TWI819620B - Substrate processing methods - Google Patents

Abstract

The substrate processing method of the present invention includes a processing step, a replacement step, and a removal step. In the processing step, the rinse liquid is supplied to the substrate W. The replacement step is to replace the rinse liquid on the substrate W with the second treatment liquid J. The removal step is to remove the second processing liquid J from the substrate W. The second treatment liquid J contains an organic solvent and additives. Additives inhibit the dehydration reaction of organic solvents. Therefore, the substrate processing method can appropriately process the substrate W.

Description

Substrate processing methods

The present invention relates to a substrate processing method. The substrate is, for example, a semiconductor wafer, a liquid crystal display substrate, an organic EL (Electroluminescence, electroluminescence) substrate, an FPD (Flat Panel Display) substrate, an optical display substrate, a magnetic disk substrate, an optical disk substrate, Substrates for magneto-optical discs, substrates for photomasks, and substrates for solar cells.

Patent Document 1 discloses a substrate processing method for processing a substrate. The substrate processing method of Patent Document 1 includes a processing step, a replacement step, and a removal step. In the processing step, the rinse liquid is supplied to the substrate. The replacement process is to replace the rinse liquid on the substrate with an organic solvent. The removal process removes the organic solvent from the substrate. Through the removal process, the substrate is dried. [Prior technical literature] [Patent Document]

[Patent document 1] Japanese Patent Application Publication No. 2012-156561

[Problem to be solved by the invention]

Even with previous substrate processing methods, there are cases where the substrate cannot be processed appropriately. For example, when the substrate has a pattern, even with the previous substrate processing method, the pattern may be damaged. For example, when the pattern is fine, even conventional substrate processing methods may not be able to sufficiently suppress pattern collapse.

The present invention was made in view of such circumstances, and an object thereof is to provide a substrate processing method capable of appropriately processing a substrate. [Technical means to solve problems]

The present invention was obtained through intensive research based on these findings and has the following configuration. That is, the present invention is a substrate processing method including: a processing step of supplying a first processing liquid to a substrate; a replacement step of replacing the first processing liquid on the substrate with a second processing liquid containing an organic solvent and an additive; and In the step of removing the second treatment liquid from the substrate, the additive inhibits the dehydration reaction of the organic solvent.

The substrate processing method includes a processing step, a replacement step, and a removal step. The processing step is to supply the first processing liquid to the substrate. The replacement step is to replace the first processing liquid on the substrate with the second processing liquid. Through the replacement process, the first processing liquid is removed from the substrate. The removal step is to remove the second processing liquid from the substrate. By removing the second processing liquid from the substrate, the substrate is dried.

The second treatment liquid contains an organic solvent and additives. Additives inhibit the dehydration reaction of organic solvents. Specifically, the additive suppresses the generation of water in the second treatment liquid. Therefore, the second treatment liquid does not contain water substantially. In other words, the amount of water contained in the second treatment liquid is extremely small. Therefore, the surface tension of the second treatment liquid is relatively small. Therefore, the second processing liquid does not exert significant force on the substrate. As a result, the substrate can be better protected.

As described above, according to the substrate processing method, the substrate can be processed while better protecting the substrate. Therefore, the substrate processing method can appropriately process the substrate.

In the above substrate processing method, it is preferable that the additive reduces protons in the second processing liquid. The smaller the number of protons, the less likely it is for the dehydration reaction of the organic solvent to occur. Therefore, the additive can better inhibit the dehydration reaction of organic solvents.

In the above substrate processing method, it is preferred that the additive includes a proton-accepting base. The additive contains alkali. By the base accepting protons, the protons are reduced. Therefore, the base effectively reduces the protons in the second treatment liquid.

In the above substrate processing method, it is preferable that the additive material contains at least one of bicarbonate ions and carbonate ions. Bicarbonate ion is an example of a base. Bicarbonate ions accept protons better. Therefore, bicarbonate ions effectively reduce protons in the second treatment liquid. Likewise, carbonate ions are examples of bases. Carbonate ions accept protons better. Therefore, carbonate ions can effectively reduce protons in the second treatment liquid.

In the above substrate treatment method, it is preferable that the above additive contains anions generated from a weak acid. The additive contains anions generated from weak acids. Anions generated from weak acids accept protons better. Therefore, the anions generated from the weak acid can effectively reduce the protons in the second treatment liquid.

In the above substrate processing method, it is preferable that the additive suppresses an increase in protons in the second processing liquid. Thereby, the additive can better inhibit the dehydration reaction of the organic solvent.

In the above substrate processing method, it is preferable that the additive includes a buffer that moderates changes in the hydrogen ion concentration in the second processing liquid. Additives include buffering agents. Buffers mitigate changes in hydrogen ion concentration in the treatment solution. Therefore, the buffer moderates the change in the amount of protons in the second treatment liquid. Therefore, the additive can better inhibit the dehydration reaction of organic solvents.

Among the above substrate processing methods, the preferred method is The above-mentioned additives include at least any one of the following compounds: carbon dioxide, 4-Toluenesulfonic acid, sodium methoxide, Sodium trifluoroacetate, oxalic acid, Lithium methoxide, Tribenzylamine, Sodium hydrogen phthalate, salicylic acid, Phenylacetic acid, Lithium hydrogen succinate, and Trimaleate. The compounds listed above are better at alleviating changes in the hydrogen ion concentration in the second treatment liquid.

In the above substrate processing method, it is preferable that the above organic solvent contains alcohol. Additives can better inhibit the dehydration reaction of alcohol.

In the above substrate processing method, it is preferable that the above organic solvent contains isopropyl alcohol. Additives can better inhibit the dehydration reaction of isopropyl alcohol.

In the above substrate processing method, it is preferable that the replacement step includes a first supply step of supplying the second processing liquid to the substrate. The replacement process includes a first supply process. The first supply step is to supply the second processing liquid to the substrate. Therefore, the replacement step preferably replaces the first processing liquid on the substrate with the second processing liquid.

In the above substrate processing method, it is preferable that the replacement step includes a second supply step of supplying the additive to the substrate. The replacement process includes a second supply process in addition to the first supply process. The second supply step supplies the additive to the substrate. Therefore, the concentration of the additive in the second treatment liquid on the substrate is controlled within an appropriate range. Therefore, the additive can better inhibit the dehydration reaction of the organic solvent on the substrate.

In the above substrate processing method, it is preferable that the replacement step includes a second supply step of supplying the additive to the substrate, and a third supply step of supplying the organic solvent to the substrate. The replacement process includes a second supply process and a third supply process. The second supply step supplies the additive to the substrate. The third supply step supplies the organic solvent to the substrate. Therefore, the replacement step generates the second treatment liquid from additives and organic solvents on the substrate. Therefore, the replacement step preferably replaces the first processing liquid on the substrate with the second processing liquid.

In the above-mentioned substrate processing method, it is preferable that in the above-mentioned replacement step, the substrate is located inside the processing container, and the processing container is sealed. In the replacement process, the substrate is located inside the processing container. In the replacement process, the processing container is sealed. Therefore, in the replacement process, the additive will not be excessively released from the second treatment liquid. Therefore, in the replacement process, the concentration of the additive in the second treatment liquid is maintained within an appropriate range. Therefore, the additive can better inhibit the dehydration reaction of organic solvents.

In the above-mentioned substrate processing method, it is preferable that the processing space in which the substrate is located is sealed during the above-mentioned replacement process. In the replacement process, the substrate is located in the processing space. During the replacement process, the processing space is closed. Therefore, in the replacement process, the additive will not be excessively released from the second treatment liquid. Therefore, in the replacement process, the concentration of the additive in the second treatment liquid is maintained within an appropriate range. Therefore, the additive can better inhibit the dehydration reaction of organic solvents.

In the above-mentioned substrate processing method, it is preferable that the cover member is disposed near the upper surface of the substrate and covers the upper surface of the substrate in the above-mentioned replacement process. In the replacement process, the cover member is arranged near the upper surface of the substrate. In the replacement process, the cover member covers the upper surface of the substrate. Therefore, the cover member can better suppress the amount of additive released from the second treatment liquid on the substrate. Therefore, during the replacement process, the concentration of the additive in the second treatment liquid on the substrate is maintained within an appropriate range. Therefore, the additive can better inhibit the dehydration reaction of the organic solvent on the substrate.

In the above-mentioned substrate processing method, it is preferable that the above-mentioned replacement step includes a first heating step of heating the substrate. The replacement process includes a first heating process. Therefore, in the replacement step, the second treatment liquid becomes high temperature. The second treatment liquid contains an organic solvent. Here, the higher the temperature of the organic solvent, the easier it is for the dehydration reaction of the organic solvent to occur. However, as mentioned above, the second treatment liquid contains additives. Therefore, even when the substitution process includes the first heating process, the additive suppresses the dehydration reaction of the organic solvent. On the contrary, when the replacement process includes the first heating process, the additive plays a significant role.

In the above-mentioned substrate processing method, it is preferable that the above-mentioned removal step includes an additional supply step of supplying the above-mentioned additive to the substrate. The removal process includes an additional supply process. The additional supply step supplies the additive to the substrate. Therefore, in the removal process, the concentration of the additive in the second treatment liquid is controlled within an appropriate range. Therefore, during the removal process, the additive can still better inhibit the dehydration reaction of the organic solvent on the substrate. The result is better protection of the substrate.

In the above-mentioned substrate processing method, it is preferable that the above-mentioned removal step includes a second heating step of heating the substrate. The removal process includes a second heating process. Therefore, in the removal process, the second treatment liquid becomes high temperature. The second treatment liquid contains an organic solvent. Here, the higher the temperature of the organic solvent, the easier it is for the dehydration reaction of the organic solvent to occur. However, as mentioned above, the second treatment liquid contains additives. Therefore, even when the removal process includes the second heating process, the dehydration reaction of the organic solvent is inhibited by the additive. On the contrary, when the removal process includes the second heating process, the additive plays a significant role.

In the above substrate processing method, it is preferable that the substrate has a surface, and the surface includes at least any one of a polycrystalline silicon film, a silicon oxide film, and a silicon nitride film. The surface of the substrate has the above structure. Therefore, the surface of the substrate is easily negatively charged. When the surface of the substrate is negatively charged, the surface of the substrate will attract protons. The second treatment liquid contains an organic solvent. The greater the amount of protons in the second treatment liquid, the easier it is for the dehydration reaction of the organic solvent to occur. However, as mentioned above, the second treatment liquid contains additives. Therefore, even when the surface of the substrate has the above-mentioned structure, the dehydration reaction of the organic solvent is inhibited by the additive. On the contrary, when the surface of the substrate has the above structure, the additive plays a significant role.

In the above substrate processing method, it is preferable that the substrate has a surface and a pattern formed on at least a part of the surface. Patterns are formed on the surface of the substrate. Therefore, protons in the second processing liquid are likely to be concentrated near the surface of the substrate. The second treatment liquid contains an organic solvent. The greater the amount of protons in the second treatment liquid, the easier it is for the dehydration reaction of the organic solvent to occur. However, as mentioned above, the second treatment liquid contains additives. Therefore, even when a pattern is formed on the surface of the substrate, the dehydration reaction of the organic solvent is inhibited by the additive. On the contrary, additives play a significant role when patterns are formed on the surface of the substrate. [Effects of the invention]

According to the substrate processing method of the present invention, the substrate can be appropriately processed.

＜1. Basic steps and basic mechanism of substrate processing method＞ The basic steps of the substrate processing method are explained. Furthermore, the basic mechanism of the substrate processing method is explained.

FIG. 1 is a flow chart showing the basic steps of the substrate processing method. The substrate processing method is a method used to process the substrate. The substrate processing method includes a processing step, a replacement step, and a removal step. The replacement process is executed after the processing process. The removal process is performed after the replacement process.

Step S1: Processing process In the processing step, the rinse liquid is supplied to the substrate W. The rinse liquid is an example of the first treatment liquid of the present invention.

FIG. 2 is a diagram schematically showing a substrate in a processing step. FIG. 2 shows a part of the substrate W. As shown in FIG.

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, or an optical disk. Cover substrate, solar cell substrate. The substrate W has a thin flat plate shape. The substrate W has a substantially circular shape in plan view.

The substrate W has a surface Ws. The surface Ws is exposed to the outside of the substrate W. The surface Ws corresponds to the exposed portion of the substrate W.

The surface Ws includes, for example, at least one of a polycrystalline silicon film, a silicon oxide film, and a silicon nitride film. In other words, the exposed portion of the substrate W includes, for example, at least one of polycrystalline silicon, silicon oxide, and silicon nitride.

The substrate W has a pattern P, for example. Pattern P has a concave and convex shape. Pattern P is formed on surface Ws. Therefore, the surface Ws has a relatively large surface area.

The pattern P has a convex part W1 and a recessed part A, for example. The convex portion W1 is a part of the substrate W. The convex part W1 is a structure. The convex portion W1 includes, for example, at least one of polycrystalline silicon, silicon oxide, and silicon nitride. The convex portion W1 bulges upward. The concave portion A is adjacent to the side of the convex portion W1. The concave part A is the space. The recessed portion A is open upward. The convex portion W1 corresponds to the wall dividing the concave portion A. The recessed portion A is, for example, extremely narrow.

The rinse liquid G comes into contact with the substrate W. Specifically, the rinse liquid G comes into contact with the surface Ws.

