TW201913792A - Substrate processing apparatus and substrate processing method - Google Patents

Abstract

A stripping liquid supply part 6 of a substrate processing apparatus 1 supplies the stripping liquid to a peripheral area 93 of an upper surface 91 of a rotating substrate 9 so as to remove the portion of the coating film on the substrate 9 on the peripheral area 93 from the substrate 9. A cup part 4 is disposed around a substrate holding part 31 and receives the stripping liquid scattering from the rotating substrate 9 to the surroundings. The stripping liquid supply part 6 includes a mixing part 61 and a fourth nozzle 64 which is a stripping liquid ejecting part. The mixing part 61 mixes the water-soluble organic solvent and the aqueous solvent to produce the stripping liquid. The fourth nozzle 64 ejects the stripping liquid delivered from the mixing section 61 toward the substrate 9. As a result, the peripheral edge portion of the coating film formed on the substrate 9 can be suitably removed, and the rebounding of the stripping liquid from the cup portion 4 can be suppressed.

Description

   Substrate processing device and substrate processing method   

The present invention relates to a technology for processing substrates.

Conventionally, various processes have been applied to substrates in the manufacturing process of semiconductor substrates (hereinafter, simply referred to as "substrates"). For example, a chemical liquid is sprayed from a nozzle onto a substrate on which a resist pattern (that is, a structure belonging to a collection of a plurality of fine structure elements) is formed on the substrate The surface is subjected to chemical treatment such as etching.

In addition, after the treatment of the chemical liquid on the substrate, a rinse process of supplying pure water to the substrate to remove the chemical liquid and a drying process of rotating the substrate at high speed to remove the liquid on the substrate are further performed. When a plurality of fine pattern elements are formed on the substrate, when rinsing and drying are sequentially performed, a liquid surface of pure water is formed between two adjacent pattern elements during drying. In this case, the surface tension of the pure water acting on the pattern element may cause the pattern element to collapse.

Therefore, Japanese Patent Laid-Open No. 2016-219471 (Document 1) has proposed a technique in which a filling material solution is filled between pattern elements, and after curing of a filling material such as a polymer (polymer) The drying process is performed to prevent the collapse of the pattern elements during the drying process. The filler material cured on the substrate can be gasified and removed by dry etching or the like in another device after drying treatment, for example.

In addition, in Japanese Patent Laid-Open No. 2008-10638 (Document 2), the substrate after etching is immersed in pure water stored in a storage tank for rinsing, and the pure water in the storage tank is replaced with IPA ( After isopropyl alcohol (isopropyl alcohol), a filler material such as naphthalene is dissolved in the IPA. Then, by evaporating IPA, a film of the filler is formed on the surface of the substrate, and after drying treatment, the naphthalene film is sublimated in the atmosphere.

However, in the device shown in Document 1, the unnecessary filler that has adhered to the peripheral area of the substrate when the filler solution is applied may fear the contamination of the transport mechanism when the substrate is transported. Therefore, it is preferable to supply the stripping liquid only to the peripheral region of the substrate, thereby stripping unnecessary filler material and removing it from the substrate.

For example, in the case where the filling material is a water-soluble polymer, pure water that is also used in other treatments in the device can be used as the stripping liquid. In this case, since the surface tension of pure water is large, the pure water scattered radially outward from the rotating substrate will bounce back in the cup-shaped liquid receiving portion arranged around the substrate. There is a possibility that the coating film of the filler material applied on the substrate may be melted. Furthermore, in the case of using IPA, which is also used in other processes, as the stripping liquid in this device, the solubility of the filler material is low, so there is a possibility that the filler material will melt on the peripheral area of the substrate. Or, there may be a possibility that the filling material remaining in the melt gathers near the inner periphery of the peripheral area and bulges into a bank shape.

In addition, as shown in Document 2, when a filler is to be dissolved in IPA impregnated with a substrate to form a film of the filler, a large amount of filler is required. On the other hand, in the single-piece substrate processing apparatus shown in Document 1, when the surface of the substrate becomes a hydrophobic surface by chemical treatment or the like, there is a possibility of The surface of the substrate is partially exposed, and the pattern elements collapse. Therefore, although it is also possible to cover the substrate surface with IPA, which is commonly used in substrate processing apparatuses, in this case, when a filler material such as a water-soluble polymer is dropped onto the liquid film of the IPA, the filler material may Cohesion makes it difficult to form the coating film of the filler on the substrate.

The present invention provides a substrate processing apparatus for processing substrates, the purpose of which is to preferably remove the peripheral portion of the coating film and suppress the rebound of the peeling liquid from the liquid receiving portion. Another object of the present invention is to prevent the upper surface of the substrate from being exposed before forming the coating film, and preferably form the coating film on the substrate.

A preferred embodiment of the substrate processing apparatus of the present invention includes: a substrate holding portion that holds the substrate in a horizontal state; and a substrate rotation mechanism that centers the substrate and the substrate holding portion with the central axis oriented in the vertical direction as a center Rotation; the coating liquid supply part is to supply the coating liquid belonging to the water-soluble polymer solution to the upper surface of the substrate and form a coating film on the upper surface to belong to the coating liquid film; the peeling liquid supply part is to rotate The peripheral area of the upper surface of the substrate is supplied with a stripping liquid, thereby peeling the portion of the coating film on the peripheral area from the substrate; and the liquid receiving portion is disposed around the substrate holding portion and receives The peeling liquid scattered around from the rotating substrate. The peeling liquid supply unit includes: a mixing unit that mixes a water-soluble organic solvent and an aqueous solvent to generate the peeling liquid; and a peeling liquid ejection unit that ejects the peeling liquid sent from the mixing unit toward the substrate. According to this substrate processing apparatus, it is possible to preferably remove the peripheral portion of the coating film, and it is possible to suppress the peeling liquid from rebounding from the liquid receiving portion.

It is preferable that the peeling liquid ejection portion ejects the peeling liquid toward the outer edge portion of the lower surface of the substrate.

It is preferable that the peeling liquid supply unit further includes a mixing ratio adjustment unit that adjusts the ratio of the water-soluble organic solvent mixed with the aqueous solvent in the mixing unit.

More preferably, the peeling liquid supply unit further includes a concentration control unit that controls the mixing ratio adjusting unit based on input information related to the peeling process of the coating film.

It is preferable that the volume concentration of the water-soluble organic solvent in the peeling liquid is 20% or more and 40% or less.

Preferably, the water-soluble organic solvent is isopropyl alcohol.

It is preferable that the substrate processing apparatus further includes a rinse liquid supply unit that supplies the rinse liquid to the upper surface of the substrate. The rinse liquid is the same kind of liquid as the aqueous solvent of the peeling liquid.

It is preferable that a structure is formed on the upper surface of the substrate in advance.

The gap in the structure is filled with the coating liquid by forming the coating film on the upper surface of the substrate.

The present invention is a substrate processing method for processing substrates. A preferred embodiment of the substrate processing method of the present invention includes: a) a step of maintaining the substrate in a horizontal state; b) a step of supplying a coating solution belonging to a water-soluble polymer solution to the upper surface of the substrate and applying it to the upper surface Forming a coating film that belongs to the film of the aforementioned coating liquid; step c), mixing a water-soluble organic solvent and an aqueous solvent to produce a peeling liquid; and step d), which is later than the steps b) and c), and The central axis of the direction is used as the center to rotate the substrate, and the peeling liquid is supplied to the peripheral region of the upper surface of the substrate, thereby peeling the portion of the coating film on the peripheral region from the substrate The peeling liquid scattered around the rotating substrate is received. According to this substrate processing method, the peripheral portion of the coating film can be preferably removed, and the spring back of the peeling liquid from the liquid receiving portion can be suppressed.

Another preferred embodiment of the substrate processing method of the present invention includes: a) a step of maintaining the substrate in a horizontal state; b) a step of supplying a rinse solution to the upper surface of the substrate; c) a step of mixing a water-soluble organic solvent and An aqueous solvent to generate a replacement liquid having a surface tension lower than that of the rinse liquid; step d), which is later than the steps b) and c), supplying the replacement liquid to the upper surface of the substrate, thereby removing the substrate The rinsing liquid on the upper surface is replaced with the replacement liquid and a replacement liquid film forming a liquid film belonging to the replacement liquid is formed on the upper surface; and the step e) is later than the step d) and will be water-soluble The coating liquid of the polymer solution is supplied onto the replacement liquid film, and a coating film belonging to the film of the coating liquid is formed on the upper surface of the substrate. According to this substrate processing method, the upper surface of the substrate can be prevented from being exposed before the coating film is formed, and the coating film can be preferably formed on the substrate.

Preferably, in the step d), the substrate is rotated about the central axis oriented in the up-down direction.

Preferably, in the step c), the ratio of the water-soluble organic solvent mixed with the water-based solvent can be adjusted.

More preferably, in the step c), the ratio of the water-soluble organic solvent mixed with the water-based solvent can be adjusted based on input information related to the formation process of the coating film.

It is preferable that the volume concentration of the water-soluble organic solvent in the replacement liquid is 15% or more and 30% or less.

Preferably, the water-soluble organic solvent is isopropyl alcohol.

Preferably, the flushing liquid is the same kind of liquid as the aqueous solvent of the replacement liquid.

It is preferable that a structure is formed on the upper surface of the substrate in advance. In the step e), the gap in the structure is filled with the coating liquid.

Preferably, in the step d), the upper surface of the substrate immediately before the supply of the replacement liquid is a hydrophobic surface.

