SUBSTRATE PROCESSING METHOD AND SUBSTRATE PROCESSING APPARATUS

Abstract

To provide a substrate processing method and a substrate processing apparatus capable of appropriately etching a substrate regardless of the size of recesses on a substrate.SOLUTION: In a substrate processing method and a substrate processing apparatus according to the present invention, an additive is dissolved in a first treatment liquid. The first treatment liquid contains iodide ions (I-). The substrate processing method includes an adjustment step and a supply step. The adjustment step suppresses the reduction of iodide ions (I-) contained in the first treatment liquid. Therefore, the first treatment liquid contains sufficient iodide ions (I-). The supply step supplies the first processing liquid adjusted in the adjustment step to the substrate. Furthermore, the supply step supplies the first etching liquid to the substrate.SELECTED DRAWING: Figure 6

Description

[Technical field]

[0001] The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate, such as a semiconductor wafer, a substrate for a liquid crystal display, a substrate for an organic electroluminescence (EL), a substrate for a flat panel display (FPD), a substrate for an optical display, a substrate for a magnetic disk, a substrate for an optical disk, a substrate for a magneto-optical disk, a substrate for a photomask, or a substrate for a solar cell. [Background technology]

[0002] The substrate processing apparatuses disclosed in Patent Documents 1 and 2 supply an etching liquid to a substrate to etch the substrate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 9-22891 [Patent Document 2] Japanese Patent Application Publication No. 9-115875 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, patterns formed on the surface of a substrate have become finer. The patterns include a plurality of protrusions (structures) and a plurality of recesses (spaces). The protrusions are made of, for example, a silicon oxide film (SiO2), a silicon nitride film (SiN), or a polysilicon film. The recesses are adjacent to the protrusions. The protrusions correspond to walls that partition the recesses. As the patterns become finer, the recesses become narrower. For example, the separation distance between two adjacent protrusions may be tens of nanometers or less. For example, the recesses may have a width of only tens of nanometers or less.

[0005] For this reason, in the etching process, an etching solution may be supplied to a narrow recess. The etching solution may etch the substrate in the narrow recess. However, the quality of the etching process may be reduced depending on the size of the recess. For example, when the recess is narrow, the substrate may not be properly etched. For example, when the recess is narrow, the etching function may be reduced.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a substrate processing method and substrate processing apparatus that can appropriately etch a substrate regardless of the size of a recess on the substrate. [Means for solving the problem]

[0007] The present inventors have conducted intensive research to solve the above problems. First, the present inventors discovered that iodide ions (I - ) was focused on. Iodide ion (I - ) is hydrophobic. The protrusions on the substrate are also hydrophobic. Therefore, iodide ions (I - ) and the convex portion is more compatible with each other than with water molecules and the convex portion.

[0008] Therefore, the present inventors have investigated the mechanism of the iodide ion (I - We investigated the supply of an etching solution containing iodide ions (I - ) easily enters the recesses on the substrate. Iodide ions (I - The ease of entry of iodide ions (I) does not depend on the size of the recess. Even if the recess is narrow, - ) easily fits into recesses.

[0009] Here, iodide ion (I - ) is an anion. More specifically, iodide ion (I - ) is a monoatomic anion consisting of one iodine atom. The etchant contains hydrogen ions (H + ) containing hydrogen ions (H +) is a cation. Therefore, the iodide ion (I - ) is the hydrogen ion (H + In other words, the iodide ion (I - ) is a hydrogen ion (H + Therefore, regardless of the size of the recess, the movement of hydrogen ions (H + ) also easily enters the recess.

[0010] Hydrogen ion (H + ) is one of the ions that etches the substrate. Therefore, the substrate can be properly etched regardless of the size of the recess.

[0011] However, the present inventors have found a new problem. The new problem is that iodide ions (I - However, even if an etching solution containing the above-mentioned fluorine-containing fluorine-containing compound is used, the etching function may vary or may be reduced. Therefore, the present inventors further investigated the new problem.

[0012] The present invention was achieved through further intensive research based on these findings, and has the following configuration. That is, the present invention is a substrate processing method for processing a substrate, comprising the steps of: - and a supplying step of supplying the first processing liquid adjusted by the adjusting step and a first etching liquid for etching the substrate to the substrate.

[0013] The additive is dissolved in the first treatment liquid. The first treatment liquid contains iodide ions (I - The substrate processing method includes a preparation step and a supply step. The preparation step is a step of adjusting iodide ions (I - For this reason, the first treatment solution is designed to have sufficient iodide ions (I -The supplying step supplies the first processing liquid prepared in the adjusting step to the substrate. Furthermore, the supplying step supplies a first etching liquid to the substrate. As described above, the first processing liquid prepared in the adjusting step contains sufficient iodide ions (I - ) is included. Therefore, regardless of the size of the recess on the substrate, iodide ions (I - ) easily enters the recesses. Regardless of the size of the recesses, hydrogen ions (H + ) and iodide ion (I - ) and easily enters recesses. As a result, the substrate can be properly etched regardless of the size of the recess.

[0014] As described above, according to the substrate processing method of the present invention, the substrate can be appropriately etched regardless of the size of the recess on the substrate.

[0015] In the above-described substrate processing method, the supplying step is performed by supplying the first processing liquid adjusted in the adjusting step. of The mixture is added to the first etching solution. 、 It is preferable to supply the mixed liquid to the substrate. In the supplying step, the mixed liquid is supplied to the substrate. Here, the mixed liquid is obtained by adding the first processing liquid prepared in the preparation step to the first etching liquid. That is, the mixed liquid contains the first processing liquid and the first etching liquid. Therefore, supplying the mixed liquid corresponds to supplying the first processing liquid and the first etching liquid. Furthermore, the fact that the mixed liquid contains the first processing liquid and the first etching liquid means that the mixed liquid contains iodide ions (I - ) and hydrogen ions (H + ) is contained in the mixture. Therefore, immediately after the mixture is supplied to the substrate, iodide ions (I - ) is a hydrogen ion (H + ) can be favorably promoted, and thus the substrate can be more appropriately etched.

[0016] In the above-mentioned substrate processing method, the first processing liquid is preferably an aqueous solution in which the additive is dissolved in pure water. For this reason, the adjusting step is performed by adjusting the amount of iodide ions (I -) can be easily prevented from decreasing.

[0017] The present invention relates to a method for processing a substrate, the method comprising the steps of: - and a supplying step of supplying a first processing liquid adjusted by the adjusting step to a substrate, wherein the first processing liquid further contains a second etching liquid for etching the substrate.

[0018] The additive is dissolved in the first treatment liquid. The first treatment liquid contains iodide ions (I - The substrate processing method includes a preparation step and a supply step. The preparation step is a step of adjusting iodide ions (I - For this reason, the first treatment solution is designed to have sufficient iodide ions (I - The first processing solution further includes a second etching solution. That is, the first processing solution contains hydrogen ions (H + In the supply step, the first processing liquid adjusted in the adjustment step is supplied to the substrate. As described above, the first processing liquid adjusted in the adjustment step contains sufficient iodide ions (I - The first treatment liquid further contains hydrogen ions (H + ) is included. Therefore, regardless of the size of the recess on the substrate, iodide ions (I - ) is a hydrogen ion (H + Immediately after the first processing liquid is supplied to the substrate, it easily enters the recesses, bringing with it hydrogen ions (H + ) is the iodide ion (I - ) and easily enters recesses. As a result, the substrate can be properly etched regardless of the size of the recess.

[0019] As described above, according to the substrate processing method of the present invention, the substrate can be appropriately etched regardless of the size of the recess on the substrate.

[0020] In the above-mentioned substrate processing method, the additive is added to the first processing solution by ionizing the iodide ion (I -It is preferable that the first treatment liquid liberates iodide ions (I - ) may be suitably included.

[0021] In the above-described substrate processing method, the additive preferably includes at least one of tetramethylammonium iodide (TMAI), tetraethylammonium iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide, ammonium iodide, and hydrogen iodide. - ) may be suitably included.

[0022] In the above-described substrate processing method, the adjusting step preferably includes reducing a concentration of dissolved oxygen in the first processing liquid. - ) can be suitably suppressed from decreasing.

[0023] In the above-described substrate processing method, the adjusting step preferably includes supplying an inert gas into the first processing liquid to generate bubbles in the first processing liquid, and the adjusting step can suitably reduce a concentration of dissolved oxygen in the first processing liquid.

[0024] In the above-described substrate processing method, the adjusting step preferably includes degassing the first processing liquid. - ) can be suitably suppressed from decreasing.

[0025] In the above-described substrate processing method, the adjusting step preferably includes filtering the first processing liquid using a gas-liquid separator to degas the first processing liquid. The adjusting step can suitably degas the first processing liquid.

[0026] In the above-described substrate processing method, the adjusting step is performed by adjusting the iodide ion (I -It is preferable to detect at least one of the concentration of iodide ions (I - In the case of detecting the concentration of iodide ions (I - In the case of detecting the oxidation-reduction potential of the first treatment liquid, the concentration of iodide ions (I - In the case of detecting the concentration of dissolved oxygen in the first treatment liquid, the adjustment step is performed by adjusting the concentration of iodide ions (I - ) can be suitably estimated.

[0027] In the above-mentioned substrate processing method, the iodide ions (I - It is preferable that the adjustment step is started and ended based on at least one of the detection results of the concentration of the first treatment liquid, the detection results of the oxidation-reduction potential of the first treatment liquid, and the detection results of the concentration of dissolved oxygen in the first treatment liquid. The adjustment step can be started at an appropriate timing. The adjustment step can be ended at an appropriate timing.

[0028] In the above-mentioned substrate processing method, the iodide ions (I - At least one of the additive and the solvent of the additive is determined based on at least one of the detection results of the concentration of the additive, the detection result of the oxidation-reduction potential of the first treatment liquid, and the detection result of the concentration of dissolved oxygen in the first treatment liquid. The above It is preferable to replenish the first processing solution. - ) can be suitably adjusted.

[0029] In the above-mentioned substrate processing method, it is preferable that the substrate has a recess. Even if the substrate has a recess, the substrate can be appropriately etched regardless of the size of the recess on the substrate.

[0030] The present invention relates to a substrate processing apparatus, comprising: -and a supply unit that supplies, to a substrate, the first processing liquid adjusted by the adjustment unit and a first etching liquid for etching the substrate.

[0031] The additive is dissolved in the first treatment liquid. The first treatment liquid contains iodide ions (I - The substrate processing apparatus includes an adjustment unit and a supply unit. The adjustment unit removes dissolved oxygen from the first processing liquid. This reduces iodide ions (I - Therefore, the first treatment liquid adjusted by the adjustment unit contains a sufficient amount of iodide ions (I - The supply unit supplies the first processing liquid and the first etching liquid adjusted by the adjustment unit to the substrate. As described above, the first processing liquid adjusted by the adjustment unit contains sufficient iodide ions (I - ) is included. Therefore, regardless of the size of the recess on the substrate, iodide ions (I - ) easily enters the recesses. Regardless of the size of the recesses, hydrogen ions (H + ) and iodide ion (I - ) and easily enters recesses. As a result, the substrate can be properly etched regardless of the size of the recess.

[0032] As described above, according to the substrate processing apparatus of the present invention, the substrate can be appropriately etched regardless of the size of the recess on the substrate.

[0033] In the above-described substrate processing apparatus, the supply unit supplies the first processing liquid adjusted by the adjustment unit. of The mixture is added to the first etching solution. 、It is preferable to supply the mixed liquid to the substrate. The liquid supply unit supplies the mixed liquid. Here, the mixed liquid is obtained by adding the first processing liquid adjusted by the adjustment unit to the first etching liquid. That is, the mixed liquid contains the first processing liquid and the first etching liquid. Therefore, supplying the mixed liquid is equivalent to supplying the first processing liquid and the first etching liquid. Furthermore, the mixed liquid containing the first processing liquid and the first etching liquid means that the mixed liquid contains iodide ions (I - ) and hydrogen ions (H + ) is contained in the mixture. Therefore, immediately after the mixture is supplied to the substrate, iodide ions (I - ) is a hydrogen ion (H + ) can be favorably promoted, and thus the substrate can be more appropriately etched.

