4 (49% HF:PGMEA = 1:300), liquid separation did not occur when the IPA concentration was 25% or higher. In the case of the etching solution under condition 5 (49% HF:PGMEA = 1:399), liquid separation did not occur when the IPA concentration was 30% or higher.

[0126] The present inventors also observed whether liquid separation occurred using the etching solutions under conditions 7 and 8 described with reference to Table 3 and the rinse solutions shown in Table 5. Specifically, as shown in Table 5 below, the present inventors confirmed whether liquid separation occurred using a rinse solution consisting solely of DIW (aqueous rinse solution). They also confirmed whether liquid separation occurred using a rinse solution containing a mixture of DIW and IPA (mixed rinse solution). They also observed whether liquid separation occurred by varying the concentration of IPA. In all experiments, the etching solution and rinse solution were mixed in a beaker. The total volume of the etching solution and rinse solution was 100 ml.

[0127]

[0128] As shown in Table 5, in the case of the etching solution under condition 7 (DHF (1:100):HCL:PGMEA = 1:1:300), liquid separation did not occur when the IPA concentration was 40% or higher. Similarly, in the case of the etching solution under condition 8 (DHF (1:100):HCL:PGMEA = 1:1:398), liquid separation did not occur when the IPA concentration was 40% or higher.

[0129] Next, the substrate processing apparatus 100 and substrate processing method of this embodiment will be described with reference to FIGS. 1 to 6. FIG. 6 is a flowchart showing the substrate processing method of this embodiment. The substrate processing method shown in FIG. 6 is performed by the substrate processing apparatus 100 described with reference to FIGS. 1 to 5. Therefore, FIG. 6 shows the operation of the substrate processing apparatus 100 of this embodiment. More specifically, FIG. 6 shows the flow of processing performed by the control unit 11 included in the substrate processing apparatus 100 of this embodiment. The processing shown in FIG. 6 includes steps S1 to S6.

[0130] 6 is initiated in response to the center robot CR loading a substrate W into the chamber 2a. When the control unit 11 initiates the process shown in FIG. 6, it controls the center robot CR and the substrate holder 3 to have the substrate holder 3 hold the substrate W horizontally (step S1, substrate holding step). Specifically, the control unit 11 controls the center robot CR to place the substrate W on the plurality of chuck members 32, and then causes the center robot CR to exit the chamber 2a. Once the substrate W is placed on the plurality of chuck members 32, the control unit 11 controls the plurality of chuck members 32 to clamp the substrate W between the plurality of chuck members 32.

[0131] After causing the substrate holder 3 to hold the substrate W horizontally, the control unit 11 controls the substrate rotation unit 4 to rotate the substrate W and the substrate holder 3 together (step S2, substrate rotation step). After causing the center robot CR to exit the chamber 2a, the control unit 11 controls the liquid receiver lifting unit 91 to move the liquid receiver 9 from the lower position to the upper position. The control unit 11 also controls the first nozzle moving unit 6 to move the first nozzle 5 from the first retracted position to the processing position.

[0132] When the rotation speed of the substrate W reaches a predetermined rotation speed, the control unit 11 executes the etching process. Specifically, the control unit 11 causes the first nozzle 5 to eject the etching liquid toward the rotating substrate W held by the substrate holder 3 (step S3, etching process). As a result, a liquid film of the etching liquid is formed on the upper surface of the substrate W. More specifically, the control unit 11 transitions the etching liquid on-off valve 102 from a closed state to an open state. As a result, the etching liquid is supplied to the first nozzle 5 via the etching liquid piping unit 101, and the etching liquid is ejected from the first nozzle 5.

[0133] When a predetermined time has elapsed since the start of discharge of the etching liquid from the first nozzle 5, the control unit 11 transitions the etching liquid on-off valve 102 from an open state to a closed state to stop discharge of the etching liquid. The control unit 11 then executes a rinse process. Specifically, the control unit 11 discharges a rinse liquid from the second nozzle 7 toward the rotating substrate W held by the substrate holder 3, thereby removing the etching liquid from the substrate W (step S4). As a result, the liquid film on the substrate W is replaced with a liquid film of the rinse liquid.