Another preferred form of the substrate processing apparatus of the present invention includes: a substrate holding portion that holds the substrate in a horizontal state; a rinse liquid supply portion that supplies the rinse liquid to the upper surface of the substrate; a replacement liquid supply portion that pairs The replacement liquid is supplied to the upper surface of the substrate, thereby replacing the rinsing liquid on the upper surface of the substrate with the replacement liquid and forming a replacement liquid film on the upper surface belonging to the liquid film of the replacement liquid; and coating The liquid supply unit supplies a coating liquid belonging to a water-soluble polymer solution to the replacement liquid film, and forms a coating film belonging to the coating liquid film on the upper surface of the substrate. The replacement liquid supply unit includes: a mixing unit that mixes a water-soluble organic solvent and an aqueous solvent to generate the replacement liquid having a surface tension smaller than the rinse liquid; and a replacement liquid ejection unit that sends out the mixing unit The replacement liquid is ejected toward the substrate. According to this substrate processing apparatus, it is possible to prevent the upper surface of the substrate from being exposed before forming the coating film, and it is possible to form the coating film on the substrate preferably.

The above-mentioned object and other objects, features, aspects, and advantages can be understood by referring to the attached drawings and the following detailed description of the present invention.

1‧‧‧Substrate processing device

4‧‧‧Body

5‧‧‧Process Liquid Supply Department

6‧‧‧ Stripping liquid supply unit

7‧‧‧Replacement fluid supply unit

9‧‧‧ substrate (semiconductor substrate)

31‧‧‧Substrate holding section

33‧‧‧ substrate rotation mechanism

35‧‧‧cover

51‧‧‧First nozzle

52‧‧‧Second nozzle

53‧‧‧The third nozzle

54‧‧‧medical solution supply source

55‧‧‧Filling fluid supply source

56‧‧‧Solvent supply source

57‧‧‧Supply source of filling material solution

61, 71‧‧‧ Mixed Department

62, 72‧‧‧ mixing ratio adjustment department

63, 73‧‧‧ Concentration Control Department

64‧‧‧Nozzle

91‧‧‧ (substrate) upper surface

92‧‧‧ (substrate) lower surface

93‧‧‧ Peripheral area

94‧‧‧Inner area

351‧‧‧ opening

621, 622, 721, 722

641‧‧‧ Nozzle moving mechanism

J1‧‧‧Central axis

S11 to S19, S21 to S29 ‧‧‧ steps

FIG. 1 is a side view of the substrate processing apparatus of the first embodiment.

2 is a side view of the substrate processing apparatus.

Fig. 3 is a block diagram showing a processing liquid supply unit.

Fig. 4 is a plan view of the substrate.

5 is a schematic diagram showing the processing flow of the substrate.

6 is a block diagram showing a processing liquid supply portion of the substrate processing apparatus of the second embodiment.

7 is a plan view of the substrate.

8 is a schematic diagram showing the processing flow of the substrate.

9 is a schematic diagram showing the rotation speed during the processing of the substrate.

FIG. 1 is a side view showing the structure of a substrate processing apparatus 1 according to the first embodiment of the present invention. The substrate processing apparatus 1 refers to a monolithic apparatus that processes a semiconductor substrate 9 (hereinafter, simply referred to as "substrate 9") piece by piece. The substrate processing apparatus 1 supplies and processes a substrate 9 with a processing liquid. In FIG. 1, a part of the configuration of the substrate processing apparatus 1 is shown in cross section.

The substrate processing apparatus 1 includes a substrate holding portion 31, a substrate rotating mechanism 33, a cover plate 35, a cup portion 4, and a processing liquid supply portion 5. The substrate holding portion 31 refers to a so-called vacuum chuck that holds the central portion of the lower main surface (hereinafter referred to as "lower surface 92") of the substrate 9 by vacuum suction. The substrate holding portion 31 is rotatably provided with the central axis J1 oriented in the vertical direction as a center. The substrate 9 is arranged above the substrate holding portion 31. The substrate 9 is sucked and held by the substrate holding portion 31 in a horizontal state. The substrate rotating mechanism 33 is arranged below the substrate holding portion 31. The substrate rotation mechanism 33 rotates the substrate 9 together with the substrate holding portion 31 with the central axis J1 as the center.

The cover plate 35 refers to a substantially circular plate-shaped member centered on the central axis J1. The cover plate 35 is located below the substrate 9 held by the substrate holding portion 31 and faces the lower surface 92 of the substrate 9 in the up-down direction. In the example shown in FIG. 1, the outer diameter of the cover plate 35 is substantially the same as the diameter of the substrate 9. The cover plate 35 is moved in the vertical direction between the first position shown in FIG. 1 and the second position shown in FIG. 2 by a lifting mechanism not shown. The second position is located below the first position. As shown in FIG. 2, in a state where the cover plate 35 is located at the second position, the cover plate 35 is engaged with the substrate rotation mechanism 33 and rotates together with the substrate 9 and the substrate holding portion 31. On the other hand, as shown in FIG. 1, in a state where the cover plate 35 is located at the first position, the cover plate 35 is separated from the substrate rotating mechanism 33 and does not rotate.

The processing liquid supply unit 5 supplies a plurality of types of processing liquid to the substrate 9 individually. The plural kinds of treatment liquids include, for example, the chemical liquid, the rinse liquid, the solvent, the filler solution, and the stripping liquid described later. The processing liquid supply unit 5 includes a first nozzle 51, a second nozzle 52, a third nozzle 53, and a fourth nozzle 64. In addition, as shown in FIG. 3 described later, the processing liquid supply unit 5 further includes a mixing unit 61, a mixing ratio adjustment unit 62, and a concentration control unit 63.

The first nozzle 51, the second nozzle 52, and the third nozzle 53 supply the processing liquid from above the substrate 9 toward the main surface (hereinafter, referred to as "upper surface 91") of the substrate 9 above. In the state shown in FIG. 1, the first nozzle 51 is located above the substrate, and the processing liquid is supplied from the first nozzle 51 toward the substrate 9. At this time, the second nozzle 52 and the third nozzle 53 are retracted radially outward from the outer edge of the substrate 9. When supplying the processing liquid from the second nozzle 52 toward the substrate 9, the first nozzle 51 and the third nozzle 53 are retracted radially outward from the outer edge of the substrate 9, and the second nozzle 52 is located on the substrate 9 Above. When supplying the processing liquid from the third nozzle 53 toward the substrate 9, the first nozzle 51 and the second nozzle 52 are retracted radially outward from the outer edge of the substrate 9, and the third nozzle 53 is located on the substrate 9 Above.

The fourth nozzle 64 is arranged below the substrate 9. The fourth nozzle 64 supplies the processing liquid from below the substrate 9 toward the outer edge of the lower surface 92 of the substrate 9. As shown in FIG. 1, the fourth nozzle 64 is inserted into the opening 351 provided in the outer peripheral portion of the cover plate 35 in the state where the cover plate 35 is located at the first position, and discharges the processing liquid. On the other hand, as shown in FIG. 2, in the state where the cover plate 35 is located at the second position, the fourth nozzle 64 is moved downward by the nozzle moving mechanism 641 and retracted toward the lower side than the cover plate 35. In a state where the fourth nozzle 64 is retracted toward the lower side than the cover plate 35, the supply of the processing liquid from the fourth nozzle 64 to the substrate 9 is not performed.

The cup portion 4 shown in FIGS. 1 and 2 refers to an annular member centered on the central axis J1. The cup body portion 4 is arranged around the substrate 9, the substrate holding portion 31 and the cover plate 35 and covers the sides and below of the substrate 9, the substrate holding portion 31 and the cover plate 35. The cup portion 4 refers to a liquid receiving portion that receives a processing liquid or the like scattered from the rotating substrate 9 toward the surroundings. The inner side surface of the cup body portion 4 is formed by a water-repellent material, for example. The cup body portion 4 is in a state of being stationary in the circumferential direction regardless of the rotation and stationary of the substrate 9. A drain port (not shown) is provided at the bottom of the cup portion 4 to discharge the processing liquid received by the cup portion 4 to the outside of the substrate processing apparatus 1. The cup body portion 4 is moved up and down between the processing position and the retreat position by a lifting mechanism not shown in the figure. As shown in FIG. 1, the processing position is a position around the substrate 9, and the retreat position is lower than the processing position side.

FIG. 3 is a block diagram showing the processing liquid supply part 5 of the substrate processing apparatus 1. The configuration other than the processing liquid supply unit 5 is also shown in FIG. 3. The first nozzle 51 is connected to the chemical solution supply source 54 and the rinse solution supply source 55. The second nozzle 52 is connected to the solvent supply source 56. The third nozzle 53 is connected to the filling material solution supply source 57. The fourth nozzle 64 is connected to the rinse liquid supply source 55 and the solvent supply source 56 through the mixing section 61.

The first nozzle 51 supplies the chemical solution sent from the chemical solution supply source 54 to the central portion of the upper surface 91 of the substrate 9. As the chemical solution, for example, a cleaning solution containing diluted hydrofluoric acid (DHF) or ammonia water can be used. In addition, other types of cleaning liquid or chemical liquid other than the cleaning liquid may be sent from the chemical liquid supply source 54 to the first nozzle. In addition, the first nozzle 51 is configured to supply the rinsing liquid sent from the rinsing liquid supply source 55 to the central portion of the upper surface 91 of the substrate 9 in a state where the sending of the chemical liquid from the chemical liquid supply source 54 is stopped. As the rinsing liquid, for example, an aqueous processing liquid such as DIW (De-ionized Water; deionized water), carbonated water, ozone water, or hydroxide water can be used. In this embodiment, DIW is used as the rinse liquid.

The first nozzle 51 is included in the chemical solution supply portion that supplies the chemical solution to the upper surface 91 of the substrate 9. The chemical solution supply source 54 may be included in the chemical solution supply unit. In addition, the first nozzle 51 is also included in the rinse liquid supply portion that supplies the rinse liquid to the upper surface 91 of the substrate 9. The rinse liquid supply source 55 described above may be included in the rinse liquid supply unit. The lower end of the first nozzle 51 is provided with, for example, a discharge port for a chemical liquid and a discharge port for a rinse liquid, and different types of processing liquid are supplied to the upper surface 91 of the substrate 9 through different pipes and discharge ports. In addition, the first nozzle 51 may also include a processing liquid nozzle for chemical liquid and a processing liquid nozzle for rinse liquid.