The rinse liquid G is, for example, deionized water (DIW). The rinse liquid G consists, for example, of deionized water only.

Flush G contains protons q. Proton q is a hydrogen ion (H ⁺ ). Proton q is a positive ion.

When the surface Ws comes into contact with the rinse liquid G, the surface Ws sometimes becomes negatively charged. In other words, when the surface Ws comes into contact with the rinse liquid G, the surface Ws sometimes has a negative potential. When the surface Ws includes at least any one of a polycrystalline silicon film, a silicon oxide film, and a silicon nitride film, the surface Ws is easily negatively charged. When the rinse liquid G is deionized water, the surface Ws is more likely to be negatively charged.

When surface Ws is negatively charged, surface Ws will attract proton q. When the surface Ws is negatively charged, protons q are tightly concentrated near the surface Ws. When the surface Ws is negatively charged, protons q are tightly concentrated near the pattern P. As the pattern P becomes finer, the amount of protons q located near the surface Ws increases. As the recess A becomes narrower, the amount of protons q located near the surface Ws increases.

Step S2: Replacement process The replacement step is to replace the rinse liquid G on the substrate W with the second treatment liquid. Through the replacement process, the rinse liquid G is removed from the substrate W.

FIG. 3 is a diagram schematically showing the substrate W in the replacement process. The second processing liquid J comes into contact with the substrate W. Specifically, the second treatment liquid J comes into contact with the surface Ws. The rinse liquid G has been removed from the substrate W. Therefore, the rinse liquid G is not shown in FIG. 3 .

The second treatment liquid J contains an organic solvent and additives. The second treatment liquid J is composed of only an organic solvent and additives, for example. The additives are, for example, dissolved in organic solvents. An organic solvent corresponds to a solvent, for example. Additives correspond to solutes, for example. Organic solvent liquid. The additive can be any of liquid, gas and solid.

Organic solvents will be explained. Organic solvents have relatively small surface tension. For example, the surface tension of organic solvents is less than that of water.

For example, organic solvents include alcohol. For example, organic solvents consist solely of alcohols.

For example, organic solvents include isopropyl alcohol (IPA). For example, the organic solvent consists solely of isopropyl alcohol (IPA).

For example, the organic solvent includes at least one of methanol and ethanol.

For example, the organic solvent includes at least one of hydrofluoroether (HFE), acetone, and trans-1,2-dichloroethylene.

Describe additives. Additives inhibit the dehydration reaction of organic solvents. The dehydration reaction is, for example, an intermolecular dehydration reaction. The dehydration reaction is, for example, an intramolecular dehydration reaction. If the dehydration reaction of the organic solvent occurs, water will be generated in the second treatment liquid J. The additive suppresses the generation of water in the second treatment liquid J.

For example, when the organic solvent contains alcohol, the additive inhibits the dehydration reaction of the alcohol. For example, when the organic solvent contains isopropyl alcohol, the additive inhibits the dehydration reaction of isopropyl alcohol. If the intermolecular dehydration reaction of isopropyl alcohol occurs, diisopropyl ether and water will be generated in the second treatment liquid J.

For example, the additive reduces the proton q in the second treatment liquid J. The smaller the amount of proton q in the second treatment liquid J, the less likely it is for the dehydration reaction of the organic solvent to occur. Therefore, when the additive reduces the amount of protons q in the second treatment liquid J, the additive better suppresses the dehydration reaction of the organic solvent.

In Figure 3, there are relatively few protons q in the second treatment liquid J. For example, the amount of protons q in the second treatment liquid J is smaller than the amount of protons q in the rinse liquid G.

For example, the additive includes a base that accepts proton q. The base accepts proton q. The reception of proton q by a base is equivalent to the reduction of proton q. When the additive contains a base, the additive preferably reduces the proton q in the second treatment liquid J.

For example, the additive includes at least one of bicarbonate ions (HCO ₃ ^- ) and carbonate ions (CO ₃ ^2- ). Bicarbonate ion (HCO ₃ ^- ) is also called bicarbonate ion. Bicarbonate ion (HCO ₃ ^- ) and carbonate ion (CO ₃ ^2- ) are examples of bases respectively. Therefore, the hydrogen carbonate ion (HCO ₃ ^- ) and the carbonate ion (CO ₃ ^2- ) each easily receive the proton q. Specifically, hydrogen carbonate ions (HCO ₃ ^- ) are combined with protons q (H ⁺ ) to become carbonic acid (H ₂ CO ₃ ). Carbonate ions (CO ₃ ^2- ) combine with protons q (H ⁺ ) to become bicarbonate ions (HCO ₃ ^- ).

For example, additives include anions generated from weak acids. In other words, the additive contains anions obtained by ionization of a weak acid. The additive contains anions derived from weak acids. Anions generated from weak acids accept protons better. Therefore, when the additive contains anions generated from a weak acid, the additive preferably reduces protons in the second treatment liquid J.

Here, weak acid is defined. A weak acid is, for example, an acid having an acid dissociation constant pKa of -3 or more. A weak acid is, for example, an acid whose acid dissociation constant pKa is -3 or more in water at 25°C.

For example, the additive suppresses the increase of proton q in the second treatment liquid J. When the proton q in the second treatment liquid J does not increase, the dehydration reaction of the organic solvent will not be promoted. When the additive suppresses the increase of proton q in the second treatment liquid J, the additive better suppresses the dehydration reaction of the organic solvent.

For example, the additive moderates the change in the amount of proton q in the second treatment liquid J. For example, the additive reduces the change amount of proton q in the second treatment liquid J. When the additive moderates the change in the amount of proton q in the second treatment liquid J, the additive better suppresses the dehydration reaction of the organic solvent.

For example, additives include buffering agents. The buffer relieves changes in the hydrogen ion concentration in the second treatment liquid J. Hydrogen ion concentration is also called pH value. The concentration of hydrogen ions is equivalent to the concentration of protons q. Therefore, when the additive contains a buffer, the additive can better alleviate the change in the amount of proton q in the second treatment liquid J. When the additive contains a buffer, the additive can better reduce the change amount of proton q in the second treatment liquid J.

For example, the additive includes at least any one of the following compounds a1-a12. Compound a1: carbon dioxide Compound a2: 4-toluenesulfonic acid Compound a3: sodium methoxide Compound a4: sodium trifluoroacetate Compound a5: oxalic acid Compound a6: lithium methoxide Compound a7: tribenzylamine Compound a8: sodium hydrogen phthalate Compound a9: salicylic acid Compound a10: phenylacetic acid Compound a11: lithium hydrogen succinate Compound a12: trimaleate

Compounds a1 to a12 are examples of buffering agents respectively. Therefore, the compounds a1 to a12 each moderate the change in the hydrogen ion concentration in the second treatment liquid J well. Compounds a1 to a12 each reduce the change in hydrogen ion concentration in the second treatment liquid J relatively well.

Furthermore, the behavior of carbon dioxide in the second treatment liquid J is the same as or similar to the behavior of carbon dioxide in water. Part of the carbon dioxide becomes bicarbonate ions (HCO ₃ ^- ) in water. Similarly, part of the carbon dioxide is converted into hydrogen carbonate ions (HCO ₃ ^- ) in the second treatment liquid J.

As mentioned above, the additive inhibits the dehydration reaction of the organic solvent. As a result, the second treatment liquid J does not contain water substantially. In other words, the second treatment liquid J contains very little water. For example, the concentration of water contained in the second treatment liquid J is less than 5000 ppm. For example, the concentration of water contained in the second treatment liquid J is less than 2000 ppm.

Step S3: Removal process The removal process is to remove the second processing liquid J on the substrate W from the substrate W. By removing the second processing liquid J from the substrate W, the substrate W is dried.

FIG. 4 is a diagram schematically showing the substrate W in the removal process. The illustration of proton q is omitted in Fig. 4 .

The second processing liquid J on the substrate W is gradually removed. The amount of the second processing liquid J on the substrate W decreases. As mentioned above, the second treatment liquid J does not contain water substantially. Therefore, the surface tension of the second treatment liquid J is relatively small. Therefore, the second processing liquid J does not exert significant force on the substrate W. The term "significant force" refers to a force that is large enough to damage the substrate W, for example. The so-called damage refers to, for example, the damage of the pattern P. The second processing liquid J is removed from the substrate W without applying significant force to the substrate W. Therefore, pattern P will not collapse. The convex part W1 will not collapse.

FIG. 5 is a diagram schematically showing the substrate W in the removal process. The second processing liquid J is completely removed from the substrate W. The substrate W is dried.

In this way, the present substrate processing method processes the substrate W while appropriately protecting the substrate W. This substrate processing method processes the substrate W while appropriately protecting the surface Ws of the substrate W. Therefore, this substrate processing method appropriately processes the substrate W.

For reference, a comparative example is illustrated. The comparative example has the same processing step, replacement step and removal step as this substrate processing method. The processing steps and removal steps of the comparative example are substantially the same as those of the substrate processing method. The replacement process of the comparative example is different from the replacement process of this substrate processing method. In the replacement process of the comparative example, the rinse liquid G was replaced with the replacement liquid. Displacement fluid contains organic solvents and no additives.

FIG. 6 is a diagram schematically showing the substrate W in the replacement process of the comparative example. The replacement liquid K comes into contact with the substrate W. As mentioned above, replacement liquid K does not contain additives. As a result, the amount of protons q in the replacement liquid K is relatively large. For example, the amount of protons q in the replacement liquid K and the amount of protons q in the flushing liquid G are approximately the same. The greater the amount of protons q in the replacement liquid K, the easier it is for the dehydration reaction of the organic solvent to occur. If the dehydration reaction of the organic solvent occurs, water r will be generated in the replacement liquid K. As a result, the replacement liquid K contains water r. The concentration of water r contained in the replacement liquid K is relatively high. The concentration of the water r contained in the replacement liquid K is higher than the concentration of the water contained in the second treatment liquid J. Therefore, the replacement liquid K has a relatively large surface tension. The surface tension of the replacement liquid K is greater than the surface tension of the second treatment liquid J.

FIG. 7 is a diagram schematically showing the substrate W in the removal process of the comparative example. The illustration of proton q is omitted in Fig. 7 .

The replacement liquid K on the substrate W is gradually removed. As mentioned above, the surface tension of replacement liquid K is relatively large. Therefore, the replacement liquid K exerts significant force on the substrate W. As a result, the surface Ws of the substrate W is damaged. For example, pattern P collapses. For example, the convex portion W1 collapses.

FIG. 8 is a diagram schematically showing the substrate W in the removal process of the comparative example. All the replacement liquid K is removed from the substrate W. The substrate W is dried.

In this way, the comparative example cannot properly protect the substrate W. In the comparative example, the surface Ws of the substrate W cannot be properly protected. Therefore, the comparative example cannot process the substrate W appropriately.

Below, a plurality of embodiments for implementing the above substrate processing method will be described.

<2. First Embodiment> <2-1. Overview of substrate processing equipment> FIG. 9 is a top view showing the inside of the substrate processing apparatus 1 . The substrate processing apparatus 1 processes the substrate W.

The substrate processing apparatus 1 includes a transfer unit 3 and a processing block 7 . The processing block 7 is connected to the transmission unit 3 . The transfer unit 3 supplies the substrate W to the processing block 7 . The processing block 7 processes the substrate W. The transfer unit 3 collects the substrate W from the processing block 7 .

In this specification, for the sake of convenience, the direction in which the carrying part 3 and the processing block 7 are arranged is called the "front and rear direction X". X is horizontal in the front and rear direction. The direction from the processing block 7 toward the carrying unit 3 in the front-rear direction X is called "front". The direction opposite to the front is called "rear". The horizontal direction orthogonal to the front-rear direction X is called "width direction Y". One direction of "width direction Y" is appropriately called "right". The direction opposite to the right is called "left". The direction perpendicular to the horizontal direction is called "vertical direction Z". In each figure, for reference, front, back, right, left, upper, and lower are shown appropriately.

The carrier unit 3 includes a plurality of (for example, four) carrier placement units 4 . Each carrier placing part 4 places one carrier C respectively. The carrier C accommodates a plurality of substrates W. The carrier C is, for example, FOUP (Front Opening Unified Pod), SMIF (Standard Mechanical Interface), or OC (Open Cassette).

The transfer unit 3 is provided with a transport mechanism 5 . The conveyance mechanism 5 is arranged behind the carrier placement part 4 . The transport mechanism 5 transports the substrate W. The transport mechanism 5 can enter and exit the carrier C placed on the carrier placement portion 4 . The conveying mechanism 5 includes a hand 5a and a hand driving part 5b. The hand 5a supports the substrate W. The hand driving part 5b is connected to the hand 5a. The hand driving part 5b moves the hand 5a. The hand driving part 5b moves the hand 5a in the front-back direction X, the width direction Y, and the vertical direction Z, for example. The hand driving part 5b rotates the hand 5a in a horizontal plane, for example.

The processing block 7 is provided with a transport space 8 and a transport mechanism 9 . The transport mechanism 9 is installed in the transport space 8 . The transport mechanism 9 transports the substrate W. The conveyance mechanism 9 and the conveyance mechanism 5 can transfer the substrate W to each other. The conveying mechanism 9 is provided with a hand 9a and a hand driving part 9b. The hand 9a supports the substrate W. The hand driving part 9b is connected to the hand 9a. The hand driving part 9b moves the hand 9a. The hand driving part 9b moves the hand 9a in the front-back direction X, the width direction Y, and the vertical direction Z, for example. The hand driving part 9b rotates the hand 9a in a horizontal plane, for example.

