WO2020021903A1

WO2020021903A1 - Substrate processing method and substrate processing device

Info

Publication number: WO2020021903A1
Application number: PCT/JP2019/023720
Authority: WO
Inventors: 博史阿部; 学奥谷; 正幸尾辻; 幸史吉田
Original assignee: 株式会社Ｓｃｒｅｅｎホールディングス
Priority date: 2018-07-25
Filing date: 2019-06-14
Publication date: 2020-01-30
Also published as: JP2020017613A; TWI708339B; TW202015198A; JP7231350B2

Abstract

Provided is a method for supplying a pre-dying treatment liquid, which includes an adsorbing material to be adsorbed onto the surface of a pattern formed on a substrate, on the surface of the horizontally-held substrate and adsorbing the adsorbing material to the surface of the pattern. An adsorption film that includes the adsorbing material adsorbed to the surface of the pattern is formed along the surface of the pattern by removing the pre-dying treatment liquid of a portion on the surface of the horizontally-held substrate by the rotation of the substrate around the vertical axis of rotation. The adsorption film is removed from the surface of the substrate by changing the adsorption film to gas.

Description

Substrate processing method and substrate processing apparatus

This application claims priority based on Japanese Patent Application No. 2018-139166 filed on Jul. 25, 2018, the entire content of which is incorporated herein by reference.

The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. The substrates to be processed include, for example, semiconductor wafers, flat panel display (FPD) substrates such as liquid crystal displays and organic EL (electroluminescence) displays, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, Substrates for masks, ceramic substrates, solar cells, and the like are included.

製造 In a manufacturing process of a semiconductor device, a liquid crystal display device, and the like, processing is performed as necessary on a substrate such as a semiconductor wafer or a glass substrate for a liquid crystal display device. Such processing includes supplying a processing liquid such as a chemical liquid or a rinsing liquid to the substrate. After the processing liquid is supplied, the processing liquid is removed from the substrate, and the substrate is dried.

場合 When a pattern is formed on the surface of the substrate, when the substrate is dried, a force due to the surface tension of the processing solution attached to the substrate is applied to the pattern, and the pattern may collapse. As a countermeasure, a method of supplying a liquid having a low surface tension, such as IPA (isopropyl alcohol), to the substrate, or supplying a hydrophobizing agent for bringing the contact angle of the liquid to the pattern close to 90 degrees to the substrate is adopted. However, even when IPA or a hydrophobizing agent is used, the collapse force for collapsing the pattern does not become zero. Therefore, depending on the strength of the pattern, even if these measures are taken, the collapse of the pattern cannot be sufficiently prevented. There is.

In recent years, sublimation drying has attracted attention as a technique for preventing the collapse of patterns. For example, Patent Literature 1 discloses a substrate processing method and a substrate processing apparatus for performing sublimation drying. In sublimation drying described in Patent Document 1, a melt of a sublimable substance is supplied to the surface of a substrate, and DIW on the substrate is replaced with a melt of the sublimable substance. Thereafter, the melt of the sublimable substance on the substrate is cooled, and a solidified substance of the sublimable substance is formed. Thereafter, the solidified body of the sublimable substance on the substrate is sublimated. Thereby, the melt of the sublimable substance is removed from the substrate, and the substrate is dried.

JP 2015-146969 A

In Patent Document 1, the sublimable substance melt is solidified not only between two adjacent convex patterns but also above the pattern. Freezing point depression occurs when the liquid is placed in a very narrow space. In a substrate such as a semiconductor wafer, since the space between two adjacent patterns is narrow, the freezing point of the sublimable substance located between the patterns is lowered. Thus, the freezing point of the sublimable material located between the patterns is lower than the freezing point of the sublimable material located above the pattern.

If only the freezing point of the sublimable substance located between the patterns is low, the surface layer of the melt of the sublimable substance, that is, the liquid layer located in the range from the upper surface (liquid level) of the sublimable substance to the upper surface of the pattern, is first. And the melt of the sublimable substance located between the patterns may remain as a liquid without solidifying. In this case, an interface between a solid (solidified substance of the sublimable substance) and a liquid (melt of the sublimable substance) is formed in the vicinity of the pattern, and a collapse force that collapses the pattern may occur. If the pattern becomes more brittle due to the miniaturization of the pattern, the pattern collapses even with such a weak collapse force.

If the pattern collapses in a state where the melt of the sublimable substance located between the patterns is not solidified, the tips of two adjacent patterns may come into contact with each other. In this case, even when the solidified body of the sublimable substance is sublimated, the adhesive state in which the tips of the patterns are in contact with each other is maintained, and the pattern may not return to the vertical state. Therefore, even if sublimation drying is performed, there is a case where the collapse of the pattern cannot be sufficiently prevented depending on the strength of the pattern.

Therefore, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of reducing collapse of a pattern generated when a substrate is dried by sublimation drying and reducing the collapse rate of the pattern. It is.

In one embodiment of the present invention, a drying pretreatment liquid containing an adsorbing substance that is adsorbed on the surface of the pattern formed on the substrate is supplied to the surface of the substrate held horizontally, and the adsorption is performed on the surface of the pattern. A drying pretreatment liquid supply step of adsorbing a substance, and removing a part of the drying pretreatment liquid on the surface of the substrate held horizontally by rotating the substrate around a vertical rotation axis, A liquid removal step including a spin-off step of forming an adsorption film containing the adsorbed substance adsorbed on the surface of the pattern along the surface of the pattern; and removing the adsorption film from the surface of the substrate by changing the adsorption film to a gas. Provided is a substrate processing method including an adsorption film removing step.

According to this configuration, the pre-drying liquid containing the adsorbed substance is supplied to the surface of the substrate held horizontally. The adsorbing substance contained in the pretreatment liquid adsorbs on the surface of the pattern formed on the substrate. Then, with the adsorbed substance adsorbed on the surface of the pattern, the substrate is rotated about a vertical rotation axis while holding the substrate horizontally. As a result, the pre-drying treatment liquid is discharged from the surface of the substrate by centrifugal force, and the amount of the pre-drying treatment liquid on the surface of the substrate decreases.

(4) When the substrate is rotated at a certain rotation speed, most of the pretreatment liquid for drying is removed from the surface of the substrate, but the adsorbed substance adsorbed on the surface of the pattern remains on the substrate. Thereby, an adsorption film containing the adsorbed substance adsorbed on the surface of the pattern is formed along the surface of the pattern. In other words, the space between two adjacent patterns is not completely filled with the adsorbing film, but the surface of the pattern is coated with the adsorbing film so that the surfaces of the adsorbing film face each other in the width direction of the pattern via the space. You.

On the other hand, when the pre-drying treatment liquid on the substrate is reduced to a certain extent, the upper surface (liquid level) of the pre-drying treatment liquid moves between two adjacent convex patterns. That is, the interface between the gas and the liquid (the pre-drying treatment liquid) moves between the patterns, and the collapse force due to the surface tension of the pre-drying treatment liquid is applied to the pattern via the adsorption film. At this time, even if two adjacent patterns collapse in the direction approaching each other, at least a part of the surface of the pattern is coated with the adsorbing film, so that the two patterns are not directly in contact with each other but adsorbed. Contact through a membrane.

後 After forming the adsorption film on the surface of the pattern, the adsorption film is changed into a gas. Thereby, the adsorption film is removed from the surface of the substrate. If two adjacent patterns collapse in a direction approaching each other when removing the pre-drying treatment liquid, the adsorption film is removed from between the two patterns. If the pattern is not plastically deformed or damaged, the collapsed pattern returns to the vertical state by the restoring force of the pattern when the adsorption film is removed. In other words, even if the pattern collapses before the adsorption film is removed, the pattern returns to the vertical state after the adsorption film is removed. Thereby, not only when the pattern strength is high but also when the pattern strength is low, the final pattern collapse rate can be improved.

The pattern may be a structure formed of a single material or a structure including a plurality of layers stacked in the thickness direction of the substrate. The surface of the pattern includes a side surface that is perpendicular or substantially perpendicular to a plane of the substrate orthogonal to the thickness direction of the substrate, and a top surface that is parallel or substantially parallel to the plane of the substrate. The adsorption film is, for example, a thin film having a surface parallel or substantially parallel to the surface of the pattern. When the adsorption film is formed on the entire surface of the pattern, the surface of the adsorption film includes an upper surface parallel or substantially parallel to the upper surface of the pattern, and a side surface parallel or substantially parallel to the side surface of the pattern. Instead of the entire surface of the pattern, only a part of the surface of the pattern may be covered with the adsorption film. For example, only the upper end of the surface of the pattern including the upper end of the side surface of the pattern and the upper surface of the pattern, or only the upper surface of the pattern may be covered with the adsorption film.

In the above embodiment, at least one of the following features may be added to the substrate processing method.

The adsorbing film removing step is a pattern restoring step of restoring the shape of the collapsed pattern with a restoring force of the pattern by removing the adsorbing film from between the two collapsed patterns that are in contact with each other via the adsorption film. including.

According to this configuration, as described above, even if two adjacent patterns collapse in a direction approaching each other, the two patterns do not directly contact each other but come into contact via the adsorption film. Therefore, if the pattern is not plastically deformed or damaged, the collapsed pattern is recovered by the elastic recovery force when the adsorption film is removed. As a result, even when the pattern strength is low, the final pattern collapse rate can be improved.

前 Before removing the adsorption film, a part of the adsorption film is interposed between the two collapsed patterns. If the shape of the collapsed pattern returns to the original shape after the removal of the adsorption film, a part of the two collapsed patterns may directly contact before removing the adsorption film. Even in such a case, if the adsorption film is removed, the adhesive force for maintaining the two patterns in a collapsed state is weakened. Therefore, if the pattern is not plastically deformed or damaged, the collapsed pattern is in a vertical state due to the restoring force of the pattern. Return to

The adsorbed substance is a substance that is chemically adsorbed on the surface of the pattern.

The adsorbed substance is a substance that physically adsorbs on the surface of the pattern.

The pre-drying treatment liquid supply step, before forming the adsorption film, while stopping the rotation of the substrate, or at a rotation speed smaller than the rotation speed of the substrate when forming the adsorption film, the substrate And rotating the surface of the pattern to contact the pre-drying liquid with the surface of the pattern.

According to this configuration, before forming the adsorption film, the drying pretreatment liquid is applied to the surface of the pattern while stopping the rotation of the substrate or while maintaining the rotation speed of the substrate at a small value (adsorption acceleration speed). Make contact. Since the rotation speed of the substrate is zero or small, the flow of the pretreatment liquid at the interface between the pretreatment liquid and the surface of the pattern becomes gentle, and the adsorption of the adsorbed substance on the surface of the pattern is promoted. Thereby, more adsorbed substances can be adsorbed on the surface of the pattern.

厚み The thickness of the adsorption film is smaller than the height of the pattern.

According to this configuration, a thin adsorption film is formed on the surface of the pattern. That is, the thickness of the adsorption film is smaller than the height of the pattern. Since the adsorption film is thin, the adsorption film can be removed in a short time, and the amount of energy required for removing the adsorption film can be reduced. When the adsorption film is removed by heating, the heating time of the substrate can be shortened, so that a change in the surface of the substrate such as oxidation can be suppressed. Further, even when unnecessary substances such as residues are generated on the substrate when the adsorption film is changed to gas, the volume of the unnecessary substance is small because the volume of the adsorption film is small. Therefore, unnecessary substances can be removed in a short time. In some cases, it is not necessary to remove unnecessary matter.

The drying pretreatment liquid is a solution containing the adsorbed substance and a solvent that dissolves in the adsorbed substance.