[0134] More specifically, after the discharge of the etching liquid has stopped, the control unit 11 controls the first nozzle moving unit 6 to move the first nozzle 5 from the processing position to the first retracted position. The control unit 11 also controls the second nozzle moving unit 8 to move the second nozzle 7 from the second retracted position to the processing position. Thereafter, the control unit 11 transitions the first rinse liquid on-off valve 221 to the third rinse liquid on-off valve 223 from the closed state to the open state. As a result, a rinse liquid containing water and an organic solvent (mixed rinse liquid) is supplied from the second nozzle 7 to the substrate W.

[0135] When a predetermined time has elapsed since the start of supply of the rinse liquid from the second nozzle 7, the control unit 11 stops the discharge of the rinse liquid by transitioning the first rinse liquid on-off valve 221 to the third rinse liquid on-off valve 223 from an open state to a closed state. After stopping the discharge of the rinse liquid, the control unit 11 controls the second nozzle moving unit 8 to move the second nozzle 7 from the processing position to the second retracted position.

[0136] After stopping the discharge of the rinse liquid, the control unit 11 executes a drying process (step S5). Specifically, the control unit 11 controls the substrate rotation unit 4 to increase the rotation speed of the substrate W, thereby rotating the substrate W at high speed. As a result, the rinse liquid is scattered from the substrate W, and the substrate W is dried.

[0137] When a predetermined time has elapsed since increasing the rotation speed of the substrate W, the control unit 11 controls the substrate rotation unit 4 to stop the rotation of the substrate W. Thereafter, the control unit 11 controls the center robot CR to unload the substrate W from the chamber 2a (step S6). As a result, the process shown in FIG. 6 is completed.

[0138] Specifically, after stopping the rotation of the substrate W, the control unit 11 controls the liquid receiver lifting unit 91 to move the liquid receiver 9 from the upper position to the lower position. The control unit 11 also controls the substrate holder 3 to release the clamping of the substrate W by the chuck members 32. Thereafter, the control unit 11 controls the center robot CR to transport the substrate W out of the chamber 2a.

[0139] Next, an example of the rinsing step (step S4) shown in Fig. 6 will be described with reference to Fig. 1 to Fig. 9. Fig. 7 is a flowchart showing an example of the rinsing step (step S4 in Fig. 6).

[0140] 7 , when the rinsing process is started, the control unit 11 changes the second rinse liquid on-off valve 222 from a closed state to an open state, thereby supplying water from the second rinse liquid piping unit 202 to the first rinse liquid piping unit 201 (step S41). The control unit 11 also changes the third rinse liquid on-off valve 223 from a closed state to an open state, thereby supplying an organic solvent from the third rinse liquid piping unit 203 to the first rinse liquid piping unit 201 (step S42). The control unit 11 then changes the first rinse liquid on-off valve 221 from a closed state to an open state, thereby supplying a mixed rinse liquid (a rinse liquid containing water and an organic solvent) from the first rinse liquid piping unit 201 to the second nozzle 7 (step S43). As a result, the mixed rinse liquid is ejected from the second nozzle 7.

[0141] 7, the first rinse liquid on-off valve 221 to the third rinse liquid on-off valve 223 are transitioned from the closed state to the open state in the order of the second rinse liquid on-off valve 222, the third rinse liquid on-off valve 223, and the first rinse liquid on-off valve 221. However, the order in which the first rinse liquid on-off valve 221 to the third rinse liquid on-off valve 223 are transitioned from the closed state to the open state is not limited to the order shown in FIG. 7. For example, the first rinse liquid on-off valve 221 to the third rinse liquid on-off valve 223 may be transitioned from the closed state to the open state in this order. Furthermore, the control unit 11 may transition the first rinse liquid on-off valve 221 to the third rinse liquid on-off valve 223 from the closed state to the open state simultaneously, or may transition at least two of the first rinse liquid on-off valve 221 to the third rinse liquid on-off valve 223 from the closed state to the open state at different times.