The processing block 7 includes a plurality of processing units 11 . The processing unit 11 is arranged on the side of the transfer space 8 . The processing unit 11 is arranged on the side of the transport mechanism 9 . Each processing unit 11 processes the substrate W.

The processing unit 11 includes a substrate holding portion 13 . The substrate holding part 13 holds the substrate W.

The transport mechanism 9 can enter and exit each processing unit 11 . The transport mechanism 9 can deliver the substrate W to the substrate holding portion 13 . The transport mechanism 9 can obtain the substrate W from the substrate holding part 13 .

FIG. 10 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 9 and the processing unit 11 . The control unit 10 is electrically connected to the transport mechanisms 5 and 9 and the processing unit 11 so as to be able to communicate with each other.

The control unit 10 is implemented by a central processing unit (CPU) that performs various processes, a RAM (Random-Access Memory) that is a working area for arithmetic processing, a storage medium such as a fixed disk, and the like. The control unit 10 has various information stored in the storage medium in advance. The information held by the control unit 10 is, for example, transportation information for controlling the transportation mechanisms 5 and 9 . The information possessed by the control unit 10 is, for example, processing information used to control the processing unit 11 . The processing information may also be referred to as the processing process recipe.

An operation example of the substrate processing apparatus 1 will be briefly described.

The transfer 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 9 of the processing block 7 .

The transport mechanism 9 distributes the substrate W from the transfer unit 3 to the processing unit 11 . Specifically, the transport mechanism 9 transports the substrate W from the transport mechanism 5 to the substrate holding portion 13 of each processing unit 11 .

The processing unit 11 processes the substrate W held by the substrate holding part 13 . The processing unit 11 performs liquid processing on the substrate W, for example.

After the processing unit 11 processes the substrate W, the transport mechanism 9 returns the substrate W from the processing unit 11 to the carrier 3 . Specifically, the transport mechanism 9 transports the substrate W from the substrate holding part 13 to the transport mechanism 5 .

The transfer unit 3 collects the substrate W from the processing block 7 . Specifically, the transport mechanism 5 transports the substrate W from the transport mechanism 9 to the carrier C.

<2-2. Structure of the processing unit 11> FIG. 11 is a diagram showing the structure of the processing unit 11 of the first embodiment. Each processing unit 11 has the same structure. The processing unit 11 is classified as monolithic. That is, each processing unit 11 processes only one substrate W at a time.

The substrate holding portion 13 supports one substrate W. The substrate holding portion 13 supports the substrate W in a substantially horizontal posture.

The substrate W has an upper surface Wt and a lower surface Wb. The upper surface Wt and the lower surface Wb are respectively part of the surface Ws of the substrate W. The upper surface Wt includes the above-mentioned pattern P, for example. The lower surface Wb is in contact with the substrate holding portion 13 , for example. The lower surface Wb may also be called the back surface of the substrate W.

The processing unit 11 includes a rotation drive unit 14 . The rotation drive unit 14 rotates the substrate holding unit 13 . The substrate W held by the substrate holding portion 13 rotates integrally with the substrate holding portion 13 . The substrate W held by the substrate holding portion 13 rotates around the rotation axis B. The rotation axis B passes through the center of the substrate W and extends along the vertical direction Z, for example.

The processing unit 11 includes one or more (for example, three) supply units 15a, 15b, and 15c. Each of the supply parts 15a to 15c supplies the processing liquid to the substrate W, respectively. Specifically, each of the supply units 15 a to 15 c supplies the processing liquid to the substrate W held by the substrate holding unit 13 . Each of the supply parts 15a to 15c supplies the processing liquid to the upper surface Wt of the substrate W held by the substrate holding part 13, respectively.

The processing liquid supplied to the substrate W from the supply part 15a is a chemical liquid. The chemical liquid is, for example, an etching liquid. The chemical solution contains, for example, at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF). The processing liquid supplied to the substrate W from the supply part 15b is a rinse liquid G. The processing liquid supplied to the substrate W from the supply part 15c is the second processing liquid J.

The supply part 15a is equipped with the nozzle 16a. Similarly, supply parts 15b and 15c are equipped with nozzles 16b and 16c, respectively. The nozzle 16a sprays the chemical liquid. The nozzle 16b sprays the flushing liquid G. The nozzle 16c sprays the second processing liquid J.

The supply part 15a includes a pipe 17a and a valve 18a. The pipe 17a is connected to the nozzle 16a. The valve 18a is provided in the pipe 17a. When the valve 18a is opened, the nozzle 16a sprays the chemical liquid. When the valve 18b is closed, the nozzle 16a does not eject chemical liquid. Similarly, supply parts 15b and 15c are equipped with pipes 17b and 17c and valves 18b and 18c, respectively. The pipes 17b and 17c are connected to the nozzles 16b and 16c respectively. Valves 18b and 18c are respectively provided in pipes 17b and 17c. The valve 18b controls the discharge of the flushing liquid G from the nozzle 16b. The valve 18c controls the discharge of the second treatment liquid J from the nozzle 16c.

The supply part 15a is connected to the chemical solution supply source 19a. The supply part 15a communicates with the chemical solution supply source 19a. The chemical solution supply source 19a is connected to the pipe 17a, for example. The medical solution supply source 19a supplies the medical solution to the supply part 15a.

The supply part 15b is connected to the rinse liquid supply source 19b. The supply part 15b communicates with the rinse liquid supply source 19b. The flushing liquid supply source 19b is connected to the pipe 17b, for example. The rinse liquid supply source 19b supplies the rinse liquid G to the supply part 15b.

The chemical solution supply source 19 a may be an essential component of the substrate processing apparatus 1 . For example, the chemical liquid supply source 19 a may be a chemical liquid tank included in the substrate processing apparatus 1 . Alternatively, the chemical solution supply source 19 a may not be an essential component of the substrate processing apparatus 1 . For example, the chemical solution supply source 19 a may be a physical device provided outside the substrate processing apparatus 1 . Likewise, the rinse liquid supply source 19 b may be an essential component of the substrate processing apparatus 1 . Alternatively, the rinse liquid supply source 19b may not be an essential component of the substrate processing apparatus 1 .

The substrate processing apparatus 1 includes a second processing liquid generating unit 21 . The second processing liquid generating unit 21 is connected to the supply part 15c. The second processing liquid generating unit 21 communicates with the supply part 15c. The second processing liquid generating unit 21 is connected to the pipe 17c, for example. The second processing liquid generation unit 21 transports the second processing liquid J to the supply part 15c.

Here, the second processing liquid generation unit 21 can supply the second processing liquid J to the supply parts 15c provided in the plurality of processing units 11 . Alternatively, the second processing liquid generating unit 21 may supply the second processing liquid J only to the supply part 15c provided in one processing unit 11. The same applies to the chemical solution supply source 19a and the flushing liquid supply source 19b.

The processing unit 11 may further include a cup (not shown). The cup is arranged around the substrate holding portion 13 . The cup catches the processing liquid scattered from the substrate W held by the substrate holding portion 13 .

Refer to Figure 10. The control unit 10 controls the rotation drive unit 14 . The control part 10 controls the supply parts 15a-15c. Specifically, the control unit 10 controls the valves 18a-18c.

<2-3. Structure of the second treatment liquid generating unit 21> Refer to Figure 11. The second processing liquid generating unit 21 generates the second processing liquid J.

The second processing liquid production unit 21 includes a tank 22 . The groove 22 is connected to the supply part 15c. The groove 22 communicates with the supply part 15c. The tank 22 communicates with the nozzle 16c via the pipe 17c, for example. The second processing liquid generating unit 21 generates the second processing liquid J in the tank 22 .

The second processing liquid generating unit 21 includes supply parts 23a and 23b. The supply part 23a supplies the additive to the tank 22. The supply part 23b supplies the organic solvent to the tank 22.

The supply part 23a includes a pipe 24a and a valve 25a. The pipe 24a is connected to the tank 22. The pipe 24a communicates with the tank 22. The valve 25a is provided in the pipe 24a. When the valve 25a is opened, the supply part 23a supplies the additive to the tank 22. When the valve 25a is closed, the supply part 23a does not supply the additive to the tank 22. Similarly, the supply part 23b is equipped with the pipe 24b and the valve 25b. The pipe 24b is connected to the tank 22. The pipe 24b communicates with the tank 22. The valve 25b is provided in the pipe 24b. Valve 25b controls the supply of organic solvent to tank 22.

The supply part 23a is connected to the additive supply source 29a. The supply part 23a communicates with the additive supply source 29a. The additive supply source 29a is connected to the pipe 24a, for example. The additive supply source 29a supplies the additive to the supply part 23a. The supply part 23b is connected to the organic solvent supply source 29b. The supply part 23b is connected to the organic solvent supply source 29b. The organic solvent supply source 29b is connected to the pipe 24b, for example. The organic solvent supply source 29b supplies the organic solvent to the supply part 23b. The additive supply source 29a and the organic solvent supply source 29b may be components of the substrate processing apparatus 1, or may not be components of the substrate processing apparatus 1.

Refer to Figure 10. The control unit 10 controls the second processing liquid generating unit 21 . The control unit 10 and the second processing liquid generation unit 21 are electrically connected so as to be communicable.

The control unit 10 controls the supply units 23a and 23b. The control unit 10 controls the valves 25a and 25b. Specifically, the control unit 10 has second processing liquid generation information for controlling the second processing liquid generation unit 21 . The second processing liquid generation information is stored in the storage medium of the control unit 10 in advance.

<2-4. Operation example of the second treatment liquid generating unit 21> For convenience, refer to Figure 11. The second processing liquid generating unit 21 generates the second processing liquid J according to the control of the control unit 10 . Specifically, the supply part 23a supplies the additive to the tank 22. The supply part 23b supplies the organic solvent to the tank 22. The additives are mixed with the organic solvent in tank 22 . The additive and the organic solvent become the second treatment liquid J in the tank 22 . Furthermore, the second treatment liquid J is stored in the tank 22 .

Here, the control unit 10 can adjust the production amount of the second processing liquid J by controlling the supply units 23a and 23b, for example. For example, the control unit 10 can adjust the storage amount of the second processing liquid J in the tank 22 by controlling the supply units 23a and 23b. The control unit 10 can adjust the concentration of the additive in the second treatment liquid J by controlling the supply units 23a and 23b, for example.

<2-5. Operation example of processing unit 11> FIG. 12 is a flowchart showing the steps of the substrate processing method according to the first embodiment. The substrate processing method is executed together with the operation of the second processing liquid generating unit 21 described above. The substrate processing method is essentially performed by the processing unit 11 . The processing unit 11 operates according to the control of the control unit 10 .

The substrate processing method includes a chemical solution supply process (step S1a) and a rinse liquid supply process (step S1b). The chemical solution supply process and the rinse liquid supply process are examples of the processing process (step S1).

The substrate processing method includes a first supply step (step S2a). The first supply process is an example of the replacement process (step S2).

The substrate processing method includes a spin drying step (step S3a). The spin drying process is an example of the removal process (step S3).

Furthermore, the substrate processing method includes a rotation starting process (step S11) and a rotation stopping process (step S12). The substrate processing method will be described in detail.

Step S11: Rotation start process The substrate holding part 13 holds the substrate W. The substrate W is held in a substantially horizontal posture. The substrate W starts to rotate. Specifically, the rotation drive unit 14 rotates the substrate holding unit 13 . The substrate W rotates around the rotation axis B integrally with the substrate holding portion 13 . The processing step, the replacement step and the removal step are performed while the substrate W is rotating.

Step S1a: Chemical solution supply process The supply part 15a supplies the chemical solution to the substrate W. Specifically, valve 18a is opened. The nozzle 16a sprays the chemical liquid. The chemical solution is supplied to the upper surface Wt of the substrate W. For example, the substrate W is etched with a chemical solution. For example, the natural oxide film is removed from the substrate W using a chemical solution.

Thereafter, the supply part 15a stops supplying the chemical solution to the substrate W. Specifically, valve 18a is closed. The nozzle 16a stops ejecting the liquid medicine.

Step S1b: Rinse liquid supply process The supply part 15b supplies the rinse liquid G to the substrate W. Specifically, valve 18b is opened. The nozzle 16b sprays the flushing liquid G. The rinse liquid G is supplied to the upper surface Wt of the substrate W. For example, the substrate W is washed with the rinse liquid G. For example, the chemical liquid is removed from the substrate W using the rinse liquid G.

Thereafter, the supply part 15b stops supplying the rinse liquid G to the substrate W. Specifically, valve 18b is closed. The nozzle 16b stops spraying the flushing liquid G.

Step S2a: First supply step The supply part 15c supplies the second processing liquid J to the substrate W. Specifically, valve 18c is opened. The nozzle 16c sprays the second processing liquid J. The second processing liquid J is supplied to the upper surface Wt of the substrate W. By supplying the second processing liquid J, the rinse liquid G on the substrate W is replaced with the second processing liquid J. That is, the rinse liquid G is removed from the substrate W by the second processing liquid J. A film of the second treatment liquid J is formed on the upper surface Wt of the substrate W.

Thereafter, the supply part 15c stops supplying the second processing liquid J to the substrate W. Specifically, valve 18c is closed. The nozzle 16c stops discharging the second treatment liquid J.