[0034] In the above-mentioned substrate processing apparatus, the first processing liquid is preferably an aqueous solution in which the additive is dissolved in pure water. For this reason, the adjusting unit adjusts the amount of iodide ions (I - ) can be easily prevented from decreasing.

[0035] The present invention relates to a substrate processing apparatus, comprising: - and a supply unit that supplies the first processing liquid adjusted by the adjustment unit to a substrate, wherein the first processing liquid includes a second etching liquid for etching a substrate.

[0036] The additive is dissolved in the first treatment liquid. The first treatment liquid contains iodide ions (I - The substrate processing apparatus includes an adjustment unit and a supply unit. The adjustment unit removes dissolved oxygen from the first processing liquid. Therefore, iodide ions (I - Therefore, the first treatment liquid adjusted by the adjustment unit contains a sufficient amount of iodide ions (I - The first processing solution further includes a second etching solution. That is, the first processing solution contains hydrogen ions (H +The supply unit supplies the first processing liquid adjusted by the adjustment unit to the substrate. As described above, the first processing liquid adjusted by the adjustment unit contains sufficient iodide ions (I - The first treatment liquid further contains hydrogen ions (H + ) is included. Therefore, regardless of the size of the recess on the substrate, iodide ions (I - ) is a hydrogen ion (H + Immediately after the first processing liquid is supplied to the substrate, hydrogen ions (H + ) is the iodide ion (I - ) and easily enters recesses. As a result, the substrate can be properly etched regardless of the size of the recess.

[0037] As described above, according to the substrate processing apparatus of the present invention, the substrate can be appropriately etched regardless of the size of the recess on the substrate.

[0038] In the above-mentioned substrate processing apparatus, the iodide ions (I - The control unit preferably includes a first sensor that detects the concentration of iodide ions (I - ) can be conveniently monitored.

[0039] In the above-mentioned substrate processing apparatus, it is preferable that the control unit controls the adjustment unit based on a detection result of the first sensor. The control unit can appropriately control the adjustment unit.

[0040] In the above-mentioned substrate processing apparatus, it is preferable that the substrate processing apparatus further includes a first replenishing unit that replenishes the first processing liquid with a solvent of the additive, and the control unit controls the first replenishing unit to replenish the solvent to the first processing liquid based on a detection result of the first sensor. The control unit can suitably dilute the first processing liquid.

[0041] In the above-mentioned substrate processing apparatus, the adjustment unit preferably includes a bubble generating unit that supplies an inert gas into the first processing liquid to generate bubbles in the first processing liquid. The adjustment unit includes a bubble generating unit. Thus, the adjustment unit can suitably reduce the concentration of dissolved oxygen in the first processing liquid.

[0042] In the above-described substrate processing apparatus, the adjustment unit preferably includes a gas-liquid separation unit that filters the first processing liquid and degasses the first processing liquid. The adjustment unit includes the gas-liquid separation unit. Therefore, the adjustment unit can degas the first processing liquid in an appropriate manner. Therefore, the adjustment unit can reduce the concentration of dissolved oxygen in the first processing liquid in an appropriate manner.

[0043] In the above-mentioned substrate processing apparatus, it is preferable that the substrate has a recess. Even if the substrate has a recess, the substrate can be appropriately etched regardless of the size of the recess on the substrate. Effect of the Invention

[0044] According to the substrate processing method and substrate processing apparatus of the present invention, the substrate can be appropriately etched regardless of the size of the recess on the substrate. [Brief description of the drawings]

[0045] [Figure 1] 1A to 1C are diagrams illustrating an operation of etching a substrate. [Diagram 2] 1A to 1C are diagrams illustrating an operation of etching a substrate. [Diagram 3] 1A to 1C are diagrams illustrating an operation of etching a substrate. [Figure 4] FIG. 2 is a plan view showing the inside of the substrate processing apparatus. [Diagram 5] FIG. 2 is a control block diagram of the substrate processing apparatus. [Figure 6] FIG. 2 is a diagram showing the configurations of a processing unit and a processing liquid adjusting unit according to the first embodiment. [Figure 7] FIG. 13 is a diagram showing the configurations of a processing unit and a processing liquid adjusting unit according to a second embodiment. [Figure 8] FIG. 13 is a diagram showing the configurations of a processing unit and a processing liquid adjusting unit according to a third embodiment. [Figure 9] FIG. 13 is a diagram showing the configurations of a processing unit and a processing liquid adjusting unit according to a fourth embodiment. [Figure 10] 13 is a diagram showing the configuration of a processing unit and a processing liquid adjusting unit according to a modified embodiment. FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0046] <1. Iodide ion (I - Principle of etching process using Iodide ion (I - The present inventors speculate that the mechanism behind the variation in etching function when using the etching gas containing 1,2-dichloromethane (1,2-dichloromethane) is as follows.

[0047] 1, 2, and 3 are diagrams each showing an operation of etching a substrate W. The substrate W is, for example, a semiconductor wafer, a substrate for a liquid crystal display, a substrate for an organic EL (Electroluminescence), a substrate for an FPD (Flat Panel Display), a substrate for an optical display, a substrate for a magnetic disk, a substrate for an optical disk, a substrate for a magneto-optical disk, a substrate for a photomask, or a substrate for a solar cell. The substrate W has a thin, flat plate shape. The substrate W has a substantially circular shape in a plan view.

[0048] Referring to FIG. 1, the substrate W has a pattern-formed surface W1. The pattern-formed surface W1 is composed of, for example, a silicon oxide film (SiO2), a silicon nitride film (SiN), or a polysilicon film. The pattern-formed surface W1 has a protrusion W2 and a recess A. The protrusion W2 is a part of the substrate W. The protrusion W2 is a structure. The protrusion W2 is also composed of a thermal oxide film (SiO2). The recess A is a space. The recess A is adjacent to the protrusion W2. The protrusion W2 corresponds to a wall that partitions the recess A. The protrusion W2 is hydrophobic.

[0049] The processing liquid is supplied to the pattern forming surface W1 of the substrate W. The processing liquid is a mixture of an etching liquid and iodide ions (I -) because the processing solution contains an etching solution, the processing solution contains hydrogen ions (H + ) containing hydrogen ions (H + ) is one of the ions that etches the substrate W. Hydrogen ions (H + ) is a cation. - ) is an anion. More specifically, iodide ion (I - ) is a monovalent monatomic anion. - ) has hydrophobic properties.

[0050] The protruding part W2 and the iodide ion (I - ) are both hydrophobic. Therefore, the protrusion W2 and the iodide ion (I - ) is more compatible with the protrusion W2 than with water molecules. Therefore, the iodide ions (I - ) easily enters recess A. Iodide ions (I - The ease with which iodide ions (I) can enter does not depend on the size of the recess A. This is because the recess A is adjacent to the protrusion W2. Even if the recess A is narrow, iodide ions (I - ) easily enters recess A.

[0051] Iodide ion (I - ) is an anion, and hydrogen ion (H + ) is a cation. Therefore, the iodide ion (I - ) and hydrogen ions (H + ) attract each other. Iodide ions (I - ) is a hydrogen ion (H + In other words, the iodide ion (I - ) is a hydrogen ion (H + Therefore, regardless of the size of the recess A, the movement of hydrogen ions (H + ) also easily enters the recess A. As a result, hydrogen ions (H + ) concentration does not decrease.

[0052] Hydrogen ion (H +) is one of the ions that etches the substrate. Therefore, the substrate W can be appropriately etched regardless of the size of the recess.

[0053] Referring to FIG. 2, two iodide ions (I - ) can become molecular iodine (I2). 2I - → I2+2e - This results in the production of iodide ions (I - ) decreases. Iodine molecules (I2) increase.

[0054] Iodine molecules (I2) are electrically neutral. Therefore, the iodine molecule (I2) and the hydrogen ion (H + ) do not attract each other. Iodine molecules (I2) are hydrogen ions (H + In other words, the iodine molecule (I2) does not move with the hydrogen ion (H + Therefore, the iodine molecule (I2) does not promote the transfer of hydrogen ions (H + ) into the recess A. Even if an iodine molecule (I2) enters the recess A, it does not take a hydrogen ion (H + ) cannot easily enter recess A. As a result, hydrogen ions (H + ) is reduced, and therefore the substrate W cannot be properly etched, i.e., the etching function is reduced.

[0055] Furthermore, iodine molecules (I2) may adhere to the substrate W as impurities or dust. In this case, the quality of the etching process is significantly reduced.

[0056] See Figure 3. Iodide ion (I - ) is the triiodide ion (I3 - ) may occur. I - + I2 → I3 - This results in the production of iodide ions (I - ) decreases. Triiodide ion (I3 - ) will increase.

[0057] Triiodide ion (I3 - ) is an anion. Therefore, triiodide ion (I3 - ) and hydrogen ions (H + ) attract each other. Triiodide ion (I3 - ) is a hydrogen ion (H + In other words, triiodide ion (I3 - ) is a hydrogen ion (H + ) can be promoted. Therefore, triiodide ion (I3 - ) is a hydrogen ion (H + ) into the recess A. However, the triiodide ion (I3 - ) is a monovalent polyatomic anion consisting of three iodine atoms. Therefore, the triiodide ion (I3 - ) is a hydrogen ion (H + For example, the transfer of three iodide ions (I - ) is composed of three hydrogen ions (H + ), whereas one triiodide ion (I3 - ) contains only one hydrogen ion (H + ) at the recess A. + ) is reduced, and therefore the substrate W cannot be properly etched, i.e., the etching function is reduced.

[0058] As mentioned above, the etching function is reduced due to the iodide ion (I - In other words, the present inventors have found that the cause of the decrease in the etching function is the decrease in iodide ions (I - The present inventors have found that the change in the composition of iodide ions (I - The present inventors have further studied steps and means for suppressing the decrease in the amount of the ion exchange resin (O2) and the amount of the ion exchange resin (O2) in ...).

[0059] 2. First embodiment <2-1. Overview of substrate processing equipment> 4 is a plan view showing the inside of the substrate processing apparatus 1. The substrate processing apparatus 1 performs processing on a substrate W. The processing includes an etching processing. The processing is performed in a room temperature environment. The room temperature is, for example, a temperature within a range of 5°C to 35°C.

[0060] The substrate processing apparatus 1 includes an indexer unit 3 and a processing block 7. The processing block 7 is connected to the indexer unit 3. The indexer unit 3 supplies a substrate W to the processing block 7. The processing block 7 processes the substrate W. The indexer unit 3 retrieves the substrate W from the processing block 7.

[0061] For convenience, in this specification, the direction in which the indexer unit 3 and the processing block 7 are aligned is referred to as the "front-rear direction X." The front-rear direction X is horizontal. Within the front-rear direction X, the direction from the processing block 7 toward the indexer unit 3 is referred to as the "front." The direction opposite to the front is referred to as the "rear." The horizontal direction perpendicular to the front-rear direction X is referred to as the "width direction Y." One direction in the "width direction Y" is referred to as the "right" as appropriate. The direction opposite to the right is referred to as the "left." The direction perpendicular to the horizontal direction is referred to as the "vertical direction Z." In each figure, for reference, front, back, right, left, top, and bottom are indicated as appropriate.

[0062] The indexer unit 3 includes a plurality of (for example, four) carrier placement units 4. Each carrier placement unit 4 places one carrier C thereon. The carrier C stores a plurality of substrates W. The carrier C is, for example, a Front Opening Unified Pod (FOUP), a Standard Mechanical Interface (SMIF), or an Open Cassette (OC).

[0063] The indexer unit 3 includes a transport mechanism 5. The transport mechanism 5 is disposed behind the carrier placement unit 4. The transport mechanism 5 transports the substrate W. The transport mechanism 5 is accessible to the carrier C placed on the carrier placement unit 4. The transport mechanism 5 includes a hand 5a and a hand drive unit 5b. The hand 5a supports the substrate W. The hand drive unit 5b is connected to the hand 5a. The hand drive unit 5b moves the hand 5a. The hand drive unit 5b moves the hand 5a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand drive unit 5b rotates the hand 5a, for example, in a horizontal plane.

[0064] The processing block 7 includes a transport mechanism 8. The transport mechanism 8 transports the substrate W. The transport mechanism 8 and the transport mechanism 5 are capable of transferring the substrate W to each other. The transport mechanism 8 includes a hand 8a and a hand driver 8b. The hand 8a supports the substrate W. The hand driver 8b is connected to the hand 8a. The hand driver 8b moves the hand 8a. The hand driver 8b moves the hand 8a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand driver 8b rotates the hand 8a, for example, in a horizontal plane.