[0142] In this embodiment, the control unit 11 executes a concentration adjustment process to adjust the concentration of the organic solvent when a predetermined time has elapsed since the start of discharge of the rinse liquid (mixed rinse liquid) (step S44, concentration adjustment step). The concentration adjustment process includes controlling the second flow rate adjustment valve 233 to adjust the flow rate of the organic solvent supplied to the first rinse liquid piping unit 201 so that the concentration of the organic solvent at the end of discharge of the rinse liquid from the second nozzle 7 is lower than the concentration of the organic solvent at the start of discharge of the rinse liquid from the second nozzle 7. Note that the concentration of the organic solvent at the end of discharge of the rinse liquid from the second nozzle 7 may be "0".

[0143] In this embodiment, the control unit 11 controls the third rinse liquid on-off valve 223 to stop the supply of the organic solvent while the rinse liquid (mixed rinse liquid) is being discharged (step S45). Specifically, the control unit 11 transitions the third rinse liquid on-off valve 223 from an open state to a closed state while the rinse liquid (mixed rinse liquid) is being discharged. As a result, the supply of the organic solvent to the first rinse liquid piping unit 201 is stopped while the rinse liquid (mixed rinse liquid) is being discharged. After the supply of the organic solvent is stopped, a water rinse liquid (a rinse liquid containing only water out of water and an organic solvent) is supplied to the substrate W from the second nozzle 7.

[0144] When a predetermined time has elapsed since the supply of the organic solvent was stopped, the control unit 11 transitions the second rinse liquid on-off valve 222 from the open state to the closed state, thereby stopping the supply of water to the first rinse liquid piping unit 201 (step S46). The control unit 11 also transitions the first rinse liquid on-off valve 221 from the open state to the closed state. As a result, the discharge of the rinse liquid (water rinse liquid) from the second nozzle 7 is stopped, and the process shown in FIG. 7 is completed.

[0145] Next, with reference to FIG. 8, an example of the process of adjusting the concentration of the organic solvent (step S44 in FIG. 7) and the process of stopping the supply of the organic solvent during the discharge of the rinse liquid (step S45 in FIG. 7) will be described.

[0146] Fig. 8 is a diagram showing an example of the flow rate of the rinse liquid. Specifically, the upper graph in Fig. 8 shows the flow rate of water. The lower graph in Fig. 8 shows the flow rate of the organic solvent. In the upper graph in Fig. 8, the horizontal axis represents time, and the vertical axis represents the flow rate of water. In the lower graph in Fig. 8, the horizontal axis represents time, and the vertical axis represents the flow rate of the organic solvent.

[0147] As shown in FIG. 8, the control unit 11 may control the second flow rate adjustment valve 233 so that the flow rate of the organic solvent is gradually reduced while the rinse liquid is being discharged, thereby gradually reducing the concentration of the organic solvent while the rinse liquid is being discharged.

[0148] Specifically, at time t1, the control unit 11 transitions the first rinse liquid on-off valve 221 to the third rinse liquid on-off valve 223 from a closed state to an open state. As a result, water is supplied from the second rinse liquid piping unit 202 to the first rinse liquid piping unit 201, and the organic solvent is supplied from the third rinse liquid piping unit 203 to the first rinse liquid piping unit 201. Furthermore, the control unit 11 controls the first flow rate adjustment valve 232 so that the flow rate of water is constant at a flow rate FR1 from time t1 to time t2. Furthermore, the control unit 11 controls the second flow rate adjustment valve 233 so that the flow rate of the organic solvent is constant at a flow rate FR2 from time t1 to time t2.

[0149] At time t2, the control unit 11 starts the concentration adjustment process. Specifically, the control unit 11 controls the second flow rate adjustment valve 233 so that the flow rate of the organic solvent is gradually reduced from the flow rate FR2 from time t2 to time t3. As a result, the concentration of the organic solvent in the rinse liquid discharged from the second nozzle 7 is gradually reduced.