The second nozzle 52 supplies the solvent sent from the solvent supply source 56 to the central portion of the upper surface 91 of the substrate 9. As the solvent, for example, a water-soluble organic solvent such as IPA (isopropyl alcohol), methanol, ethanol, acetone, or the like can be used. The surface tension of the solvent is smaller than the above-mentioned rinse liquid. In this embodiment, IPA is used as a solvent. The second nozzle 52 is included in the solvent supply portion that supplies the solvent to the upper surface 91 of the substrate 9. The above-mentioned solvent supply source 56 may be included in this solvent supply unit.

The third nozzle 53 supplies the filling material solution sent from the filling material solution supply source 57 to the central portion of the upper surface 91 of the substrate 9. Filling material solution refers to a solution in which a solid solute is dissolved in a solvent. As the solute system, a water-soluble polymer (hereinafter, simply referred to as "polymer") can be used. That is, the filling material solution refers to a water-soluble polymer solution. The polymer is, for example, a water-soluble polymer resin such as acrylic resin. The solvent of the filling material solution is aqueous, for example, DIW, PGEE (Propylene Glycol Ethyl Ether; propylene glycol ether), PGME (Propylene Glycol Methyl Ether; propylene glycol methyl ether) or EL (Ethyl Lactate; ethyl lactate) can be used. The specific gravity of the filling material solution is greater than the above-mentioned solvents.

The filler solution refers to a coating liquid applied to the upper surface 91 of the substrate 9. The above-mentioned polymer in the film of the filling material solution (that is, the coating film) applied to the upper surface 91 of the substrate 9 is solidified by vaporization of the solvent. In addition, the residual solvent component in the polymer may be removed by heating the substrate 9. The third nozzle 53 is included in the coating liquid supply portion that supplies the coating liquid to the upper surface 91 of the substrate 9 and forms a coating film on the upper surface 91 that belongs to the coating liquid film. The above-mentioned filling material solution supply source 57 may be included in the coating liquid supply part.

The mixing unit 61 mixes the rinse liquid (that is, the aqueous solvent) sent from the rinse liquid supply source 55 and the solvent (that is, the water-soluble organic solvent) sent from the solvent supply source 56 to thereby generate The peeling liquid of the processing liquid used in the peeling process mentioned above. The peeling liquid refers to the diluted solvent after the solvent is diluted by the rinse liquid. In this embodiment, the peeling liquid generated in the mixing unit 61 refers to the diluted IPA after diluting the IPA with DIW. The mixing unit 61 may be, for example, a static mixer (that is, a static mixer) without a driving unit, or may be dynamic mixing in which the washing liquid and the solvent are stirred and mixed by rotating a stirring blade or the like器 (dynamic mixer). In addition, the mixing unit 61 may temporarily store one of the processing liquid of the rinsing liquid and the solvent in the storage tank, and supply the other processing liquid to the one processing liquid in the storage tank to thereby mix the rinsing liquid And solvent.

The fourth nozzle 64 ejects the peeling liquid sent from the mixing section 61 toward the outer edge of the lower surface 92 of the substrate 9. The peeling liquid supplied from the fourth nozzle 64 to the lower surface 92 of the substrate 9 is wound into the upper surface 91 via the side surface (that is, the outer edge) of the substrate 9 and supplied to the peripheral region 93 (that is, the edge portion) of the upper surface 91. The fourth nozzle 64 and the mixing portion 61 are included in the peeling liquid supply portion 6 that supplies the peeling liquid to the peripheral area 93 of the upper surface 91 of the substrate 9. The peeling liquid supply unit 6 may include a rinse liquid supply source 55 and a solvent supply source 56.

FIG. 4 is a plan view showing the substrate 9. In FIG. 4, for easy understanding of the drawing, parallel oblique lines are marked on the inner region 94 of the upper surface 91 of the substrate 9 as the radially inner region of the peripheral region 93, and the peripheral region 93 is displayed with a two-dot chain line Boundary with inner region 94. On the upper surface 91 of the substrate 9, a structure (for example, a circuit pattern used in a product) belonging to a collection of a plurality of fine structure elements is formed in the inner region 94 in advance. This structure is not formed in the peripheral region 93.

The mixing ratio adjusting section 62 adjusts the ratio of the solvent in the mixing section 61 mixed with the rinse liquid. In the example shown in FIG. 3, the mixing ratio adjustment unit 62 includes valves 621 and 622. The valve 621 is arranged between the rinse liquid supply source 55 and the mixing unit 61 and changes the flow rate of the rinse liquid supplied from the rinse liquid supply source 55 to the mixing unit 61. The valve 622 is arranged between the solvent supply source 56 and the mixing section 61 and changes the flow rate of the solvent supplied from the solvent supply source 56 to the mixing section 61.

The concentration control unit 63 controls the mixing ratio adjustment unit 62, thereby setting the ratio of the solvent in the mixing unit 61 to the rinse liquid to a desired ratio. In other words, the concentration control unit 63 adjusts the components of the peeling liquid generated in the mixing unit 61 to the desired components. In the substrate processing apparatus 1, the flow rate of the rinse liquid and the solvent is adjusted by the mixing ratio adjustment section 62, whereby the peeling liquid sent from the mixing section 61 can also be changed while maintaining the ratio of the solvent mixed in the rinse liquid Of traffic. The concentration control unit 63 and the mixing ratio adjustment unit 62 are included in the above-mentioned peeling liquid supply unit 6.

The substrate 9 in the substrate processing apparatus 1 is provided in the order of chemical treatment, rinse treatment, solvent replacement treatment, filling material filling treatment, peeling treatment (that is, edge rinse treatment) and drying treatment, for example. get on. FIG. 5 is a schematic diagram showing an example of the processing flow of the substrate 9 in the device 1 at the substrate.

First, the substrate 9 on which the structure described above is formed on the upper surface 91 is held in a horizontal state by the substrate holding portion 31 (step S11). Next, the rotation of the substrate 9 is started, and the chemical liquid is supplied from the first nozzle 51 to the substrate 9 rotating at a relatively high rotation speed (for example, 800 rpm). Then, by supplying the chemical solution for a predetermined period of time, the chemical solution process (for example, the cleaning process by the cleaning solution) on the substrate 9 is performed (step S12). In the chemical liquid treatment of the substrate 9, the cover plate 35 is located at the first position, and a gap between the substrate 9 and the cover plate 35 is formed with a flow of inert gas from the radially inner side toward the radially outer side. Thereby, the chemical solution that has been supplied to the upper surface 91 of the substrate 9 can be prevented or suppressed from being wound into the lower surface 92 via the side surface of the substrate 9.

When the supply of the chemical liquid is stopped, the first nozzle 51 supplies the rinse liquid to the substrate 9 that is rotating at a relatively high rotation speed (for example, 800 rpm as in step S12). Then, the rinsing process for the substrate 9 is performed by supplying the rinsing liquid for a predetermined time (step S13). In the rinsing process, the chemical liquid on the substrate 9 can be washed away by the rinsing liquid (for example, DIW) supplied from the first nozzle 51. When the above predetermined time passes, the rotation speed of the substrate 9 is gradually reduced and set to a rotation speed much lower than the above rotation speed (hereinafter, referred to as "liquid film holding speed"). The rotation speed of the substrate 9 is reduced to, for example, 10 rpm. In this state, a liquid film of rinse liquid is formed and held on the upper surface 91 of the substrate 9. Furthermore, the liquid film holding speed may be 0 rpm.

In the rinsing process for the substrate 9, the cover plate 35 is also located at the first position, and a gap between the substrate 9 and the cover plate 35 is formed with a flow of inert gas from the radially inner side toward the radially outer side. Thereby, it is possible to prevent or suppress the rinse liquid supplied to the upper surface 91 of the substrate 9 from getting into the lower surface 92 via the side surface of the substrate 9.

Then, the supply of the rinse liquid is stopped, and the solvent is supplied from the second nozzle 52 to the substrate 9 rotating at the above-described liquid film holding speed. Then, while continuing to supply the solvent, the rotation speed of the substrate 9 is gradually increased from the liquid film holding speed, and the substrate 9 is rotated at a relatively high rotation speed (for example, 800 rpm). As a result, the solvent spreads radially outward from the center of the upper surface 91 of the substrate 9, and the rinse liquid on the substrate 9 is replaced with the solvent. A thin liquid film (hereinafter, referred to as "solvent film") in which a solvent is formed and held on the upper surface 91 of the substrate 9 is formed.

Since the surface tension of the solvent is small, it easily enters the gap in the structure of the upper surface 91 of the substrate 9 (that is, the space between adjacent structure elements in the structure). Therefore, the gap in the structure can be filled with a solvent (step S14). The solvent film has a thickness at least substantially covering the height of the structure or more. When the replacement process of the rinse liquid by the solvent (that is, the solvent replacement process) ends, the supply of the solvent is stopped.

In the supply of the solvent to the substrate 9, the cover plate 35 is also located at the first position, and the gap between the substrate 9 and the cover plate 35 is also formed with a flow of inert gas from the radially inner side to the radially outer side. Thereby, it is possible to prevent or suppress the solvent supplied to the upper surface 91 of the substrate 9 from getting into the lower surface 92 via the side surface of the substrate 9.