[0065] The processing block 7 includes a plurality of processing units 11. The processing units 11 are disposed to the sides of the transport mechanism 8. Each processing unit 11 performs processing on the substrate W.

[0066] The processing unit 11 includes a substrate holding part 13. The substrate holding part 13 holds a substrate W.

[0067] The transport mechanism 8 is accessible to each processing unit 11. The transport mechanism 8 can deliver the substrate W to the substrate holding portion 13. The transport mechanism 8 can take the substrate W from the substrate holding portion 13.

[0068] 5 is a control block diagram of the substrate processing apparatus 1. The substrate processing apparatus 1 includes a control unit 10. The control unit 10 controls the transport mechanisms 5 and 8 and the processing unit 11.

[0069] The control unit 10 is realized by a central processing unit (CPU) that executes various processes, a random-access memory (RAM) that serves as a working area for the processes, a storage medium such as a fixed disk, etc. The control unit 10 has various types of information that are stored in advance in the storage medium. The information held by the control unit 10 is, for example, transport information for controlling the transport mechanisms 5 and 8. The information held by the control unit 10 is, for example, processing information for controlling the processing unit 11. The processing information is also called a processing recipe.

[0070] An example of the operation of the substrate processing apparatus 1 will now be briefly described.

[0071] The indexer unit 3 supplies the substrate W to the processing block 7. Specifically, the transport mechanism 5 delivers the substrate W from the carrier C to the transport mechanism 8 of the processing block 7.

[0072] The processing block 7 distributes the substrate W from the indexer section 3 to the processing units 11. Specifically, the transport mechanism 8 transports the substrate W from the transport mechanism 5 to the substrate holder 13 of each processing unit 11.

[0073] The processing unit 11 processes the substrate W held by the substrate holding part 13. The processing unit 11 etches the substrate W, for example.

[0074] After the processing unit 11 has processed the substrate W, the processing block 7 returns the substrate W from the processing unit 11 to the indexer unit 3. Specifically, the transport mechanism 8 transports the substrate W from the substrate holder 13 to the transport mechanism 5.

[0075] The indexer unit 3 retrieves the substrate W from the processing block 7. Specifically, the transport mechanism 5 transports the substrate W from the transport mechanism 8 to the carrier C.

[0076] <2-2. Configuration of processing unit 11> 6 is a diagram showing the configuration of the processing units 11. Each processing unit 11 has the same structure. The processing units 11 are classified as single-wafer processing units. That is, each processing unit 11 processes only one substrate W at a time.

[0077] The substrate holding part 13 holds one substrate W. The substrate holding part 13 holds the substrate W in a horizontal position. The substrate holding part 13 holds the peripheral portion or the lower surface of the substrate W. When the substrate W is held by the substrate holding part 13, the pattern-formed surface W1 of the substrate W faces upward. When the substrate W is held by the substrate holding part 13, the pattern-formed surface W1 of the substrate W is located on the upper surface of the substrate W.

[0078] The processing unit 11 includes a rotation drive unit 14. The rotation drive unit 14 is connected to the substrate holding unit 13. The rotation drive unit 14 rotates the substrate holding unit 13. The substrate W held by the substrate holding unit 13 rotates integrally with the substrate holding unit 13. The substrate W held by the substrate holding unit 13 rotates about a rotation axis B. The rotation axis B passes through the center of the substrate W, for example, and extends in the vertical direction Z.

[0079] The processing unit 11 includes a first nozzle 15a, a second nozzle 15b, and a third nozzle 15c. Hereinafter, when the first to third nozzles 15a-15c are not to be distinguished from one another, they will simply be referred to as "nozzles 15." Each nozzle 15 ejects liquid or gas onto the substrate W. Each nozzle 15 is movable between a processing position and a standby position. The processing position is, for example, a position above the substrate W held by the substrate holding part 13. The standby position is, for example, a position not above the substrate W held by the substrate holding part 13.

[0080] The processing unit 11 includes a housing 16. The housing 16 has a substantially box-like shape. The housing 16 accommodates a substrate holder 13, a rotary drive unit 14, and a nozzle 15 inside the housing 16.

[0081] The processing unit 11 may further include a cup (not shown). The cup is installed inside the housing 16. The cup is disposed around the substrate holder 13. The cup receives liquid splashed from the substrate W held by the substrate holder 13.

[0082] The processing unit 11 includes pipes 17a, 17b, and 17c and valves 18a, 18b, and 18c. The pipes 17a-17c are connected to the first to third nozzles 15a-15c, respectively. The valves 18a-18c are provided in the pipes 17a-17c, respectively. At least a portion of the pipe 17a may be provided outside the housing 16. The pipes 17b and 17c may also be arranged similarly to the pipe 17a. The valve 18a may be provided outside the housing 16. The valves 18b and 18c may also be arranged similarly to the valve 18a.

[0083] The substrate processing apparatus 1 includes a processing liquid adjustment unit 20. The processing liquid adjustment unit 20 is connected to a pipe 17a. The processing liquid adjustment unit 20 is connected in communication with a first nozzle 15a.

[0084] The processing liquid adjustment unit 20 sends the processing liquid to the first nozzle 15a. The first nozzle 15a ejects the processing liquid. The processing liquid adjustment unit 20 may supply the processing liquid to a plurality of processing units 11.

[0085] The first nozzle 15a is an example of a supply section in the present invention.

[0086] The pipe 17b is connected to a rinse liquid supply source 19b. The rinse liquid supply source 19b is connected in communication with the second nozzle 15b. The rinse liquid supply source 19b sends the rinse liquid to the second nozzle 15b. The second nozzle 15b ejects the rinse liquid. The rinse liquid is, for example, pure water.

[0087] The pipe 17c is connected to a gas supply source 19c. The gas supply source 19c is connected in communication with the third nozzle 15c. The gas supply source 19c sends gas to the third nozzle 15c. The third nozzle 15c ejects the gas. The third nozzle 15c blows out the gas. The gas is, for example, an inert gas. The gas is, for example, nitrogen.

[0088] The rinsing liquid supply source 19b may be a component of the substrate processing apparatus 1. Alternatively, the rinsing liquid supply source 19b does not have to be a component of the substrate processing apparatus 1. For example, the rinsing liquid supply source 19b may be a utility facility installed outside the substrate processing apparatus 1. Similarly, the gas supply source 19c may be a component of the substrate processing apparatus 1, or it does not have to be a component of the substrate processing apparatus.

[0089] Please refer to Figure 5. The control unit 10 controls the rotary drive unit 14 and the valves 18a-18c.

[0090] <2-3. Configuration of the processing liquid adjustment unit 20> 6, in the first embodiment, the processing liquid adjustment unit 20 supplies the adjusted first processing liquid to the first nozzle 15a. Furthermore, the processing liquid adjustment unit 20 supplies the first etching liquid to the first nozzle 15a.

[0091] The treatment liquid adjustment unit 20 includes a first tank 21. The first tank 21 stores a first treatment liquid.

[0092] The first treatment liquid contains an additive. The additive is dissolved in the first treatment liquid. The first treatment liquid contains iodide ions (I - ).

[0093] The additive releases iodide ions (I - The additive may, for example, comprise at least one of the compounds a1)-a6) listed below. a1) Tetramethylammonium iodide (TMAI) a2) Tetraethylammonium iodide (TEAI) a3) Tetrapropylammonium iodide (TPAI) a4) Tetrabutylammonium iodide a5) Ammonium iodide a6) Hydrogen iodide

[0094] The first treatment liquid is an aqueous solution in which an additive is dissolved in pure water. The pure water corresponds to a solvent for the additive.

[0095] The first processing liquid does not contain an etching liquid, and is composed only of an additive and pure water.

[0096] The treatment liquid adjustment unit 20 includes an adjustment section 23. The adjustment section 23 is connected in communication with the first tank 21.

[0097] The adjustment unit 23 adjusts the amount of iodide ions (I - Specifically, the adjustment unit 23 removes the dissolved oxygen from the first treatment liquid. This reduces the amount of iodide ions (I - ) is suppressed.

[0098] The adjustment unit 23 includes a bubble generating unit 24. The bubble generating unit 24 supplies an inert gas into the first treatment liquid to generate bubbles in the first treatment liquid. That is, the bubble generating unit 24 bubbles the first treatment liquid with the inert gas. As a result, the dissolved oxygen in the first treatment liquid is replaced with the inert gas and removed from the first treatment liquid. Specifically, the bubble generating unit 24 supplies an inert gas into the first treatment liquid in the first tank 21. The inert gas is, for example, nitrogen gas.

[0099] The bubble generating unit 24 includes a pipe 24a and a valve 24b. The pipe 24a is connected in communication with the first tank 21. The pipe 24a has a first end disposed in the first processing liquid in the first tank 21. The first end of the pipe 24a is disposed at a position lower than the liquid level of the first processing liquid in the first tank 21. The pipe 24a has a second end connected to an inert gas supply source 25. The valve 24b is provided in the pipe 24a. When the valve 24b is opened, the pipe 24a blows out an inert gas from the first end of the pipe 24a into the first processing liquid in the first tank 21.

[0100] The treatment liquid adjustment unit 20 includes an exhaust section 27. The exhaust section 27 exhausts the gas within the first tank 21 to the outside of the first tank 21.

[0101] The exhaust unit 27 includes an exhaust pipe 27a and a valve 27b. The exhaust pipe 27a is connected in communication with the first tank 21. The exhaust pipe 27a has a first end that is disposed at the upper part of the first tank 21. The first end of the exhaust pipe 27a is disposed at a position higher than the liquid level of the first processing liquid in the first tank 21. The exhaust pipe 27a has a second end that is open to the outside of the first tank 21. The valve 27b is provided in the exhaust pipe 27a. When the valve 27b is opened, the inside of the first tank 21 is opened to the outside of the first tank 21.

[0102] The processing liquid adjustment unit 20 includes a first replenishing section 28. The first replenishing section 28 replenishes the first processing liquid with a solvent for the additive. Specifically, the first replenishing section 28 replenishes the first tank 21 with a solvent for the additive (i.e., pure water).

[0103] The first refilling unit 28 includes a pipe 28a and a valve 28b. The pipe 28a is connected in communication with the first tank 21. The pipe 28a is further connected in communication with a pure water supply source 29. The valve 28b is provided on the pipe 28a. When the valve 28b is open, the pipe 28a supplies pure water to the first tank 21.

[0104] The treatment liquid adjustment unit 20 includes a circulation pipe 36 and a pump 37. The circulation pipe 36 circulates the first treatment liquid. The circulation pipe 36 circulates the first treatment liquid outside the first tank 21. The circulation pipe 36 has an upstream end 36a and a downstream end 36b. The upstream end 36a and the downstream end 36b are each connected to the first tank 21. The pump 37 is provided in the circulation pipe 36. The pump 37 sends the first treatment liquid from the upstream end 36a of the circulation pipe 36 to the downstream end 36b of the circulation pipe 36. When the pump 37 is operating, the first treatment liquid flows out from the first tank 21 to the circulation pipe 36 through the upstream end 36a of the circulation pipe 36. Furthermore, the first treatment liquid returns from the circulation pipe 36 to the first tank 21 through the downstream end 36b of the circulation pipe 36.

[0105] The treatment liquid adjustment unit 20 includes a filter 38. The filter 38 filters the first treatment liquid. The filter 38 removes foreign matter from the first treatment liquid. The filter 38 is provided in the circulation pipe 36. The filter 38 is disposed downstream of the pump 37. The filter 38 filters the first treatment liquid flowing through the circulation pipe 36.

[0106] The treatment liquid adjustment unit 20 includes a first sensor 41. The first sensor 41 detects iodide ions (I - The first sensor 41 detects the concentration of iodide ions (I - The first sensor 41 is, for example, an ultraviolet absorbance detector or an ultraviolet / visible absorbance detector. The first sensor 41 is provided in the circulation pipe 36. The first sensor 41 is disposed downstream of the filter 38. The first sensor 41 detects the concentration of iodide ions (I - ) concentration is detected.