[0150] In this embodiment, when the concentration adjustment process is started, the control unit 11 controls the first flow rate adjustment valve 232 to gradually increase the flow rate of water from the flow rate FR1 in accordance with the gradual decrease in the flow rate of the organic solvent. As a result, the flow rate of the rinse liquid discharged from the second nozzle 7 becomes constant. Furthermore, by increasing the flow rate of water, it is possible to remove from the substrate W any organic solvent residue of the etching liquid remaining on the substrate W.

[0151] At time t3, the control unit 11 controls the third rinse liquid on-off valve 223 to stop the supply of the organic solvent. Thereafter, at time t4, the control unit 11 controls the second rinse liquid on-off valve 222 to stop the supply of water. Therefore, from time t3 to time t4, a water rinse liquid (a rinse liquid containing only water out of water and an organic solvent) is discharged from the second nozzle 7.

[0152] The concentration adjustment process may be started, for example, at the timing when the organic solvent of the etching liquid is substantially removed from the substrate W. The timing when the organic solvent of the etching liquid is substantially removed from the substrate W is determined, for example, by experiment.

[0153] 8, the flow rate of the organic solvent is reduced in three steps, but the flow rate of the organic solvent may be reduced in one step, in two steps, or in four or more steps.

[0154] Next, with reference to FIG. 9, another example of the process of adjusting the concentration of the organic solvent (step S44 in FIG. 7) and the process of stopping the supply of the organic solvent during the discharge of the rinse liquid (step S45 in FIG. 7) will be described.

[0155] Fig. 9 is a diagram showing another example of the flow rate of the rinse liquid. Specifically, the upper graph in Fig. 9 shows the flow rate of water. The lower graph in Fig. 9 shows the flow rate of the organic solvent. In the upper graph in Fig. 9, the horizontal axis represents time, and the vertical axis represents the flow rate of water. In the lower graph in Fig. 9, the horizontal axis represents time, and the vertical axis represents the flow rate of the organic solvent.

[0156] As shown in FIG. 9, the control unit 11 may control the second flow rate adjustment valve 233 so that the flow rate of the organic solvent gradually decreases while the rinse liquid is being discharged, thereby gradually decreasing the concentration of the organic solvent while the rinse liquid is being discharged.

[0157] Specifically, the control unit 11 controls the second flow rate adjustment valve 233 to gradually decrease the flow rate of the organic solvent from time t2 to time t3, thereby gradually decreasing the concentration of the organic solvent in the rinse liquid discharged from the second nozzle 7.

[0158] In this embodiment, when the concentration adjustment process is started, the control unit 11 controls the first flow rate adjustment valve 232 to gradually increase the flow rate of water in accordance with the decrease in the flow rate of the organic solvent. As a result, the flow rate of the rinse liquid discharged from the second nozzle 7 becomes constant. Furthermore, by increasing the flow rate of water, it is possible to remove from the substrate W any organic solvent residue of the etching liquid remaining on the substrate W.

[0159] The embodiment of the present invention has been described above with reference to Figures 1 to 9. According to this embodiment, the etching liquid can be stably penetrated deep into the pattern formed on the upper surface of the substrate W.

[0160] Furthermore, according to this embodiment, the amount of organic solvent supplied during the rinsing process can be reduced, thereby reducing the amount of organic solvent used and reducing the environmental impact.

[0161] Furthermore, according to this embodiment, the supply of the organic solvent can be stopped during the rinsing process, thereby reducing the amount of organic solvent used and the environmental impact.

[0162] In this embodiment, the supply of the organic solvent is stopped after the flow rate of the organic solvent is reduced, but the supply of the organic solvent may be stopped during the discharge of the rinse liquid without reducing the flow rate of the organic solvent. Also, in this embodiment, the supply of the organic solvent is stopped during the discharge of the rinse liquid, but this process may be omitted. For example, after the flow rate of the organic solvent is reduced, the organic solvent may be supplied until the end of the rinse process.