When the solvent replacement process is completed, the third nozzle 53 supplies a filling material solution as a coating liquid to the substrate 9 rotating while maintaining a relatively high rotation speed in step S14. When a predetermined amount of the filling material solution is supplied onto the substrate 9, the supply of the filling material solution is stopped. The filling material solution supplied from the third nozzle 53 to the solvent film on the substrate 9 expands radially outward from the central portion of the upper surface 91 by the rotation of the substrate 9. As a result, a liquid film of the filling material solution is formed on the solvent film on the substrate 9. Furthermore, the number of rotations of the substrate 9 at the time of forming the liquid film of the filling material solution does not necessarily need to be maintained at a fixed level, and may be changed as appropriate. For example, the filling material solution may be supplied with the rotation of the substrate 9 stopped, and then, a liquid film of the filling material solution may be formed on the solvent film by the rotation of the substrate 9.

Thereafter, the rotation speed of the substrate 9 is reduced, for example, to the above-mentioned liquid film holding speed. As described above, the substantially entire upper surface 91 of the substrate 9 is covered by the solvent film, and the substantially entire upper surface of the solvent film is covered by the liquid film of the filling material solution. Because the specific gravity of the filling material solution is greater than that of the solvent, the solvent film and the liquid film of the filling material solution will be replaced up and down. Thereby, the solvent of the gap in the structure existing on the upper surface 91 of the substrate 9 can be replaced by the filling material solution, and the gap in the structure can be filled by the filling material solution (step S15). In other words, step S15 refers to the filling material filling process (that is, the filling material embedding process) in which the filling material is embedded between adjacent structural elements in the structure. On the substrate 9, the liquid film of the filling material solution is located on the upper surface 91, and the solvent film is located on the liquid film of the filling material solution.

When step S15 ends, the rotation speed of the substrate 9 is increased and the solvent film on the liquid film of the filling material solution is removed from the substrate 9. In addition, the excess part of the filling material solution can also be removed from the substrate 9. The rotation speed of the substrate 9 at this time refers to the degree to which the filling material embedded in the gap of the structure of the substrate 9 (that is, between adjacent structural elements) in step S15 does not detach outward by centrifugal force speed. For example, the substrate 9 is rotated at 300 rpm to 500 rpm. Thereby, a coating film that is a liquid film of the filler solution is formed on the upper surface 91 of the substrate 9 (step S16). The coating film has a thickness necessary to cover the entire structure. The coating film is cured on the substrate 9 by vaporization of the solvent contained in the filler solution.

During the supply of the filling material solution to the substrate 9, the cover plate 35 is located at the second position and is rotated by the substrate rotating mechanism 33 together with the substrate 9 and the substrate holding portion 31. As a result, the processing liquid (for example, rinsing liquid or solvent) that has adhered to the cover plate 35 moves radially outward and scatters radially outward from the outer edge of the cover plate 35.

Thereafter, in the mixing unit 61, the rinse liquid and the solvent are mixed to generate a peeling liquid (step S17). In step S17, as described above, the ratio of the solvent in the mixing unit 61 mixed with the rinse liquid can be adjusted. Specifically, the input information related to the peeling treatment of the coating film is stored in the concentration control section 63 in advance, and the concentration control section 63 controls the mixing ratio adjusting section 62 based on the input information, whereby the solvent in the mixing section 61 can be adjusted Proportion of mixing in the rinse solution. The input information includes, for example, the thickness of the coating film on the substrate 9, the type of the filling material solution forming the coating film, the type of the substrate 9, or the material of the cup portion 4. In step S17, the volume concentration of the solvent in the stripping liquid is preferably 20% or more and 40% or less. In other words, the volume mixing ratio of the solvent and the rinse liquid when the peeling liquid is generated in the mixing section 61 is 2: 8 to 4: 6. Furthermore, the volume concentration of the solvent in the stripping solution may be less than 20%, or may be greater than 40%.

Next, with the substrate 9 rotated, the peeling liquid generated in the mixing section 61 is ejected toward the outer edge portion of the lower surface 92 of the substrate 9 through the fourth nozzle 64. The rotation speed of the substrate 9 may be, for example, 300 rpm to 500 rpm as in step S16, or may be increased stepwise to a higher speed than the rotation speed of step S16. The peeling liquid supplied from the fourth nozzle 64 to the lower surface 92 of the substrate 9 is wound into the upper surface 91 via the side surface of the substrate 9 and supplied to the peripheral region 94 of the rotating upper surface 91 of the substrate 9 over the entire circumference. With this, a portion of the coating film on the upper surface 91 of the substrate 9 (that is, the liquid film of the filling material solution) located on the peripheral region 93 can be peeled from the substrate 9 and removed (step S18) . In step S18, in addition to removing the filler material solution that has adhered to the peripheral region 93 of the upper surface 91 of the substrate 9, the filler material solution that has adhered to the side surface of the substrate 9 and the outer edge portion of the lower surface 92 can also be removed. In the peeling process for the substrate 9, the cover plate 35 is located at the first position.

The stripping liquid used in step S18 may be produced by mixing an aqueous solvent and a water-soluble organic solvent, and it is not necessarily necessary to mix the rinse liquid from the rinse liquid supply source 55 and the solvent from the solvent supply source 56 generate. For example, an aqueous medium supplied from a supply source different from the rinse liquid supply source 55 and a water-soluble organic solvent supplied from a supply source different from the solvent supply source 56 may be mixed in the mixing unit 61 to generate a peeling liquid. The above-mentioned aqueous solvent may be a liquid (for example, carbonated water, ozone water, or hydrogen water) different from the rinse liquid sent from the rinse liquid supply source 55. In addition, the water-soluble organic solvent may be a liquid different from the solvent sent from the solvent supply source 56 (for example, PGEE, PGME, EL, methanol, ethanol, or acetone).

When step S17 and step S18 are completed, the substrate 9 is dried (step S19). In step S19, the substrate holding portion 31 is rotated at a high speed in a state where the substrate holding portion 31 has held the substrate 9. As a result, the peeling liquid applied to the peripheral region 93 of the substrate 9 is scattered by the centrifugal force from the outer edge of the substrate 9 to the outside in the radial direction and is removed from the substrate 9. In the above steps S12 to S19, the processing liquid such as the chemical liquid, rinse liquid, solvent, filling material solution, and peeling liquid that has been scattered radially outward from the substrate 9 is received by the cup 4 The outside of the substrate processing apparatus 1 is discharged.

After the drying process is completed, the substrate 9 is carried out from the substrate processing apparatus 1 and transported to the next processing apparatus (not shown). Then, the substrate 9 is heated in the next processing device, and a process of curing the filler material in the gap (that is, between adjacent structural elements) in the structures embedded in the substrate 9 is performed. When the substrate 9 is transported from the substrate processing apparatus 1 to the next processing apparatus, the filling material of the peripheral area 93 of the substrate 9 has been removed, so that the transport mechanism can be prevented from being contaminated by the filling material. In the substrate processing apparatus 1, the above-mentioned processes from step S11 to step S19 are sequentially performed on a plurality of substrates 9.

As described above, the substrate processing apparatus 1 includes the substrate holding portion 31, the substrate rotating mechanism 33, the coating liquid supply portion, the peeling liquid supply portion 6, and the cup portion 4 as the liquid receiving portion. The substrate holding portion 31 holds the substrate 9 in a horizontal state. The substrate rotating mechanism 33 rotates the substrate 9 together with the substrate holding portion 31 with the center axis J1 oriented in the vertical direction as the center. The coating liquid supply unit supplies a coating liquid (ie, a filler solution) that is a water-soluble polymer solution to the upper surface 91 of the substrate 9, and forms a coating film that is a film of the coating liquid on the upper surface 91. The peeling liquid supply unit 6 supplies the peeling liquid to the peripheral region 93 of the upper surface 91 of the rotating substrate 9, thereby peeling the portion of the coating film on the peripheral region 93 from the substrate 9. The cup body portion 4 is arranged around the substrate holding portion 31 and receives the peeling liquid scattered from the rotating substrate 9 toward the surroundings. The peeling liquid supply unit 6 includes a mixing unit 61 and a fourth nozzle 64 as a peeling liquid ejection unit. The mixing unit 61 mixes a water-soluble organic solvent and an aqueous solvent to generate a peeling liquid. The fourth nozzle 64 ejects the peeling liquid sent from the mixing unit 61 toward the substrate 9.

In this way, by supplying the peeling liquid containing the aqueous solvent to the peripheral region 93 of the substrate 9, the peripheral portion of the coating film that has been formed on the substrate 9 can be preferably removed. In addition, since the stripping liquid contains a water-soluble organic solvent, the surface tension of the stripping liquid is reduced compared to the case of not containing a water-soluble organic solvent. With this, it is possible to suppress the peeling liquid that has scattered from the substrate 9 and hit the cup body 4 from rebounding from the cup body 4. As a result, it is possible to prevent or suppress the peeling liquid rebounded from the cup portion 4 from adhering to the coating film on the substrate 9 and melting the coating film.

As described above, the fourth nozzle 64 ejects the peeling liquid toward the outer edge portion of the lower surface 92 of the substrate 9. Thereby, it is possible to suppress the amount of the peeling liquid supplied to the upper surface 91 of the substrate 9 (that is, the upper surface 91) while suppressing the amount of the peeling liquid being sprayed toward the upper surface 91 of the substrate 9 Control with good accuracy. As a result, it is possible to accurately adjust the width of the peripheral area 93 while suppressing an excessive increase in the width of the peripheral area 93 (that is, the edge rinse width) to which the peeling liquid is supplied on the upper surface 91 of the substrate 9. In addition, since it is not necessary to retract the fourth nozzle 64 from above the substrate 9 when carrying the substrate 9 into the substrate processing apparatus 1 and when carrying the substrate 9 out of the substrate processing apparatus 1, the substrate processing apparatus can be simplified 1. Construction. In addition, the time required to process the substrate 9 of the substrate processing apparatus 1 can also be shortened.

As described above, the peeling liquid supply unit 6 further includes the mixing ratio adjustment unit 62 that adjusts the ratio of the water-soluble organic solvent mixed in the aqueous solvent in the mixing unit 61. With this, the water-soluble organic solvent in the peeling liquid can be easily realized in accordance with the thickness of the coating film on the substrate 9, the type of the filling material solution forming the coating film, the type of the substrate 9, or the material of the cup portion 4, etc. The better volume concentration.