[0107] The treatment liquid adjustment unit 20 includes a second sensor 42. The second sensor 42 detects the concentration of dissolved oxygen in the first treatment liquid. The second sensor 42 detects the concentration of dissolved oxygen in the first treatment liquid, for example, by electrochemical analysis (diaphragm electrode method). The second sensor 42 is provided in the circulation pipe 36. The second sensor 42 is disposed downstream of the filter 38. The second sensor 42 detects the concentration of dissolved oxygen in the first treatment liquid flowing through the circulation pipe 36.

[0108] The processing liquid adjustment unit 20 includes a third sensor 43. The third sensor 43 detects the amount of the first processing liquid stored in the first tank 21. The third sensor 43 is, for example, a liquid level sensor. The third sensor 43 detects, for example, the height position of the liquid level of the first processing liquid stored in the first tank 21. The third sensor 43 is attached to the first tank 21.

[0109] The processing liquid adjustment unit 20 includes a second tank 51. The second tank 51 stores a first etching liquid for etching the substrate W. The first etching liquid contains hydrogen ions (H + The first etching liquid is not adjusted by the adjustment unit 23.

[0110] The first etching solution contains at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF).

[0111] The first etching solution may further include an alcohol. For example, the first etching solution may include at least one of the alcohols b1) to b7) listed below. b1) Methyl alcohol b2) Ethyl alcohol b3) 2-Propanol b4) n-Butyl alcohol b5) tert-butyl alcohol b6) Cyclohexanol b7) Ethylene glycol

[0112] The first etching solution may further comprise at least one of the acids c1)-c7) listed below. c1) Hydrochloric acid c2) Sulfuric acid c3) Nitric acid c4) Acetic acid c5) Phosphoric acid c6) Hydrogen peroxide c7) Citric acid

[0113] The processing liquid adjustment unit 20 includes a circulation pipe 52 and a pump 53. The circulation pipe 52 circulates the first etching liquid. The circulation pipe 52 circulates the first etching liquid outside the second tank 51. The circulation pipe 52 has an upstream end 52a and a downstream end 52b. The upstream end 52a and the downstream end 52b are each connected in communication with the second tank 51. The pump 53 is connected to the circulation pipe 52. 52 The pump 53 is provided in the circulation pipe. 52 The upstream end 52a of the circulation pipe 52 When the pump 53 is operated, the first etching liquid flows from the second tank 51 through the upstream end 52a of the circulation pipe 52 into the circulation pipe 52. Furthermore, the first etching liquid flows from the circulation pipe 52 back to the second tank 51 through the downstream end 52b of the circulation pipe 52.

[0114] The processing liquid adjustment unit 20 includes a filter 54. The filter 54 filters the first etching liquid. The filter 54 removes foreign matter from the first etching liquid. The filter 54 is provided in the circulation pipe 52. The filter 54 is disposed downstream of the pump 53. The filter 54 filters the first etching liquid flowing through the circulation pipe 52.

[0115] The processing liquid adjustment unit 20 includes a liquid delivery section 56. The liquid delivery section 56 delivers the first processing liquid and the first etching liquid to the first nozzle 15a.

[0116] The liquid delivery section 56 includes a pipe 57a and a valve 57b. The pipe 57a branches off from the circulation pipe 36. The pipe 57a is connected to the circulation pipe 36. The connection position of the pipe 57a and the circulation pipe 36 is downstream of the filter 38. The connection position of the pipe 57a and the circulation pipe 36 is upstream of the first sensor 41 and the second sensor 42. The valve 57b is provided in the pipe 57a.

[0117] The liquid delivery section 56 includes a pipe 58a and a valve 58b. The pipe 58a branches off from the circulation pipe 52. The pipe 58a is connected to the circulation pipe 52. The connection position of the pipe 58a and the circulation pipe 52 is downstream of the filter 54. The valve 58b is provided in the pipe 58a.

[0118] The liquid delivery unit 56 includes a joint 59. The joint 59 is connected to the pipes 17a, 57a, and 58a. The joint 59 is, for example, a three-way joint. The pipes 17a, 57a, and 58a communicate with each other via the joint 59.

[0119] Please refer to Fig. 5. The control unit 10 controls the treatment liquid adjustment unit 20. The control unit 10 is electrically connected to the treatment liquid adjustment unit 20 so as to be able to communicate with each other.

[0120] The control unit 10 acquires the detection results of the first to third sensors 41-43.

[0121] The control unit 10 controls the adjustment unit 23. Control unit 10 controls the air bubble generating unit 24. 10 controls valve 24b.

[0122] The control unit 10 controls the exhaust unit 27. The control unit 10 controls the valve 27b.

[0123] The control unit 10 controls the first replenishing unit 28. The control unit 10 controls the valve 28b.

[0124] The control unit 10 controls the pumps 37 and 53 .

[0125] The control unit 10 controls the liquid delivery unit 56. The control unit 10 controls the valves 57b and 58b.

[0126] The control unit 10 has adjustment information for controlling the treatment liquid adjustment unit 20. The adjustment information is stored in advance in a storage medium of the control unit 10.

[0127] <2-4. Operational Example of Processing Liquid Adjustment Unit 20 and Processing Unit 11> 6, a description will be given of an example of the operation of the processing liquid adjustment unit 20. The processing liquid adjustment unit 20 operates under the control of the control unit 10.

[0128] The treatment liquid adjustment unit 20 executes an adjustment step. In the adjustment step, the valve 24b is opened. In the adjustment step, the bubble generating section 24 supplies an inert gas into the first treatment liquid to generate bubbles in the first treatment liquid. Therefore, the adjustment step removes the dissolved oxygen from the first treatment liquid. That is, the adjustment step reduces the concentration of dissolved oxygen in the first treatment liquid. As a result, the adjustment step reduces the concentration of iodide ions (I - ) decrease.

[0129] During the adjustment step, the valve 27b is open. The exhaust unit 27 exhausts the gas in the first tank 21 to the outside of the first tank 21. The exhaust unit 27 exhausts the oxygen gas removed from the first treatment liquid to the outside of the first tank 21.

[0130] During the adjustment process, the pump 37 is operated. Therefore, the first treatment liquid circulates through the circulation pipe 36. The filter 38 filters the first treatment liquid. The first sensor 41 detects the amount of iodide ions (I - The second sensor 42 detects the concentration of dissolved oxygen in the first treatment liquid. The third sensor 43 detects the amount of the first treatment liquid stored in the first tank 21. The control unit 10 monitors the detection results of the first to third sensors 41-43.

[0131] Here, the period during which the adjustment process is performed may be independent of the detection results of the first sensor 41 and the second sensor 42. For example, the adjustment process may be performed at all times except when the treatment liquid adjustment unit 20 sends treatment liquid to the first nozzle 15a.

[0132] Alternatively, the period for which the adjustment process is performed may depend on at least one of the detection result of the first sensor 41 and the detection result of the second sensor .

[0133] For example, the adjustment process may be started based on at least one of the detection results of the first sensor 41 and the detection results of the second sensor 42. For example, the iodide ions (I - For example, the adjustment process may be started when the concentration of dissolved oxygen in the first treatment liquid is high. Here, the concentration of iodide ions (I - The control unit 10 judges whether the concentration of dissolved oxygen in the first treatment liquid is low or not. The control unit 10 also judges whether the concentration of dissolved oxygen in the first treatment liquid is high or not. When the control unit 10 makes these judgments, the control unit 10 may refer to adjustment information as appropriate. The adjustment information preferably includes a target value, a threshold value, or a reference value to be used for these judgments. The control unit 10 determines the timing to start the adjustment process based on at least one of the detection results of the first sensor 41 and the detection results of the second sensor 42.

[0134] For example, the adjustment process may be terminated based on at least one of the detection results of the first sensor 41 and the detection results of the second sensor 42. For example, the iodide ion (I - When the concentration of dissolved oxygen in the first treatment liquid is low, the adjustment process may be terminated. -The control unit 10 determines whether the concentration of dissolved oxygen in the first treatment liquid is high or not. The control unit 10 also determines whether the concentration of dissolved oxygen in the first treatment liquid is low or not. The control unit 10 determines the timing to end the adjustment process based on at least one of the detection result of the first sensor 41 and the detection result of the second sensor 42.

[0135] Preferably, pump 37 is operational even when the conditioning process is not being performed.

[0136] The first refilling unit 28 refills the first tank 21 with pure water under the control of the control unit 10.

[0137] For example, the first replenishing unit 28 may replenish the first tank 21 with pure water based on the detection result of the first sensor 41. Specifically, the iodide ions (I - When the concentration of iodide ions (I - Whether or not the concentration of the residual ink 21 is excessively high is determined by the control unit 10. The control unit 10 controls the first replenishing unit 28 based on the first sensor 41.

[0138] For example, based on the detection result of the third sensor 43, the first replenishment unit 28 may replenish the first tank 21 with pure water. Specifically, when the amount of the first processing liquid in the first tank 21 is small, the first replenishment unit 28 may replenish the first tank 21 with pure water. Whether the amount of the first processing liquid in the first tank 21 is small or not is determined by the control unit 10. The control unit 10 controls the first replenishment unit 28 based on the third sensor 43.

[0139] When the first replenishing unit 28 replenishing the first tank 21 with pure water, the adjustment step may or may not be performed. When the first replenishing unit 28 replenishing the first tank 21 with pure water, it is preferable that the exhaust unit 27 opens the inside of the first tank 21 to the outside of the first tank 21. Even when the first replenishing unit 28 replenishing the first tank 21 with pure water, it is preferable that the pump 37 is operated.

[0140] During the adjustment step, it is preferable that the liquid delivery unit 56 does not deliver the first processing liquid to the first pipe 17a. When the valve 24b is open, the valve 57b is preferably closed.

[0141] As described above, the first treatment liquid is adjusted in the adjustment step (adjustment unit 23). The first treatment liquid adjusted in the adjustment step (adjustment unit 23) contains sufficient iodide ions (I - ).

[0142] On the other hand, the pump 53 is operated in the second tank 51. Therefore, the first etching liquid circulates through the circulation pipe 52. The filter 54 filters the first etching liquid.

[0143] The liquid delivery unit 56 delivers the first processing liquid adjusted in the adjustment step (adjustment unit 23) to the first nozzle 15a together with the first etching liquid. Specifically, while the pumps 37 and 53 are operating, the valves 57b and 58b are open. The first processing liquid flows from the circulation pipe 36 to the pipe 57a. The first etching liquid flows from the circulation pipe 52 to the pipe 58a. The first processing liquid and the first etching liquid join together at the joint 59. The first processing liquid is added to the first etching liquid. The mixture of the first processing liquid and the first etching liquid flows from the joint 59 to the pipe 17a.

[0144] It is preferable that the adjustment step is not being performed when the liquid delivery unit 56 delivers the first treatment liquid to the first pipe 17a. Specifically, it is preferable that the air bubble generating unit 24 does not generate air bubbles in the first treatment liquid when the liquid delivery unit 56 delivers the first treatment liquid to the first pipe 17a. It is preferable that the valve 57b opens after the valve 24b closes.

[0145] When the valve 18a is opened, the supply step is performed. In the supply step, the first nozzle 15a ejects the first processing liquid and the first etching liquid onto the substrate W. The first nozzle 15a supplies the mixed liquid of the first processing liquid and the first etching liquid onto the substrate W.

[0146] Next, a brief explanation will be given of an example of the operation of the processing unit 11. The processing unit 11 operates according to the control of the control unit 10.

[0147] The substrate holding unit 13 holds the substrate W. The rotation drive unit 14 rotates the substrate W held by the substrate holding unit 13.

[0148] The substrate W is cleaned. The valve 18b opens. The second nozzle 15b ejects the rinsing liquid onto the substrate W held by the substrate holder 13. The rinsing liquid is supplied to the pattern formation surface W1. The substrate W is cleaned by the rinsing liquid. Then, the valve 18b closes. The second nozzle 15b stops ejecting the rinsing liquid.

[0149] The substrate W is etched. The supplying step starts. Specifically, the valve 18a opens. The first nozzle 15a ejects the first processing liquid adjusted in the adjusting step and the first etching liquid onto the substrate W. Specifically, the first nozzle 15a ejects a mixed liquid obtained by adding the first processing liquid adjusted in the adjusting step to the first etching liquid onto the substrate W held by the substrate holding part 13. The mixed liquid is supplied to the pattern formation surface W1. The substrate W is etched by the mixed liquid.