[0163] The embodiments of the present invention have been described above with reference to the drawings (FIGS. 1 to 9). However, the present invention is not limited to the above embodiments and can be implemented in various forms without departing from the spirit of the present invention. Furthermore, the components disclosed in the above embodiments can be modified as appropriate. For example, some of the components shown in one embodiment may be added to the components of another embodiment, or some of the components shown in one embodiment may be deleted from the embodiment.

[0164] The drawings mainly show each component in a schematic manner to facilitate understanding of the invention, and the thickness, length, number, spacing, etc. of each component shown in the drawings may differ from the actual ones due to the convenience of creating the drawings. Furthermore, the configuration of each component shown in the above embodiment is merely an example and is not particularly limited, and it goes without saying that various modifications are possible within a range that does not substantially deviate from the effects of the present invention.

[0165] 1 to 9, the drying process (step S5 in FIG. 6) is performed after the rinsing process (step S4 in FIG. 6), but the substitution process may be performed between the rinsing process and the drying process. The substitution process refers to a process of substituting a liquid film of IPA for a liquid film of water on the substrate W.

[0166] 1 to 9, the substrate W is dried by rotating it at high speed in the drying process (step S5 in FIG. 6), but the drying process is not limited to this. For example, the substrate processing apparatus 100 may be configured to dry the substrate W by spraying an inert gas onto the substrate W after the replacement process. Alternatively, the substrate processing apparatus 100 may be configured to dry the substrate W by changing the atmosphere around the substrate W to an inert gas atmosphere after the replacement process.

[0167] Furthermore, in the embodiment described with reference to FIGS. 1 to 9, the first rinse liquid piping section 201, the second rinse liquid piping section 202, and the third rinse liquid piping section 203 are connected at one location (connection location P), but the second rinse liquid piping section 202 and the third rinse liquid piping section 203 may be connected to the first rinse liquid piping section 201 at different locations.

[0168] 1 to 9, the first rinse liquid piping section 201, the second rinse liquid piping section 202, and the third rinse liquid piping section 203 are directly connected, but the first rinse liquid piping section 201, the second rinse liquid piping section 202, and the third rinse liquid piping section 203 may be connected to one another via a multiple valve. When a multiple valve is used, water and an organic solvent may be mixed within the multiple valve.

[0169] Furthermore, in the embodiment described with reference to Figures 1 to 9, the components of the etching solution were mixed within the fluid cabinet 100A, but the components of the etching solution may also be mixed within the piping that supplies the etching solution to the first nozzle 5.

[0170] 1 to 9, the first nozzle 5 discharges the etching liquid from a position facing the center of the top surface of the substrate W, but the first nozzle 5 may discharge the etching liquid from positions facing each of a plurality of positions in the radial direction of the substrate W, or may discharge the etching liquid while moving above the substrate W. Alternatively, the etching liquid may be discharged from a position facing the center of the substrate W and a position facing the peripheral edge of the substrate W.

[0171] 1 to 9, the substrate processing apparatus 100 includes the first nozzle 5 and the second nozzle 7. However, the substrate processing apparatus 100 may include a single nozzle that selectively discharges at least one of the etching liquid and the rinsing liquid. In other words, the substrate processing apparatus 100 may include a single nozzle that exclusively discharges the etching liquid and the rinsing liquid.

[0172] 1 to 9, the substrate holding unit 3 has a clamping chuck mechanism, but the substrate holding unit 3 is not limited to a clamping chuck mechanism. For example, the substrate holding unit 3 may have a vacuum chuck mechanism.

[0173] The present invention is useful in an apparatus and method for processing a substrate.

[0174] This application claims priority from Japanese Patent Application No. 2024-010075, filed on January 26, 2024, the entire contents of which are incorporated herein by reference.

Claims

1. A substrate processing apparatus comprising: a substrate holding unit that holds a substrate horizontally; a substrate rotation unit that rotates the substrate and the substrate holding unit together; a first nozzle that sprays an etching solution toward the rotating substrate held by the substrate holding unit; and a second nozzle that sprays a rinse solution toward the rotating substrate held by the substrate holding unit to remove the etching solution from the substrate, wherein the etching solution contains an organic solvent and a chemical solution, the rinse solution contains an organic solvent and water, and the organic solvent has a higher affinity for the organic solvent than the water.