According to this configuration, the pretreatment liquid for drying, which is a solution in which the adsorbed substance and the solvent are uniformly dissolved, is supplied to the substrate. When supplying the melt of the adsorbing substance to the substrate, if the freezing point of the adsorbing substance is equal to or higher than room temperature, it is necessary to heat the adsorbing substance to maintain the adsorbing substance in a liquid state. If the adsorbed substance is dissolved in the solvent, even if the freezing point of the adsorbed substance is higher than room temperature, if the freezing point of the dried pretreatment liquid can be made lower than room temperature due to the freezing point drop caused by mixing of the adsorbed substance and the solvent, the dried pretreated liquid can be cooled to room temperature Can be kept liquid. Therefore, energy consumption required for processing the substrate can be reduced.

(4) When the freezing point of the adsorbed substance is higher than room temperature, the freezing point of the pretreatment liquid for drying may be lower than room temperature. In this case, the drying pretreatment liquid at room temperature may be supplied to the surface of the substrate. The solvent may be a single substance or a mixed substance in which two or more substances are dissolved. In any case, the solvent may include a high vapor pressure substance having a higher vapor pressure than the adsorption substance.

The liquid removing step further includes a gas supply step of discharging gas toward the surface of the substrate when a part of the pre-drying treatment liquid on the surface of the substrate is removed by rotation of the substrate. .

According to this configuration, when a part of the pre-drying treatment liquid on the surface of the substrate is removed by rotation of the substrate, the gas is discharged toward the surface of the substrate. The pre-drying treatment liquid on the substrate is discharged from the substrate at a gas pressure. At the same time, a part of the pretreatment liquid on the substrate evaporates due to the supply of gas. This makes it possible to quickly remove the unnecessary pretreatment liquid from the surface of the substrate.

The liquid removing step is a liquid heating step of heating the pre-drying liquid on the surface of the substrate while removing a part of the pre-drying liquid on the surface of the substrate by rotating the substrate. Further included.

According to this configuration, the drying pretreatment liquid on the surface of the substrate is heated when a part of the pretreatment liquid on the surface of the substrate is removed by rotation of the substrate. Thereby, the temperature of the pre-drying treatment liquid increases, and the evaporation of the pre-drying treatment liquid is promoted. Therefore, the unnecessary pretreatment liquid for drying can be quickly removed from the surface of the substrate.

The liquid heating step is a heating gas supply step of discharging a heating gas having a higher temperature than the drying pretreatment liquid on the front surface of the substrate toward at least one of the front surface and the back surface of the substrate, A heating liquid supply step of discharging a heating liquid having a higher temperature than the drying pretreatment liquid toward the back surface of the substrate, and a heating member having a temperature higher than the drying pretreatment liquid on the front surface of the substrate being separated from the substrate; A proximity heating step of arranging the substrate on the front side or the back side thereof, a contact heating step of bringing a heating member having a higher temperature than the drying pretreatment liquid on the surface of the substrate into contact with the back side of the substrate, Irradiating the drying pretreatment liquid on the surface with light. The light irradiation step is a whole irradiation step of simultaneously irradiating the entire surface of the substrate with light, or the irradiation region while irradiating light only to an irradiation region representing a partial region in the surface of the substrate. The method may include a partial irradiation step of moving within the surface of the substrate, or may include both the entire irradiation step and the partial irradiation step.

The adsorbing film removing step, a sublimation step of sublimating the adsorbing film, a decomposition step of changing the adsorbing film from a solid or a liquid to a gas by decomposition (for example, thermal decomposition or photolysis) of the adsorbing film; (For example, an oxidation reaction), the method may include at least one of a reaction step of changing the adsorption film from a solid or a liquid to a gas and a plasma irradiation step of irradiating the adsorption film with plasma.

The sublimation step includes a substrate rotation step of rotating the substrate about a vertical rotation axis while holding the substrate horizontally, a gas supply step of blowing a gas such as an inert gas or air onto the adsorption film, and heating the adsorption film. Heating step, pressure reducing step of reducing the pressure of the atmosphere in contact with the adsorption film, light irradiation step of irradiating the adsorption film with light, and ultrasonic vibration applying step of applying ultrasonic vibration to the adsorption film, At least one of them may be included. The decomposition step may include at least one of the heating step, the light irradiation step, and the ultrasonic vibration applying step. The reaction step may include an oxidation step of oxidizing the adsorption film by bringing an active gas such as ozone gas into contact with the adsorption film.

Another embodiment of the present invention is to supply a drying pretreatment liquid containing an adsorbing substance to be adsorbed on the surface of the pattern formed on the substrate to the surface of the substrate that is held horizontally, A drying pretreatment liquid supply unit for adsorbing the adsorbed substance, and removing a part of the drying pretreatment liquid on the surface of the substrate held horizontally by rotating the substrate around a vertical rotation axis. A liquid removal unit including a spin-off unit that forms an adsorption film containing the adsorbed substance adsorbed on the surface of the pattern along the surface of the pattern, and changing the adsorption film to gas from the surface of the substrate. A substrate processing apparatus including an adsorption film removing unit for removing the substrate. According to this configuration, the same effect as the above-described effect can be obtained.

The above or other objects, features, and effects of the present invention will be apparent from the following description of embodiments with reference to the accompanying drawings.

FIG. 1 is a schematic view of a substrate processing apparatus according to a first embodiment of the present invention as viewed from above. It is the schematic diagram which looked at the substrate processing apparatus from the side. It is the mimetic diagram which looked at the inside of the wet processing unit provided in the substrate processing device horizontally. FIG. 3 is a schematic view of the inside of a dry processing unit provided in the substrate processing apparatus, viewed horizontally. It is a block diagram showing hardware of a control equipment. FIG. 4 is a process chart for describing an example of substrate processing performed by the substrate processing apparatus. FIG. 6 is a schematic diagram illustrating a state of the substrate when the processing illustrated in FIG. 5 is performed. FIG. 6 is a schematic diagram illustrating a state of the substrate when the processing illustrated in FIG. 5 is performed. FIG. 6 is a schematic diagram illustrating a state of the substrate when the processing illustrated in FIG. 5 is performed. FIG. 6 is a schematic diagram illustrating a state of the substrate when the processing illustrated in FIG. 5 is performed. It is the mimetic diagram which looked horizontally at the spin chuck, a blocking member, and a hot plate concerning a 2nd embodiment of the present invention. It is the schematic diagram which looked at the spin chuck and hot plate which concerns on 2nd Embodiment of this invention from the upper part. It is the mimetic diagram which looked horizontally at a spin chuck, a blocking member, and a hot plate when a liquid removal process is performed. FIG. 4 is a schematic view of a spin chuck, a blocking member, and a hot plate viewed horizontally when an adsorption film removing step is being performed. 9 is a table for describing processing examples 1 to 5; It is a schematic diagram which shows the state of the board | substrate when HFE on a board | substrate is replaced by the pre-drying process liquid. It is a schematic diagram which shows the cross section of the adsorption film | membrane which contacts only the upper end part of the surface of a pattern. FIG. 11B is a schematic diagram illustrating a state of the adsorption film when the pattern illustrated in FIG. 11A collapses. FIG. 3 is a schematic diagram showing a state where the electromagnetic wave generator irradiates only a partial area on the upper surface of the substrate with the electromagnetic wave. It is a schematic diagram which shows the state in which the electromagnetic wave generator irradiates an electromagnetic wave to the whole area | region of the upper surface of a board | substrate simultaneously. FIG. 3 is a schematic diagram illustrating a state in which an active gas supply device supplies an active gas to a substrate.

In the following description, it is assumed that the atmospheric pressure in the substrate processing apparatus 1 is maintained at the atmospheric pressure in the clean room in which the substrate processing apparatus 1 is installed (for example, 1 atm or a value near the atmospheric pressure), unless otherwise specified. .

FIG. 1A is a schematic view of the substrate processing apparatus 1 according to the first embodiment of the present invention as viewed from above. FIG. 1B is a schematic view of the substrate processing apparatus 1 as viewed from the side.

As shown in FIG. 1A, the substrate processing apparatus 1 is a single-wafer processing apparatus that processes a disk-shaped substrate W such as a semiconductor wafer one by one. The substrate processing apparatus 1 includes a load port LP that holds a carrier C containing a substrate W, a plurality of processing units 2 that process the substrate W transported from the carrier C on the load port LP, and a carrier on the load port LP. A transfer robot that transfers the substrate W between C and the processing unit 2 and a control device 3 that controls the substrate processing apparatus 1 are provided.

The transfer robot includes an indexer robot IR for loading and unloading the substrate W to and from the carrier C on the load port LP, and a center robot CR for loading and unloading the substrate W to and from the plurality of processing units 2. The indexer robot IR transports the substrate W between the load port LP and the center robot CR, and the center robot CR transports the substrate W between the indexer robot IR and the processing unit 2. The center robot CR includes a hand H1 that supports the substrate W, and the indexer robot IR includes a hand H2 that supports the substrate W.

(4) The plurality of processing units 2 form a plurality of towers TW arranged around the center robot CR in plan view. FIG. 1A shows an example in which four towers TW are formed. The center robot CR can access any of the towers TW. As shown in FIG. 1B, each tower TW includes a plurality (for example, three) of processing units 2 stacked vertically.

The plurality of processing units 2 include a wet processing unit 2w for processing the substrate W with a processing liquid such as a chemical solution or a rinsing liquid, and a dry processing unit 2d for processing the substrate W without supplying a processing liquid. The wet processing unit 2w and the dry processing unit 2d may be included in the same tower TW, or may be included in separate towers TW. 1A and 1B show an example in which the uppermost processing unit 2 of each tower TW is a dry processing unit 2d, and the other processing units 2 are wet processing units 2w.

FIG. 2 is a schematic view of the inside of the wet processing unit 2w provided in the substrate processing apparatus 1 as viewed horizontally.

The wet processing unit 2w includes a box-shaped chamber 4 having an internal space, and a spin chuck that rotates around a vertical rotation axis A1 passing through the center of the substrate W while horizontally holding one substrate W in the chamber 4. 10 and a cylindrical processing cup 21 surrounding the spin chuck 10 around the rotation axis A1.

The chamber 4 includes a box-shaped partition wall 5 provided with a loading / unloading port 5b through which the substrate W passes, and a shutter 7 for opening and closing the loading / unloading port 5b. The FFU 6 (fan filter unit) is arranged on a blower port 5 a provided above the partition wall 5. The FFU 6 always supplies clean air (air filtered by a filter) to the inside of the chamber 4 from the blower port 5a. The gas in the chamber 4 is exhausted from the chamber 4 through an exhaust duct 8 connected to the bottom of the processing cup 21. Thereby, a down flow of clean air is always formed in the chamber 4. The flow rate of the exhaust gas discharged to the exhaust duct 8 is changed according to the opening of the exhaust valve 9 arranged in the exhaust duct 8.

The spin chuck 10 includes a disk-shaped spin base 12 held in a horizontal position, a plurality of chuck pins 11 for holding the substrate W in a horizontal position above the spin base 12, and a central portion of the spin base 12. It includes a spin shaft 13 extending downward, and a spin motor 14 that rotates the spin base 12 and the plurality of chuck pins 11 by rotating the spin shaft 13. The spin chuck 10 is not limited to a sandwich type chuck in which the plurality of chuck pins 11 are brought into contact with the outer peripheral surface of the substrate W, and causes the back surface (lower surface) of the substrate W, which is a non-device formation surface, to be attracted to the upper surface 12 u of the spin base 12. Thus, a vacuum-type chuck that holds the substrate W horizontally may be used.