[0150] Then, the supplying step ends. Specifically, the valve 18a closes. The first nozzle 15a stops discharging the mixed liquid.

[0151] The substrate W is cleaned. The valve 18b opens. The second nozzle 15b ejects the rinsing liquid onto the substrate W held by the substrate holder 13. The rinsing liquid is supplied to the pattern formation surface W1. The substrate W is cleaned by the rinsing liquid. Then, the valve 18b closes. The second nozzle 15b stops ejecting the rinsing liquid.

[0152] The substrate W is dried. The valve 18c opens. The third nozzle 15c ejects gas onto the substrate W held by the substrate holding part 13. The gas is supplied to the pattern formation surface W1. The substrate W is dried. Then, the valve 18c closes. The third nozzle 15c stops ejecting the gas.

[0153] The rotation driver 14 stops the rotation of the substrate W. The substrate W comes to rest. The processing unit 11 finishes the processing of the substrate W.

[0154] 2-5. Effects of the First Embodiment The additive is dissolved in the first treatment liquid. The first treatment liquid contains iodide ions (I - The substrate processing method of the first embodiment includes an adjusting step and a supplying step. The adjusting step is to adjust the amount of iodide ions (I - For example, the adjustment step suppresses the decrease of iodide ions (I - ) to molecular iodine (I2). For example, the adjustment process - ) is triiodide ion (I3 - ) is suppressed. For this reason, the first treatment liquid has a sufficient amount of iodide ions (I - The supplying step supplies the first processing liquid prepared in the adjusting step to the substrate. Furthermore, the supplying step supplies a first etching liquid to the substrate. As described above, the first processing liquid prepared in the adjusting step contains sufficient iodide ions (I - ) is included. Therefore, regardless of the size of the recess A on the substrate W, iodide ions (I - ) easily enters the recess A. Regardless of the size of the recess A, hydrogen ions (H + ) and iodide ion (I - ) and easily enters the recess A. As a result, the substrate W can be appropriately etched regardless of the size of the recess A.

[0155] As described above, according to the substrate processing method, regardless of the size of the recess A on the substrate W, the substrate W can be appropriately etched.

[0156] In the supply step, the mixed liquid is supplied to the substrate W. Here, the mixed liquid is obtained by adding the first processing liquid prepared in the preparation step to the first etching liquid. That is, the mixed liquid contains the first processing liquid and the first etching liquid. Therefore, supplying the mixed liquid is equivalent to supplying the first processing liquid and the first etching liquid. Furthermore, the fact that the mixed liquid contains the first processing liquid and the first etching liquid means that the mixed liquid contains iodide ions (I - ) and hydrogen ions (H + Therefore, immediately after the mixed solution is supplied to the substrate W, the iodide ions (I - ) is a hydrogen ion (H + ) can be favorably promoted, and thus the substrate W can be more appropriately etched.

[0157] The first treatment liquid is an aqueous solution in which the additive is dissolved in pure water. Therefore, the adjustment step is performed to adjust the amount of iodide ions (I - ) can be easily prevented from decreasing.

[0158] The first treatment liquid is composed of only additives and pure water. Therefore, the adjustment step is performed to remove iodide ions (I - ) can be easily prevented from decreasing.

[0159] The first treatment liquid does not contain an etching liquid. Therefore, the adjustment step is performed to adjust the amount of iodide ions (I - ) can be easily prevented from decreasing.

[0160] The additive releases iodide ions (I - ) is liberated. Therefore, the first treatment liquid liberates iodide ions (I - ) may be suitably included.

[0161] The additive contains at least one of the above-mentioned compounds a1) to a6). Therefore, the first treatment liquid contains iodide ions (I - ) may be suitably included.

[0162] The adjustment step reduces the concentration of dissolved oxygen in the first treatment liquid. For this reason, the adjustment step reduces the concentration of iodide ions (I - ) can be suitably suppressed from decreasing.

[0163] In the adjusting step, an inert gas is supplied into the first treatment liquid to generate bubbles in the first treatment liquid, and therefore, the adjusting step can suitably reduce the concentration of dissolved oxygen in the first treatment liquid.

[0164] The adjustment step is to adjust the amount of iodide ions (I - For this reason, the concentration of iodide ions (I - ) concentration can be conveniently grasped.

[0165] The adjustment step detects the concentration of dissolved oxygen in the first treatment liquid. For this purpose, the adjustment step detects the concentration of iodide ions (I - The concentration of dissolved oxygen and iodide ions (I - This is because the present inventors have found that there is a certain relationship between the change in the composition of iodide ions (I - ) is either molecular iodine (I2) or triiodide ion (I3 - ) composition is unlikely to change.

[0166] Iodide ions (I - The adjustment process is started based on at least one of the detection results of the concentration of the dissolved oxygen in the first treatment liquid and the detection results of the concentration of the dissolved oxygen in the first treatment liquid. Therefore, the adjustment process can be started at an appropriate timing.

[0167] Iodide ions (I - The adjustment process is terminated based on at least one of the detection results of the concentration of the dissolved oxygen in the first treatment liquid and the detection results of the concentration of the dissolved oxygen in the first treatment liquid. Therefore, the adjustment process can be terminated at an appropriate timing.

[0168] Iodide ions (I -Based on the detection result of the concentration of the additive, the solvent of the additive (i.e., pure water) is replenished to the first treatment liquid. Therefore, the first treatment liquid can be suitably diluted.

[0169] The first etching solution is hydrogen ions (H + ) Therefore, the substrate W can be suitably etched.

[0170] The first etching solution contains at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF), and therefore the substrate W can be suitably etched.

[0171] The first etching liquid contains alcohol, which allows the substrate W to be etched more effectively.

[0172] The first etching solution contains at least one of the alcohols b1)-b7) described above, which allows the substrate W to be etched more effectively.

[0173] The first etching solution contains at least one of the acids c1) to c7) described above, which allows the substrate W to be etched more effectively.

[0174] The substrate processing apparatus 1 includes an adjustment unit 23. The adjustment unit 23 removes dissolved oxygen from the first processing liquid. As a result, iodide ions (I - Therefore, the first treatment liquid adjusted by the adjustment unit 23 contains a sufficient amount of iodide ions (I - ). The substrate processing apparatus 1 includes a first nozzle 15a. The first nozzle 15a supplies the first processing liquid adjusted by the adjustment unit 23 to the substrate W. Furthermore, the first nozzle 15a supplies a first etching liquid to the substrate W. As described above, the first processing liquid adjusted by the adjustment unit 23 contains a sufficient amount of iodide ions (I - ) is included. Therefore, regardless of the size of the recess A on the substrate W, iodide ions (I - ) easily enters the recess A. Regardless of the size of the recess A, hydrogen ions (H + ) and iodide ion (I- ) and easily enters the recess A. As a result, the substrate W can be appropriately etched regardless of the size of the recess A.

[0175] As described above, according to the substrate processing apparatus 1, the substrate W can be appropriately etched regardless of the size of the recess A on the substrate W.

[0176] The first nozzle 15a supplies the mixed liquid. Here, the mixed liquid is obtained by adding the first processing liquid adjusted by the adjustment unit 23 to the first etching liquid. That is, the mixed liquid contains the first processing liquid and the first etching liquid. Therefore, supplying the mixed liquid is equivalent to supplying the first processing liquid and the first etching liquid. Furthermore, the fact that the mixed liquid contains the first processing liquid and the first etching liquid means that the mixed liquid contains iodide ions (I - ) and hydrogen ions (H + Therefore, immediately after the mixed solution is supplied to the substrate W, the iodide ions (I - ) is a hydrogen ion (H + ) can be favorably promoted, and thus the substrate W can be more appropriately etched.

[0177] The first treatment liquid is an aqueous solution in which an additive is dissolved in pure water. Therefore, the adjusting unit 23 adjusts the amount of iodide ions (I - ) can be easily prevented from decreasing.

[0178] The first treatment liquid is composed of only additives and pure water. Therefore, the adjustment unit 23 adjusts the amount of iodide ions (I - ) can be easily prevented from decreasing.

[0179] The first processing liquid does not contain an etching liquid. Therefore, the adjusting unit 23 adjusts the amount of iodide ions (I - ) can be easily prevented from decreasing.

[0180] The substrate processing apparatus 1 includes a first sensor 41 and a control unit 10. The first sensor 41 detects iodide ions (I -The control unit 10 obtains the detection result of the first sensor 41. Therefore, the control unit 10 detects the concentration of iodide ions (I - ) can be conveniently monitored.

[0181] The control unit 10 controls the adjustment unit 23 based on the detection result of the first sensor 41. Therefore, the control unit 10 can appropriately control the adjustment unit 23.

[0182] The substrate processing apparatus 1 includes a first replenishing unit 28. The first replenishing unit 28 replenishes the first processing liquid with a solvent for the additive (i.e., pure water). The control unit 10 controls the first replenishing unit 28 to replenish the first processing liquid with the solvent for the additive (i.e., pure water) based on the detection result of the first sensor 41. This allows the control unit 10 to appropriately dilute the first processing liquid.

[0183] The substrate processing apparatus 1 includes a second sensor 42. The second sensor 42 detects the concentration of dissolved oxygen in the first processing liquid. The control unit 10 acquires the detection result of the second sensor 42. Therefore, the control unit 10 can suitably monitor the concentration of dissolved oxygen in the first processing liquid.

[0184] The control unit 10 controls the adjustment unit 23 based on the detection result of the second sensor 42. Therefore, the control unit 10 can control the adjustment unit 23 appropriately.

[0185] The substrate processing apparatus 1 includes a third sensor 43. The third sensor 43 detects the amount of the first processing liquid stored in the first tank 21. The control unit 10 acquires the detection result of the second sensor 42. Therefore, the control unit 10 can appropriately monitor the amount of the first processing liquid stored in the first tank 21.

[0186] The control unit 10 controls the first replenishing unit 28 based on the detection result of the third sensor 43. Therefore, the control unit 10 can properly maintain the amount of the first treatment liquid stored in the first tank 21. For example, when the adjustment unit 23 removes dissolved oxygen from the first treatment liquid, the first treatment liquid (e.g., pure water) may evaporate, and the amount of the first treatment liquid stored in the first tank 21 may decrease. Even in such a case, the control unit 10 can properly maintain the amount of the first treatment liquid stored in the first tank 21.

[0187] The adjustment unit 23 includes an air bubble generating unit 24. The air bubble generating unit 24 supplies an inert gas into the first treatment liquid to generate air bubbles in the first treatment liquid. Thus, the adjustment unit 23 can suitably reduce the concentration of dissolved oxygen in the first treatment liquid.

[0188] The adjustment unit 23 includes the bubble generating unit 24. Therefore, the adjustment unit 23 can be realized at low cost.

[0189] The substrate processing apparatus 1 includes an exhaust unit 27. The exhaust unit 27 exhausts the oxygen gas removed from the first processing liquid to the outside of the first tank 21. Thus, the adjustment unit 23 can effectively reduce the concentration of dissolved oxygen in the first processing liquid.

[0190] The substrate processing apparatus 1 includes a joint 59. The joint 59 adds the first processing liquid adjusted by the adjustment unit 23 to the first etching liquid. Thus, the mixture of the first processing liquid and the first etching liquid can be sent to the first nozzle 15a.

[0191] 3. Second embodiment A substrate processing apparatus 1 according to a second embodiment will be described with reference to the drawings. Note that the same components as those in the first embodiment are denoted by the same reference numerals and detailed description thereof will be omitted.

[0192] The second embodiment is substantially the same as the first embodiment in terms of the outline of the substrate processing apparatus 1 and the configuration of the processing unit 11. The configuration of the processing liquid adjustment unit 20 of the second embodiment will be described below.

[0193] <3-1. Configuration of the processing liquid adjustment unit 20> 7 is a diagram showing the configurations of the processing unit 11 and the processing liquid adjustment unit 20 of the second embodiment. In the second embodiment, the processing liquid adjustment unit 20 supplies the adjusted first processing liquid to the first nozzle 15a. Furthermore, the processing liquid adjustment unit 20 supplies the first etching liquid to the first nozzle 15a. The processing liquid adjustment unit 20 of the second embodiment differs from the processing liquid adjustment unit 20 of the first embodiment in the configuration of the adjustment section 23.