In addition, the peeling liquid supply unit 6 further includes a concentration control unit 63 that controls the mixing ratio adjusting unit 62 based on input information related to the peeling process of the coating film. Thereby, the water-soluble organic solvent in the peeling liquid can be automatically adjusted according to the thickness of the coating film on the substrate 9, the type of the filling material solution forming the coating film, the type of the substrate 9, or the material of the cup portion 4, etc. Volume concentration.

As described above, the volume concentration of the water-soluble organic solvent in the stripping liquid is preferably 20% or more and 40% or less. Thereby, it is possible to preferably take into consideration simultaneously: peeling of the coating film on the peripheral region 93 of the substrate 9 and suppression of the rebound of the peeling liquid from the cup portion 4. When the volume concentration is within the range of 20% or less, the surface tension of the stripping solution will gradually decrease as the volume concentration increases. Therefore, by setting the volume concentration to 20% or more, it is possible to reduce the surface tension of the peeling liquid and preferably suppress the rebound of the peeling liquid from the cup portion 41.

In the substrate processing apparatus 1, the aforementioned water-soluble organic solvent is IPA. In this way, by using the IPA that is also used in the substrate 9 for other processing in the substrate processing apparatus 1 to generate the peeling liquid, the structure related to the generation of the peeling liquid can be simplified. As a result, the structure of the substrate processing apparatus 1 can also be simplified. In the example shown in FIG. 3, the substrate processing apparatus 1 further includes a solvent supply unit that supplies a solvent to the upper surface 91 of the substrate 9, and the solvent refers to the same kind of liquid as the water-soluble organic solution of the peeling liquid. In this way, the structure of the substrate processing apparatus 1 can be simplified.

As described above, the substrate processing apparatus 1 further includes the rinse liquid supply unit that supplies the rinse liquid to the upper surface 91 of the substrate 9, and the rinse liquid refers to the same kind of liquid as the aqueous solvent of the peeling liquid. With this, the structure related to the generation of the peeling liquid can be simplified, and as a result, the structure of the substrate processing apparatus 1 can also be simplified.

As described above, a structure is formed on the upper surface 91 of the substrate 9 in advance. Then, in the substrate processing apparatus 1, by forming the above-mentioned coating film on the upper surface 91 of the substrate 9, the gap in the structure can be filled with the coating liquid. As a result, it is possible to prevent or suppress the collapse of the structure due to the surface tension of the treatment liquid acting on the structure.

Next, the substrate processing apparatus 1 according to the second embodiment of the present invention will be described. The substrate processing apparatus 1 of the second embodiment has substantially the same structure as the substrate processing apparatus 1 shown in FIGS. 1 and 2. In the following description, the symbols of the components of the substrate processing apparatus 1 are the same as the components shown in FIGS. 1 and 2.

6 is a block diagram showing the processing liquid supply unit 5 of the substrate processing apparatus 1 of the second embodiment. In FIG. 6, the configuration other than the processing liquid supply unit 5 is also shown. The first nozzle 51 is connected to the chemical solution supply source 54 and the rinse solution supply source 55. The second nozzle 52 is connected to the rinse liquid supply source 55 and the solvent supply source 56 through the mixing section 71. The third nozzle 53 is connected to the filling material solution supply source 57. The fourth nozzle 64 is connected to the solvent supply source 56.

The first nozzle 51 supplies the chemical solution sent from the chemical solution supply source 54 to the central portion of the upper surface 91 of the substrate 9. As the chemical solution, for example, a cleaning solution containing dilute hydrofluoric acid (DHF) can be used. In this embodiment, DHF is used as a chemical solution. In addition, other types of cleaning liquid or chemical liquid other than the cleaning liquid may be sent from the chemical liquid supply source 54 to the first nozzle 51. In addition, the first nozzle 51 is configured to supply the rinsing liquid sent from the rinsing liquid supply source 55 to the central portion of the upper surface 91 of the substrate 9 in a state where the feeding of the chemical liquid from the chemical liquid supply source 54 has stopped. As the rinse liquid, for example, an aqueous treatment liquid such as DIW, carbonated water, ozone water, or hydrogen water can be used. In this embodiment, DIW is used as the rinse liquid.

The first nozzle 51 is included in the chemical solution supply portion that supplies the chemical solution to the upper surface 91 of the substrate 9. The chemical solution supply source 54 may be included in the chemical solution supply unit. In addition, the first nozzle 51 is also included in the rinse liquid supply portion that supplies the rinse liquid to the upper surface 91 of the substrate 9. The rinse liquid supply source 55 described above may be included in the rinse liquid supply unit. For example, the lower end of the first nozzle 51 is provided with, for example, a discharge port for a chemical liquid and a discharge port for a rinse liquid, and different types of processing liquid are supplied to the upper surface 91 of the substrate 9 through different pipes and discharge ports. In addition, the first nozzle 51 may include a processing liquid nozzle for the chemical liquid and a processing liquid nozzle for the rinse liquid.

The mixing unit 71 mixes the rinsing liquid (that is, an aqueous solvent) sent from the rinsing liquid supply source 55 and the solvent sent from the solvent supply source 56, thereby generating a replacement liquid as a replacement process described later Treatment fluid used. Displacement fluid refers to the diluted solvent after diluting the solvent with the rinse fluid. As the solvent, for example, a water-soluble organic solvent such as IPA (isopropyl alcohol), methanol, ethanol, acetone, PGEE (propylene glycol ether), PGME (propylene glycol methyl ether), or EL (ethyl lactate) can be used. The surface tension of the solvent is smaller than the above-mentioned rinse liquid. In this embodiment, IPA is used as a solvent. That is, the replacement liquid generated in the mixing unit 71 refers to the diluted IPA after diluting the IPA with DIW. The surface tension of the replacement fluid is also smaller than that of the flushing fluid.

The mixing unit 71 may be, for example, a static mixer without a drive unit (that is, a static mixer), or a dynamic mixer that mixes the washing liquid and the solvent by rotating a stirring blade or the like. In addition, the mixing unit 71 may temporarily store one of the processing liquid of the rinsing liquid and the solvent in the storage tank, and supply the other processing liquid to the one processing liquid in the storage tank to thereby mix the rinsing liquid And solvent.

The second nozzle 52 refers to a replacement liquid discharge portion that discharges the replacement liquid sent from the mixing portion 71 toward the center of the upper surface 91 of the substrate 9. The second nozzle 52 and the mixing unit 71 are included in the replacement liquid supply unit 7 that supplies the replacement liquid to the upper surface 91 of the substrate 9. The replacement liquid supply unit 7 may include a rinse liquid supply source 55 and a solvent supply source 56.

The mixing ratio adjustment unit 72 adjusts the ratio of the solvent mixed in the rinse liquid in the mixing unit 71. In the example shown in FIG. 6, the mixing ratio regulator 72 includes valves 721 and 722. The valve 721 is arranged between the rinse liquid supply source 55 and the mixing unit 71 and changes the flow rate of the rinse liquid supplied from the rinse liquid supply source 55 to the mixing unit 71. The valve 722 is arranged between the solvent supply source 56 and the mixing section 71 and changes the flow rate of the solvent supplied from the solvent supply source 56 to the mixing section 71.

The concentration control unit 73 controls the mixing ratio adjustment unit 72, thereby setting the ratio of the solvent mixed in the rinse liquid in the mixing unit 71 to a desired ratio. In other words, the concentration control unit 73 adjusts the components of the replacement liquid generated in the mixing unit 71 to the desired components. In the substrate processing apparatus 1, the flow rate of the rinsing liquid and the solvent is adjusted by the mixing ratio adjusting part 72, whereby the ratio sent by the mixing part 71 can be changed while maintaining the ratio of the solvent mixed in the rinsing liquid Displacement fluid flow. The concentration control unit 73 and the mixing ratio adjustment unit 72 are included in the replacement liquid supply unit 7 described above.

The third nozzle 53 supplies the filling material solution sent from the filling material solution supply source 57 to the central portion of the upper surface 91 of the substrate 9. Filling material solution refers to a solution in which a solid solute is dissolved in a solvent. As the solute system, a water-soluble polymer (hereinafter, simply referred to as "polymer") can be used. That is, the filling material solution refers to a water-soluble polymer solution. The polymer is, for example, a water-soluble polymer resin such as acrylic resin. The solvent of the filling material solution is aqueous, for example, DIW, PGEE, PGME, or EL can be used. The specific gravity of the filling material solution is larger than that of the replacement liquid mentioned above.

The filler solution refers to a coating liquid applied to the upper surface 91 of the substrate 9. The above-mentioned polymer in the film of the filling material solution (that is, the coating film) applied to the upper surface 91 of the substrate 9 is solidified by vaporization of the solvent. In addition, the residual solvent component in the polymer may be removed by heating the substrate 9. The third nozzle 53 is included in the coating liquid supply portion that supplies the coating liquid to the upper surface 91 of the substrate 9 and forms a coating film on the upper surface 91 that belongs to the coating liquid film. The above-mentioned filling material solution supply source 57 may be included in the coating liquid supply part.

The fourth nozzle 64 ejects the solvent (that is, the peeling liquid) sent from the solvent supply source 56 toward the outer edge portion of the lower surface 92 of the substrate 9. The peeling liquid supplied from the fourth nozzle 64 to the lower surface 92 of the substrate 9 is wound into the upper surface 91 via the side surface (ie, outer edge) of the substrate 9 and supplied to the peripheral area 93 (ie, edge portion) of the upper surface 91 . The fourth nozzle 64 is included in the peeling liquid supply portion that supplies the peeling liquid to the peripheral region 93 of the upper surface 91 of the substrate 9. The solvent supply source 56 may be included in the peeling liquid supply unit.