The processing cup 21 includes a plurality of guards 24 for receiving the processing liquid discharged outward from the substrate W, a plurality of cups 23 for receiving the processing liquid guided downward by the plurality of guards 24, a plurality of guards 24 and a plurality of guards. And a cylindrical outer wall member 22 surrounding the cup 23. FIG. 2 shows an example in which four guards 24 and three cups 23 are provided, and the outermost cup 23 is integrated with the third guard 24 from the top.

The guard 24 includes a cylindrical portion 25 surrounding the spin chuck 10 and an annular ceiling portion 26 extending obliquely upward from the upper end of the cylindrical portion 25 toward the rotation axis A1. The plurality of ceiling portions 26 are vertically overlapped, and the plurality of cylindrical portions 25 are arranged concentrically. The annular upper end of the ceiling 26 corresponds to the upper end 24u of the guard 24 surrounding the substrate W and the spin base 12 in plan view. The plurality of cups 23 are arranged below the plurality of cylindrical portions 25, respectively. The cup 23 has an annular liquid receiving groove for receiving the processing liquid guided downward by the guard 24.

The wet processing unit 2w includes a guard elevating unit 27 for individually elevating and lowering a plurality of guards 24. The guard elevating unit 27 positions the guard 24 at an arbitrary position from the upper position to the lower position. FIG. 2 shows a state in which two guards 24 are arranged at the upper position and the remaining two guards 24 are arranged at the lower position. The upper position is a position where the upper end 24u of the guard 24 is located above the holding position where the substrate W held by the spin chuck 10 is located. The lower position is a position where the upper end 24u of the guard 24 is disposed below the holding position.

(4) When supplying the processing liquid to the rotating substrate W, at least one guard 24 is arranged at the upper position. In this state, when the processing liquid is supplied to the substrate W, the processing liquid is shaken off the substrate W by centrifugal force. The processing liquid shaken off collides with the inner surface of the guard 24 horizontally facing the substrate W, and is guided to the cup 23 corresponding to the guard 24. Thus, the processing liquid discharged from the substrate W is collected in the processing cup 21.

The wet processing unit 2w includes a plurality of nozzles for discharging a processing liquid toward the substrate W held by the spin chuck 10. The plurality of nozzles include a chemical liquid nozzle 31 for discharging a chemical liquid toward the upper surface of the substrate W, a rinsing liquid nozzle 35 for discharging a rinsing liquid toward the upper surface of the substrate W, and a pre-drying processing liquid toward the upper surface of the substrate W. And a replacement liquid nozzle 43 that discharges a replacement liquid toward the upper surface of the substrate W.

The chemical liquid nozzle 31 may be a scan nozzle that can move horizontally in the chamber 4 or a fixed nozzle fixed to the partition 5 of the chamber 4. The same applies to the rinsing liquid nozzle 35, the pre-drying processing liquid nozzle 39, and the replacement liquid nozzle 43. In FIG. 2, the chemical liquid nozzle 31, the rinsing liquid nozzle 35, the pre-drying processing liquid nozzle 39, and the replacement liquid nozzle 43 are scan nozzles, and four nozzle moving units respectively corresponding to these four nozzles are provided. An example is shown.

The chemical liquid nozzle 31 is connected to a chemical liquid pipe 32 for guiding the chemical liquid to the chemical liquid nozzle 31. When the chemical liquid valve 33 interposed in the chemical liquid pipe 32 is opened, the chemical liquid is continuously discharged downward from the discharge port of the chemical liquid nozzle 31. The chemical discharged from the chemical nozzle 31 includes sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, aqueous ammonia, aqueous hydrogen peroxide, an organic acid (for example, citric acid, oxalic acid, etc.), and an organic alkali (for example, TMAH: It may be a liquid containing at least one of tetramethylammonium hydroxide, a surfactant, and a corrosion inhibitor, or may be another liquid.

Although not shown, the chemical liquid valve 33 includes a valve body provided with an internal flow path through which a chemical liquid flows and an annular valve seat surrounding the internal flow path, a valve body movable with respect to the valve seat, and a valve body. An actuator for moving the valve body between a closed position in contact with the valve seat and an open position where the valve body is away from the valve seat. The same applies to other valves. The actuator may be a pneumatic actuator or an electric actuator, or may be another actuator. The control device 3 opens and closes the chemical liquid valve 33 by controlling the actuator.

The chemical liquid nozzle 31 is connected to a nozzle moving unit 34 that moves the chemical liquid nozzle 31 in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 34 moves the chemical solution between the processing position where the chemical solution discharged from the chemical solution nozzle 31 lands on the upper surface of the substrate W and the standby position where the chemical solution nozzle 31 is positioned around the processing cup 21 in plan view. The nozzle 31 is moved horizontally.

The rinsing liquid nozzle 35 is connected to a rinsing liquid pipe 36 for guiding the rinsing liquid to the rinsing liquid nozzle 35. When the rinse liquid valve 37 interposed in the rinse liquid pipe 36 is opened, the rinse liquid is continuously discharged downward from the discharge port of the rinse liquid nozzle 35. The rinsing liquid discharged from the rinsing liquid nozzle 35 is, for example, pure water (deionized water: DIW (Deionized Water)). The rinsing liquid may be any of carbonated water, electrolytic ionic water, hydrogen water, ozone water, and hydrochloric acid water having a dilute concentration (for example, about 10 to 100 ppm).

The rinse liquid nozzle 35 is connected to a nozzle moving unit 38 that moves the rinse liquid nozzle 35 in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 38 includes a processing position where the rinsing liquid discharged from the rinsing liquid nozzle 35 lands on the upper surface of the substrate W, and a standby position where the rinsing liquid nozzle 35 is positioned around the processing cup 21 in plan view. The rinse liquid nozzle 35 is moved horizontally between them.

(4) The pre-drying treatment liquid nozzle 39 is connected to a pre-drying treatment liquid pipe 40 that guides the pre-drying treatment liquid to the pre-drying treatment liquid nozzle 39. When the pre-drying treatment liquid valve 41 interposed in the pre-drying treatment liquid pipe 40 is opened, the pre-drying treatment liquid is continuously discharged downward from the discharge port of the pre-drying treatment liquid nozzle 39. Similarly, the replacement liquid nozzle 43 is connected to a replacement liquid pipe 44 that guides the replacement liquid to the replacement liquid nozzle 43. When the replacement liquid valve 45 interposed in the replacement liquid pipe 44 is opened, the replacement liquid is continuously discharged downward from the discharge port of the replacement liquid nozzle 43.

(4) The pre-drying treatment liquid contains an adsorbed substance adsorbed on the surface of the pattern P1 (see FIG. 6A) and a dissolved substance that is soluble in the adsorbed substance. The drying pretreatment liquid is a solution in which the adsorbed substance and the dissolved substance are uniformly dissolved. The adsorbed substance corresponds to a solute, and the dissolved substance corresponds to a solvent. The drying pretreatment liquid may be a melt of the adsorbed substance.

(4) The freezing point of the drying pretreatment liquid (freezing point at 1 atm. The same applies hereinafter) is lower than the freezing point of the adsorbed substance. Similarly, the freezing point of the dissolved material is lower than the freezing point of the adsorbed material. The freezing point of the drying pretreatment liquid is lower than room temperature (23 ° C. or a value close thereto). The substrate processing apparatus 1 is disposed in a clean room maintained at room temperature. Therefore, the pre-drying treatment liquid can be maintained in a liquid state without heating the pre-drying treatment liquid. However, the freezing point of the drying pretreatment liquid may be higher than room temperature, and the freezing point of the dissolved substance may be higher than the freezing point of the adsorbed substance.

The dissolved substance may be a single substance or a mixed substance in which two or more substances are dissolved. The vapor pressure of the dissolved substance is higher than the vapor pressure of the adsorbed substance. Therefore, dissolved substances evaporate more easily than adsorbed substances. The vapor pressure of the dissolved substance may be higher or lower than the vapor pressure of water. Further, the vapor pressure of the dissolved substance may be lower than the vapor pressure of the adsorbed substance.

The adsorbed substance may be a substance that is chemically adsorbed on the surface of the pattern P1. That is, the adsorbed substance may be a substance that is adsorbed on the surface of the pattern P1 by a chemical reaction between the adsorbed substance and the surface of the pattern P1. Alternatively, the adsorbing substance may be a substance that physically adsorbs on the surface of the pattern P1. That is, the adsorbed substance may be a substance that is adsorbed on the surface of the pattern P1 by an electric attractive force or an intermolecular force generated between the adsorbed substance and the surface of the pattern P1.

The adsorbed substance may be a sublimable substance that changes from a solid to a gas without passing through a liquid at normal temperature or normal pressure, or may be a substance other than the sublimable substance. For example, the adsorbent may be an iodine compound, a chlorine compound, or a bromide compound. Iodine compounds include diiodomethane, iodomethane, and 1-iodopropane. Chlorine compounds include dichloromethane. The bromide compound includes ammonium bromide. The adsorbing substance may be a thermally decomposable polymer such as an acrylic resin or an inorganic compound. The adsorbent may be an amphipathic molecule containing both hydrophilic and hydrophobic groups.

溶解 Similarly to the adsorption substance, the dissolved substance may be a sublimable substance or a substance other than the sublimable substance. The types of sublimable substances contained in the pretreatment liquid for drying may be two or more. That is, both the adsorbed substance and the dissolved substance may be sublimable substances, and a sublimable substance different in type from the adsorbed substance and the dissolved substance may be contained in the drying pretreatment liquid.

Sublimable substances include, for example, alcohols such as 2-methyl-2-propanol (alias: tert-butyl alcohol, t-butyl alcohol, tert-butyl alcohol) and cyclohexanol, fluorinated hydrocarbon compounds, 1,3, It may be any of 5-trioxane (alias: metaformaldehyde), camphor (alias: camphor, camphor), naphthalene, iodine, and cyclohexane, or a substance other than these.

Examples of the solvent include pure water, IPA, HFE (hydrofluoroether), acetone, PGMEA (propylene glycol monomethyl ether acetate), PGEE (propylene glycol monoethyl ether, 1-ethoxy-2-propanol), ethylene glycol, At least one selected from the group consisting of hydrofluorocarbons may be used. Alternatively, the sublimable substance may be a solvent. IPA and HFE are substances having a lower surface tension than water and a higher vapor pressure than water.

Hereinafter, an example will be described in which the dissolved substance corresponding to the solvent is a mixed solution of IPA and pure water, and the adsorbed substance corresponding to the solute is an iodine compound or a chlorine compound. The mass percent concentrations of IPA (IPA having a purity of 99.9 wt% or more), pure water, and an adsorbent contained in the pretreatment liquid are less than 50 wt%, less than 50 wt%, and less than 1 wt%, respectively. However, the concentration of each component is not limited to this.

(4) As described later, the replacement liquid is supplied to the upper surface of the substrate W covered with the rinse liquid film, and the pre-drying treatment liquid is supplied to the upper surface of the substrate W covered with the liquid film of the replacement liquid. The replacement liquid is a liquid that is compatible with both the rinsing liquid and the pre-drying liquid. The replacement liquid is, for example, IPA. IPA is a liquid that is compatible with both water and fluorohydrocarbon compounds. The replacement liquid may be a mixture of IPA and HFE.

When supplying a mixed solution of IPA and HFE to the substrate W, a first solvent pipe for guiding IPA as a first organic solvent and a second solvent pipe for guiding HFE as a second organic solvent are replaced with a replacement liquid pipe. 44. When one of the first solvent valve interposed in the first solvent pipe and the second solvent valve interposed in the second solvent pipe is opened, IPA or HFE is supplied to the replacement liquid pipe 44, and the first solvent valve and When both of the second solvent valves are opened, a mixed solution of IPA and HFE is supplied to the replacement solution pipe 44. HFE may be discharged to a nozzle different from the replacement liquid nozzle 43.