[0194] The first tank 21 stores the first processing liquid.

[0195] The first treatment liquid of the second embodiment is substantially the same as the first treatment liquid of the first embodiment. That is, the first treatment liquid includes an additive. The additive is dissolved in the first treatment liquid. The first treatment liquid contains iodide ions (I - The first processing liquid is an aqueous solution in which an additive is dissolved in pure water. The first processing liquid does not include an etching liquid. The first processing liquid is composed only of an additive and pure water.

[0196] The adjustment unit 23 adjusts the amount of iodide ions (I - Specifically, the adjustment unit 23 degasses the first treatment liquid. In other words, the adjustment unit 23 removes the dissolved gas from the first treatment liquid. This reduces the amount of iodide ions (I - ) is suppressed.

[0197] The adjustment unit 23 includes a gas-liquid separation unit 26. The gas-liquid separation unit 26 filters the first treatment liquid and degasses the first treatment liquid. The gas-liquid separation unit 26 is provided in the circulation pipe 36. The gas-liquid separation unit 26 degasses the first treatment liquid flowing through the circulation pipe 36.

[0198] The gas-liquid separation unit 26 includes a degassing filter 26a and an exhaust pipe 26b. The degassing filter 26a includes, for example, a hollow fiber membrane (not shown). The degassing filter 26a is connected in communication with the circulation pipe 36. The exhaust pipe 26b is connected in communication with the degassing filter 26a. The exhaust pipe 26b exhausts the gas removed from the first treatment liquid to the outside of the degassing filter 26a.

[0199] <3-2. Operation example of the processing liquid adjustment unit 20> The processing liquid adjustment unit 20 operates under the control of the control unit 10 .

[0200] The treatment liquid adjustment unit 20 performs an adjustment process. In the adjustment process, the pump 37 operates. Therefore, the first treatment liquid circulates through the circulation pipe 36. The gas-liquid separation section 26 degasses the first treatment liquid flowing through the circulation pipe 36. The degassed first treatment liquid returns to the first tank 21.

[0201] As described above, in the adjusting step, the adjusting unit 23 adjusts the first treating liquid. The first treating liquid adjusted in the adjusting step (adjusting unit 23) contains sufficient iodide ions (I - ).

[0202] The liquid delivery unit 56 delivers the first processing liquid, which has been adjusted in the adjustment step (adjustment unit 23), to the first nozzle 15a together with the first etching liquid. Specifically, while the pumps 37 and 53 are operating, the valves 57b and 58b are open. Therefore, even when the liquid delivery unit 56 delivers the first processing liquid to the first nozzle 15a, the adjustment step is performed. Specifically, even when the liquid delivery unit 56 delivers the first processing liquid to the first nozzle 15a, the gas-liquid separation unit 26 degasses the first processing liquid flowing through the circulation pipe 36.

[0203] 3-3. Effects of the Second Embodiment The second embodiment also has the same effects as the first embodiment. For example, the substrate processing method and substrate processing apparatus 1 of the second embodiment also reduce iodide ions (I -) can be suitably suppressed from decreasing. Therefore, regardless of the size of the recess A on the substrate W, the substrate W can be appropriately etched.

[0204] Furthermore, in the substrate processing method according to the second embodiment, the adjusting step degasses the first processing liquid. Therefore, the adjusting step degasses the iodide ions (I - ) can be suitably suppressed from decreasing.

[0205] In the adjustment step, the first treatment liquid is degassed by filtering the first treatment liquid by the gas-liquid separation section 26. Therefore, in the adjustment step, the first treatment liquid can be degassed suitably.

[0206] The adjustment unit 23 of the second embodiment includes a gas-liquid separation unit 26. Therefore, the adjustment unit 23 can degas the first treatment liquid suitably. Therefore, the adjustment unit 23 can suitably reduce the concentration of dissolved oxygen in the first treatment liquid.

[0207] Furthermore, the gas-liquid separation unit 26 can degas the first treatment liquid (e.g., pure water) without evaporating the first treatment liquid. Therefore, the adjustment unit 23 can suitably reduce the concentration of dissolved oxygen in the first treatment liquid while suppressing a decrease in the first treatment liquid stored in the first tank 21.

[0208] <4. Third embodiment> A substrate processing apparatus 1 according to a third embodiment will be described with reference to the drawings. Note that the same components as those in the first embodiment are denoted by the same reference numerals and detailed description thereof will be omitted.

[0209] The third embodiment is substantially the same as the first embodiment in terms of the outline of the substrate processing apparatus and the configuration of the processing unit. The configuration of the processing liquid adjustment unit 20 of the third embodiment will be described below.

[0210] <4-1. Configuration of the processing liquid adjustment unit 20> 8 is a diagram showing the configurations of a processing unit 11 and a processing liquid adjustment unit 20 according to the third embodiment. In the third embodiment, the processing liquid adjustment unit 20 supplies an adjusted first processing liquid to a first nozzle 15a. The first processing liquid of the third embodiment is partially different from the first processing liquid of the first embodiment.

[0211] The first tank 21 stores the first processing liquid.

[0212] The first treatment liquid contains an additive. The additive is dissolved in the first treatment liquid. The first treatment liquid contains iodide ions (I - The first processing liquid further includes a second etching liquid for etching the substrate W. For this reason, the second etching liquid is adjusted by the adjustment unit 23. The second etching liquid contains hydrogen ions (H + ).

[0213] The second etching solution contains at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF).

[0214] The first treatment liquid may further include an alcohol. The first treatment liquid may further include, for example, at least one of the alcohols b1)-b7) described above. The first treatment liquid may further include at least one of the acids c1)-c7) described above.

[0215] The processing liquid adjustment unit 20 includes a second replenishing section 31. The second replenishing section 31 replenishes the first processing liquid with a second etching liquid. Specifically, the second replenishing section 31 replenishes the first tank 21 with the second etching liquid.

[0216] The second replenishing unit 31 includes a pipe 31a and a valve 31b. The pipe 31a is connected to the first tank 21. The pipe 31a is further connected to an etching liquid supply source 32. The valve 31b is provided on the pipe 31a. When the valve 31b is opened, the pipe 31a supplies the second etching liquid to the first tank 21.

[0217] The treatment liquid adjustment unit 20 includes a fourth sensor 44. The fourth sensor 44 detects, for example, the hydrogen ion concentration of the first treatment liquid. The fourth sensor 44 detects, for example, the pH of the first treatment liquid. The fourth sensor 44 is, for example, a pH meter.

[0218] Although not shown in the figure, the control unit 10 acquires the detection result of the fourth sensor 44. The control unit 10 controls the second replenishment unit 31. The control unit 10 controls the valve 31b.

[0219] <4-2. Operation example of the processing liquid adjustment unit 20> The processing liquid adjustment unit 20 operates under the control of the control unit 10 .

[0220] The treatment liquid adjustment unit 20 executes the adjustment step. In the adjustment step, the valve 24b is opened. In the adjustment step, the bubble generating unit 24 supplies an inert gas into the first treatment liquid to generate bubbles in the first treatment liquid. As a result, the adjustment step causes the iodide ions (I - ) decrease.

[0221] During the adjustment process, the pump 37 operates. Therefore, the first treatment liquid circulates through the circulation pipe 36. The second sensor 42 detects the concentration of dissolved oxygen in the first treatment liquid. The fourth sensor 44 detects the hydrogen ion concentration in the first treatment liquid. The control unit 10 monitors the detection results of the second sensor 42 and the fourth sensor 44.

[0222] The first and second replenishing units 28 and 31 replenish the first tank 21 with pure water and the second etching liquid, respectively, under the control of the control unit 10.

[0223] For example, the first replenishment unit 28 may replenish the first tank 21 with pure water based on the detection result of the fourth sensor 44. Specifically, when the hydrogen ion concentration of the first treatment liquid is high (i.e., the pH of the first treatment liquid is low), the first replenishment unit 28 may replenish the first tank 21 with pure water. Here, whether the hydrogen ion concentration of the first treatment liquid is high or not is determined by the control unit 10. Whether the pH of the first treatment liquid is low or not is also determined by the control unit 10. The control unit 10 controls the first replenishment unit 28 based on the detection result of the fourth sensor 44.

[0224] For example, the second replenishing unit 31 may replenish the first tank 21 with the second etching liquid based on the detection result of the fourth sensor 44. Specifically, when the hydrogen ion concentration of the first processing liquid is low (i.e., the pH of the first processing liquid is high), the second replenishing unit 31 replenishes the first tank 21 with the second etching liquid. Second The etching liquid may be replenished. Here, whether or not the hydrogen ion concentration of the first processing liquid is low is determined by the control unit 10. Whether or not the pH of the first processing liquid is high is also determined by the control unit 10. The control unit 10 controls the second replenishment unit 31 based on the detection result of the fourth sensor 44.

[0225] For example, based on the detection result of the third sensor 43, the first replenishing unit 28 and the second replenishing unit 31 may replenishing the first tank 21 with pure water and the second etching liquid, respectively. Specifically, when the amount of the first processing liquid in the first tank 21 is small, the first replenishing unit 28 and the second replenishing unit 31 may replenishing the first tank 21 with pure water and the second etching liquid, respectively. The control unit 10 controls the third sensor 43 to detect whether the first processing liquid is present in the first tank 21 or not. 43 Based on the detection result, the first replenishment unit 28 and the second replenishment unit 31 are controlled.

[0226] When the second replenishing unit 31 replenishes the first tank 21 with the second etching liquid, the adjustment step may or may not be performed. When the second replenishing unit 31 replenishes the first tank 21 with the second etching liquid, it is preferable that the exhaust unit 27 opens the inside of the first tank 21 to the outside of the first tank 21. Even when the second replenishing unit 31 replenishes the first tank 21 with the second etching liquid, it is preferable that the pump 37 is operated.

[0227] As described above, the first treatment liquid is adjusted in the adjustment step (adjustment unit 23). The first treatment liquid adjusted in the adjustment step (adjustment unit 23) contains sufficient iodide ions (I - Furthermore, the first processing liquid adjusted in the adjusting step (adjusting unit 23) includes a second etching liquid.

[0228] The liquid sending unit 56 sends the first processing liquid adjusted in the adjusting step (adjusting unit 23) to the first nozzle 15a. Specifically, while the pump 37 is operating, the valve 57b opens. The first processing liquid flows from the circulation pipe 36 to the pipe 57a. The liquid sending unit 56 sends the first processing liquid to the pipe 17a.

[0229] When the valve 18a is opened, the supply step is performed. In the supply step, the first nozzle 15a ejects the first processing liquid onto the substrate W.

[0230] 4-3. Effects of the Third Embodiment The third embodiment also provides the same effects as the first embodiment.

[0231] The additive is dissolved in the first treatment liquid. The first treatment liquid contains iodide ions (I - The substrate processing method of the third embodiment includes an adjusting step and a supplying step. The adjusting step is to adjust the amount of iodide ions (I - For this reason, the first treatment solution is designed to have sufficient iodide ions (I - The first processing solution further includes a second etching solution. That is, the first processing solution contains hydrogen ions (H + In the supplying step, the first processing liquid adjusted in the adjusting step is supplied to the substrate. As described above, the first processing liquid adjusted in the adjusting step contains sufficient iodide ions (I - The first treatment liquid further contains hydrogen ions (H + ) is included. Therefore, regardless of the size of the recess A on the substrate W, iodide ions (I - ) is a hydrogen ion (H +Immediately after the first processing liquid is supplied to the substrate W, it easily enters the recess A, bringing with it hydrogen ions (H + ) is the iodide ion (I - ) and easily enters the recess A. As a result, the substrate W can be appropriately etched regardless of the size of the recess A.

[0232] As described above, according to the substrate processing method of the third embodiment, regardless of the size of the recess A on the substrate W, the substrate W can be appropriately etched.

[0233] The second etching solution is hydrogen ions (H + ) Therefore, the substrate W can be suitably etched.

[0234] The second etching solution contains at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF), so that the substrate W can be suitably etched.

[0235] The first processing liquid contains alcohol, which allows the substrate W to be etched more effectively.

[0236] The first processing liquid contains at least one of the alcohols b1)-b7) described above, which allows the substrate W to be etched more effectively.