Step S3a: Spin drying process The second processing liquid J is removed from the substrate W. Specifically, the centrifugal force acting on the second processing liquid J on the substrate W causes the second processing liquid J to be thrown away from the substrate W. The second processing liquid J is scattered from the substrate W. Thereby, the second processing liquid J is removed from the substrate W. The substrate W is dried.

For example, the rotation speed of the substrate W in the spin drying process is higher than the rotation speed of the substrate W in the processing process. For example, the rotation speed of the substrate W in the spin drying process is higher than the rotation speed of the substrate W in the replacement process.

Step S12: Rotation stop process The substrate W stops rotating. Specifically, the rotation drive unit 14 stops the rotation of the substrate holding unit 13 . The substrate holding part 13 and the substrate W held by the substrate holding part 13 are stationary.

<2-6. Effects of the first embodiment> The substrate processing method includes a processing step, a replacement step, and a removal step. The processing step supplies the rinse liquid G to the substrate W. The replacement step is to replace the rinse liquid G on the substrate W with the second treatment liquid J. Through the replacement process, the rinse liquid G is removed from the substrate W. The removal step removes the second treatment liquid J from the substrate W. By removing the second processing liquid J from the substrate W, the substrate W is dried.

The second treatment liquid J contains an organic solvent and additives. Additives inhibit the dehydration reaction of organic solvents. Specifically, the additive suppresses the generation of water r in the second treatment liquid J. Therefore, the second treatment liquid J does not contain water r substantially. The amount of water r contained in the second treatment liquid J is extremely small. Therefore, the surface tension of the second treatment liquid J is relatively small. Therefore, the second processing liquid J does not exert significant force on the substrate W. As a result, the substrate W can be better protected. For example, the pattern P can be better prevented from being damaged. For example, it is possible to better prevent the convex portion W1 from being broken.

As described above, according to the substrate processing method, the substrate W can be processed while the substrate W is well protected. Therefore, the substrate processing method can appropriately process the substrate W.

For example, the additive reduces the proton q in the second treatment liquid J. Therefore, the additive can better inhibit the dehydration reaction of organic solvents. The additive effectively suppresses the formation of water r in the second treatment liquid J.

The additive contains a base. The base accepts proton q. When a base accepts a proton q, the proton q decreases. Therefore, the base effectively reduces the proton q in the second treatment liquid J. Therefore, the additive can better inhibit the dehydration reaction of organic solvents. The additive effectively suppresses the formation of water r in the second treatment liquid J.

For example, the additive contains at least one of hydrogen carbonate ions (HCO ₃ ^- ) and carbonate ions (CO ₃ ^2- ). Bicarbonate ion (HCO ₃ ^- ) accepts proton q better. Therefore, bicarbonate ions (HCO ₃ ^- ) can effectively reduce protons q in the second treatment liquid J. Carbonate ion (CO ₃ ^2- ) accepts proton q better. Therefore, carbonate ions (CO ₃ ^2- ) preferably reduce protons q in the second treatment liquid J. Therefore, the additive can better inhibit the dehydration reaction of organic solvents. The additive effectively suppresses the formation of water r in the second treatment liquid J.

The additive contains anions generated from weak acids. Anions generated from weak acids accept protons better. Therefore, the anion generated from the weak acid can effectively reduce the proton q in the second treatment liquid J. Therefore, the additive can better inhibit the dehydration reaction of organic solvents. The additive effectively suppresses the formation of water r in the second treatment liquid J.

For example, the additive suppresses the increase of proton q in the second treatment liquid J. Therefore, the additive can better inhibit the dehydration reaction of organic solvents. The additive effectively suppresses the formation of water r in the second treatment liquid J.

For example, additives include buffering agents. The buffer relieves changes in the hydrogen ion concentration in the second treatment liquid J. Therefore, the buffering agent can better alleviate the change in the amount of proton q in the second treatment liquid J. For example, the buffering agent can better alleviate the increase in proton q in the second treatment liquid J. Therefore, the additive can better inhibit the dehydration reaction of organic solvents. The additive effectively suppresses the formation of water r in the second treatment liquid J.

For example, the additive includes at least any one of compounds a1-a12. Compounds a1 to a12 each moderate the change in the hydrogen ion concentration in the second treatment liquid J well. Therefore, the additive can better inhibit the dehydration reaction of organic solvents. The additive effectively suppresses the formation of water r in the second treatment liquid J.

For example, organic solvents include alcohol. In this case, the additive can better inhibit the dehydration reaction of alcohol. The additive effectively suppresses the formation of water r in the second treatment liquid J.

For example, organic solvents include isopropyl alcohol. In this case, the additive can better inhibit the dehydration reaction of isopropyl alcohol. The additive effectively suppresses the formation of water r in the second treatment liquid J.

The replacement process includes a first supply process. The first supply step is to supply the second processing liquid J to the substrate W. Therefore, the replacement process preferably replaces the rinse liquid G on the substrate W with the second processing liquid J.

The substrate W has a surface Ws. The surface Ws includes at least one of a polycrystalline silicon film, a silicon oxide film, and a silicon nitride film. Therefore, the surface Ws is easily negatively charged. When the surface Ws is negatively charged, the surface Ws attracts the proton q. The second treatment liquid J contains an organic solvent. The greater the amount of protons q in the second treatment liquid J, the easier it is for the dehydration reaction of the organic solvent to occur. However, as mentioned above, the second treatment liquid J contains additives. Therefore, even when the surface Ws includes at least any one of a polycrystalline silicon film, a silicon oxide film, and a silicon nitride film, the dehydration reaction of the organic solvent is inhibited by the additive. Even when the surface Ws includes at least one of a polycrystalline silicon film, a silicon oxide film, and a silicon nitride film, the generation of water r in the second treatment liquid J is suppressed by the additive. On the contrary, when the surface Ws includes at least one of a polycrystalline silicon film, a silicon oxide film, and a silicon nitride film, the additive plays a significant role. In other words, when the surface Ws includes at least one of a polycrystalline silicon film, a silicon oxide film, and a silicon nitride film, the function of the additive is significantly exerted. The function of the additive is to inhibit the dehydration reaction of organic solvents. The function of the additive is to suppress the generation of water r in the second treatment liquid J.

The substrate W has the pattern P. Pattern P is formed on surface Ws. Therefore, the protons q in the second treatment liquid J tend to be concentrated near the surface Ws. The second treatment liquid J contains an organic solvent. The greater the amount of protons q in the second treatment liquid J, the easier it is for the dehydration reaction of the organic solvent to occur. However, as mentioned above, the second treatment liquid J contains additives. Therefore, even when the pattern P is formed on the surface Ws, the dehydration reaction of the organic solvent is inhibited by the additive. Even when the pattern P is formed on the surface Ws, the generation of water r in the second treatment liquid J is suppressed by the additive. On the contrary, when the pattern P is formed on the surface Ws, the additive plays a significant role.

The finer the pattern P, the easier it is for the protons q in the second treatment liquid J to be concentrated near the surface Ws. However, even when the pattern P is fine, the dehydration reaction of the organic solvent is inhibited by the additives. Even when the pattern P is fine, the generation of water r in the second treatment liquid J is suppressed by the additive. On the contrary, when the pattern P is fine, the additives play a more significant role.

<3. Second Embodiment> The second embodiment will be described with reference to the drawings. In addition, the same structure as that of 1st Embodiment is attached|subjected with the same code, and detailed description is abbreviate|omitted. In the first embodiment, the second processing liquid J is generated in the second processing liquid generating unit 21 . The replacement step of the first embodiment is to supply the second processing liquid J to the substrate W. In contrast, in the substitution step of the second embodiment, the organic solvent is supplied to the substrate W and the additive is supplied to the substrate W. In the second embodiment, the second processing liquid J is generated on the substrate W.

<3-1. Structure of the processing unit 11> FIG. 13 is a diagram showing the structure of the processing unit 11 of the second embodiment. The processing unit 11 is provided with supply parts 15d and 15e in addition to the supply parts 15a and 15b. The supply part 15d supplies the additive to the substrate W. The supply part 15e supplies the organic solvent to the substrate W.

The supply part 15d is equipped with the nozzle 16d. Similarly, the supply part 15e is equipped with the nozzle 16e. Nozzle 16d sprays additive. The nozzle 16e sprays the organic solvent.

The supply part 15d is equipped with the pipe 17d and the valve 18d. The pipe 17d is connected to the nozzle 16d. The valve 18d is provided in the pipe 17d. Valve 18d controls the spraying of additive from nozzle 16d. Similarly, the supply part 15e is equipped with the pipe 17e and the valve 18e. The pipe 17e is connected to the nozzle 16e. The valve 18e is provided in the pipe 17e. Valve 18e controls the supply of organic solvent from nozzle 16e.

The supply part 15d is connected to the additive supply source 29a. The supply part 15d communicates with the additive supply source 29a. The additive supply source 29a is connected to the pipe 17d, for example. The additive supply source 29a supplies the additive to the supply part 15d. The supply part 15e is connected to the organic solvent supply source 29b. The supply part 15e communicates with the organic solvent supply source 29b. The organic solvent supply source 29b is connected to the pipe 17e, for example. The organic solvent supply source 29b supplies the organic solvent to the supply part 15e.

The control unit 10 controls the supply units 15d and 15e, but illustration is omitted. The control unit 10 controls the valves 18d and 18e.

<3-2. Operation example of processing unit 11> FIG. 14 is a flowchart showing the steps of the substrate processing method according to the second embodiment. The substrate processing method of the second embodiment includes a second supply step (step S2b) and a third supply step (step S2c). The second supply process and the third supply process are examples of the replacement process (step S2).

The substrate processing method of the second embodiment will be described in detail. In the rotation starting process (step S11), the substrate W starts to rotate. In the chemical solution supplying step (step S1a), the chemical solution is supplied to the substrate W. In the rinse liquid supply step (step S1b), the rinse liquid G is supplied to the substrate W.

After the rinse liquid supply process, the second supply process and the third supply process are executed.

In the second supply step (step S2b), the supply unit 15d supplies the additive to the substrate W. Specifically, valve 18d is opened. Nozzle 16d sprays additive. The additive is supplied to the upper surface Wt of the substrate W.

Thereafter, the supply part 15d stops supplying the additive to the substrate W. Specifically, valve 18d is closed. The nozzle 16d stops spraying the additive.

In the third supply step (step S2c), the supply unit 15e supplies the organic solvent to the substrate W. Specifically, valve 18e is opened. The nozzle 16e sprays the organic solvent. The organic solvent is supplied to the upper surface Wt of the substrate W.

Thereafter, the supply part 15e stops supplying the organic solvent to the substrate W. Specifically, valve 18e is closed. The nozzle 16e stops ejecting the organic solvent.

Here, at least part of the period during which the third supply step is performed may overlap with at least part of the period during which the second supply step is performed. For example, the second supply step and the third supply step can be executed simultaneously. For example, the third supply process may be started before the second supply process is started. For example, the third supply process may be started after the start of the second supply process and before the end of the second supply process.

Alternatively, the period during which the third supply process is performed does not need to overlap with the period during which the second supply process is performed. For example, the second supply process may be started after the third supply process is completed. For example, the third supply process may be started after the second supply process is completed.

In the second supply step and the third supply step, the organic solvent and the additive become the second processing liquid J on the substrate W.

In at least one of the second supply process and the third supply process, the rinse liquid G is removed. The rinse liquid G is removed by at least one of the organic solvent and the second treatment liquid J. For example, the rinse liquid G on the substrate W can be replaced with an organic solvent, and then the second processing liquid J can be generated on the substrate W. For example, the second processing liquid J may be generated from an organic solvent on the substrate W, and at the same time, the rinse liquid G on the substrate W may be replaced with at least one of the organic solvent and the second processing liquid J.

After the second supply process and the third supply process, a spin drying process is performed. In the spin drying step (step S3a), the second processing liquid J is removed from the substrate W. In the rotation stopping step (step S12), the substrate W stops rotating.

<3-3. Effects of the second embodiment> The second embodiment also achieves the same effects as those of the first embodiment. For example, since the second processing liquid J contains an organic solvent and an additive, the substrate W can be processed while better protecting the substrate W. Furthermore, according to the second embodiment, the following effects are achieved.

The replacement process includes a second supply process and a third supply process. The second supply step supplies the additive to the substrate W. The third supply step supplies the organic solvent to the substrate W. Therefore, in the replacement step, the second processing liquid J is generated on the substrate W from the additive and the organic solvent. Therefore, the replacement process preferably replaces the rinse liquid G on the substrate W with the second processing liquid J.

As described above, in the replacement step, the second treatment liquid J is generated on the substrate W from the additives and the organic solvent. Therefore, it is not necessary to prepare the second treatment liquid J before executing the replacement process. Therefore, the structure of the substrate processing method can be simplified. Furthermore, in the second embodiment, the second processing liquid generating unit 21 may be omitted. Therefore, the structure of the substrate processing apparatus 1 can be simplified.

As described above, in the replacement step, the second treatment liquid J is generated on the substrate W from the additives and the organic solvent. Therefore, the replacement process controls the concentration of the additive in the second treatment liquid J on the substrate W more appropriately. For example, the concentration of the additive in the second treatment liquid J on the substrate W will not be too low.