When the replacement liquid is supplied to the upper surface of the substrate W covered with the rinsing liquid film, most of the rinsing liquid on the substrate W is washed away by the replacement liquid and discharged from the substrate W. The remaining trace amount of the rinse solution dissolves in the replacement solution and diffuses into the replacement solution. The diffused rinsing liquid is discharged from the substrate W together with the replacement liquid. Therefore, the rinsing liquid on the substrate W can be efficiently replaced with the replacement liquid. For the same reason, the replacement liquid on the substrate W can be efficiently replaced with the pre-drying treatment liquid. Thereby, the rinsing liquid contained in the pre-drying treatment liquid on the substrate W can be reduced.

(4) The pre-drying treatment liquid nozzle 39 is connected to a nozzle moving unit 42 that moves the pre-drying treatment liquid nozzle 39 in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 42 has a processing position where the pre-drying processing liquid discharged from the pre-drying processing liquid nozzle 39 lands on the upper surface of the substrate W, and a position where the pre-drying processing liquid nozzle 39 is positioned around the processing cup 21 in plan view. The drying pretreatment liquid nozzle 39 is moved horizontally between the standby position to be processed.

Similarly, the replacement liquid nozzle 43 is connected to a nozzle moving unit 46 that moves the replacement liquid nozzle 43 in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 46 includes a processing position where the replacement liquid discharged from the replacement liquid nozzle 43 lands on the upper surface of the substrate W, and a standby position where the replacement liquid nozzle 43 is positioned around the processing cup 21 in a plan view. The replacement liquid nozzle 43 is moved horizontally between them.

The wet processing unit 2 w includes a blocking member 51 disposed above the spin chuck 10. FIG. 2 shows an example in which the blocking member 51 is a disk-shaped blocking plate. The blocking member 51 includes a disk portion 52 horizontally arranged above the spin chuck 10. The blocking member 51 is horizontally supported by a cylindrical support shaft 53 extending upward from the center of the disk portion 52. The center line of the disk portion 52 is arranged on the rotation axis A1 of the substrate W. The lower surface of the disk portion 52 corresponds to the lower surface 51L of the blocking member 51. The lower surface 51L of the blocking member 51 is a facing surface facing the upper surface of the substrate W. The lower surface 51L of the blocking member 51 is parallel to the upper surface of the substrate W and has an outer diameter equal to or larger than the diameter of the substrate W.

The blocking member 51 is connected to a blocking member elevating unit 54 that vertically moves the blocking member 51 up and down. The blocking member elevating unit 54 positions the blocking member 51 at an arbitrary position from the upper position (the position shown in FIG. 2) to the lower position. The lower position is a proximity position where the lower surface 51L of the blocking member 51 approaches the upper surface of the substrate W to a height at which a scan nozzle such as the chemical nozzle 31 cannot enter between the substrate W and the blocking member 51. The upper position is a separated position where the blocking member 51 is retracted to a height at which the scan nozzle can enter between the blocking member 51 and the substrate W.

The plurality of nozzles include a central nozzle 55 that discharges a processing fluid, such as a processing liquid or a processing gas, downward through an upper central opening 61 that opens at the center of the lower surface 51L of the blocking member 51. The center nozzle 55 extends vertically along the rotation axis A1. The center nozzle 55 is disposed in a through hole vertically penetrating the center of the blocking member 51. The inner peripheral surface of the blocking member 51 surrounds the outer peripheral surface of the central nozzle 55 at intervals in the radial direction (the direction orthogonal to the rotation axis A1). The center nozzle 55 moves up and down together with the blocking member 51. The discharge port of the center nozzle 55 that discharges the processing liquid is disposed above the upper central opening 61 of the blocking member 51.

The center nozzle 55 is connected to an upper gas pipe 56 for guiding the inert gas to the center nozzle 55. The substrate processing apparatus 1 may include an upper temperature controller 59 for heating or cooling the inert gas discharged from the central nozzle 55. When the upper gas valve 57 interposed in the upper gas pipe 56 is opened, the inert gas is discharged from the center nozzle 55 at a flow rate corresponding to the opening degree of the flow control valve 58 for changing the flow rate of the inert gas. Is continuously discharged downward. The inert gas discharged from the center nozzle 55 is a nitrogen gas. The inert gas may be a gas other than nitrogen gas such as helium gas or argon gas.

内 The inner peripheral surface of the blocking member 51 and the outer peripheral surface of the center nozzle 55 form a cylindrical upper gas flow path 62 extending vertically. The upper gas passage 62 is connected to an upper gas pipe 63 that guides the inert gas to the upper central opening 61 of the blocking member 51. The substrate processing apparatus 1 may include an upper temperature controller 66 for heating or cooling the inert gas discharged from the upper central opening 61 of the blocking member 51. When the upper gas valve 64 interposed in the upper gas pipe 63 is opened, the inert gas flows in the upper center of the shut-off member 51 at a flow rate corresponding to the opening of the flow control valve 65 for changing the flow rate of the inert gas. The liquid is continuously discharged downward from the opening 61. The inert gas discharged from the upper central opening 61 of the blocking member 51 is a nitrogen gas. The inert gas may be a gas other than nitrogen gas such as helium gas or argon gas.

The plurality of nozzles include a lower surface nozzle 71 that discharges the processing liquid toward the center of the lower surface of the substrate W. The lower surface nozzle 71 includes a nozzle disk portion disposed between the upper surface 12u of the spin base 12 and the lower surface of the substrate W, and a nozzle tubular portion extending downward from the nozzle disk portion. The discharge port of the lower nozzle 71 is open at the center of the upper surface of the nozzle disk. When the substrate W is held by the spin chuck 10, the ejection port of the lower surface nozzle 71 vertically faces the central portion of the lower surface of the substrate W.

The lower nozzle 71 is connected to a heating fluid pipe 72 that guides hot water (pure water higher than room temperature), which is an example of a heating fluid, to the lower nozzle 71. Pure water supplied to the lower nozzle 71 is heated by a lower heater 75 interposed in a heating fluid pipe 72. When the heating fluid valve 73 interposed in the heating fluid pipe 72 is opened, the hot water continuously flows upward from the discharge port of the lower surface nozzle 71 at a flow rate corresponding to the opening of the flow rate adjustment valve 74 that changes the flow rate of the hot water. Is discharged. Thereby, the warm water is supplied to the lower surface of the substrate W.

The lower nozzle 71 is further connected to a cooling fluid pipe 76 that guides cold water (pure water having a temperature lower than room temperature), which is an example of a cooling fluid, to the lower nozzle 71. The pure water supplied to the lower nozzle 71 is cooled by a cooler 79 interposed in the cooling fluid pipe 76. When the cooling fluid valve 77 interposed in the cooling fluid pipe 76 is opened, the cold water continuously flows upward from the discharge port of the lower surface nozzle 71 at a flow rate corresponding to the opening of the flow rate adjustment valve 78 that changes the flow rate of the cold water. Is discharged. Thereby, the cold water is supplied to the lower surface of the substrate W.

The outer peripheral surface of the lower nozzle 71 and the inner peripheral surface of the spin base 12 form a cylindrical lower gas flow path 82 extending vertically. The lower gas flow path 82 includes a lower central opening 81 that opens at the center of the upper surface 12u of the spin base 12. The lower gas flow path 82 is connected to a lower gas pipe 83 that guides an inert gas to a lower central opening 81 of the spin base 12. The substrate processing apparatus 1 may include a lower temperature controller 86 that heats or cools the inert gas discharged from the lower center opening 81 of the spin base 12. When the lower gas valve 84 interposed in the lower gas pipe 83 is opened, the inert gas flows at the lower center of the spin base 12 at a flow rate corresponding to the opening of the flow rate adjustment valve 85 for changing the flow rate of the inert gas. The liquid is continuously discharged upward from the opening 81.

The inert gas discharged from the lower center opening 81 of the spin base 12 is a nitrogen gas. The inert gas may be a gas other than nitrogen gas such as helium gas or argon gas. When the substrate W is held by the spin chuck 10 and the lower central opening 81 of the spin base 12 discharges nitrogen gas, the nitrogen gas flows between the lower surface of the substrate W and the upper surface 12u of the spin base 12 in all directions. Flows radially. Thereby, the space between the substrate W and the spin base 12 is filled with the nitrogen gas.

FIG. 3 is a schematic view of the inside of the dry processing unit 2d provided in the substrate processing apparatus 1 as viewed horizontally.

The dry processing unit 2d includes a box-shaped chamber 4 having an internal space, and a heating unit 91 for heating the substrate W in the chamber 4. The heating unit 91 includes a hot plate 92 for horizontally supporting and heating the substrate W, a plurality of lift pins 97 for horizontally supporting the substrate W above the hot plate 92, and a lift elevating unit 98 for vertically moving the plurality of lift pins 97. And

The hot plate 92 is an example of a heating member that heats the substrate W. The hot plate 92 includes a heating element 93 that generates Joule heat when energized, and an outer case 94 that horizontally supports the substrate W and houses the heating element 93. The heating element 93 and the outer case 94 are arranged below the substrate W. The heating element 93 is connected to a wiring (not shown) that supplies power to the heating element 93. The temperature of the heating element 93 is changed by the control device 3. When the control device 3 causes the heating element 93 to generate heat, the entire substrate W is uniformly heated.

The outer case 94 of the hot plate 92 includes a disc-shaped base portion 95 disposed below the substrate W, and a plurality of hemispherical protrusions 96 protruding upward from the upper surface of the base portion 95. The upper surface of the base portion 95 is parallel to the lower surface of the substrate W, and has an outer diameter equal to or larger than the outer diameter of the substrate W. The plurality of protrusions 96 contact the lower surface of the substrate W at a position separated upward from the upper surface of the base portion 95. The plurality of protrusions 96 are arranged at a plurality of positions on the upper surface of the base 95 so that the substrate W is supported horizontally. The substrate W is supported horizontally with the lower surface of the substrate W separated upward from the upper surface of the base portion 95.

The plurality of lift pins 97 are inserted into the plurality of through holes penetrating the hot plate 92, respectively. The lift pins 97 include hemispherical upper ends that come into contact with the lower surface of the substrate W. The upper ends of the plurality of lift pins 97 are arranged at the same height. The lift elevating unit 98 includes an upper position where the upper ends of the plurality of lift pins 97 are located above the hot plate 92 (a position indicated by a two-dot chain line in FIG. 3), and an upper end of the plurality of lift pins 97 which corresponds to the hot plate 92. The plurality of lift pins 97 are moved in the vertical direction between the retracted lower position (the position indicated by the solid line in FIG. 3).

FIG. 4 is a block diagram showing hardware of the control device 3.

The control device 3 is a computer including a computer main body 3a and a peripheral device 3d connected to the computer main body 3a. The computer main body 3a includes a CPU 3b (central processing unit) for executing various instructions, and a main storage device 3c for storing information. The peripheral device 3d includes an auxiliary storage device 3e that stores information such as a program P, a reading device 3f that reads information from the removable medium M, and a communication device 3g that communicates with another device such as a host computer.

The control device 3 is connected to the input device and the display device. The input device is operated when an operator such as a user or a maintenance person inputs information to the substrate processing apparatus 1. The information is displayed on the screen of the display device. The input device may be any of a keyboard, a pointing device, and a touch panel, or may be other devices. A touch panel display serving also as an input device and a display device may be provided in the substrate processing apparatus 1.