FIG. 7 is a plan view showing the substrate 9. In FIG. 7, for easy understanding of the drawing, parallel diagonal lines are marked on the inner surface 94 of the upper surface 91 of the substrate 9 as the radially inner area of the peripheral area 93, and the peripheral area 93 and the inner area are shown by a two-dot chain line The boundary of 94. On the upper surface 91 of the substrate 9, a structure (for example, a circuit pattern used in a product) belonging to a collection of a plurality of fine structure elements is formed in the inner region 94 in advance. This structure is not formed in the peripheral region 93.

The processing of the substrate 9 in the substrate processing apparatus 1 is performed in the order of chemical solution processing, rinsing processing, replacement processing, filling material filling processing, peeling processing (that is, edge rinsing processing), and drying processing, for example. 8 is a schematic diagram showing an example of the processing flow of the substrate 9 in the substrate processing apparatus 1. 9 is a schematic diagram showing an example of the rotation speed during the processing of the substrate 9. The horizontal axis of Fig. 9 has nothing to do with the actual processing time.

First, the substrate 9 on which the structure described above is formed on the upper surface 91 is held in a horizontal state by the substrate holding portion 31 (step S21). Next, the rotation of the substrate 9 is started, and the chemical liquid is supplied from the first nozzle 51 to the substrate 9 rotating at a relatively high rotation speed (for example, 800 rpm). Then, by supplying the chemical solution for a predetermined time, the chemical solution process for the substrate 9 is performed (step S22). In this embodiment, DHF is used as a chemical solution, and the upper surface 91 of the substrate 9 is washed. As a result, the upper surface 91 of the substrate 9 becomes a hydrophobic surface.

In the chemical liquid treatment of the substrate 9, the cover plate 35 is located at the first position, and a gap between the substrate 9 and the cover plate 35 is formed with a flow of inert gas from the radially inner side toward the radially outer side. Thereby, it is possible to prevent or suppress the chemical solution supplied to the upper surface 91 of the substrate 9 from passing around the lower surface 92 via the side surface of the substrate 9.

When the supply of the chemical liquid is stopped, the first nozzle 51 supplies the rinse liquid to the substrate 9 that is rotating at a relatively high rotation speed (for example, 800 rpm as in step S22). Then, by continuing the supply of the rinse liquid for a predetermined time, the rinse process for the substrate 9 is performed (step S23). In the rinsing process, the chemical liquid on the substrate 9 can be washed away by the rinsing liquid (for example, DIW) supplied from the first nozzle 51. In the rinsing process for the substrate 9, the cover plate 35 is also located at the first position, and a gap between the substrate 9 and the cover plate 35 is formed with a flow of inert gas from the radially inner side toward the radially outer side. Thereby, it is possible to prevent or suppress the rinse liquid supplied to the upper surface 91 of the substrate 9 from getting into the lower surface 92 via the side surface of the substrate 9.

In the substrate processing apparatus 1, the mixing unit 71 mixes the rinse liquid as an aqueous solvent and the solvent as a water-soluble organic solvent to generate a replacement liquid (step S24), for example, it is performed simultaneously with the rinse process of the substrate 9. In step S24, as described above, the ratio of the solvent mixed in the rinse liquid in the mixing unit 71 can be adjusted. Specifically, the input information related to the formation process of the coating film is stored in the concentration control section 73 in advance, and the concentration control section 73 controls the mixing ratio adjustment section 72 based on the input information, whereby the mixing in the mixing section 71 can be adjusted The proportion of solvent in the rinse solution.

The input information includes, for example, the type of the filler solution forming the coating film, the nature of the upper surface 91 of the substrate 9, or the type of the above-mentioned chemical treatment. In step S24, the volume concentration of the solvent in the replacement liquid is preferably 15% or more and 30% or less. In other words, the volume mixing ratio of the solvent and the rinse liquid when the replacement liquid is generated in the mixing unit 71 is 3:17 to 3: 7. Furthermore, the volume concentration of the solvent in the replacement fluid may be less than 15%, or may be greater than 30%.

When step S23 and step S24 are completed, the supply of the rinse liquid is stopped while gradually decreasing the rotation speed of the substrate 9, and the replacement liquid is supplied from the second nozzle 52 to the upper surface 91 of the substrate 9. At this time, the rotation speed of the substrate 9 is a rotation speed much lower than the above-mentioned rotation speed. The rotation speed of the substrate 9 is, for example, 0 rpm to 10 rpm. The replacement liquid supplied to the substrate 9 expands radially outward from the central portion of the upper surface 91.

Then, while the supply of the replacement liquid to the substrate 9 is continued, the rotation speed of the substrate 9 is gradually increased to a relatively high rotation speed (for example, 800 rpm). As a result, the replacement liquid expands radially outward from the center of the upper surface 91 of the substrate 9, and the rinse liquid on the substrate 9 moves radially outward. Then, the rinsing liquid can be removed from the substrate 9 (that is, the rinsing liquid is replaced with a replacement liquid), and a thin liquid film of the replacement liquid is formed on the upper surface 91 of the substrate 9 (hereinafter, referred to as "replacement liquid film") ) And keep it. In the substrate processing apparatus 1, the rotation speed of the substrate 9 when the replacement liquid film is formed is set so that the thickness of the replacement liquid film becomes a desired thickness.

Since the surface tension of the replacement fluid is small, it easily enters the gap in the structure of the upper surface 91 of the substrate 9 (i.e., the space between adjacent structure elements in the structure). Therefore, the gap in the structure can be filled with the replacement fluid (step S25). The replacement liquid film has a thickness at least substantially covering the height of the structure or more. When the replacement process of the flushing liquid by the replacement liquid ends, the supply of replacement liquid is stopped.

During the supply of the replacement liquid to the substrate 9, the cover plate 35 is also located at the first position, and the gap between the substrate 9 and the cover plate 35 is also formed with a flow of inert gas from the radially inner side to the radially outer side. Thereby, the replacement liquid supplied to the upper surface 91 of the substrate 9 can be prevented or suppressed from being wound into the lower surface 92 via the side surface of the substrate 9.

The replacement liquid used in step S25 may be produced by mixing an aqueous solvent and a water-soluble organic solvent, and it is not necessarily necessary to mix the rinse liquid from the rinse liquid supply source 55 and the solvent from the solvent supply source 56 generate. For example, an aqueous solvent supplied from a supply source different from the rinse liquid supply source 55 and a water-soluble organic solvent supplied from a supply source different from the solvent supply source 56 may be mixed in the mixing unit 71 to generate a peeling liquid. The above-mentioned aqueous solvent may be a liquid (for example, carbonated water, ozone water, or hydrogen water) different from the rinse liquid sent from the rinse liquid supply source 55. In addition, the water-soluble organic solvent may be a liquid different from the solvent sent from the solvent supply source 56 (for example, PGEE, PGME, EL, methanol, ethanol, or acetone).

When step S25 ends, the third nozzle 53 supplies a filling material solution as a coating liquid to the substrate 9 rotating while maintaining a relatively high rotation speed in step S25. When a predetermined amount of the filling material solution is supplied onto the substrate 9, the supply of the filling material solution is stopped. The filling material solution supplied from the third nozzle 53 to the replacement liquid film on the substrate 9 expands radially outward from the central portion of the upper surface 91 by the rotation of the substrate 9. As a result, a liquid film of the filling material solution is formed on the replacement liquid film on the substrate 9. In addition, the number of rotations of the substrate 9 at the time of forming the liquid film of the filling material solution does not necessarily need to be maintained at a fixed level, and may be changed as appropriate. For example, a liquid film of the filling material solution may be formed on the replacement liquid film by supplying the filling material solution in a state where the rotation of the substrate 9 has stopped, and then rotating the substrate 9.

Thereafter, the rotation speed of the substrate 9 is reduced, for example, to 10 rpm. As described above, the substantially entire upper surface 91 of the substrate 9 is covered by the replacement liquid film, and the substantially entire upper surface of the replacement liquid film is covered by the liquid film filled with the material solution. Since the specific gravity of the filling material solution is greater than that of the replacement liquid, the replacement liquid film and the liquid film of the filling material solution are replaced up and down. Thereby, the replacement liquid of the gap in the structure existing on the upper surface 91 of the substrate 9 can be replaced by the filling material solution, and the gap in the structure can be filled by the filling material solution (step S26). In other words, step S26 refers to the filling material filling process (that is, the filling material embedding process) in which the filling material is buried between adjacent structural elements in the structure. On the substrate 9, the liquid film of the filling material solution is on the upper surface 91, and the replacement liquid film is on the liquid film of the filling material solution.

When step S26 ends, the rotation speed of the substrate 9 is increased to remove the replacement liquid film on the liquid film of the filling material solution from the substrate 9. In addition, the excess part of the filling material solution is also removed from the substrate 9. At this time, the rotation speed of the substrate 9 is such that the filler material embedded in the gap of the structure of the substrate 9 (that is, between adjacent structural elements) in step S26 does not detach outward by centrifugal force speed. For example, the substrate 9 is rotated at 300 rpm to 500 rpm. Thereby, a coating film as a liquid film of the filler solution is formed on the upper surface 91 of the substrate 9 (step S27). The coating film has a necessary thickness to cover the entire structure. The coating film is cured on the substrate 9 by vaporizing the solvent contained in the filler solution.

During the supply of the filling material solution to the substrate 9, the cover plate 35 is located at the second position and is rotated by the substrate rotating mechanism 33 together with the substrate 9 and the substrate holding portion 31. As a result, the processing liquid (for example, chemical liquid, rinsing liquid, or replacement liquid) that has adhered to the cover plate 35 moves radially outward and scatters radially outward from the outer edge of the cover plate 35.