However, the additive may be easily released from the second treatment liquid J. The additive may be easily released from the second treatment liquid J into the air. In other words, the additive may easily escape from the second treatment liquid J. For example, when the additive contains compound a1 (ie, carbon dioxide), the additive is easily released from the second treatment liquid J. However, as described above, the second supply process and the third supply process generate the second processing liquid J on the substrate W. Therefore, even when the additive is easily released from the second processing liquid J, the concentration of the additive in the second processing liquid J on the substrate W is maintained within an appropriate range. On the contrary, when the additive is easily released from the second treatment liquid J, the second supply step and the third supply step will exert significant benefits.

For example, at least part of the period during which the third supply process is performed overlaps with at least part of the period during which the second supply process is performed. In this case, the time required for the replacement process is preferably shortened.

For example, the third supply step is started, and then the second supply step is started. In this case, the rinse liquid G on the substrate W is removed by the organic solvent, and then the second processing liquid J is generated on the substrate W. Thereby, the second treatment liquid J can be generated efficiently. Can reduce the amount of additives used.

For example, after the third supply process is completed, the second supply process is started. Thereby, the second treatment liquid J can be generated more efficiently. Can further reduce the amount of additives used.

<4. Third Embodiment> The third embodiment will be described with reference to the drawings. In addition, the same structures as those in the first and second embodiments are denoted by the same reference numerals, and detailed descriptions are omitted. In the third embodiment, additives are added to the second treatment liquid J on the substrate W.

<4-1. Structure of the processing unit 11> FIG. 15 is a diagram showing the structure of the processing unit 11 of the third embodiment. The processing unit 11 includes supply units 15a, 15b, 15c, and 15d. The structure of the supply parts 15a-15c has been demonstrated in the 1st Embodiment. The structure of the supply part 15d has been demonstrated in the 2nd Embodiment.

<4-2. Operation example of processing unit 11> FIG. 16 is a flowchart showing the steps of the substrate processing method according to the third embodiment. The substrate processing method of the third embodiment includes, in addition to the first supply process (step S2a), a second supply process (step S2b). The first supply process and the second supply process are each examples of the replacement process (step S2).

The substrate processing method of the third embodiment includes, in addition to the spin drying step (step S3a), an additional supply step (step S3b). The spin drying process and the additional supply process are each an example of the removal process (step S3).

The substrate processing method of the third embodiment will be described in detail. In the rotation starting process (step S11), the substrate W starts to rotate. In the chemical solution supplying step (step S1a), the chemical solution is supplied to the substrate W. In the rinse liquid supply step (step S1b), the rinse liquid G is supplied to the substrate W. After the rinse liquid supply process, the first supply process and the second supply process are executed. In the first supply step (step S2a), the second processing liquid J is supplied to the substrate W. In the second supply step (step S2b), the additive is supplied to the substrate W. In the second supply step, the additive is added to the second processing liquid J on the substrate W.

Here, at least part of the period during which the second supply process is performed may overlap with at least part of the period during which the first supply process is performed. For example, the first supply process and the second supply process may be executed simultaneously. For example, the second supply process may be started after the first supply process is started and before the first supply process is completed.

Alternatively, the period during which the second supply process is performed does not need to overlap with the period during which the first supply process is performed. For example, the second supply process may be started after the first supply process is completed.

After the first supply process and the second supply process, a spin drying process and an additional supply process are performed. In the spin drying process (step S3a), the second processing liquid J is removed from the substrate W.

In the additional supply step (step S3b), the supply unit 15d supplies the additive to the substrate W. Specifically, valve 18d is opened. Nozzle 16d sprays additive. The additive is supplied to the upper surface Wt of the substrate W.

Thereafter, the supply part 15d stops supplying the additive to the substrate W. Specifically, valve 18d is closed. The nozzle 16d stops spraying the additive.

Here, at least part of the period during which the additional supply process is performed may overlap with at least part of the period during which the spin drying process is performed. For example, the spin drying process and the additional supply process can be executed simultaneously. For example, the additional supply process may be started after the start of the spin drying process and before the end of the spin drying process.

Alternatively, the period during which the additional supply process is performed does not need to overlap with the period during which the spin drying process is performed. For example, the spin drying process may be started after the additional supply process is completed.

It is preferable to end the additional supply process before the end of the spin drying process. It is preferable to end the additional supply process before all the second processing liquid J on the substrate W is removed from the substrate W.

The second supply process and the additional supply process may be continuous in time. That is, the additive can be continuously supplied to the substrate W through the supply part 15d from before the replacement process is completed to after the removal process is started.

After the spin drying process and the additional supply process, the spin stop process is performed. In the rotation stopping step (step S12), the substrate W stops rotating.

<4-3. Effects of the third embodiment> The third embodiment also achieves the same effects as those of the first embodiment. Furthermore, according to the third embodiment, the following effects are achieved.

The replacement process includes a second supply process in addition to the first supply process. The second supply step supplies the additive to the substrate. The second supply step is to replenish additives into the second processing liquid J on the substrate W. Therefore, the concentration of the additive in the second treatment liquid J on the substrate W is controlled within an appropriate range. For example, the concentration of the additive in the second treatment liquid J on the substrate W will not be significantly reduced. Therefore, the additive can better inhibit the dehydration reaction of the organic solvent on the substrate W. The additive can better suppress the formation of water r in the second treatment liquid J.

For example, after the first supply process is completed, the second supply process is started. In this case, the second supply step can effectively replenish the additive to the second processing liquid J on the substrate W.

For example, the second supply process is started after the first supply process is started and before the first supply process is completed. In this case, the change in the concentration of the additive in the second treatment liquid J is better suppressed.

As mentioned above, the replacement process includes the second supply process. Therefore, even when the additive is easily released from the second processing liquid J, the concentration of the additive in the second processing liquid J on the substrate W is appropriately controlled. On the contrary, when the additive is easily released from the second treatment liquid J, the second supply step will exert more significant benefits.

The removal process includes an additional supply process. The additional supply step supplies the additive to the substrate W. The additional supply step is to replenish additives into the second processing liquid J on the substrate W. Therefore, during the removal process, the concentration of the additive in the second treatment liquid J on the substrate W is also controlled within an appropriate range. For example, during the removal process, the concentration of the additive in the second treatment liquid J on the substrate W will not be significantly reduced. Therefore, during the removal process, the additive can still effectively inhibit the dehydration reaction of the organic solvent on the substrate W. During the removal process, the additives also effectively and continuously inhibit the dehydration reaction of the organic solvent on the substrate W. In the removal process, the additives can still effectively inhibit the formation of water r in the second treatment liquid J. As a result, the substrate W can be better protected.

As mentioned above, the removal process includes an additional supply process. Therefore, even when the additive is easily released from the second processing liquid J, the concentration of the additive in the second processing liquid J on the substrate W is appropriately controlled during the removal process. On the contrary, when the additive is easily released from the second treatment liquid J, the additional supply step will have more significant benefits.

<5. Fourth Embodiment> The fourth embodiment will be described with reference to the drawings. In addition, the same structures as those in the first to third embodiments are denoted by the same reference numerals, and detailed descriptions are omitted. In the fourth embodiment, the substrate W is processed in a closed space.

<5-1. Structure of the processing unit 11> FIG. 17 is a diagram showing the structure of the processing unit 11 of the fourth embodiment. The processing unit 11 includes a housing 31 . The housing 31 has a substantially box shape. The housing 31 is in contact with the transfer space 8 .

The case 31 accommodates the substrate holding portion 13 . When the substrate W is held by the substrate holding part 13 , the substrate W is accommodated in the housing 31 . Housing 31 houses nozzles 16a-16c.

Specifically, the housing 31 partitions the space 31a. The space 31a is located inside the housing 31. The substrate holding part 13 is provided in the space 31a. Nozzles 16a-16c are also provided in space 31a.

The casing 31 has a substrate transfer port 31b. The substrate transfer port 31b is arranged on the side wall of the housing 31, for example. The substrate transfer port 31b connects the space 31a and the transfer space 8 . The substrate W can pass through the substrate transfer port 31b.

The processing unit 11 is provided with a shutter 32 . The shutter 32 opens and closes the substrate transfer port 31b. Specifically, the processing unit 11 is provided with a shutter moving mechanism (not shown). The shutter moving mechanism moves the shutter 32 . The shutter 32 is moved to the first position and the second position by the shutter moving mechanism. In FIG. 17 , the baffle 32 in the first position is represented by a solid line. When the shutter 32 is located at the first position, the shutter 32 closes the substrate transfer port 31b. In Fig. 17, the baffle 32 located at the second position is indicated by a dotted line. When the shutter 32 is located at the second position, the shutter 32 opens the substrate transfer port 31b. When the baffle 32 is located at the second position, the space 31a is opened to the transfer space 8 via the substrate transfer port 31b. When the baffle 32 is in the second position, the housing 31 is open.

The processing unit 11 is provided with a sealing member 33 . The sealing member 33 brings the housing 31 and the baffle 32 into close contact. For example, the sealing member 33 is attached to at least one of the housing 31 and the baffle 32 . The sealing member 33 is an O-ring, for example. When the baffle 32 is in the first position, the baffle 32 is in close contact with the housing 31 via the sealing member 33 . As a result, when the shutter 32 is in the first position, the housing 31 is sealed. When the baffle 32 is in the first position, the space 31a is closed. When the baffle 32 is located at the first position, the space 31a is blocked from the transfer space 8 .

The control unit 10 controls the shutter moving mechanism, but the illustration is omitted.

The casing 31 is an example of a processing container in the present invention. The space 31a is an example of the processing space in the present invention.

<5-2. Operation example of processing unit 11> FIG. 18 is a flowchart showing the steps of the substrate processing method according to the fourth embodiment. The substrate processing method of the fourth embodiment further includes a sealing process (step S21) and an opening process (step S22).

The substrate processing method according to the fourth embodiment will be described in detail. After the transport mechanism 9 places the substrate W on the substrate holding part 13, the sealing process is performed. In the sealing process (step S21), the housing 31 is sealed. Specifically, the shutter 32 moves from the second position to the first position. Thereby, the space 31a is closed. The substrate W held by the substrate holding part 13 is accommodated in the housing 31 . The substrate W held by the substrate holding part 13 is located in the space 31a.

After the sealing process, the treatment process (steps S1a, S1b), the replacement process (step S2a), and the removal process (step S3a) are performed. In a state where the substrate W is accommodated in the housing 31 and the housing 31 is sealed, the processing process, the replacement process, and the removal process are performed. In other words, in a state where the space 31a where the substrate W is located is closed, the processing step, the replacement step, and the removal step are performed. The treatment process includes a chemical solution supply process (step S1a) and a rinse liquid supply process (step S1b). The replacement process includes a first supply process (step S2a). The removal process includes a spin drying process (step S3a).

After the removal process, the opening process is performed. In the opening process (step S22), the housing 31 is opened. Specifically, the shutter 32 moves from the first position to the second position. Thereby, the space 31a is opened. The housing 31 allows the transport mechanism 9 to pick up the substrate W on the substrate holding part 13 .

<5-3. Effects of the fourth embodiment> The fourth embodiment also achieves the same effects as those of the first embodiment. Furthermore, according to the fourth embodiment, the following effects are achieved.

In the replacement process, the substrate W is located inside the housing 31, and the housing 31 is sealed. In the replacement process, the space 31a where the substrate W is located is sealed. In the replacement process, the space 31a where the substrate W is located is closed. Therefore, during the replacement process, the additive will not be excessively released from the second treatment liquid J on the substrate W. During the replacement process, the additive will not be excessively released from the second treatment liquid J on the substrate W into the space 31a. Therefore, in the replacement process, the concentration of the additive in the second treatment liquid J is maintained within an appropriate range. For example, in the replacement process, the concentration of the additive in the second treatment liquid J will not be significantly reduced. Even when the additive is easily released from the second processing liquid J, the concentration of the additive in the second processing liquid J on the substrate W is appropriately maintained. Therefore, the additive can better inhibit the dehydration reaction of organic solvents. The additive effectively suppresses the formation of water r in the second treatment liquid J.

Similarly, during the removal process, the substrate W is located inside the housing 31 and the housing 31 is sealed. During the removal process, the space 31a where the substrate W is located is sealed. During the removal process, the space 31a where the substrate W is located is closed. Therefore, during the removal process, the additive will not be excessively released from the second treatment liquid J on the substrate W. During the removal process, the additive will not be excessively released from the second treatment liquid J on the substrate W into the space 31a. Therefore, during the removal process, the concentration of the additive in the second treatment liquid J is also maintained within an appropriate range. Therefore, during the removal process, the additives can still better inhibit the dehydration reaction of the organic solvent. In the removal process, the additives can still effectively inhibit the formation of water r in the second treatment liquid J. As a result, the substrate W can be better protected.

<6. Fifth Embodiment> The fifth embodiment will be described with reference to the drawings. In addition, the same structures as those in the first to fourth embodiments are denoted by the same reference numerals, and detailed descriptions are omitted. In the replacement process of the fifth embodiment, the space for processing the substrate W is sealed by a member different from the housing 31 .

<6-1. Structure of the processing unit 11> FIG. 19 is a diagram showing the structure of the processing unit 11 of the fifth embodiment. In FIG. 19 , the baffle 32 is omitted. The processing unit 11 is provided with an internal container 41 . The inner container 41 is provided inside the housing 31 . The inner container 41 accommodates the substrate holding part 13 . When the substrate W is held by the substrate holding portion 13 , the substrate W is accommodated in the inner container 41 .