(4) The CPU 3b executes the program P stored in the auxiliary storage device 3e. The program P in the auxiliary storage device 3e may be installed in the control device 3 in advance, or may be sent from the removable medium M to the auxiliary storage device 3e through the reading device 3f, It may be transmitted from an external device such as a host computer to the auxiliary storage device 3e through the communication device 3g.

The auxiliary storage device 3e and the removable medium M are non-volatile memories that retain data even when power is not supplied. The auxiliary storage device 3e is, for example, a magnetic storage device such as a hard disk drive. The removable medium M is, for example, an optical disk such as a compact disk or a semiconductor memory such as a memory card. The removable medium M is an example of a computer-readable recording medium on which the program P is recorded. The removable medium M is a non-transitory tangible recording medium (non-transitory / tangible / recording / medium).

The auxiliary storage device 3e stores a plurality of recipes. The recipe is information that defines processing contents, processing conditions, and processing procedures for the substrate W. The plurality of recipes differ from each other in at least one of the processing content, processing conditions, and processing procedure of the substrate W. The control device 3 controls the substrate processing apparatus 1 so that the substrate W is processed according to the recipe specified by the host computer. The following steps are executed by the control device 3 controlling the substrate processing apparatus 1. In other words, the control device 3 is programmed to execute the following steps.

Next, an example of processing of the substrate W will be described.

The substrate W to be processed is, for example, a semiconductor wafer such as a silicon wafer. The surface of the substrate W corresponds to a device formation surface on which devices such as transistors and capacitors are formed. The substrate W may be a substrate W on which a pattern P1 (see FIG. 6A) is formed on the surface of the substrate W, which is a pattern formation surface, or a substrate W on which the pattern P1 is not formed on the surface of the substrate W. You may. In the latter case, the pattern P1 may be formed in a chemical solution supply step described later.

FIG. 5 is a process chart for explaining an example of the processing of the substrate W performed by the substrate processing apparatus 1. 6A to 6D are schematic diagrams showing the state of the substrate W when the processing shown in FIG. 5 is being performed. In the following, reference is made to FIG. 2, FIG. 3, and FIG. 6A to 6D will be referred to as appropriate.

(4) When the substrate W is processed by the substrate processing apparatus 1, a loading step (step S1 in FIG. 5) for loading the substrate W into the wet processing unit 2w is performed.

Specifically, in a state where the blocking member 51 is located at the upper position, all the guards 24 are located at the lower position, and all the scan nozzles are located at the standby position, the center robot CR (FIG. 1A) moves the hand H1 into the wet processing unit 2w while supporting the substrate W with the hand H1. Then, the center robot CR places the substrate W on the hand H1 on the plurality of chuck pins 11 with the surface of the substrate W facing upward. Thereafter, the plurality of chuck pins 11 are pressed against the outer peripheral surface of the substrate W, and the substrate W is gripped. After placing the substrate W on the spin chuck 10, the center robot CR retracts the hand H1 from inside the wet processing unit 2w.

Next, the upper gas valve 64 and the lower gas valve 84 are opened, and the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the spin base 12 start discharging nitrogen gas. Thereby, the space between the substrate W and the blocking member 51 is filled with the nitrogen gas. Similarly, the space between the substrate W and the spin base 12 is filled with nitrogen gas. Meanwhile, the guard elevating unit 27 raises at least one guard 24 from the lower position to the upper position. Thereafter, the spin motor 14 is driven, and the rotation of the substrate W is started (Step S2 in FIG. 5). Thereby, the substrate W rotates at the liquid supply speed.

Next, a chemical solution supply step (step S3 in FIG. 5) of supplying the chemical solution to the upper surface of the substrate W and forming a liquid film of the chemical solution covering the entire upper surface of the substrate W is performed.

Specifically, the nozzle moving unit 34 moves the chemical solution nozzle 31 from the standby position to the processing position in a state where the blocking member 51 is located at the upper position and at least one guard 24 is located at the upper position. . Thereafter, the chemical liquid valve 33 is opened, and the chemical liquid nozzle 31 starts discharging the chemical liquid. When a predetermined time elapses after the chemical liquid valve 33 is opened, the chemical liquid valve 33 is closed, and the discharge of the chemical liquid is stopped. Thereafter, the nozzle moving unit 34 moves the chemical liquid nozzle 31 to the standby position.

(4) The chemical liquid discharged from the chemical liquid nozzle 31 lands on the upper surface of the substrate W rotating at the liquid supply speed, and then flows outward along the upper surface of the substrate W by centrifugal force. Therefore, the chemical solution is supplied to the entire upper surface of the substrate W, and a liquid film of the chemical solution covering the entire upper surface of the substrate W is formed. When the chemical liquid nozzle 31 is discharging the chemical liquid, the nozzle moving unit 34 may move the liquid landing position so that the liquid landing position on the upper surface of the substrate W passes through the central portion and the outer peripheral portion, The liquid landing position may be stationary at the center.

Next, a rinsing liquid supply step (step S4 in FIG. 5) of supplying pure water, which is an example of a rinsing liquid, to the upper surface of the substrate W to wash out the chemical liquid on the substrate W.

Specifically, the nozzle moving unit 38 moves the rinse liquid nozzle 35 from the standby position to the processing position with the blocking member 51 positioned at the upper position and at least one guard 24 positioned at the upper position. Let it. Thereafter, the rinsing liquid valve 37 is opened, and the rinsing liquid nozzle 35 starts discharging the rinsing liquid. Before the discharge of pure water is started, the guard elevating unit 27 may move at least one guard 24 vertically in order to switch the guard 24 that receives the liquid discharged from the substrate W. When a predetermined time has elapsed since the opening of the rinse liquid valve 37, the rinse liquid valve 37 is closed, and the discharge of the rinse liquid is stopped. Thereafter, the nozzle moving unit 38 moves the rinse liquid nozzle 35 to the standby position.

(4) The pure water discharged from the rinsing liquid nozzle 35 lands on the upper surface of the substrate W rotating at the liquid supply speed, and then flows outward along the upper surface of the substrate W by centrifugal force. The chemical on the substrate W is replaced with pure water discharged from the rinse liquid nozzle 35. As a result, a liquid film of pure water covering the entire upper surface of the substrate W is formed. When the rinsing liquid nozzle 35 is discharging pure water, the nozzle moving unit 38 may move the liquid landing position so that the pure water landing position on the upper surface of the substrate W passes through the central portion and the outer peripheral portion. Alternatively, the liquid landing position may be stationary at the center.

Next, a replacement liquid supply step (step S5 in FIG. 5) of supplying a replacement liquid that is soluble in both the rinsing liquid and the pre-drying treatment liquid to the upper surface of the substrate W and replacing the pure water on the substrate W with the replacement liquid is performed. Will be

Specifically, the nozzle moving unit 46 moves the replacement liquid nozzle 43 from the standby position to the processing position in a state where the blocking member 51 is located at the upper position and at least one guard 24 is located at the upper position. Let it. Thereafter, the replacement liquid valve 45 is opened, and the replacement liquid nozzle 43 starts discharging the replacement liquid. Before the discharge of the replacement liquid is started, the guard elevating unit 27 may move at least one guard 24 vertically in order to switch the guard 24 that receives the liquid discharged from the substrate W. When a predetermined time has elapsed since the replacement liquid valve 45 was opened, the replacement liquid valve 45 is closed, and the discharge of the replacement liquid is stopped. Thereafter, the nozzle moving unit 46 moves the replacement liquid nozzle 43 to the standby position.

The replacement liquid discharged from the replacement liquid nozzle 43 lands on the upper surface of the substrate W rotating at the liquid supply speed, and then flows outward along the upper surface of the substrate W by centrifugal force. The pure water on the substrate W is replaced with the replacement liquid discharged from the replacement liquid nozzle 43. As a result, a liquid film of the replacement liquid covering the entire upper surface of the substrate W is formed. When the replacement liquid nozzle 43 is discharging the replacement liquid, the nozzle moving unit 46 may move the liquid landing position so that the liquid landing position on the upper surface of the substrate W passes through the central portion and the outer peripheral portion. Alternatively, the liquid landing position may be stationary at the center.

Next, a pre-drying treatment liquid supply step (Step S6 in FIG. 5) of supplying the pre-drying treatment liquid to the upper surface of the substrate W and forming a liquid film of the pre-drying treatment liquid on the substrate W is performed.

Specifically, in a state where the blocking member 51 is located at the upper position and at least one guard 24 is located at the upper position, the nozzle moving unit 42 moves the pre-drying processing liquid nozzle 39 from the standby position to the processing position. Move to Thereafter, the pre-drying treatment liquid valve 41 is opened, and the pre-drying treatment liquid nozzle 39 starts discharging the pre-drying treatment liquid. Before the discharge of the pre-drying treatment liquid is started, the guard elevating unit 27 may move at least one guard 24 vertically to switch the guard 24 that receives the liquid discharged from the substrate W.

(4) The pre-drying treatment liquid discharged from the pre-drying treatment liquid nozzle 39 lands on the upper surface of the substrate W rotating at the liquid supply speed, and then flows outward along the upper surface of the substrate W by centrifugal force. The replacement liquid on the substrate W is replaced with the pre-drying processing liquid discharged from the pre-drying processing liquid nozzle 39. Thus, a liquid film of the pre-drying treatment liquid covering the entire upper surface of the substrate W is formed. When the pre-drying treatment liquid nozzle 39 is discharging the pre-drying treatment liquid, the nozzle moving unit 42 immerses the pre-drying treatment liquid so that the liquid landing position on the upper surface of the substrate W passes through the central portion and the outer peripheral portion. The position may be moved, or the liquid landing position may be stopped at the center.

FIG. 6A shows an example of a cross section of the substrate W supplied with the pre-drying treatment liquid. When the pre-drying treatment liquid comes into contact with the upper surface of the substrate W including the surface of the pattern P1 (the surface of the substrate W), the adsorbed substance contained in the pre-drying treatment liquid is adsorbed on the upper surface of the substrate W. A similar phenomenon occurs everywhere on the upper surface of the substrate W, and the adsorbed substance contained in the pre-drying treatment liquid is adsorbed on each part of the upper surface of the substrate W. FIG. 6A shows an example in which one molecule of the adsorbing substance is adsorbed on each part of the upper surface of the substrate W, and a monomolecular film of the adsorbing substance is formed along the upper surface of the substrate W. In this example, the boundary is drawn between the pre-drying treatment liquid adsorbed on the upper surface of the substrate W and the pre-drying liquid not adsorbed on the upper surface of the substrate W. No such boundary exists.

After the formation of the liquid film of the pre-drying treatment liquid, the adsorption promotion that promotes the adsorption of the adsorbed substance to the upper surface of the substrate W while maintaining the entire upper surface of the substrate W covered with the liquid film of the pre-drying treatment liquid The process (Step S7 in FIG. 5) is performed.

Specifically, the spin motor 14 lowers the rotation speed of the substrate W while the pre-drying processing liquid nozzle 39 is discharging the pre-drying processing liquid. At this time, the spin motor 14 may stop the rotation of the substrate W, or may rotate the substrate W at an adsorption promoting speed lower than the liquid supply speed (for example, a speed exceeding 0 and 20 rpm or less). After the rotation speed of the substrate W decreases, the pre-drying treatment liquid valve 41 is closed, and the discharge of the pre-drying treatment liquid is stopped. Further, the nozzle moving unit 42 moves the pre-drying treatment liquid nozzle 39 to the standby position, and the blocking member elevating unit 54 lowers the blocking member 51 from the upper position to the lower position.