[0237] The first processing liquid contains at least one of the acids c1) to c7) described above, which allows the substrate W to be etched more effectively.

[0238] The adjustment unit 23 removes the dissolved oxygen from the first treatment liquid. - Therefore, the first treatment liquid adjusted by the adjustment unit 23 contains a sufficient amount of iodide ions (I - The first processing solution further includes a second etching solution. That is, the first processing solution contains hydrogen ions (H +The first nozzle 15a supplies the first processing liquid adjusted by the adjustment unit 23 to the substrate W. As described above, the first processing liquid adjusted by the adjustment unit 23 contains a sufficient amount of iodide ions (I - The first treatment liquid further contains hydrogen ions (H + ) is included. Therefore, regardless of the size of the recess A on the substrate W, iodide ions (I - ) is a hydrogen ion (H + Immediately after the first processing liquid is supplied to the substrate W, hydrogen ions (H + ) is the iodide ion (I - ) and easily enters the recess A. As a result, the substrate W can be appropriately etched regardless of the size of the recess A.

[0239] As described above, according to the substrate processing apparatus 1 of the third embodiment, the substrate W can be appropriately etched regardless of the size of the recess A on the substrate W.

[0240] The substrate processing apparatus 1 includes a fourth sensor 44. The fourth sensor 44 detects the hydrogen ion concentration of the first processing liquid. The control unit 10 acquires the detection result of the fourth sensor 44. Therefore, the control unit 10 can appropriately monitor the hydrogen ion concentration of the first processing liquid.

[0241] The substrate processing apparatus 1 includes a first replenishment unit 28 and a second replenishment unit 31. The first replenishment unit 28 replenishes the first processing liquid with pure water. The second replenishment unit 31 replenishes the first processing liquid with the second etching liquid. The control unit 10 controls the first replenishment unit 28 and the second replenishment unit 31 based on the detection result of the fourth sensor 44. Therefore, the control unit 10 can appropriately maintain the concentration of the second etching liquid in the first processing liquid.

[0242] The substrate processing apparatus 1 includes a third sensor 43. The control unit 10 controls the first replenishing unit 28 and the second replenishing unit 31 based on the detection result of the third sensor 43. Therefore, the control unit 10 can replenishing the first tank 21 with pure water and the second etching liquid while appropriately maintaining the concentration of the second etching liquid in the first processing liquid. For example, when the adjustment unit 23 removes the dissolved oxygen in the first processing liquid from the first processing liquid, the first processing liquid may evaporate and the amount of the first processing liquid stored in the first tank 21 may decrease. Even in such a case, the control unit 10 can appropriately maintain the amount of the first processing liquid stored in the first tank 21.

[0243] <5. Fourth embodiment> A substrate processing apparatus 1 according to a fourth embodiment will be described with reference to the drawings. Note that the same components as those in the first embodiment are denoted by the same reference numerals and detailed description thereof will be omitted.

[0244] The fourth embodiment is substantially the same as the first embodiment in terms of the outline of the substrate processing apparatus and the configuration of the processing unit. The configuration of the processing liquid adjustment unit 20 of the fourth embodiment will be described below.

[0245] <5-1. Configuration of the processing liquid adjustment unit 20> 9 is a diagram showing the configurations of the processing unit 11 and the processing liquid adjustment unit 20 of the fourth embodiment. In the fourth embodiment, the processing liquid adjustment unit 20 supplies an adjusted first processing liquid to the first nozzle 15a. The processing liquid adjustment unit 20 of the fourth embodiment differs from the processing liquid adjustment unit 20 of the third embodiment in the configuration of the adjustment section 23.

[0246] The first tank 21 stores the first processing liquid.

[0247] The first treatment liquid of the fourth embodiment is substantially the same as the first treatment liquid of the third embodiment. The first treatment liquid includes an additive. The additive is dissolved in the first treatment liquid. The first treatment liquid contains iodide ions (I - The first processing liquid further includes a second etching liquid for etching the substrate W. The second etching liquid is adjusted by the adjustment unit 23.

[0248] The adjustment unit 23 degasses the first treatment liquid. As a result, the adjustment unit 23 removes iodide ions (I - ) is suppressed from decreasing. Specifically, the adjustment unit 23 includes a gas-liquid separation unit 26. The gas-liquid separation unit 26 is provided in the circulation pipe 36. The gas-liquid separation unit 26 has already been described in the second embodiment.

[0249] <5-2. Operation example of the processing liquid adjustment unit 20> The processing liquid adjustment unit 20 operates under the control of the control unit 10 .

[0250] The treatment liquid adjustment unit 20 performs an adjustment process. In the adjustment process, the pump 37 operates. The first treatment liquid circulates through the circulation pipe 36. The gas-liquid separation section 26 degasses the first treatment liquid flowing through the circulation pipe 36. The degassed first treatment liquid returns to the first tank 21.

[0251] As described above, the first treatment liquid is adjusted in the adjustment step (adjustment unit 23). The first treatment liquid adjusted in the adjustment step (adjustment unit 23) contains sufficient iodide ions (I - Furthermore, the first processing liquid adjusted in the adjusting step (adjusting unit 23) includes a second etching liquid.

[0252] The liquid sending unit 56 sends the first processing liquid adjusted in the adjusting step (adjusting unit 23) to the first nozzle 15a. Specifically, the valve 57b opens while the pump 37 is operating. Therefore, even when the liquid sending unit 56 sends the first processing liquid to the first nozzle 15a, the adjusting step is performed.

[0253] <5-4. Effects of the Fourth Embodiment> The fourth embodiment also provides the same effects as the first embodiment.

[0254] Furthermore, in the substrate processing method according to the fourth embodiment, the adjusting step degass the first processing liquid. Therefore, the adjusting step degasses the iodide ions (I - ) can be suitably suppressed from decreasing.

[0255] In the adjustment step, the first treatment liquid is degassed by filtering the first treatment liquid by the gas-liquid separation section 26. Therefore, in the adjustment step, the first treatment liquid can be degassed suitably.

[0256] The adjustment section 23 includes a gas-liquid separation section 26. Therefore, the adjustment section 23 can degas the first treatment liquid suitably. Therefore, the adjustment section 23 can suitably reduce the concentration of dissolved oxygen in the first treatment liquid.

[0257] Furthermore, the gas-liquid separation unit 26 can degas the first treatment liquid (e.g., pure water) without evaporating the first treatment liquid. Therefore, the adjustment unit 23 can suitably reduce the concentration of dissolved oxygen in the first treatment liquid while suppressing a decrease in the first treatment liquid stored in the first tank 21.

[0258] The present invention is not limited to the embodiments, and can be modified as follows.

[0259] (1) In the first and second embodiments, the first processing liquid is an aqueous solution in which an additive is dissolved in pure water. However, the present invention is not limited to this. For example, the first processing liquid may further include a second etching liquid. For example, the first processing liquid may include at least one of the above-mentioned alcohols b1)-b7). For example, the first processing liquid may include at least one of the above-mentioned acids c1)-c7).

[0260] (2) In the first and second embodiments, the supplying step supplies a mixed liquid of the first processing liquid and the first etching liquid to the substrate W. However, this is not limited to this. The supplying step may supply the first processing liquid and the first etching liquid separately to the substrate W.

[0261] FIG. 10 is a diagram showing the configuration of a processing unit 11 and a processing liquid adjustment unit 20 of a modified embodiment. The same components as those in the first embodiment are denoted by the same reference numerals and detailed description thereof will be omitted. The processing unit 11 includes a fourth nozzle 15d in addition to a first nozzle 15a. The second and third nozzles 15b-15c are not shown in FIG. 10.

[0262] Pipe 57a of liquid delivery unit 56 is connected to the first nozzle 15a. Pipe 58a of liquid delivery unit 56 is connected to the fourth nozzle 15d. Pipe 57a is not connected to pipe 58a. Pipe 57a is not connected to the fourth nozzle 15d. Pipe 58a is not connected to the first nozzle 15a. Therefore, liquid delivery unit 56 delivers the first processing liquid to the first nozzle 15a. Liquid delivery unit 56 does not deliver the first etching liquid to the first nozzle 15a. Liquid delivery unit 56 delivers the first etching liquid to the fourth nozzle 15d. Liquid delivery unit 56 does not deliver the first processing liquid to the fourth nozzle 15d.

[0263] As a result, the first nozzle 15a ejects the first processing liquid onto the substrate W held by the substrate holding part 13. The fourth nozzle 15d ejects the first etching liquid onto the substrate W held by the substrate holding part 13. After the first nozzle 15a and the fourth nozzle 15d eject the first processing liquid and the first etching liquid, respectively, the first processing liquid is added to the first etching liquid. The first processing liquid is added to the first etching liquid on the substrate W (pattern formation surface W1). The substrate W can also be appropriately etched by this modified embodiment.

[0264] Both the first nozzle 15a and the fourth nozzle 15d are examples of a supply section in the present invention.

[0265] (3) In the first to fourth embodiments, the processing units 11 are classified as single-wafer types. However, this is not limited to this. For example, the processing units 11 may be classified as batch types. In other words, the processing units 11 may process a plurality of substrates W at once.

[0266] Although not shown, the processing unit 11 includes a processing tank and a substrate holding mechanism. The processing tank stores a processing liquid. The processing liquid is, for example, a mixed liquid of a first processing liquid and a first etching liquid. Alternatively, the processing liquid is, for example, a first processing liquid containing a second etching liquid. The substrate holding mechanism holds a plurality of substrates W in the processing tank. The substrate holding mechanism immerses the plurality of substrates W in the processing liquid stored in the processing tank.

[0267] Here, the processing tank of the processing unit 11 may be provided separately from the first tank 21 and the second tank 51 of the processing liquid adjustment unit 20. Alternatively, the first tank 21 or the second tank 51 of the processing liquid adjustment unit 20 may be used as the processing tank of the processing unit 11.

[0268] The treatment tank is an example of a supply section in the present invention.

[0269] (4) In the first to fourth embodiments, the adjustment unit 23 includes either one of the air bubble generating unit 24 and the gas-liquid separating unit 26. However, this is not limited to this. The adjustment unit 23 includes the air bubble generating unit 24 and the gas-liquid separation unit 26 may be provided.

[0270] (5) In the first and second embodiments, the first and second sensors 41, 42 are provided in the circulation pipe 36. However, this is not limited to this. For example, at least one of the first and second sensors 41, 42 may be provided in the first tank 21. For example, the first sensor 41 detects iodide ions (I - For example, the second sensor 42 may detect the concentration of dissolved oxygen in the first treatment liquid in the first tank 21.

[0271] (6) In the third and fourth embodiments, the substrate processing apparatus 1 does not include the first sensor 41. However, this is not limited to this. In the third and fourth embodiments, the substrate processing apparatus 1 may include the first sensor 41.

[0272] (7) In the first to fourth embodiments, the oxidation-reduction potential of the first treatment liquid may be detected.

[0273] Please refer to Fig. 10. The processing solution adjustment unit 20 of the modified embodiment includes a fifth sensor 45. The fifth sensor 45 detects the oxidation-reduction potential of the first processing solution. Specifically, the fifth sensor 45 detects the oxidation-reduction potential of the first processing solution in the first tank 21. The fifth sensor is, for example, an oxidation-reduction potentiometer.

[0274] Although not shown in the figure, the control unit 10 acquires the detection result of the fifth sensor 45. The control unit 10 monitors the detection result of the fifth sensor 45, for example.

[0275] In this modified embodiment, the adjustment step detects the oxidation-reduction potential of the first treatment liquid. For this reason, the adjustment step detects the amount of iodide ions (I - The concentration of iodide ions (I - The present inventors have found that there is a certain relationship between the composition change of iodide ions (I - ) is either molecular iodine (I2) or triiodide ion (I3 - ) composition is unlikely to change.

[0276] The adjustment step is to adjust the amount of iodide ions (I - At least one of the concentration of the oxidative stress, the oxidation-reduction potential of the first treatment liquid, and the concentration of dissolved oxygen in the first treatment liquid may be detected.

[0277] For example, the adjustment process may be started based on the detection result of the fifth sensor 45. For example, the adjustment process may be started when the oxidation-reduction potential of the first treatment liquid is high. Here, whether or not the oxidation-reduction potential of the first treatment liquid is high is determined by the control unit 10. The control unit 10 determines the timing to start the adjustment process based on the detection result of the fifth sensor 45.