Specifically, the inner container 41 divides the space 41a. The space 41a is located inside the inner container 41. The space 41a of the inner container 41 is smaller than the space 31a of the housing 31. The substrate holding part 13 is provided in the space 41a.

The inner container 41 has a first member 42 . The first member 42 is arranged on the side of the substrate holding part 13 . The first member 42 is arranged around the substrate holding portion 13 . The first member 42 has a substantially cylindrical shape, for example. The first member 42 is open upward, for example. The first member 42 corresponds to the main body of the inner container 41, for example. For example, the first member 42 may be a cup. For example, the first member 42 can catch the processing liquid scattered from the substrate W held by the substrate holding portion 13 . Alternatively, the first member 42 may be another member different from the cup.

The inner container 41 has a second member 43 . The second member 43 is arranged above the first member 42 . The second member 43 is arranged above the substrate holding portion 13 . The second member corresponds to the lid of the inner container 41 .

The inner container 41 is provided with a sealing member 44 . The sealing member 44 brings the first member 42 and the second member 43 into close contact. For example, the sealing member 44 is attached to at least one of the first member 42 and the second member 43 . The sealing member 44 is an O-ring, for example.

The processing unit 11 is provided with an internal container moving mechanism 45 . The inner container moving mechanism 45 opens and closes the inner container 41. Specifically, the inner container moving mechanism 45 moves the second member 43 relative to the first member 42 .

The inner container moving mechanism 45 moves the second member 43 to the first position and the second position. In FIG. 19 , the second member 43 located at the first position is indicated by a solid line. When the second member 43 is located at the first position, the second member 43 is in close contact with the first member 42 via the sealing member 44 . Therefore, when the second member 43 is located at the first position, the inner container 41 is sealed. When the second member 43 is located at the first position, the space 41a is closed. In FIG. 19 , the second member 43 located at the second position is indicated by a dotted line. The second position is, for example, a position above the first position. When the second member 43 is located at the second position, the inner container 41 is opened. When the second member 43 is located at the second position, the space 41a is open.

The nozzle 16c is attached to the second member 43. The nozzle 16c moves integrally with the second member 43. When the second member 43 is located at the first position, the nozzle 16c is located at the processing position. In Fig. 19, the nozzle 16c located at the processing position is indicated by a solid line. The processing position of the nozzle 16 c is, for example, a position above the substrate W held by the substrate holding part 13 . When the second member 43 is located at the second position, the nozzle 16c is located at the standby position. In Fig. 19, the nozzle 16c in the standby position is indicated by a dotted line. The standby position of the nozzle 16c is, for example, a position above the processing position of the nozzle 16c.

The processing unit 11 is provided with a nozzle moving mechanism 47a. The nozzle moving mechanism 47a moves the nozzle 16a. The nozzle 16a moves to the standby position and the processing position by the nozzle moving mechanism 47a. Figure 19 shows the nozzle 16a in the standby position. When the nozzle 16a is in the standby position, the nozzle 16a is located outside the inner container 41. When the nozzle 16a is in the standby position, the nozzle 16a is located outside the sealed inner container 41. When the nozzle 16a is in the standby position, the nozzle 16a allows the inner container 41 to open and close. The processing position of the nozzle 16 a is, for example, a position above the substrate W held by the substrate holding portion 13 , but illustration is omitted. When the second member 43 is in the second position, the inner container 41 allows the nozzle 16a to move to the processing position.

Similarly, the processing unit 11 is provided with the nozzle moving mechanism 47b. The nozzle moving mechanism 47b moves the nozzle 16b. The nozzle 16b moves to the standby position and the processing position by the nozzle moving mechanism 47b. Figure 19 shows the nozzle 16b in the standby position. When the nozzle 16b is in the standby position, the nozzle 16b is located outside the inner container 41. When the nozzle 16b is in the standby position, the nozzle 16b is located outside the sealed inner container 41. When the nozzle 16b is in the standby position, the nozzle 16b allows the inner container 41 to open and close. The processing position of the nozzle 16 b is, for example, a position above the substrate W held by the substrate holding part 13 , but illustration is omitted. When the second member 43 is in the second position, the inner container 41 allows the nozzle 16b to move to the processing position.

The control unit 10 controls the inner container moving mechanism 45, but the illustration is omitted. The control unit 10 controls the nozzle moving mechanisms 47a and 47b.

The inner container 41 is an example of a processing container in the present invention. The space 41a is an example of the processing space in the present invention.

<6-2. Operation example of processing unit 11> FIG. 20 is a flowchart showing the steps of the substrate processing method according to the fifth embodiment. The substrate processing method of the fifth embodiment further includes a sealing process (step S23) and an opening process (step S24).

The substrate processing method according to the fifth embodiment will be described in detail. With the substrate W accommodated in the inner container 41 and the inner container 41 open, the rotation starting process, the chemical solution supply process, and the rinse liquid supply process are executed. In a state where the substrate W is accommodated in the inner container 41 and the inner container 41 is open, the substrate W is located in the space 41a, the second member 43 is located in the second position, and the space 41a is open. The chemical solution supply process (step S1a) and the rinse liquid supply process (step S1b) are examples of processing processes. Therefore, in the processing steps (steps S1a and S1b), the space 41a in which the substrate W is located is opened.

In the chemical liquid supply process, the nozzle 16a moves from the standby position to the processing position. When the nozzle 16a is located at the processing position, the nozzle 16a supplies the chemical solution to the substrate W. Thereafter, the nozzle 16a moves from the processing position to the standby position.

In the rinse liquid supply process, the nozzle 16b moves from the standby position to the processing position. When the nozzle 16b is located at the processing position, the nozzle 16b supplies the rinse liquid G to the substrate W. Thereafter, the nozzle 16b moves from the processing position to the standby position.

After the flushing liquid supply process is completed, the sealing process is performed. In the sealing process (step S23), the inner container 41 is sealed. Specifically, the second member 43 moves from the second position to the first position. Thereby, the space 41a is closed. The substrate W is accommodated in the inner container 41 . The substrate W is located in the space 41a.

After the sealing process, the first supply process and the spin drying process are performed. The first supply process (step S2a) is an example of the replacement process. The spin drying process (step S3a) is an example of the removal process. In a state where the substrate W is accommodated in the inner container 41 and the inner container 41 is sealed, the replacement process (step S2a) and the removal process (step S3a) are performed. In other words, the replacement process and the removal process are performed in a state where the space 41a where the substrate W is located is closed.

Then, the rotation stop process is executed. After the rotation stop process, the opening process is performed. In the opening process (step S24), the inner container 41 is opened. Specifically, the second member 43 moves from the first position to the second position. Thereby, the space 41a is opened.

<6-3. Effects of the fifth embodiment> The fifth embodiment also achieves the same effects as those of the first embodiment. Furthermore, according to the fifth embodiment, the following effects are achieved.

In the replacement process, the substrate W is located inside the inner container 41, and the inner container 41 is sealed. In the replacement process, the space 41a where the substrate W is located is sealed. In the replacement process, the space 41a where the substrate W is located is closed. Therefore, during the replacement process, the additive will not be excessively released from the second treatment liquid J on the substrate W. During the replacement process, the additive will not be excessively released from the second treatment liquid J on the substrate W into the space 41a. Therefore, in the replacement process, the concentration of the additive in the second treatment liquid J is maintained within an appropriate range. For example, in the replacement process, the concentration of the additive in the second treatment liquid J will not be excessively reduced. Therefore, the additive can better inhibit the dehydration reaction of organic solvents. The additive effectively suppresses the formation of water r in the second treatment liquid J.

In particular, the space 41a of the inner container 41 is smaller than the space 31a of the housing 31. Therefore, the additive is not easily released from the second treatment liquid J. The additive is not easily released from the second treatment liquid J into the space 41a. Therefore, in the replacement process, the concentration of the additive in the second treatment liquid J is not easily reduced. Therefore, in the replacement process, the concentration of the additive in the second treatment liquid J can be more easily controlled.

In the removal process, the substrate W is located inside the inner container 41, and the inner container 41 is sealed. During the removal process, the space 41a where the substrate W is located is sealed. During the removal process, the space 41a where the substrate W is located is closed. Therefore, during the removal process, the additive will not be excessively released from the second treatment liquid J on the substrate W. During the removal process, the additive will not be excessively released from the second treatment liquid J on the substrate W into the space 41a. Therefore, during the removal process, the concentration of the additive in the second treatment liquid J is also maintained within an appropriate range. Therefore, during the removal process, the additives can still better inhibit the dehydration reaction of the organic solvent. In the removal process, the additives can still effectively inhibit the formation of water r in the second treatment liquid J. As a result, the substrate W can be better protected.

<7. 6th Embodiment> The sixth embodiment will be described with reference to the drawings. In addition, the same structures as those in the first to fifth embodiments are denoted by the same reference numerals, and detailed descriptions are omitted. In the replacement process of the sixth embodiment, the upper surface Wt of the substrate W is covered. In the replacement process of the sixth embodiment, the upper surface Wt of the substrate W is blocked.

<7-1. Structure of the processing unit 11> FIG. 21 is a diagram showing the structure of the processing unit 11 according to the sixth embodiment. The processing unit 11 is provided with a cover member 51 . The cover member 51 has, for example, a substantially flat plate shape. The cover member 51 has a size equal to or larger than that of the substrate W in plan view, but is not shown in the figure.

The processing unit 11 is provided with a cover member moving mechanism 52 . The cover member moving mechanism 52 moves the cover member 51 relative to the substrate W held by the substrate holding portion 13 .

The cover member 51 moves to the first position by the cover member moving mechanism 52 . In FIG. 21 , the cover member 51 located in the first position is indicated by a solid line. When the cover member 51 is located at the first position, the cover member 51 is located above the substrate W. More specifically, the first position is a position above the processing liquid (for example, the second processing liquid J) on the substrate W. When the cover member 51 is located at the first position, the cover member 51 is located near the upper surface Wt of the substrate W. When the cover member 51 is located at the first position, the cover member 51 covers the upper surface Wt of the substrate W.

The cover member 51 moves to the second position by the cover member moving mechanism 52 . In FIG. 21 , the cover member 51 located at the second position is indicated by a dotted line. The second position is, for example, a position above the first position. When the cover member 51 is located at the second position, the cover member 51 is also located above the substrate W. However, when the cover member 51 is located at the second position, the cover member 51 is away from the upper surface Wt of the substrate W. Specifically, the distance between the second position and the upper surface Wt is greater than the distance between the first position and the upper surface Wt.

The space above the substrate W is called an upper space M. The upper space M is limited below the cover member 51 . The cover member 51 expands and contracts the upper space M. Specifically, when the cover member 51 moves between the first position and the second position, the upper space M expands and contracts in the vertical direction Z. When the cover member 51 is in the first position, the upper space M is narrow. When the cover member 51 is in the second position, the upper space M is larger.

The nozzle 16c is attached to the cover member 51. The nozzle 16c moves integrally with the cover member 51. When the cover member 51 is in the first position, the nozzle 16c is in the processing position. In Fig. 21, the nozzle 16c located at the processing position is indicated by a solid line. The processing position of the nozzle 16 c is, for example, a position above the substrate W held by the substrate holding part 13 . When the cover member 51 is in the second position, the nozzle 16c is in the standby position. In Fig. 21, the nozzle 16c in the standby position is indicated by a dotted line. The standby position of the nozzle 16c is, for example, a position above the processing position of the nozzle 16c.

Figure 21 shows the nozzles 16a, 16b in the standby position. When the nozzles 16a and 16b are in the standby position, the nozzles 16a and 16b are located outside the cover member 51. When the nozzles 16a and 16b are in the standby position, the nozzles 16a and 16b allow the cover member 51 to move to the first position. The processing positions of the nozzles 16 a and 16 b are, for example, positions above the substrate W held by the substrate holding portion 13 , but illustration is omitted. When the cover member 51 is in the second position, the cover member 51 allows the nozzles 16a, 16b to move to the processing position.

The control unit 10 controls the cover member moving mechanism 52, but the illustration is omitted.

<7-2. Operation example of processing unit 11> FIG. 22 is a flowchart showing the steps of the substrate processing method according to the sixth embodiment. The substrate processing method of the sixth embodiment further includes a blocking step (step S25) and a blocking releasing step (step S26).

The substrate processing method according to the sixth embodiment will be described in detail. With the cover member 51 in the second position, the rotation starting process (step S11), the chemical liquid supply process (step S1a), and the rinse liquid supply process (step S1b) are executed. When the cover member 51 is in the second position, the upper space M is wider. The chemical solution supply process (step S1a) and the rinse liquid supply process (step S1b) are each examples of processing processes. Therefore, in the processing steps (steps S1a and S1b), the upper space M is wider.

After the flushing liquid supply process is completed, the blocking process is executed. In the blocking process (step S25), the upper surface Wt of the substrate W is blocked. Specifically, the cover member 51 moves from the second position to the first position. The cover member 51 is arranged near the upper surface Wt of the substrate W. The cover member 51 covers the upper surface Wt of the substrate W. The upper space M is reduced by the cover member 51 . The upper space M is narrower.

After the blocking process, the first supply process and the spin drying process are performed. The first supply process (step S2a) is an example of the replacement process. The spin drying process (step S3a) is an example of the removal process. In the state where the upper surface Wt of the substrate W is blocked, the replacement process (step S2a) and the removal process (step S3a) are performed.