(4) When the rotation speed of the substrate W decreases, the centrifugal force applied to the pre-drying processing liquid on the substrate W decreases, and the flow rate of the pre-drying processing liquid discharged from the substrate W decreases. Further, since the centrifugal force applied to the pre-drying treatment liquid on the substrate W is small, the pre-drying treatment liquid stays on the upper surface of the substrate W by the force acting between the pre-drying treatment liquid and the substrate W. Therefore, even after the discharge of the pre-drying treatment liquid is stopped, the state where the entire upper surface of the substrate W is covered with the liquid film of the pre-drying treatment liquid is maintained. Since the rotation speed of the substrate W is zero or low, the flow of the pre-drying treatment liquid at the interface between the pre-drying treatment liquid and the pattern P1 becomes gentle, and the adsorption of the adsorbed substance on the surface of the pattern P1 is promoted.

Next, in order to form the adsorption film 101 (see FIG. 6B) containing the adsorbed substance, the substrate W is rotated at a liquid removal speed to remove a part of the pre-drying treatment liquid on the upper surface of the substrate W. A removal step (step S8 in FIG. 5) is performed.

Specifically, in a state where the blocking member 51 is located at the lower position, and the upper central opening 61 of the blocking member 51 is discharging nitrogen gas, the spin motor 14 controls the rotation speed of the substrate W to be lower than the adsorption promotion speed. Is also increased to a large liquid removal rate and maintained at the liquid removal rate. The liquid removal rate may be equal to or different from the liquid supply rate. When the rotation speed of the substrate W increases, the flow rate of the pre-drying processing liquid discharged from the substrate W increases, and the pre-drying processing liquid on the upper surface of the substrate W decreases.

When the substrate W rotates at the liquid removal speed, most of the pre-drying processing liquid is removed from the upper surface of the substrate W. However, the adsorbed substance adsorbed on the surface of the pattern P1 remains on the substrate W due to the force acting between the adsorbed substance and the substrate W. The surface layer of the pre-drying solution remaining on the upper surface of the substrate W including the surface of the pattern P1 is concentrated by drying and changes to a solid thin film. Thus, as shown in FIG. 6B, an adsorption film 101 containing the adsorbed substance adsorbed on the surface of the pattern P1 is formed along the surface of the pattern P1. Only the surface layer of the pre-drying treatment liquid remaining on the upper surface of the substrate W may be changed to solid, or the whole may be changed to solid. Alternatively, the pre-drying treatment liquid remaining on the upper surface of the substrate W may change into a gel state.

(4) The adsorption film 101 corresponds to a sacrificial film that is finally removed from the substrate W. The adsorption film 101 may be a solidified film obtained by solidifying the pretreatment liquid for drying. In the example shown in FIG. 6B, the adsorption film 101 includes a side film 101s covering the side surface Ps of the pattern P1, an upper surface film 101u covering the upper surface Pu of the pattern P1, and a bottom covering the bottom surface of the substrate W (the plane Ws of the substrate W). And a surface film 101b. The upper end of the side surface film 101s and the upper surface film 101u constitute a leading end film that covers the leading end of the pattern P1. The thickness T1 of the attraction film 101 is smaller than the height Hp of the pattern P1. The thickness T1 of the attraction film 101 may be smaller than the width Wp of the pattern P1, or may be smaller than the distance G1 between two adjacent patterns P1. The adsorption film 101 may be a monomolecular film of an adsorption substance. In this case, the thickness T1 of the adsorption film 101 is several nanometers or several angstroms.

FIG. 6B shows a state immediately after two adjacent patterns P1 collapse in the direction approaching each other. When the pre-drying treatment liquid on the substrate W is reduced to a certain extent, the upper surface (liquid level) of the pre-drying treatment liquid moves between two adjacent convex patterns P1. That is, the interface between the gas and the liquid (the pre-drying treatment liquid) moves between the patterns P1, and the collapse force caused by the surface tension of the pre-drying treatment liquid is applied to the pattern P1 via the adsorption film 101. At this time, even if two adjacent patterns P1 collapse in a direction approaching each other, at least a part of the surface of the pattern P1 is coated with the adsorption film 101, so that the two patterns P1 are in direct contact with each other. Instead, they are in contact with each other via the adsorption film 101.

(4) The collapsed pattern P1 attempts to return to a vertical state perpendicular to the bottom surface of the substrate W (the plane Ws of the substrate W) by the restoring force (elasticity) of the pattern P1. On the other hand, when the two side films 101s respectively covering the tip portions of the two collapsed patterns P1 come into contact with each other, an adhesive force is generated between the two side films 101s. When the adhesive force is stronger than the restoring force of the pattern P1, the collapsed pattern P1 does not return to the vertical state, but is maintained in a collapsed state inclined with respect to the bottom surface of the substrate W.

FIG. 6C shows a state where a certain amount of time has elapsed after two adjacent patterns P1 collapsed in a direction approaching each other. When the pre-drying treatment liquid is removed from the substrate W, a part of the pre-drying treatment liquid on the substrate W is vaporized and flows in all directions. The drying pretreatment liquid vaporized near the roots of the two collapsed patterns P1 adheres to the adsorption film 101 interposed between the tips of the two patterns P1. Therefore, as shown by the broken-line circles in FIG. 6C, the suction film 101 is thicker near the tip portions of the two collapsed patterns P1 than at other positions.

In order to form the adsorbing film 101 containing the adsorbing substance, when a part of the pre-drying treatment liquid on the upper surface of the substrate W is removed by rotation of the substrate W, the pre-drying treatment on the upper surface of the substrate W is performed. The liquid may be heated. For example, the heating fluid valve 73 may be opened to discharge hot water to the lower nozzle 71, or the nitrogen gas heated by the lower temperature controller 86 may be discharged to the lower center opening 81 of the spin base 12. If the pre-drying treatment liquid on the upper surface of the substrate W is heated, the time required for forming the adsorption film 101 can be reduced.

After the adsorption film 101 is formed, a transfer step (step S10 in FIG. 5) of transferring the dried or substantially dried substrate W from the wet processing unit 2w to the dry processing unit 2d is performed.

{Specifically, the spin motor 14 is stopped, and the rotation of the substrate W is stopped (Step S9 in FIG. 5). Further, the blocking member elevating unit 54 raises the blocking member 51 to the upper position, and the guard elevating unit 27 lowers all the guards 24 to the lower position. Further, the upper gas valve 64 and the lower gas valve 84 are closed, and the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the spin base 12 stop discharging nitrogen gas. Thereafter, the center robot CR causes the hand H1 to enter the wet processing unit 2w. The center robot CR supports the substrate W on the spin chuck 10 with the hand H1 after the plurality of chuck pins 11 release the grip of the substrate W. Thereafter, the center robot CR retracts the hand H1 from inside the wet processing unit 2w while supporting the substrate W with the hand H1. Thereby, the substrate W is unloaded from the wet processing unit 2w.

After the substrate W is carried out of the wet processing unit 2w, the center robot CR supports the substrate W with the hand H1 while holding the substrate H with the dry processing unit while the plurality of lift pins 97 are located at the upper position. Enter into 2d. Then, the center robot CR places the substrate W on the hand H1 on the plurality of lift pins 97 with the surface of the substrate W facing upward. Thereafter, the lift elevating unit 98 lowers the plurality of lift pins 97 to the lower position. Thus, the substrate W on the plurality of lift pins 97 is placed on the hot plate 92. After placing the substrate W on the plurality of lift pins 97, the center robot CR retracts the hand H1 from inside the dry processing unit 2d.

Next, an adsorption film removal step (step S11 in FIG. 5) of changing the adsorption film 101 on the substrate W into a gas and removing the gas from the upper surface of the substrate W is performed.

Specifically, the hot plate 92 heats the adsorption film 101 on the substrate W via the substrate W at a removal temperature (for example, a temperature higher than 100 ° C.). When the adsorption substance contained in the adsorption film 101 is a sublimable substance, when the adsorption film 101 is heated at the removal temperature, the adsorption film 101 on the substrate W changes into a gas without passing through a liquid. When the adsorbing substance contained in the adsorbing film 101 is a substance other than the sublimable substance, when the adsorbing film 101 is heated at the removal temperature, the adsorbing film 101 on the substrate W changes into a gas by thermal decomposition. The gas (gas containing the adsorbed substance) generated from the adsorption film 101 is discharged from the inside of the dry processing unit 2d through the exhaust duct 8. Thus, the adsorption film 101 is removed from the upper surface of the substrate W.

(6) Even if the pattern P1 collapses when the pre-drying treatment liquid is removed, if the adsorption film 101 is removed, as shown in FIG. 6D, the adsorption film 101 disappears from between the tips of the two collapsed patterns P1. This weakens the adhesive force for maintaining the two patterns P1 in the collapsed state. If the pattern P1 is not plastically deformed or damaged, the collapsed pattern P1 returns to the vertical state due to the restoring force of the pattern P1 (see the black arrow in FIG. 6D). Therefore, even if the pattern P1 collapses when the surplus pre-drying treatment liquid is removed, the pattern P1 returns to the vertical state after the adsorption film 101 is removed. Thereby, even when the strength of the pattern P1 is low, the final collapse rate of the pattern P1 can be improved.

(4) After removing the adsorption film 101, an unloading step of unloading the substrate W from the dry processing unit 2d (Step S12 in FIG. 5) is performed.

Specifically, the lift elevating unit 98 raises the plurality of lift pins 97 from the lower position to the upper position. As a result, the substrate W on the hot plate 92 is lifted by the plurality of lift pins 97, and separates upward from the hot plate 92. Thereafter, the center robot CR causes the hand H1 to enter the dry processing unit 2d. In this state, the lift elevating unit 98 lowers the plurality of lift pins 97 to the lower position. Thereby, the substrate W on the plurality of lift pins 97 is placed on the hand H1. After the substrate W is placed on the hand H1, the center robot CR retracts the hand H1 from the inside of the dry processing unit 2d. Thereby, the processed substrate W is unloaded from the dry processing unit 2d.

As described above, in the present embodiment, the pre-drying liquid containing the adsorbed substance is supplied to the surface of the substrate W which is held horizontally. The adsorption substance contained in the pre-drying treatment liquid is adsorbed on the surface of the pattern P1 formed on the substrate W. Then, with the adsorbed substance adsorbed on the surface of the pattern P1, the substrate W is rotated about a vertical rotation axis A1 while holding the substrate W horizontally. As a result, the pre-drying liquid is discharged from the surface of the substrate W by centrifugal force, and the amount of the pre-drying liquid on the surface of the substrate W decreases.

(4) When the substrate W is rotated at a certain rotational speed, most of the pretreatment liquid for drying is removed from the surface of the substrate W, but the adsorbed substance adsorbed on the surface of the pattern P1 remains on the substrate W. As a result, the adsorption film 101 including the adsorption substance adsorbed on the surface of the pattern P1 is formed along the surface of the pattern P1. That is, the space between the two adjacent patterns P1 is not filled with the adsorbing film 101 without a gap, but the surface of the pattern P1 is opposed to each other in the width direction of the pattern P1 via the space. It is coated with the adsorption film 101.

On the other hand, when the pre-drying treatment liquid on the substrate W decreases to a certain extent, the upper surface (liquid level) of the pre-drying treatment liquid moves between two adjacent convex patterns P1. That is, the interface between the gas and the liquid (the pre-drying treatment liquid) moves between the patterns P1, and the collapse force caused by the surface tension of the pre-drying treatment liquid is applied to the pattern P1 via the adsorption film 101. At this time, even if two adjacent patterns P1 collapse in a direction approaching each other, at least a part of the surface of the pattern P1 is coated with the adsorption film 101, so that the two patterns P1 are in direct contact with each other. Instead, they are in contact with each other via the adsorption film 101.