2. The substrate processing apparatus according to claim 1, wherein the organic solvent is water-insoluble.

3. The substrate processing apparatus according to claim 1 or 2, wherein the organic solvent has a lower relative dielectric constant than the chemical solution.

4. A substrate processing apparatus according to any one of claims 1 to 3, wherein the etching solution contains, as the organic solvent, a first organic solvent and a second organic solvent different from the first organic solvent, and the first organic solvent and the second organic solvent have different relative dielectric constants.

5. The substrate processing apparatus according to claim 1, wherein the etching liquid further contains a surfactant.

6. The substrate processing apparatus according to claim 1, wherein the etching solution further contains an additive that increases the hydrogen ion concentration of the etching solution.

7. The substrate processing apparatus according to claim 1, wherein the chemical solution is an acidic chemical solution.

8. A substrate processing apparatus according to any one of claims 1 to 7, wherein the etching liquid contains a first chemical liquid and a second chemical liquid different from the first chemical liquid, and both the first chemical liquid and the second chemical liquid are acidic chemical liquids.

9. The substrate processing apparatus according to claim 1, wherein the concentration of the organic solvent in the rinse liquid is 25% or more.

10. A substrate processing apparatus as described in any one of claims 1 to 9, further comprising: a first liquid piping section that supplies the rinsing liquid to the second nozzle; a second liquid piping section that supplies the water to the first liquid piping section; a third liquid piping section that supplies the organic solvent to the first liquid piping section; a flow rate adjustment valve provided in the third liquid piping section that adjusts the flow rate of the organic solvent supplied from the third liquid piping section to the first liquid piping section; and a controller that controls the flow rate adjustment valve to adjust the concentration of the organic solvent in the rinsing liquid, wherein the controller controls the flow rate adjustment valve so that the concentration of the organic solvent at the end of the discharge of the rinsing liquid from the second nozzle is lower than the concentration of the organic solvent at the start of the discharge of the rinsing liquid from the second nozzle.

11. The substrate processing apparatus according to claim 10, wherein the controller controls the flow rate adjustment valve so that the concentration of the organic solvent decreases stepwise or gradually during the discharge of the rinse liquid.

12. A substrate processing apparatus as described in claim 10 or claim 11, further comprising an on-off valve provided in the third liquid piping section for controlling the supply of the organic solvent from the third liquid piping section to the first liquid piping section and the stop of the supply, wherein the controller controls the on-off valve to stop the supply of the organic solvent while the rinse liquid is being ejected.

13. A substrate processing method comprising: a substrate holding step of holding a substrate horizontally; a substrate rotation step of rotating the substrate; an etching step of discharging an etching solution from a first nozzle toward the rotating substrate; and a rinsing step of discharging a rinsing solution from a second nozzle toward the rotating substrate to remove the etching solution from the substrate, wherein the etching solution contains an organic solvent and a chemical solution, the rinsing solution contains an organic solvent and water, and the organic solvent has a higher affinity for the organic solvent than the water.

14. The substrate processing method of claim 13, wherein the rinsing step includes: a step of supplying the water to a liquid piping section that supplies the rinsing liquid to the second nozzle; a step of supplying the organic solvent to the liquid piping section; and a concentration adjustment step of adjusting the flow rate of the organic solvent supplied to the liquid piping section so that the concentration of the organic solvent at the end of the discharge of the rinsing liquid from the second nozzle is lower than the concentration of the organic solvent at the start of the discharge of the rinsing liquid from the second nozzle.

15. The substrate processing method according to claim 14, wherein the concentration adjusting step adjusts the flow rate of the organic solvent so that the concentration of the organic solvent decreases stepwise or gradually while the rinse liquid is being discharged.

16. The substrate processing method according to claim 14 or 15, further comprising the step of stopping the supply of the organic solvent to the liquid piping section while the rinse liquid is being discharged.

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