Then, the rotation stop process is executed. After the rotation stop process, the interruption release process is executed. In the shielding releasing process (step S26), the shielding of the upper surface Wt of the substrate W is released. Specifically, the cover member 51 moves from the first position to the second position. Through this, the upper space M expands. The upper surface Wt of the substrate W is substantially open.

<7-3. Effects of the sixth embodiment> The sixth embodiment also achieves the same effects as those of the first embodiment. Furthermore, according to the sixth embodiment, the following effects are achieved.

In the replacement process, the cover member 51 is disposed near the upper surface Wt of the substrate W. In the replacement process, the cover member 51 covers the upper surface Wt of the substrate W. Therefore, the cover member 51 can better suppress the amount of additive released from the second processing liquid J on the substrate W. The cover member 51 can better suppress the additive from being released from the second treatment liquid J on the substrate W. During the replacement process, the additive will not be excessively released from the second treatment liquid J on the substrate W. Therefore, during the replacement process, the concentration of the additive in the second treatment liquid J on the substrate W is maintained within an appropriate range. For example, in the replacement process, the concentration of the additive in the second treatment liquid J will not be significantly reduced. Even when the additive is easily released from the second processing liquid J, the concentration of the additive in the second processing liquid J on the substrate W is appropriately maintained. Therefore, the additive can better inhibit the dehydration reaction of the organic solvent on the substrate W. The additive effectively suppresses the formation of water r in the second treatment liquid J.

In the replacement process, the cover member 51 is arranged above the substrate W. Therefore, the additive is not easily released from the second treatment liquid J during the replacement step. Therefore, in the replacement step, the concentration of the additive in the second treatment liquid J can be easily controlled.

The cover member 51 is configured to be movable to the first position and the second position. The distance between the first position and the upper surface Wt is smaller than the distance between the second position and the upper surface Wt. The upper space M when the cover member 51 is in the first position is smaller than the upper space M when the cover member 51 is in the second position. In the replacement process, the cover member 51 is arranged at the first position. Therefore, the cover member 51 can better suppress the amount of additive released from the second treatment liquid J during the replacement process. In the replacement process, the cover member 51 can better suppress the additive from being released from the second treatment liquid J. In the replacement process, the additive is not easily released from the second treatment liquid J into the upper space M. On the other hand, during the processing step, the cover member 51 is arranged at the second position. Therefore, the cover member 51 does not hinder the supply of the chemical solution and the rinse liquid G to the substrate W during the processing process. That is, in the processing step, the chemical solution and the rinse liquid G can be supplied to the substrate W favorably.

The first position is above the substrate W. The second position is the position above the first position. Therefore, the cover member 51 can easily move between the first position and the second position.

In the removal process, the cover member 51 is disposed near the upper surface Wt of the substrate W. In the removal process, the cover member 51 covers the upper surface Wt of the substrate W. Therefore, during the removal process, the cover member 51 also suppresses the amount of additive released from the second processing liquid J on the substrate W. During the removal process, the cover member 51 can also better inhibit the additive from being released from the second treatment liquid J on the substrate W. During the removal process, the additive will not be excessively released from the second treatment liquid J on the substrate W. Therefore, during the removal process, the concentration of the additive in the second treatment liquid J on the substrate W is also maintained within an appropriate range. Therefore, during the removal process, the additive can still effectively inhibit the dehydration reaction of the organic solvent on the substrate W. Throughout the replacement process and the removal process, the additives can better and continuously suppress the dehydration reaction of the organic solvent on the substrate W. In the removal process, the additives can still effectively inhibit the formation of water r in the second treatment liquid J. As a result, the substrate W can be better protected.

<8. 7th Embodiment> The seventh embodiment will be described with reference to the drawings. In addition, the same structures as those in the first to sixth embodiments are denoted by the same reference numerals, and detailed descriptions are omitted.

In the replacement process of the seventh embodiment, the substrate W is heated. In the removal process of the seventh embodiment, the substrate W is heated.

<8-1. Structure of the processing unit 11> FIG. 23 is a diagram showing the structure of the processing unit 11 according to the seventh embodiment. The processing unit 11 includes a heating unit 61 . The heating part 61 is provided inside the housing 31 (not shown). The heating unit 61 heats the substrate W held by the substrate holding unit 13 .

The heating unit 61 includes, for example, a first heating unit 62 and a second heating unit 63. The first heating unit 62 is disposed below the substrate W held by the substrate holding unit 13 . The first heating part 62 can be attached to the substrate holding part 13, for example. The second heating unit 63 is disposed above the substrate W held by the substrate holding unit 13 .

The first heating unit 62 includes, for example, a resistance heater. Resistive heaters may also be called electric heaters. Resistive heaters include, for example, electric wires. The first heating unit 62 includes, for example, a lamp heater. Lamp heaters can also be called light heaters. The lamp heater includes, for example, a light source that irradiates light. The first heating unit 62 supplies a high-temperature fluid to the lower surface Wb of the substrate W, for example. The high-temperature fluid has a temperature capable of heating the substrate W. The high-temperature fluid is, for example, a gas or a liquid.

The second heating unit 63 includes, for example, at least one of a resistance heater and a lamp heater.

The control unit 10 controls the heating unit 61, but illustration is omitted. The control unit 10 controls the first heating unit 62 and the second heating unit 63.

<8-2. Operation example of processing unit 11> FIG. 24 is a flowchart showing the steps of the substrate processing method according to the seventh embodiment. The substrate processing method of the seventh embodiment includes a first heating step (S2d) and a second heating step (step S3c). The first supply process (step S2a) and the first heating process (step S2d) are examples of the replacement process (step S2). The spin drying process (step S3a) and the second heating process (step S3c) are examples of the removal process (step S3).

The substrate processing method according to the seventh embodiment will be described in detail. After the rotation starting process, the chemical solution supply process, and the rinse liquid supply process, the first supply process and the first heating process are executed. In the first supply step, the second processing liquid J is supplied to the substrate W. In the first heating step, the substrate W is heated. Specifically, the heating unit 61 heats the substrate W. For example, at least one of the first heating part 62 and the second heating part 63 heats the substrate W.

Here, at least part of the period during which the first heating step is performed may overlap with at least part of the period during which the first supply step is performed. For example, the first supply step and the first heating step may be executed simultaneously. For example, the first heating process may be started after the first supply process is started and before the first supply process is ended.

Alternatively, the period during which the first heating process is performed does not need to overlap with the period during which the first supply process is performed. For example, the first heating step may be started after the first supply step is completed.

After the first supply process and the first heating process are completed, the spin drying process and the second heating process are executed. In the spin drying process, the second processing liquid J is removed from the substrate W. In the second heating step, the substrate W is heated. Specifically, the heating unit 61 heats the substrate W. For example, at least one of the first heating part 62 and the second heating part 63 heats the substrate W.

Here, at least part of the period during which the second heating process is performed may overlap with at least part of the period during which the spin drying process is performed. For example, the spin drying process and the second heating process may be performed simultaneously. For example, the second heating process may be started after the start of the spin drying process and before the end of the spin drying process.

Alternatively, the period during which the second heating process is performed does not need to overlap with the period during which the spin drying process is performed. For example, the second heating process may be started after the spin drying process is completed. For example, the spin drying process may be started after the second heating process is completed.

The first heating step and the second heating step may be continuous in time. That is, the substrate W can be continuously heated by the heating unit 61 from before the replacement process is completed to after the removal process is started.

After the spin drying process and the second heating process, the spin stopping process is performed.

<8-3. Effects of the seventh embodiment> The seventh embodiment also achieves the same effects as those of the first embodiment. Furthermore, according to the seventh embodiment, the following effects are achieved.

The replacement process includes a first heating process of heating the substrate. Therefore, in the replacement process, the second processing liquid J on the substrate W is heated. Therefore, in the replacement step, the rinse liquid G on the substrate W is smoothly replaced with the second processing liquid J. In other words, in the replacement process, the second processing liquid J efficiently removes the rinse liquid G on the substrate W from the substrate W.

The removal process includes a second heating process of heating the substrate. Therefore, in the removal process, the second processing liquid J on the substrate W is heated. Therefore, in the removal process, the second processing liquid J on the substrate W is efficiently removed. In other words, during the removal process, the substrate W is dried in a shorter time.

The second treatment liquid J contains an organic solvent. The higher the temperature of the organic solvent, the easier it is for the dehydration reaction of the organic solvent to occur. However, as mentioned above, the second treatment liquid J contains additives. Therefore, even when the substitution process includes the first heating process, the additive inhibits the dehydration reaction of the organic solvent. Even when the replacement process includes the first heating process, the additive can better suppress the generation of water r in the second treatment liquid J. On the contrary, when the replacement process includes the first heating process, the additive will play a significant role.

For the same reason, even when the removal process includes the second heating process, the dehydration reaction of the organic solvent will be inhibited by the additive. Even when the removal process includes the second heating process, the generation of water r in the second treatment liquid J is suppressed by the additive. On the contrary, when the removal process includes the second heating process, the additive will play a significant role.

The present invention is not limited to the embodiment, and can be implemented with changes as described below.

(1) In the first to seventh embodiments, the first treatment liquid is the rinse liquid G. But it is not limited to this. The first treatment liquid may include a treatment liquid other than the rinse liquid G. For example, the first treatment liquid may be a chemical liquid. For example, the replacement process may replace the chemical liquid on the substrate W with the second treatment liquid J.

(2) In the first, third to seventh embodiments, the second processing liquid J is generated in the tank 22 . But it is not limited to this. For example, the second processing liquid generating unit 21 may generate the second processing liquid J in the flow path connected to the supply part 15c.

For example, the second processing liquid generation unit 21 includes a joint member. The second processing liquid generating unit 21 generates the second processing liquid J in the joint member. Specifically, the joint member connects the supply parts 15c, 23a, and 23b. For example, the joint member is connected to the pipes 17c, 24a, and 24b. For example, the joint component contains a three-way joint. For example, the joint member may include a mixing valve. The supply part 23a supplies the additive to the joint member. The supply part 23b supplies the organic solvent to the joint member. Additives and organic solvents are mixed in the joint components. The additive and the organic solvent become the second treatment liquid J in the joint member. The second processing liquid J flows from the joint member to the supply part 15c.

(3) In the first to seventh embodiments, before the second processing liquid J is supplied to the substrate W, water can be removed from the second processing liquid J. Water may also be removed from the organic solvent before the organic solvent is supplied to the substrate W. Water can also be removed from the additive before it is supplied to the substrate W.

For example, the second processing liquid generation unit 21 may include an adsorption unit. The adsorption part is immersed in the 2nd processing liquid J in the tank 22, for example. The adsorption part adsorbs water contained in the second treatment liquid J. The water adsorbed by the adsorption part corresponds to the water removed from the second treatment liquid J. The adsorption part has, for example, a particle shape or a particle shape. The adsorption part is, for example, zeolite.

For example, at least one of the processing unit 11 and the second processing liquid generation unit 21 may be provided with a separation unit. The separation part is provided in at least one of the pipes 17c, 17d, 17e, 24a, and 24b, for example. For example, the separation unit on the pipe 17c separates water from the second treatment liquid J flowing through the pipe 17c. Thereby, the separation part on the pipe 17c removes water from the 2nd processing liquid J. For example, the separation parts on the pipes 17d and 24a respectively separate water from the additive flowing through the pipes 17d and 24a. Thereby, the separation parts on the pipes 17d and 24a remove water from the additive respectively. For example, the separation parts on the pipes 17e and 24b respectively separate water from the organic solvent flowing through the pipes 17e and 24b. Thereby, the separation parts on the pipes 17e and 24b remove water from the organic solvent respectively. The separation unit is, for example, a separation filter. The separation part is, for example, a zeolite membrane.

(4) In the first, third to seventh embodiments, the second treatment liquid J is generated in the second treatment liquid production unit 21 . But it is not limited to this. For example, the second processing liquid J may be produced in the supply part 15c.

For example, the second treatment liquid J may be generated in the nozzle 16c. Specifically, the nozzle 16c is connected to the supply parts 23a and 23b. For example, the nozzle 16c is connected to the pipes 24a and 24b. The supply part 23a supplies the additive to the nozzle 16c. The supply part 23b supplies the organic solvent to the nozzle 16c. The additives are mixed with the organic solvent in nozzle 16c. The additive and the organic solvent become the second treatment liquid J in the nozzle 16c. The second treatment liquid J is sprayed from the nozzle 16c.

(5) In the first to seventh embodiments, the processing unit 11 is provided with the nozzles 16a-16c. But it is not limited to this. For example, the processing unit 11 may be equipped with a common nozzle instead of the nozzles 16a-16c. The common nozzle is shared by the supply parts 15a, 15b, and 15c. Specifically, the common nozzle is connected to the pipes 17a, 17b, and 17c. When the valve 18a is opened, the common nozzle sprays the chemical liquid. Likewise, when the valve 18b is opened, the flushing liquid G is sprayed out from the common nozzle. When the valve 18c is opened, the common nozzle sprays the second treatment liquid J. Through this modified embodiment, the treatment process and the replacement process can also be performed better.

(6) In the seventh embodiment, one of the first heating step and the second heating step may be omitted.

(7) In the first to seventh embodiments, the processing unit 11 is classified into a single-chip type. But it is not limited to this. For example, the processing unit 11 may also be classified as a batch type. That is, the processing unit 11 can process a plurality of substrates W at one time. In the first to seventh embodiments, the substrate W is rotated during the processing step, the replacement step, and the removal step. But it is not limited to this. For example, in at least any one of the processing step, the replacement step, and the removal step, the substrate W does not need to rotate.