After the adsorption film 101 is formed on the surface of the pattern P1, the adsorption film 101 is changed to a gas. Thereby, the adsorption film 101 is removed from the surface of the substrate W. If two adjacent patterns P1 collapse in a direction approaching each other when removing the pre-drying treatment liquid, the adsorption film 101 is removed from between the two patterns P1. If the pattern P1 is not plastically deformed or damaged, the collapsed pattern P1 returns to the vertical state by the restoring force of the pattern P1 when the adsorption film 101 is removed. In other words, even if the pattern P1 collapses before the adsorption film 101 is removed, the pattern P1 returns to the vertical state after the adsorption film 101 is removed. Thus, not only when the intensity of the pattern P1 is high, but also when the intensity of the pattern P1 is low, the final collapse rate of the pattern P1 can be improved. When the same processing as the above-described example of the processing of the substrate W was performed using the sample on which the pattern P1 was formed, it was confirmed that the collapse rate of the pattern P1 was actually improved.

In the present embodiment, before forming the adsorption film 101, the drying pretreatment liquid is applied to the pattern P1 while stopping the rotation of the substrate W or maintaining the rotation speed of the substrate W at a small value (adsorption acceleration speed). Contact surface. Since the rotation speed of the substrate W is zero or low, the flow of the pre-drying treatment liquid at the interface between the pre-drying treatment liquid and the surface of the pattern P1 becomes gentle, and the adsorption of the adsorbed substance on the surface of the pattern P1 is promoted. Thereby, more adsorption substances can be adsorbed on the surface of the pattern P1.

In the present embodiment, the thin adsorption film 101 is formed on the surface of the pattern P1. That is, the thickness T1 of the adsorption film 101 (see FIG. 6B) is smaller than the height Hp of the pattern P1 (see FIG. 6A). Since the adsorbing film 101 is thin, the adsorbing film 101 can be removed in a short time, and the amount of energy required for removing the adsorbing film 101 can be reduced. When the adsorbing film 101 is removed by heating, the heating time of the substrate W can be shortened, so that a change in the surface of the substrate W such as oxidation can be suppressed. Furthermore, even when unnecessary substances such as residues are generated on the substrate W when the adsorption film 101 is changed to gas, the volume of the adsorption film 101 is small, so that the generation amount of unnecessary substances is small. Therefore, unnecessary substances can be removed in a short time. In some cases, it is not necessary to remove unnecessary matter.

In the present embodiment, the pre-drying liquid, which is a solution in which the adsorbed substance and the solvent are uniformly dissolved, is supplied to the substrate W. When supplying the melt of the adsorbing substance to the substrate W, if the freezing point of the adsorbing substance is equal to or higher than room temperature, it is necessary to heat the adsorbing substance in order to maintain the adsorbing substance as a liquid. If the adsorbed substance is dissolved in the solvent, even if the freezing point of the adsorbed substance is higher than room temperature, if the freezing point of the dried pretreatment liquid can be made lower than room temperature due to the freezing point drop caused by mixing of the adsorbed substance and the solvent, the dried pretreated liquid can be cooled to room temperature Can be kept liquid. Therefore, energy consumption required for processing the substrate W can be reduced.

In the present embodiment, when a part of the pre-drying treatment liquid on the surface of the substrate W is removed by rotation of the substrate W, nitrogen gas, which is an example of gas, is discharged toward the surface of the substrate W. The pre-drying treatment liquid on the substrate W is discharged from the substrate W at a gas pressure. At the same time, a part of the pre-drying treatment liquid on the substrate W evaporates due to the supply of gas. Thereby, the unnecessary pre-drying treatment liquid can be quickly removed from the surface of the substrate W.

Next, a second embodiment will be described.

The main difference between the second embodiment and the first embodiment is that the built-in heater 111 is built in the blocking member 51 and a hot plate 92 is provided instead of the lower surface nozzle 71.

FIG. 7A is a schematic view of the spin chuck 10, the blocking member 51, and the hot plate 92 according to the second embodiment of the present invention viewed horizontally. FIG. 7B is a schematic view of the spin chuck 10 and the hot plate 92 as viewed from above. 7A, 7B, 8A, and 8B, the same components as those shown in FIGS. 1 to 6D described above are denoted by the same reference numerals as those in FIG. 1 and the like, and description thereof is omitted. .

内蔵 As shown in FIG. 7A, the built-in heater 111 is disposed inside the disk portion 52 of the blocking member 51. The built-in heater 111 moves up and down together with the blocking member 51. The substrate W is arranged below the built-in heater 111. The built-in heater 111 is, for example, a heating element that generates Joule heat when energized. The temperature of the built-in heater 111 is changed by the control device 3. When the control device 3 causes the built-in heater 111 to generate heat, the entire substrate W is uniformly heated.

The hot plate 92 is arranged above the spin base 12. As shown in FIG. 7B, the center line of the hot plate 92 is arranged on the rotation axis A1 of the substrate W. Even if the spin chuck 10 rotates, the hot plate 92 does not rotate. The outer diameter of the hot plate 92 is smaller than the diameter of the substrate W. The plurality of chuck pins 11 are arranged around the hot plate 92. The substrate W is disposed above the hot plate 92.

As shown in FIG. 7A, the hot plate 92 is horizontally supported by a support shaft 113 extending downward from the center of the hot plate 92. The hot plate 92 can move up and down with respect to the spin base 12. The hot plate 92 is connected to a plate elevating unit 114 via a support shaft 113. The plate elevating unit 114 vertically elevates the hot plate 92 between an upper position (a position indicated by a solid line in FIG. 7A) and a lower position (a position indicated by a two-dot chain line in FIG. 7A). The upper position is a contact position where the hot plate 92 contacts the lower surface of the substrate W. The lower position is a close position where the hot plate 92 is located between the lower surface of the substrate W and the upper surface 12u of the spin base 12 while being away from the substrate W.

The plate lifting unit 114 positions the hot plate 92 at an arbitrary position from the upper position to the lower position. When the hot plate 92 is raised to the upper position in a state where the substrate W is supported by the plurality of chuck pins 11 and the gripping of the substrate W is released, the plurality of protrusions 96 of the hot plate 92 , And the substrate W is supported by the hot plate 92. Thereafter, the substrate W is lifted by the hot plate 92 and moves upward away from the plurality of chuck pins 11. In this state, when the hot plate 92 is lowered to the lower position, the substrate W on the hot plate 92 is placed on the plurality of chuck pins 11, and the hot plate 92 is separated from the substrate W downward. Thus, the substrate W is transferred between the plurality of chuck pins 11 and the hot plate 92.

FIG. 8A is a schematic view of the spin chuck 10, the blocking member 51, and the hot plate 92 viewed horizontally when the liquid removing step is being performed.

ＡIn FIG. 8A, the blocking member 51 and the hot plate 92 are arranged at respective lower positions. In the liquid removing step (Step S8 in FIG. 5), the control device 3 removes the built-in heater 111 and the hot plate 92 while the substrate W is partially removed by the rotation of the substrate W on the upper surface of the substrate W. May be heated to heat the pre-drying treatment liquid on the upper surface of the substrate W. If the pre-drying treatment liquid on the upper surface of the substrate W is heated, the time required for forming the adsorption film 101 can be reduced.

FIG. 8B is a schematic view of the spin chuck 10, the blocking member 51, and the hot plate 92 viewed horizontally when the adsorption film removing step is being performed.

ＢIn FIG. 8B, the blocking member 51 is arranged at the lower position, and the hot plate 92 is arranged at the upper position. The hot plate 92 may be arranged not at the upper position where the hot plate 92 is in contact with the substrate W but at a lower position where the hot plate 92 is separated from the substrate W. The controller 3 may heat at least one of the built-in heater 111 and the hot plate 92 to heat the adsorption film 101 on the substrate W at the removal temperature in the adsorption film removal step (Step S11 in FIG. 5). In this case, the adsorption film 101 on the substrate W can be removed in the wet processing unit 2w. Further, if both the built-in heater 111 and the hot plate 92 generate heat, the time required for removing the adsorption film 101 can be reduced.

Note that, instead of causing the built-in heater 111 and the hot plate 92 to heat the adsorption film 101 on the substrate W, a heating gas higher than room temperature is discharged toward the upper surface of the substrate W, so that the adsorption film 101 on the substrate W is discharged. 101 may be heated at the removal temperature. For example, the nitrogen gas heated by the upper temperature controller 59 (see FIG. 2) may be discharged to the central nozzle 55, or the nitrogen gas heated by the upper temperature controller 66 (see FIG. May be ejected to the upper central opening 61 of the ink jet head.

When a part of the pre-drying treatment liquid on the surface of the substrate W is removed, the pre-drying treatment liquid on the substrate W is heated by using at least one of the built-in heater 111, the hot plate 92, and the heating gas. The formation of the film 101 and the removal of the adsorption film 101 can proceed simultaneously. In this case, the adsorption film 101 is changed to a gas while removing a part of the pre-drying treatment liquid on the surface of the substrate W, not after removing a part of the pre-drying treatment liquid on the surface of the substrate W. Can be.

(4) When the adsorption film 101 on the substrate W is removed in the wet processing unit 2w, the collapse duration for maintaining the pattern P1 in the collapsed state is shorter than in the case where the adsorption film 101 is removed in the dry processing unit 2d. If the collapse duration is long, the shape of the collapsed pattern P1 is stored, and the elastic recovery force for restoring the shape may be weakened. If the adsorption film 101 on the substrate W is removed by the wet processing unit 2w, the collapse duration can be shortened, so that the pattern P1 maintained in the collapsed state even after the adsorption film 101 is removed can be reduced.

Other Embodiments The present invention is not limited to the contents of the above-described embodiments, and various modifications are possible.

For example, the liquid removing step (step S8 in FIG. 5) may be performed without performing the adsorption promoting step (step S7 in FIG. 5).

When the rinsing liquid such as pure water on the substrate W can be replaced with the pre-drying treatment liquid, pure water as an example of the rinsing liquid is replaced with IPA as an example of the replacement liquid as in processing example 1 in FIG. A drying pretreatment liquid supply step may be performed without performing the replacement liquid supply step.

５Five processes are shown at the top of FIG. Pure water, which is an example of the rinsing liquid, is described as DIW. The spin-off means that a part of the pretreatment liquid for drying is removed by the rotation of the substrate W. The circles in FIG. 9 indicate that the steps shown in the uppermost row are executed, and the blanks in FIG. 9 indicate that the steps shown in the uppermost row are not executed. Processing example 2 in FIG. 9 corresponds to an example of processing of the substrate W illustrated in FIG.

As shown in Processing Example 3 in FIG. 9, instead of supplying IPA to the substrate W before supplying the pre-drying treatment liquid, IPA may be supplied to the substrate W after spin-off. As shown in Processing Example 4 in FIG. 9, IPA may be supplied to the substrate W not only before supplying the pre-drying treatment liquid but also after spin-off. When the adsorption film 101 is formed by spin-off, unnecessary substances such as residues may be generated on the substrate W. Even in such a case, if IPA is supplied to the substrate W after the spin-off, unnecessary substances on the substrate W can be washed away with the IPA.

Also, as shown in Processing Example 5 in FIG. 9, HFE may be supplied to the substrate W after supplying IPA, and then the pre-drying treatment liquid may be supplied to the substrate W. That is, the replacement liquid supply step includes a first replacement liquid supply step of supplying IPA, which is an example of a first replacement liquid, to the substrate W, and a second replacement liquid of supplying HFE, an example of the second replacement liquid, to the substrate W. And a supplying step. Although not shown, IPA may be supplied to the substrate W after spin-off in the processing example 5 of FIG.