Next, in a state where the substrate 9 is rotated, the peeling liquid is ejected from the fourth nozzle 64 toward the outer edge portion of the lower surface 92 of the substrate 9. The rotation speed of the substrate 9 may be, for example, 300 rpm to 500 rpm as in step S27, and may be increased stepwise to a higher speed than that in step S27. The peeling liquid supplied from the fourth nozzle 64 to the lower surface 92 of the substrate 9 is wound into the upper surface 91 through the side surface of the substrate 9 and is supplied to the peripheral area 93 of the upper surface 91 of the rotating substrate 9 over the entire circumference . Thereby, the peeling process of peeling off and removing the portion of the coating film on the upper surface 91 of the substrate 9 (that is, the liquid film of the filling material solution) located on the peripheral area 93 from the substrate 9 (step S28) . In step S28, in addition to removing the filler material solution that has adhered to the peripheral region 93 of the upper surface 91 of the substrate 9, the filler material solution that has adhered to the side surface of the substrate 9 and the outer edge portion of the lower surface 92 can also be removed. In the peeling process for the substrate 9, the cover plate 35 is located at the first position.

When step S28 ends, the substrate 9 is dried (step S29). In step S29, the substrate holding portion 31 is rotated at a high speed while the substrate holding portion 31 has held the substrate 9. As a result, the peeling liquid applied to the peripheral region 93 of the substrate 9 is scattered by the centrifugal force from the outer edge of the substrate 9 to the outside in the radial direction and is removed from the substrate 9. In the above steps S22 to S29, the processing liquids such as the chemical liquid, the rinsing liquid, the replacement liquid, the filling material solution, and the peeling liquid that are scattered radially outward from the substrate 9 are received by the cup body 4 and It is discharged to the outside of the substrate processing apparatus 1.

After the drying process is completed, the substrate 9 is carried out from the substrate processing apparatus 1 and transported to the next processing apparatus (not shown). Then, the substrate 9 is heated in the next processing device, and a process of curing the filler material in the gap (that is, between adjacent structural elements) in the structures embedded in the substrate 9 is performed. When the substrate 9 is transported from the substrate processing apparatus 1 to the next processing apparatus, the filler material in the peripheral region 93 of the substrate 9 has been removed, so that the transport mechanism can be prevented from being contaminated by the filler material. In the substrate processing apparatus 1, the above-mentioned processes from step S21 to step S29 are sequentially performed on a plurality of substrates 9.

As described above, the substrate processing apparatus 1 includes the substrate holding portion 31, the rinse liquid supply portion, the replacement liquid supply portion 7, and the coating liquid supply portion. The substrate holding portion 31 holds the substrate 9 in a horizontal state. The rinse liquid supply unit supplies the rinse liquid to the upper surface 91 of the substrate 9. The replacement liquid supply unit 7 supplies the replacement liquid to the upper surface 91 of the substrate 9, thereby replacing the rinsing liquid on the upper surface 91 of the substrate 9 with the replacement liquid, and forming a replacement of the liquid film belonging to the replacement liquid on the upper surface 91 Liquid film. The coating liquid supply unit supplies a coating liquid (that is, a filling material solution) belonging to a water-soluble polymer solution onto the replacement liquid film, and forms a coating film belonging to the coating liquid film on the upper surface 91 of the substrate 9. The replacement liquid supply unit 7 includes a mixing unit 71 and a second nozzle 52 as a replacement liquid discharge unit. The mixing unit 71 mixes a water-soluble organic solvent and an aqueous solvent to generate a replacement liquid having a surface tension smaller than that of the rinse liquid. The second nozzle 52 ejects the replacement liquid sent from the mixing unit 71 toward the substrate 9.

In this way, the water-soluble organic solvent and the aqueous solvent are mixed to generate a replacement liquid having a surface tension smaller than that of the rinsing liquid, and the rinsing liquid on the substrate 9 is replaced with the replacement liquid, whereby the substrate 9 can be preferably coated with the replacement liquid film Upper surface 91. Thereby, it is possible to prevent the upper surface 91 of the substrate 9 from being exposed from the rinsing liquid film and contacting the outside air between the rinsing process and the filling material filling process. In other words, it is possible to prevent the upper surface 91 of the substrate 9 from being exposed from the liquid film before the coating film is formed. In addition, as described above, since the replacement fluid contains an aqueous solvent, it is possible to prevent the filler solution from agglomerating in the replacement fluid membrane. As a result, a coating film can be preferably formed on the substrate 9.

The substrate processing apparatus 1 further includes a substrate rotating mechanism 33. The substrate rotating mechanism 33 rotates the substrate 9 together with the substrate holding portion 31 with the center axis J1 oriented in the vertical direction as the center. In the substrate processing apparatus 1, when the replacement liquid film is formed (step S25), the substrate 9 is rotated by the substrate rotating mechanism 33. This makes it easy to set the thickness of the replacement liquid film to a desired thickness. As a result, since the thickness of the replacement liquid film can be prevented from becoming excessively large, the amount of the filler material solution supplied to the replacement liquid film in step S26 can be reduced.

As described above, the replacement liquid supply unit 7 further includes the mixing ratio adjustment unit 72 that adjusts the ratio of the water-soluble organic solvent mixed in the aqueous solvent in the mixing unit 71. In this way, the water-soluble organic solvent in the replacement liquid can be easily realized in accordance with the type of the filling material solution forming the coating film, the nature of the upper surface 91 of the substrate 9, or the type of the above-mentioned chemical treatment, etc. Volume concentration.

In addition, the replacement liquid supply unit 7 further includes a concentration control unit 73 that controls the mixing ratio adjustment unit 72 based on input information related to the formation process of the coating film. By this, the volume concentration of the water-soluble organic solvent in the replacement liquid can be automatically adjusted in accordance with the type of the filling material solution forming the coating film, the nature of the upper surface 91 of the substrate 9, or the type of the above-mentioned chemical treatment.

As described above, the volume concentration of the water-soluble organic solvent in the replacement liquid is preferably 15% or more and 30% or less. Thereby, it is possible to preferably take into consideration simultaneously: preventing the exposure of the upper surface 91 of the substrate 9 and the formation of the coating film on the substrate 9.

Table 1 and Table 2 show the experimental results in the first and second embodiments, respectively. In the first embodiment and the second embodiment, the plurality of volume concentrations of the water-soluble organic solvent in the replacement liquid are applied to the substrate 9 from the above-mentioned steps S21 to S27. In the first embodiment and the second embodiment, the processing conditions are the same except that the types of filler materials contained in the filler material solution are different. The symbol ○ in the table indicates that it is preferable to prevent exposure of the upper surface 91 of the substrate 9 or formation of a coating film on the substrate 9. The X symbol in the table indicates that the upper surface 91 of the substrate 9 has been exposed, or the coating film is not preferably formed on the substrate 9. The △ symbol in the table shows the state between the ○ symbol and the × symbol. It can be understood from Tables 1 and 2 that by setting the volume concentration of the water-soluble organic solvent in the replacement liquid to 15% or more and 30% or less, it is preferable to simultaneously take into account: prevent the exposure of the upper surface 91 of the substrate 9, And the formation of a coating film on the substrate 9.

In the substrate processing apparatus 1, the aforementioned water-soluble organic solvent is IPA. In this way, by using the IPA that is also used in the substrate 9 in other processes (the peeling process in the above example) in the substrate processing apparatus 1 to generate the replacement liquid, the structure related to the generation of the replacement liquid can be simplified. As a result, the structure of the substrate processing apparatus 1 can also be simplified.

As described above, the flushing liquid sent from the flushing liquid supply source 55 is the same kind of liquid as the aqueous solvent of the replacement liquid. With this, the structure related to the generation of the replacement liquid can be simplified, and as a result, the structure of the substrate processing apparatus 1 can also be simplified. In addition, the solvent sent from the solvent supply source 56 is the same kind of liquid as the water-soluble organic solvent of the replacement liquid. In this way, the structure of the substrate processing apparatus 1 can be simplified.

As described above, a structure is formed on the upper surface 91 of the substrate 9 in advance. Then, in the substrate processing apparatus 1, by forming the above-mentioned coating film on the upper surface 91 of the substrate 9, the gap in the structure can be filled with the coating liquid. As a result, it is possible to prevent or suppress the collapse of the structure due to the surface tension of the treatment liquid acting on the structure.

In the substrate processing apparatus 1, the upper surface 91 of the substrate 9 immediately before the supply of the replacement liquid is started in step S25 is a hydrophobic surface. In this manner, by switching the rinse liquid supplied to the substrate 9 to the replacement liquid, it is possible to preferably prevent the upper surface 91 of the substrate 9 from being exposed from the liquid film before the coating film is formed.

Various changes can be made in the substrate processing apparatus 1 described above.

The fourth nozzle 64 may be disposed above the substrate 9. In this case, the peeling liquid can be ejected from the fourth nozzle 64 toward the peripheral area 93 of the upper surface 91 of the substrate 9.

The concentration control unit 63 may be omitted in the peeling liquid supply unit 6. In this case, the operator operates the mixing ratio adjusting section 62 based on the input information such as the thickness of the coating film on the substrate 9, thereby adjusting the ratio of the water-soluble organic solvent mixed in the aqueous solvent in the mixing section 61. In addition, in the peeling liquid supply part 6, the ratio of the water-soluble organic solvent mixed with the aqueous solvent may be fixed. In this case, the mixing ratio adjustment unit 62 may be omitted.

For example, in the above example, although the substrate 9 is subjected to a cleaning process by DHF, thereby making the upper surface 91 of the substrate 9 a hydrophobic surface, even if the substrate 9 is caused by the material of the substrate 9 or the like In the case where the upper surface 91 is a hydrophobic surface from the beginning, the substrate processing apparatus 1 can simultaneously take into consideration: preventing the exposure of the upper surface 91 of the substrate 9 and the formation of a coating film on the substrate 9. The substrate processing apparatus 1 can also be used for processing the substrate 9 whose upper surface 91 is not a hydrophobic surface (that is, a hydrophilic surface).