The structure of the processing unit 11 classified as a batch type is illustrated, but the illustration is omitted. The processing unit 11 includes a processing tank, a substrate holding unit, and a lifting and lowering drive unit. The supply parts 15a-15c are connected to the processing tank. The treatment tank stores the treatment liquid. The substrate holding unit holds a plurality of substrates W at a time. The substrate holding portion supports the substrate W in a substantially vertical posture. The elevation drive unit elevates and lowers the substrate holding unit relative to the processing tank. The substrate holding portion moves to the lower position and the upper position by the lifting and lowering driving portion. When the substrate holding part is in the lower position, the substrate W held by the substrate holding part is located inside the processing tank. When the substrate holding portion is in the lower position, the substrate W held by the substrate holding portion is stationary. When the substrate holding part is in the upper position, the substrate W held by the substrate holding part is located above the processing tank. When the substrate holding part is in the upper position, the substrate W held by the substrate holding part is stationary.

The treatment process includes, for example, a chemical solution supply process and a rinse liquid supply process.

In the chemical solution supply process, the supply part 15a supplies the chemical solution to the treatment tank. The treatment tank stores chemical liquid. The substrate holding portion is in the lower position. The substrate W held by the substrate holding portion is immersed in the chemical solution in the treatment tank. In this way, the chemical liquid is supplied to the substrate W.

In the flushing liquid supply process, the chemical liquid is discharged from the treatment tank. The supply part 15b supplies the rinse liquid G to the treatment tank. The processing tank stores the rinse liquid G. The substrate holding portion is in the lower position. The substrate W held by the substrate holding portion is immersed in the rinse liquid G in the processing tank. In this way, the rinse liquid G is supplied to the substrate W.

In the replacement process, the rinse liquid G is discharged from the treatment tank. The supply part 15c supplies the second processing liquid J to the processing tank. The treatment tank stores the second treatment liquid J. The substrate holding portion is in the lower position. The substrate W held by the substrate holding portion is immersed in the second processing liquid J in the processing tank. In this way, the rinse liquid G is replaced with the second treatment liquid J. The second processing liquid J is supplied to the substrate W.

In the removal process, the substrate holding part moves from the lower position to the upper position. The substrate W held by the substrate holding portion is lifted up from the second processing liquid J in the processing tank. Thereby, the second processing liquid J is removed from the substrate W.

In this way, in this modified embodiment, the treatment process, the replacement process, and the removal process can be well performed.

(8) In the first to seventh embodiments, the substrate W has the pattern P. But it is not limited to this. For example, the substrate W may not have the pattern P. For example, the pattern P may not be formed on the surface Ws of the substrate W. Even when the substrate W does not have the pattern P, the substrate processing method can process the substrate W while better protecting the substrate W. Therefore, even when the substrate W does not have the pattern P, the substrate processing method can appropriately process the substrate W.

(9) Regarding the first to seventh embodiments and each modified embodiment described in the above (1) to (8), each configuration can be further replaced with the configuration of other modified embodiments or combined with them, etc. to suitably proceed. change.

For example, the second supply process (step S2b) of the second and third embodiments can be applied to the fourth to seventh embodiments. Specifically, the substrate processing methods of the fourth to seventh embodiments may include a second supply step.

For example, the third supply step (step S2c) of the third embodiment can be applied to the first, second, fourth to seventh embodiments. Specifically, the substrate processing methods of the first, second, fourth to seventh embodiments may include a third supply step.

For example, the first heating step (step S2d) of the seventh embodiment can be applied to the first to sixth embodiments. Specifically, the substrate processing methods of the first to sixth embodiments may include a first heating step.

For example, the additional supply process (step S3b) of the third embodiment can be applied to the first, second, fourth to seventh embodiments. Specifically, the substrate processing methods of the first, second, fourth to seventh embodiments may include an additional supply step.

For example, the second heating step (step S3c) of the seventh embodiment can be applied to the first to sixth embodiments. Specifically, the substrate processing methods of the first to sixth embodiments may include a second heating step.

For example, the housing 31 of the fourth and fifth embodiments can be applied to the first to third, sixth and seventh embodiments. Specifically, the processing unit 11 of the first to third, sixth, and seventh embodiments may include the housing 31 of the fourth and fifth embodiments.

For example, the inner container 41 of the fifth embodiment can be applied to the first to fourth, sixth, and seventh embodiments. Specifically, the processing unit 11 of the first to fourth, sixth, and seventh embodiments may include the inner container 41 of the fifth embodiment.

For example, the cover member 51 of the sixth embodiment can be applied to the first to fifth and seventh embodiments. Specifically, the processing unit 11 of the first to fifth and seventh embodiments may include the cover member 51 of the sixth embodiment.

For example, the heating unit 61 of the seventh embodiment can be applied to the first to sixth embodiments. For example, the processing unit 11 of the first to sixth embodiments may include the heating unit 61 of the seventh embodiment. For example, the processing unit 11 of the first to sixth embodiments may include the first heating unit 62 of the seventh embodiment. For example, the processing unit 11 of the first to sixth embodiments may include the second heating unit 63 of the seventh embodiment.

1:Substrate processing device 3: Transmission Department 4: Vehicle mounting part 5:Transportation mechanism 5a:Hand 5b:Hand drive part 7: Processing blocks 8:Transportation space 9:Transportation mechanism 9a:Hand 9b:Hand drive part 10:Control Department 11: Processing unit 13:Substrate holding part 14: Rotary drive part 15a: Supply department (medical solution supply department) 15b: Supply part (rinsing liquid supply part) 15c: Supply part (second processing liquid supply part) 15d: Supply Department (Additive Supply Department) 15e: Supply Department (Organic Solvent Supply Department) 16a: Nozzle (liquid nozzle) 16b: Nozzle (rinsing fluid nozzle) 16c: Nozzle (second treatment liquid nozzle) 16d: Nozzle (additive nozzle) 16e: Nozzle (organic solvent nozzle) 17a:Piping 17b:Piping 17c:Piping 17d:Piping 17e:Piping 18a: valve 18b: valve 18c: valve 18d: valve 18e: valve 19a: Liquid medicine supply source 19b: Flushing fluid supply source 21: Second treatment liquid generation unit 22:Slot 23a: Supply Department 23b: Supply Department 24a:Piping 24b:Piping 25a: valve 25b: valve 29a: Additive supply source 29b: Organic solvent supply source 31: Shell (processing container) 31a: Space (processing space) 31b:Substrate transfer port 32:Baffle 33:Sealing components 41: Internal container (processing container) 41a: Space (processing space) 42: 1st component 43: 2nd component 44:Sealing components 45: Internal container moving mechanism 47a:Nozzle moving mechanism 47b: Nozzle moving mechanism 51:Cover member 52: Cover member moving mechanism 61:Heating part 62: 1st heating section 63: 2nd heating section A: concave part B:Rotation axis C:Vehicle G: Rinse liquid (first treatment liquid) J: 2nd treatment liquid K: replacement fluid M: Upper space P:Pattern q: proton r:water S1: Processing process S1a: Chemical solution supply process (processing process) S1b: Rinse liquid supply process (processing process) S2: Replacement process S2a: 1st supply process (replacement process) S2b: Second supply process (replacement process) S2c: 3rd supply process (replacement process) S2d: 1st heating process (replacement process) S3: Removal process S3a: Spin drying process (removal process) S3b: Additional supply process (removal process) S3c: 2nd heating process (removal process) S11: Rotation start process S12: Rotation stop process S21: Sealed process S22: Opening process S23: Sealed process S24: Open process S25: Interruption process S26: Interruption release process W: substrate W1: convex part Wb: lower surface Ws: Surface of substrate Wt: upper surface

FIG. 1 is a flow chart showing the basic steps of the substrate processing method. FIG. 2 is a diagram schematically showing a substrate in a processing step. FIG. 3 is a diagram schematically showing the substrate in the replacement process. FIG. 4 is a diagram schematically showing the substrate in the removal process. FIG. 5 is a diagram schematically showing the substrate in the removal process. FIG. 6 is a diagram schematically showing the substrate in the replacement process of the comparative example. FIG. 7 is a diagram schematically showing the substrate in the removal process of the comparative example. FIG. 8 is a diagram schematically showing the substrate in the removal process of the comparative example. FIG. 9 is a top view showing the inside of the substrate processing apparatus. Figure 10 is a control block diagram of the substrate processing device. FIG. 11 is a diagram showing the structure of the processing unit and the second processing liquid generating unit of the first embodiment. FIG. 12 is a flowchart showing the steps of the substrate processing method according to the first embodiment. FIG. 13 is a diagram showing the structure of the processing unit of the second embodiment. FIG. 14 is a flowchart showing the steps of the substrate processing method according to the second embodiment. FIG. 15 is a diagram showing the structure of the processing unit and the second processing liquid generating unit according to the third embodiment. FIG. 16 is a flowchart showing the steps of the substrate processing method according to the third embodiment. FIG. 17 is a diagram showing the structure of the processing unit and the second processing liquid generating unit according to the fourth embodiment. FIG. 18 is a flowchart showing the steps of the substrate processing method according to the fourth embodiment. FIG. 19 is a diagram showing the structure of the processing unit and the second processing liquid generating unit according to the fifth embodiment. FIG. 20 is a flowchart showing the steps of the substrate processing method according to the fifth embodiment. FIG. 21 is a diagram showing the structure of the processing unit and the second processing liquid generating unit according to the sixth embodiment. FIG. 22 is a flowchart showing the steps of the substrate processing method according to the sixth embodiment. FIG. 23 is a diagram showing the structure of the processing unit and the second processing liquid generating unit according to the seventh embodiment. FIG. 24 is a flowchart showing the steps of the substrate processing method according to the seventh embodiment.

A: concave part

J: 2nd treatment liquid

P:Pattern

q: proton

W: substrate

W1: convex part

Ws: Surface of substrate

Claims (17)

A substrate processing method, which includes: a processing step of supplying a first processing liquid to a substrate; a replacement step of replacing the first processing liquid on the substrate with a second processing liquid containing an organic solvent and an additive; and removing A step of removing the second treatment liquid from the substrate; and the additive inhibits the dehydration reaction of the organic solvent; and the removal step includes an additional supply step of supplying the additive to the substrate. A substrate processing method, which includes: a processing step of supplying a first processing liquid to a substrate; a replacement step of replacing the first processing liquid on the substrate with a second processing liquid containing an organic solvent and an additive; and removing The step is to remove the second treatment liquid from the substrate; and the additive inhibits the dehydration reaction of the organic solvent, and the removal step includes a second heating step of heating the substrate. A substrate processing method, which includes: a processing step of supplying a first processing liquid to a substrate; a replacement step of replacing the first processing liquid on the substrate with a second processing liquid containing an organic solvent and an additive; and removing A process of removing the above-mentioned second processing liquid from the substrate; and The additive inhibits the dehydration reaction of the organic solvent. The substrate has a surface, and the surface includes at least one of a polycrystalline silicon film, a silicon oxide film, and a silicon nitride film. A substrate processing method, which includes: a processing step of supplying a first processing liquid to a substrate; a replacement step of replacing the first processing liquid on the substrate with a second processing liquid containing an organic solvent and an additive; and removing The process includes removing the second treatment liquid from a substrate, and the additive inhibits the dehydration reaction of the organic solvent. The substrate has a surface and a pattern formed on at least a part of the surface. The substrate processing method according to any one of claims 1 to 4, wherein the additive reduces protons in the second treatment liquid. The substrate processing method according to any one of claims 1 to 4, wherein the additive includes a proton-accepting base. The substrate processing method according to any one of claims 1 to 4, wherein the additive contains at least one of bicarbonate ions and carbonate ions. The substrate processing method according to any one of claims 1 to 4, wherein the additive includes a buffer that moderates changes in the hydrogen ion concentration in the second processing liquid. The substrate treatment method according to any one of claims 1 to 4, wherein the additive includes at least any one of the following compounds: carbon dioxide, 4-toluenesulfonic acid, sodium methoxide, sodium trifluoroacetate, oxalic acid, lithium methoxide , tribenzylamine, sodium hydrogen phthalate, salicylic acid, phenylacetic acid, lithium hydrogen succinate, and trimaleate. The substrate processing method according to any one of claims 1 to 4, wherein the organic solvent includes alcohol. The substrate processing method as claimed in any one of items 1 to 4, wherein The above-mentioned organic solvent includes isopropyl alcohol. The substrate processing method according to any one of claims 1 to 4, wherein the replacement step includes a first supply step of supplying the second processing liquid to the substrate. The substrate processing method of claim 12, wherein the replacement step includes a second supply step of supplying the additive to the substrate. The substrate processing method according to any one of claims 1 to 4, wherein the replacement step includes: a second supply step of supplying the additive to the substrate, and a third supply step of supplying the organic solvent to the substrate. The substrate processing method according to any one of claims 1 to 4, wherein in the replacement process, the substrate is located inside the processing container, and the processing container is sealed. The substrate processing method according to any one of claims 1 to 4, wherein in the above replacement process, the cover member is arranged near the upper surface of the substrate and covers the upper surface of the substrate. The substrate processing method according to any one of claims 1 to 4, wherein the replacement step includes a first heating step of heating the substrate.