[0278] For example, the adjustment process may be terminated based on the detection result of the fifth sensor 45. For example, the adjustment process may be terminated when the oxidation-reduction potential of the first treatment liquid is low. Here, whether or not the oxidation-reduction potential of the first treatment liquid is low is determined by the control unit 10. The control unit 10 determines the timing to terminate the adjustment process based on the detection result of the fifth sensor 45.

[0279] For example, the iodide ion (I -The adjustment step may be started based on at least one of the detection results of the concentration of iodide ions (I - The adjusting step may be terminated based on at least one of the detection results of the concentration of the oxidative stress (CO2), the detection results of the oxidation-reduction potential of the first treatment liquid, and the detection results of the concentration of dissolved oxygen in the first treatment liquid.

[0280] For example, the adjustment step may replenish the first processing liquid with a solvent for the additive (i.e., pure water) based on the detection result of the fifth sensor 45. For example, the first replenishing unit 28 may replenish the first tank 21 with pure water based on the detection result of the fifth sensor 45. For example, the control unit 10 may control the first replenishing unit 28 based on the detection result of the fifth sensor 45.

[0281] For example, the iodide ion (I - The first treatment liquid may be replenished with a solvent for the additive (i.e., a solvent) based on at least one of the detection results of the concentration of the additive, the detection results of the oxidation-reduction potential of the first treatment liquid, and the detection results of the concentration of dissolved oxygen in the first treatment liquid.

[0282] (8) In the first to fourth embodiments, the substrate processing apparatus 1 may further include a configuration for replenishing the first processing liquid with an additive.

[0283] 10, the treatment liquid adjustment unit 20 includes a third replenishing section 33. The third replenishing section 33 replenishes the first treatment liquid with an additive. Specifically, the third replenishing section 33 replenishes the first tank 21 with the additive.

[0284] The third replenishing unit 33 includes a pipe 33a and a valve 33b. The pipe 33a is connected to the first tank 21. The pipe 33a is further connected to an additive supply source 34. The valve 33b is provided on the pipe 33a. When the valve 33b is opened, the pipe 33a supplies the additive to the first tank 21.

[0285] The control unit 10 controls the third supplement unit 33.

[0286] The adjustment step is to adjust the amount of iodide ions (I - At least one of the additive and the solvent for the additive (pure water) may be replenished to the first treatment liquid based on at least one of the detection results of the concentration of iodide ions (I), the detection results of the oxidation-reduction potential of the first treatment liquid, and the detection results of the concentration of dissolved oxygen in the first treatment liquid. The control unit 10 may control at least one of the first replenishing unit 28 and the third replenishing unit 33 based on at least one of the first sensor 41, the second sensor 42, and the fifth sensor 45. According to this modified embodiment, the iodide ions (I - ) can be suitably adjusted.

[0287] (9) In the first and third embodiments, the adjustment step includes supplying an inert gas into the first treatment liquid to generate bubbles in the first treatment liquid. In the second and fourth embodiments, the adjustment step includes degassing the first treatment liquid. However, this is not limited to this. In the first to fourth embodiments, the adjustment step may include supplying an inert gas into the first treatment liquid to generate bubbles in the first treatment liquid and degassing the first treatment liquid. In the first to fourth embodiments, the adjustment step may include at least one of supplying an inert gas into the first treatment liquid to generate bubbles in the first treatment liquid and degassing the first treatment liquid. The adjustment unit 23 may include both the bubble generation unit 24 and the gas-liquid separation unit 26. The adjustment unit 23 may include at least one of the bubble generation unit 24 and the gas-liquid separation unit 26.

[0288] (10) In the first and second embodiments, the first processing liquid is added to the first etching liquid at the joint 59. However, this is not limited to this. The liquid delivery unit 56 may include a mixer or a mixing valve for mixing the first processing liquid and the first etching liquid.

[0289] (11) In the first to fourth embodiments, the pipe 57a is connected to the circulation pipe 36. Therefore, the liquid delivery unit 56 delivers the first processing liquid flowing through the circulation pipe 36 to the first nozzle 15a. However, this is not limited to this. The pipe 57a of the liquid delivery unit 56 may be connected to the first tank 21. The liquid delivery unit 56 may deliver the first processing liquid in the first tank 21 to the first nozzle 15a. The pipe 58a of the liquid delivery unit 56 in the first and second embodiments may also be modified in a similar manner.

[0290] (12) The first to fourth embodiments and each of the modified embodiments described above in (1) to (11) may be further modified as appropriate by replacing or combining each configuration with the configuration of another modified embodiment. [Explanation of symbols]

[0291] 1 ... Substrate processing equipment 10 ... Control section 11 … Processing unit 13... Board holding part 15a … First nozzle (supply section) 15b … No. 2 nozzle 15c ... 3rd nozzle 15d … 4th nozzle (supply section) 20 … Processing liquid adjustment unit 21 … 1st tank 23 … Adjustment section 24 ... Bubble generating section 24a … Piping 24b … Valve 26 … Gas-liquid separation section 26a … Degassing filter 26b … Exhaust pipe 27 … Exhaust section 28 … First refill (Solvent for additives (pure water)) 31 ... Second refill (second etching solution) 33 … Third supplement (additives) 41 … First sensor (concentration of iodide ions) 42 … Second sensor (concentration of dissolved oxygen) 43 … 3rd sensor (liquid level sensor) 44 … 4th sensor (pH meter) 45 … 5th sensor (oxidation-reduction potentiometer) 51 … 2nd tank 56 ... Liquid delivery section 59 ... Joint A … Recess W … Substrate W1: Pattern forming surface W2 … Convex part X…Anteroposterior direction Y: Width direction Z: Vertical direction

Claims

1. A substrate processing method for processing a substrate, comprising the steps of: Iodide ions (I － ) reduction; a supplying step of supplying the first processing liquid adjusted in the adjusting step and a first etching liquid for etching the substrate to the substrate; Equipped with The adjusting step reduces a concentration of dissolved oxygen in the first treatment liquid. A method for processing a substrate.

2. The substrate processing method according to claim 1, The adjusting step includes supplying an inert gas into the first treatment liquid to generate bubbles in the first treatment liquid. A method for processing a substrate.

3. A substrate processing method for processing a substrate, comprising the steps of: Iodide ions (I － ) reduction; a supplying step of supplying the first processing liquid adjusted in the adjusting step and a first etching liquid for etching the substrate to the substrate; Equipped with The adjusting step includes degassing the first processing liquid. A method for processing a substrate.

4. The substrate processing method according to claim 3, The adjusting step includes filtering the first treatment liquid using a gas-liquid separator to degas the first treatment liquid. A method for processing a substrate.

5. A substrate processing method for processing a substrate, comprising the steps of: Iodide ions (I － ) reduction; a supplying step of supplying the first processing liquid adjusted in the adjusting step and a first etching liquid for etching the substrate to the substrate; Equipped with In the adjustment step, the iodide ion (I − ) is prevented from becoming at least one of an iodine molecule (I 2 ) and a triiodide ion (I 3 − ). A method for processing a substrate.

6. A substrate processing method according to any one of claims 1 to 5, The supplying step includes supplying a mixed liquid obtained by adding the first processing liquid adjusted in the adjusting step to the first etching liquid to the substrate. A method for processing a substrate.

7. The substrate processing method according to claim 1, The first treatment liquid is an aqueous solution in which the additive is dissolved in pure water. A method for processing a substrate.

8. A substrate processing method for processing a substrate, comprising the steps of: Iodide ions (I － ) reduction; a supplying step of supplying the first processing liquid adjusted in the adjusting step onto a substrate; Equipped with the first processing liquid further includes a second etching liquid for etching a substrate; The adjusting step reduces a concentration of dissolved oxygen in the first treatment liquid. A method for processing a substrate.

9. The substrate processing method according to claim 8, The adjusting step includes supplying an inert gas into the first treatment liquid to generate bubbles in the first treatment liquid. A method for processing a substrate.

10. A substrate processing method for processing a substrate, comprising the steps of: Iodide ions (I － ) reduction; a supplying step of supplying the first processing liquid adjusted in the adjusting step onto a substrate; Equipped with the first processing liquid further includes a second etching liquid for etching a substrate; The adjusting step includes degassing the first processing liquid. A method for processing a substrate.

11. The substrate processing method according to claim 10, The adjusting step includes filtering the first treatment liquid using a gas-liquid separator to degas the first treatment liquid. A method for processing a substrate.

12. A substrate processing method for processing a substrate, comprising the steps of: Iodide ions (I － ) reduction; a supplying step of supplying the first processing liquid adjusted in the adjusting step onto a substrate; Equipped with the first processing liquid further includes a second etching liquid for etching a substrate; In the adjustment step, the iodide ion (I − ) is prevented from becoming at least one of an iodine molecule (I 2 ) and a triiodide ion (I 3 − ). A method for processing a substrate.

13. The substrate processing method according to claim 1, The additive is a compound that converts the iodide ion (I － ) is liberated A method for processing a substrate.

14. The substrate processing method according to claim 1, The additive is Tetramethylammonium iodide (TMAI), Tetraethylammonium iodide (TEAI), Tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide, Ammonium iodide, and Hydrogen iodide Includes at least one of the following: A method for processing a substrate.

15. The substrate processing method according to claim 1, The adjusting step is performed by adjusting the iodide ion (I － ), an oxidation-reduction potential of the first treatment liquid, and a concentration of dissolved oxygen in the first treatment liquid. A method for processing a substrate.

16. The substrate processing method according to claim 15, The iodide ion (I － The adjustment step is started and ended based on at least one of a detection result of the concentration of the first treatment liquid, a detection result of the oxidation-reduction potential of the first treatment liquid, and a detection result of the concentration of dissolved oxygen in the first treatment liquid. A method for processing a substrate.

17. The substrate processing method according to claim 15, The iodide ion (I － ), a detection result of an oxidation-reduction potential of the first treatment liquid, and a detection result of a concentration of dissolved oxygen in the first treatment liquid, and based on this, at least one of the additive and the solvent of the additive is replenished to the first treatment liquid. A method for processing a substrate.

18. A substrate processing apparatus, comprising: The additive is dissolved and iodide ions (I － an adjusting unit that removes dissolved oxygen from the first treatment liquid, the first treatment liquid including the first treatment liquid and the second treatment liquid including the first treatment liquid; a supply unit that supplies the first processing liquid adjusted by the adjustment unit and a first etching liquid for etching the substrate to the substrate; A substrate processing apparatus comprising:

19. The substrate processing apparatus according to claim 18, The supply unit supplies a mixed liquid obtained by adding the first processing liquid adjusted by the adjustment unit to the first etching liquid to the substrate. Substrate processing equipment.

20. The substrate processing apparatus according to claim 18, The first treatment liquid is an aqueous solution in which the additive is dissolved in pure water. Substrate processing equipment.

21. A substrate processing apparatus, comprising: The additive is dissolved and iodide ions (I － an adjusting unit that removes dissolved oxygen from the first treatment liquid, the first treatment liquid including the first treatment liquid and the second treatment liquid including the first treatment liquid; a supply unit that supplies the first processing liquid adjusted by the adjustment unit to a substrate; Equipped with The first processing liquid includes a second etching liquid for etching a substrate. Substrate processing equipment.

22. The substrate processing apparatus according to claim 18, The iodide ion (I － A first sensor for detecting a concentration of A control unit that acquires a detection result of the first sensor; Equipped Substrate processing equipment.

23. The substrate processing apparatus according to claim 22, The control unit controls the adjustment unit based on a detection result of the first sensor. Substrate processing equipment.

24. The substrate processing apparatus according to claim 22 or 23, a first replenishing unit that replenishes the first processing liquid with a solvent for the additive; Equipped with The control unit controls the first replenishing unit to replenish the first processing liquid with the solvent based on a detection result of the first sensor. Substrate processing equipment.

25. The substrate processing apparatus according to claim 18, The adjusting unit includes a bubble generating unit that supplies an inert gas into the first processing liquid to generate bubbles in the first processing liquid. Substrate processing equipment.

26. The substrate processing apparatus according to claim 18, The adjustment unit includes a gas-liquid separation unit that filters the first treatment liquid and degasses the first treatment liquid. Substrate processing equipment.

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