In the substrate processing apparatus 1, during the formation of the replacement liquid film in step S25, the substrate 9 may not stand but rotate. In this case, the substrate rotating mechanism 33 may be omitted from the substrate processing apparatus 1.

In the replacement liquid supply unit 7, the concentration control unit 73 may be omitted. In this case, the operator can adjust the ratio of the water-soluble organic solvent mixed in the aqueous solvent in the mixing unit 71 by operating the mixing ratio adjustment unit 72 based on the input information such as the type of the filling material solution. In addition, in the replacement liquid supply part 7, the ratio of the water-soluble organic solvent mixed with the aqueous solvent may be fixed. In this case, the mixing ratio adjustment unit 72 may be omitted.

The substrate processing apparatus 1 described above can be used not only for semiconductor substrates, but also for glass used in flat panel displays such as liquid crystal display devices or organic EL (Electro Luminescence) displays. Processing of substrates, or processing of glass substrates used in other display devices. In addition, the above-described substrate processing apparatus 1 can also be used in processing of optical disc substrates, magnetic disc substrates, optical magnetic disc substrates, photomask substrates, ceramic substrates, solar cell substrates, and the like.

The configurations in the above-described embodiments and various modifications may be combined as appropriate as long as they do not contradict each other.

Although the invention has been described and described in detail, the description has been exemplified and not limited. In this way, it can be said that there can be various changes or forms without departing from the scope of the present invention.

Claims (34)

    A substrate processing apparatus that processes a substrate, and the substrate processing apparatus includes: a substrate holding portion that holds the substrate in a horizontal state; and a substrate rotation mechanism that holds the substrate and the substrate with a central axis oriented in the vertical direction as a center The parts rotate together; the coating liquid supply part supplies the coating liquid belonging to the water-soluble polymer solution to the upper surface of the substrate and forms a coating film on the upper surface that belongs to the film of the coating liquid; the peeling liquid supply part The peripheral region of the upper surface of the rotating substrate is supplied with a stripping liquid, thereby peeling the portion of the coating film on the peripheral region from the substrate; and the liquid receiving portion is disposed around the substrate holding portion And receiving the peeling liquid scattered around from the rotating substrate; the peeling liquid supply unit includes: a mixing unit that mixes a water-soluble organic solvent and an aqueous solvent to generate the peeling liquid; and a peeling liquid ejection unit that separates The peeling liquid sent from the mixing section is ejected toward the substrate.         The substrate processing apparatus according to claim 1, wherein the peeling liquid ejection portion ejects the peeling liquid toward the outer edge portion of the lower surface of the substrate.         The substrate processing apparatus according to claim 1, wherein the peeling liquid supply unit further includes a mixing ratio adjustment unit that adjusts the ratio of the water-soluble organic solvent mixed with the aqueous solvent in the mixing unit.         The substrate processing apparatus according to claim 3, wherein the peeling liquid supply unit further includes a concentration control unit that controls the mixing ratio adjusting unit based on input information related to the peeling process of the coating film.         The substrate processing apparatus according to claim 1, wherein the volume concentration of the water-soluble organic solvent in the stripping liquid is 20% or more and 40% or less.         The substrate processing apparatus according to claim 1, wherein the water-soluble organic solvent is isopropyl alcohol.         The substrate processing apparatus according to claim 1, further comprising: a rinse liquid supply unit that supplies a rinse liquid to the upper surface of the substrate; and the rinse liquid is a liquid of the same kind as the aqueous solvent of the peeling liquid.         The substrate processing apparatus according to any one of claims 1 to 7, wherein a structure is formed on the upper surface of the substrate in advance; the coating is formed by forming the coating film on the upper surface of the substrate Liquid to fill the gaps in the aforementioned structure.         A substrate processing method that processes a substrate, and the substrate processing method includes: a) a step of maintaining the substrate in a horizontal state; b) a step of supplying a coating solution belonging to a water-soluble polymer solution to the upper surface of the substrate A coating film forming a film belonging to the foregoing coating liquid on the upper surface; step c), a water-soluble organic solvent and an aqueous solvent are mixed to form a peeling liquid; and step d), which is later than the steps b) and c) above, in The state in which the substrate is rotated with the central axis in the up-down direction as the center, the peeling liquid is supplied to the peripheral area of the upper surface of the substrate, thereby making the position of the coating film on the peripheral area from the aforementioned When the substrate is peeled off, the peeling liquid scattered around the rotating substrate is received.         The substrate processing method according to claim 9, wherein in the step d), the peeling liquid is sprayed toward the outer edge portion of the lower surface of the substrate.         The substrate processing method according to claim 9, wherein in the step c), the ratio of the water-soluble organic solvent mixed with the water-based solvent can be adjusted.         The substrate processing method according to claim 11, wherein in the step c), the ratio of the water-soluble organic solvent mixed with the water-based solvent can be adjusted based on input information related to the peeling treatment of the coating film.         The substrate processing method according to claim 9, wherein the volume concentration of the water-soluble organic solvent in the stripping liquid is 20% or more and 40% or less.         The substrate processing method according to claim 9, wherein the water-soluble organic solvent is isopropyl alcohol.         The substrate processing method according to claim 9, further comprising: a step of supplying a rinse liquid to the upper surface of the substrate; the rinse liquid is a liquid of the same kind as the aqueous solvent of the peeling liquid.         The substrate processing method according to any one of claims 9 to 15, wherein a structure is formed on the upper surface of the substrate in advance; in the step b), the structure is filled with the coating liquid gap.         A substrate processing method that processes a substrate, and the substrate processing method includes: a) a step of maintaining the substrate in a horizontal state; b) a step of supplying a rinse solution to the upper surface of the substrate; c) a step of mixing a water-soluble organic solvent And an aqueous solvent to generate a replacement liquid having a surface tension lower than that of the rinsing liquid; step d), which is later than the steps b) and c), by supplying the replacement liquid to the upper surface of the substrate, thereby The rinsing liquid on the upper surface of the substrate is replaced with the replacement liquid and a replacement liquid film forming a liquid film of the replacement liquid is formed on the upper surface; and the step e) is later than the step d) and will be water-soluble The coating liquid of the sexual polymer solution is supplied onto the replacement liquid film, and a coating film belonging to the film of the coating liquid is formed on the upper surface of the substrate.         The substrate processing method according to claim 17, wherein in the step d), the substrate is rotated with the central axis oriented in the vertical direction as a center.         The substrate processing method according to claim 17, wherein in the step c), the ratio of the water-soluble organic solvent mixed with the water-based solvent can be adjusted.         The substrate processing method according to claim 19, wherein in the step c), the ratio of the water-soluble organic solvent mixed with the water-based solvent can be adjusted based on input information related to the formation process of the coating film.         The substrate processing method according to claim 17, wherein the volume concentration of the water-soluble organic solvent in the replacement liquid is 15% or more and 30% or less.         The substrate processing method according to claim 17, wherein the water-soluble organic solvent is isopropyl alcohol.         The substrate processing method according to claim 17, wherein the rinse liquid is the same kind of liquid as the aqueous solvent of the replacement liquid.         The substrate processing method according to any one of claims 17 to 23, wherein a structure is formed on the upper surface of the substrate in advance; in the step e), the structure is filled with the coating liquid gap.         The substrate processing method according to any one of claims 17 to 23, wherein in the step d), the upper surface of the substrate immediately before the supply of the replacement liquid is a hydrophobic surface.         A substrate processing apparatus that processes a substrate, and the substrate processing apparatus includes a substrate holding portion that holds the substrate in a horizontal state; a rinse liquid supply portion that supplies the rinse liquid to the upper surface of the substrate; a replacement liquid supply portion that is Supplying a replacement liquid to the upper surface of the substrate, thereby replacing the rinsing liquid on the upper surface of the substrate with the replacement liquid and forming a replacement liquid film belonging to the liquid film of the replacement liquid on the upper surface; and The coating liquid supply unit supplies the coating liquid belonging to the water-soluble polymer solution to the replacement liquid film, and forms a coating film belonging to the coating liquid film on the upper surface of the substrate; the replacement liquid supply unit is Equipped with: a mixing unit that mixes the water-soluble organic solvent and the aqueous solvent to generate the replacement liquid having a surface tension smaller than the rinse liquid; and a replacement liquid ejection unit that directs the replacement liquid sent from the mixing unit toward the substrate ejection.         The substrate processing apparatus according to claim 26, further comprising: a substrate rotating mechanism that rotates the substrate and the substrate holding portion together with a central axis oriented in the up and down direction; when the replacement liquid film is formed The substrate is rotated by the substrate rotation mechanism.         The substrate processing apparatus according to claim 26, wherein the replacement liquid supply unit further includes a mixing ratio adjusting unit that adjusts the ratio of the water-soluble organic solvent mixed with the aqueous solvent in the mixing unit.         The substrate processing apparatus according to claim 28, wherein the replacement liquid supply unit further includes a concentration control unit that controls the mixing ratio adjustment unit based on input information related to the coating film formation process.         The substrate processing apparatus according to claim 26, wherein the volume concentration of the water-soluble organic solvent in the replacement liquid is 15% or more and 30% or less.         The substrate processing apparatus according to claim 26, wherein the water-soluble organic solvent is isopropyl alcohol.         The substrate processing apparatus according to claim 26, wherein the rinse liquid is the same kind of liquid as the aqueous solvent of the replacement liquid.         The substrate processing apparatus according to any one of claims 26 to 32, wherein a structure is formed on the upper surface of the substrate in advance; the coating is formed by forming the coating film on the upper surface of the substrate Liquid to fill the gaps in the aforementioned structure.         The substrate processing apparatus according to any one of claims 26 to 32, wherein the upper surface of the substrate immediately before the supply of the replacement liquid is a hydrophobic surface.