In the first embodiment, an example was described in which the concentration of the adsorbed substance contained in the pretreatment liquid was less than 1 wt%, and the main components of the pretreatment liquid were IPA and pure water. In the processing example 5 of FIG. 9, the pure water on the substrate W is replaced with IPA, and then the IPA on the substrate W is replaced with HFE. Thereafter, the HFE on the substrate W is replaced with the pre-drying treatment liquid. The density of HFE is greater than the density of water and greater than the density of IPA.

When the density of the HFE is higher than the density of the pretreatment liquid, that is, when there is a specific gravity difference between the HFE and the pretreatment liquid, only the surface layer of the HFE is replaced with the pretreatment liquid as shown in FIG. As a result, a bottom layer of HFE may remain on the substrate W. In this case, the adsorbed substance is adsorbed only at the tip of the pattern P1. When spin-off is performed in this state, the adsorption film 101 is formed only at the tip of the pattern P1. In this case, since the volume of the adsorption film 101 is smaller than that in the case where the adsorption film 101 covering the entire surface of the pattern P1 is formed, the adsorption film 101 can be removed in a short time, and the energy consumption required for removing the adsorption film 101 is reduced. Can be reduced.

In the processing examples 1 to 5 of FIG. 9, the substrate W may be heated in parallel with at least one of the steps shown at the top of FIG. For example, the heating fluid valve 73 shown in FIG. Alternatively, at least one of the built-in heater 111 and the hot plate 92 of the blocking member 51 shown in FIG. 7A may generate heat. If the substrate W is heated when the liquid on the substrate W is replaced with another liquid, the liquid replacement efficiency can be improved.

吸着 As shown in FIG. 11A, the adsorption film 101 may be formed so as to be in contact with only the upper surface Pu of the pattern P1. FIG. 11A shows an example in which the adsorption film 101 is recessed downward in a space between two adjacent patterns P1 and is not in contact with the pattern P1. Such an adsorption film 101 supplies, for example, a drying pretreatment liquid having a higher viscosity than the drying pretreatment liquid used in the first embodiment to the substrate W, and the substrate W in the adsorption promoting step (step S7 in FIG. 5). It is formed by increasing the rotation speed (adsorption acceleration speed) of.

(4) When the substrate W is heated from the lower surface side of the substrate W with the IPA on the upper surface of the substrate W, the IPA on the substrate W is heated via the substrate W. When the IPA is heated at a temperature equal to or higher than the boiling point of the IPA, the IPA located between the two adjacent patterns P1 evaporates, and at least a part of the space between the two adjacent patterns P1 is filled with the vapor of the IPA. Even if the pre-drying treatment liquid is supplied to the substrate W in this state, the adsorbed substance contained in the pre-drying treatment liquid does not adsorb on the surface of the pattern P1 except for the upper surface Pu of the pattern P1. This is because the surface of the pattern P1 except the upper surface Pu of the pattern P1 is in contact with the IPA vapor. Thus, the suction film 101 that is in contact with only the upper surface Pu of the pattern P1 is formed.

If the interface between the liquid of IPA and the vapor of IPA has reached the upper surface Pu of the pattern P1, even if the adsorption film 101 is formed on the upper surface Pu of the pattern P1, the adsorption strength of the adsorption film 101 with respect to the pattern P1 is low. weak. Therefore, when the adsorption substance contained in the adsorption film 101 is a thermally decomposable polymer, the removal temperature required for thermal decomposition can be reduced, and the adsorption film 101 can be removed in a short time. Thereby, the amount of energy consumption required for removing the adsorption film 101 can be reduced.

When the adsorption film 101 as shown in FIG. 11A is formed, only the upper end portion of the surface of the pattern P1 reliably contacts the adsorption film 101, so that the stress generated in the pattern P1 can be reduced. That is, even if two adjacent patterns P1 collapse in a direction approaching each other, as shown in FIG. 11B, a part of the adsorption film 101 is sandwiched between the two patterns P1 and serves as a cushion. Therefore, it is possible to prevent the surface of the pattern P1 from being damaged.

The electromagnetic wave generator 115 shown in FIG. 12A or 12B may be provided in the dry processing unit 2d instead of or in addition to the hot plate 92. Alternatively, the active gas supply device 116 shown in FIG. 12C may be provided in the dry processing unit 2d (see FIG. 3) instead of or in addition to the hot plate 92. The electromagnetic wave generator 115 and the active gas supply device 116 may be provided in the wet processing unit 2w instead of the dry processing unit 2d.

The electromagnetic wave generator 115 shown in FIGS. 12A and 12B irradiates the adsorption film 101 on the substrate W with an electromagnetic wave to change the adsorption film 101 into a gas. The active gas supply device 116 illustrated in FIG. 12C changes the adsorption film 101 into a gas by bringing an active gas such as an ozone gas or a hydrogen fluoride-containing gas into contact with the adsorption film 101. When unnecessary substances such as residues remain on the substrate W when the adsorption film 101 is changed to gas using the hot plate 92, the unnecessary substances are thermally decomposed, oxidized, or ashed using an electromagnetic wave or an active gas. It may be removed by chemical conversion.

The electromagnetic wave generated by the electromagnetic wave generator 115 may be any of visible light, infrared light, and ultraviolet light, or may be other than these. That is, the electromagnetic wave generator 115 may be a lamp heater that emits visible light and infrared light, or may be a UV lamp that emits ultraviolet light. Further, the electromagnetic wave generator 115 may be a partial irradiation device 115A that irradiates an electromagnetic wave only to an irradiation region representing a partial region on the upper surface of the substrate W as shown in FIG. 12A, or as shown in FIG. 12B. The entire irradiation device 115B may simultaneously irradiate the entire surface of the upper surface of the substrate W with electromagnetic waves. In the former case, the partial irradiation device 115A may be moved so that the irradiation area moves within the upper surface of the substrate W.

The blocking member 51 may include a cylindrical portion extending downward from the outer peripheral portion of the disk portion 52 in addition to the disk portion 52. In this case, when the blocking member 51 is disposed at the lower position, the substrate W held by the spin chuck 10 is surrounded by the cylindrical portion.

The blocking member 51 may rotate around the rotation axis A1 together with the spin chuck 10. For example, the blocking member 51 may be placed on the spin base 12 so as not to contact the substrate W. In this case, since the blocking member 51 is connected to the spin base 12, the blocking member 51 rotates in the same direction as the spin base 12 at the same speed.

The blocking member 51 may be omitted. However, when a liquid such as pure water is supplied to the lower surface of the substrate W, it is preferable that the blocking member 51 be provided. Droplets that travel along the outer peripheral surface of the substrate W from the lower surface of the substrate W toward the upper surface of the substrate W and droplets that bounce inward from the processing cup 21 can be blocked by the blocking member 51. This is because the amount of liquid mixed in the pre-drying treatment liquid can be reduced.

(4) The wet processing unit 2w and the dry processing unit 2d may be provided in different substrate processing apparatuses instead of the same substrate processing apparatus. That is, the substrate processing apparatus 1 provided with the wet processing unit 2w and the substrate processing apparatus provided with the dry processing unit 2d are provided in the same substrate processing system. The substrate W may be transferred from the processing apparatus 1 to another substrate processing apparatus.

The substrate processing apparatus 1 is not limited to an apparatus for processing a disk-shaped substrate W, but may be an apparatus for processing a polygonal substrate W.

２Two or more of all the above-described configurations may be combined. Two or more of all of the above steps may be combined.

The pre-drying treatment liquid nozzle 39 is an example of a pre-drying treatment liquid supply unit. The spin motor 14 is an example of a spin-off unit and a liquid removing unit. The hot plate 92 and the built-in heater 111 are examples of an adsorption film removing unit. The control device 3 is an example of an adsorption promotion unit. The central nozzle 55 and the upper central opening 61 of the blocking member 51 are an example of a gas supply unit and a liquid removal unit. The lower nozzle 71 and the lower central opening 81 of the spin base 12 are examples of a liquid heating unit and a liquid removing unit.

Although the embodiments of the present invention have been described in detail, these are only specific examples used for clarifying the technical contents of the present invention, and the present invention is interpreted by limiting to these specific examples. Instead, the spirit and scope of the invention is limited only by the appended claims.

1: substrate processing apparatus 2: processing unit 3: control apparatus 10: spin chuck 14: spin motor 39: pre-drying treatment liquid nozzle 55: center nozzle 59: upper temperature controller 61: upper central opening 66 of the blocking member: upper temperature Controller 71: Lower nozzle 75: Lower heater 79: Cooler 81: Lower center opening of spin base 86: Lower temperature controller 92: Hot plate 101: Adsorption film 111: Built-in heater A1: Rotation axis Hp: Pattern height P1 : Pattern Ps: Pattern side surface Pu: Pattern upper surface T1: Adsorption film thickness W: Substrate Wp: Pattern width

Claims

A pre-drying process comprising supplying a pre-drying treatment liquid containing an adsorbing substance adsorbing on the surface of a pattern formed on a substrate to the surface of the substrate held horizontally, and adsorbing the adsorbing substance on the surface of the pattern. A liquid supply step;
An adsorption including the adsorbed substance adsorbed on the surface of the pattern by removing a part of the drying pretreatment liquid on the surface of the substrate held horizontally by rotating the substrate around a vertical rotation axis. A liquid removing step including a spin-off step of forming a film along the surface of the pattern,
A step of removing the adsorption film from the surface of the substrate by changing the adsorption film into a gas.
The adsorbing film removing step is a pattern restoring step of restoring the shape of the collapsed pattern with a restoring force of the pattern by removing the adsorbing film from between the two collapsed patterns that are in contact with each other via the adsorption film. The substrate processing method according to claim 1, comprising:
3. The substrate processing method according to claim 1, wherein the adsorbed substance is a substance that is chemically adsorbed on the surface of the pattern.
3. The substrate processing method according to claim 1, wherein the adsorbing substance is a substance that physically adsorbs on the surface of the pattern.
The pre-drying treatment liquid supply step, before forming the adsorption film, while stopping the rotation of the substrate, or at a rotation speed smaller than the rotation speed of the substrate when forming the adsorption film, the substrate 5. The substrate processing method according to claim 1, further comprising an adsorption promoting step of bringing the pre-drying treatment liquid into contact with the surface of the pattern while rotating.
(6) The substrate processing method according to any one of (1) to (5), wherein the thickness of the attraction film is smaller than the height of the pattern.
7. The substrate processing method according to claim 1, wherein the pretreatment liquid for drying is a solution containing the adsorbed substance and a solvent that dissolves in the adsorbed substance.
The liquid removing step further includes a gas supply step of discharging gas toward the surface of the substrate when a part of the pre-drying treatment liquid on the surface of the substrate is removed by rotation of the substrate. The substrate processing method according to any one of claims 1 to 7.
The liquid removing step is a liquid heating step of heating the pre-drying liquid on the surface of the substrate while removing a part of the pre-drying liquid on the surface of the substrate by rotating the substrate. The substrate processing method according to any one of claims 1 to 8, further comprising:
A pre-drying process comprising supplying a pre-drying treatment liquid containing an adsorbing substance adsorbing on the surface of a pattern formed on a substrate to the surface of the substrate held horizontally, and adsorbing the adsorbing substance on the surface of the pattern. A liquid supply unit,
An adsorption including the adsorbed substance adsorbed on the surface of the pattern by removing a part of the drying pretreatment liquid on the surface of the substrate held horizontally by rotating the substrate around a vertical rotation axis. A liquid removal unit comprising: a spin-off unit for forming a film along the surface of the pattern;
A substrate processing apparatus, comprising: an adsorption film removal unit that removes the adsorption film from the surface of the substrate by changing the adsorption film into a gas.