TWI708339B - Substrate processing method and substrate processing device - Google Patents

Abstract

The pre-drying treatment liquid containing the adsorption material to be adsorbed to the surface of the pattern formed on the substrate is supplied to the surface of the substrate that is kept level, so that the adsorption material is adsorbed on the surface of the pattern. A part of the pre-drying treatment liquid on the surface of the substrate that is kept level is removed by rotating the substrate around a vertical axis of rotation, thereby forming an adsorption film containing the adsorbed substance adsorbed on the surface of the pattern along the surface of the pattern. The adsorption film is removed from the surface of the substrate by changing the adsorption film into a gas.

Description

Substrate processing method and substrate processing device

This application claims priority based on Japanese Patent Application No. 2018-139166 filed on July 25, 2018, and all the contents of this application are incorporated herein by reference.

The present invention relates to a substrate processing method and substrate processing apparatus for processing substrates. The substrates to be processed include, for example, semiconductor wafers, liquid crystal display devices, or organic EL (electroluminescence, electroluminescence) display devices, such as FPD (Flat Panel Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disks Substrates, photomask substrates, ceramic substrates, solar cell substrates, etc.

In the manufacturing steps of semiconductor devices or liquid crystal display devices, substrates such as semiconductor wafers or glass substrates for liquid crystal display devices are processed as needed. Such processing includes supplying a processing liquid such as a chemical liquid or a rinse liquid to the substrate. After supplying the processing liquid, the processing liquid is removed from the substrate and the substrate is dried.

In the case where a pattern is formed on the surface of the substrate, there is a situation that when the substrate is dried, a force caused by the surface tension of the processing liquid attached to the substrate is applied to the pattern, and the pattern collapses. As a countermeasure, a method of supplying a liquid with low surface tension such as IPA (isopropanol) to the substrate or supplying a hydrophobizing agent that makes the contact angle of the liquid with respect to the pattern close to 90 degrees is used. However, even if IPA or a hydrophobizing agent is used, the collapse force of the pattern collapse does not become zero. Therefore, depending on the strength of the pattern, even if such countermeasures are implemented, there are cases where the collapse of the pattern cannot be sufficiently prevented.

In recent years, as a technique to prevent pattern collapse, sublimation drying has attracted attention. For example, Patent Document 1 discloses a substrate processing method and a substrate processing apparatus that perform sublimation drying. In the sublimation drying described in Patent Document 1, the molten liquid of the sublimable substance is supplied to the surface of the substrate, and the DIW on the substrate is replaced by the molten liquid of the sublimable substance. Thereafter, the molten liquid of the sublimable substance on the substrate is cooled to form a solidified body of the sublimable substance. After that, the solidified body of the sublimable substance on the substrate is sublimated. Thereby, the molten liquid of the sublimable substance is removed from the substrate, and the substrate is dried. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-142069

[The problem to be solved by the invention]

In Patent Document 1, the melt of the sublimable substance is solidified in a state where the melt of the sublimable substance is present not only between two adjacent convex patterns but also above the patterns. If the liquid is arranged in an extremely narrow space, the freezing point will decrease. In a substrate such as a semiconductor wafer, the interval between two adjacent patterns is relatively narrow, and therefore, the freezing point of the sublimable substance located between the patterns is lowered. Therefore, the freezing point of the sublimation substance located between the patterns is lower than the freezing point of the sublimation substance located above the patterns.

If the freezing point of only the sublimable substance between the patterns is low, there is a situation where the surface layer of the molten liquid of the sublimable substance, that is, the range from the upper surface (liquid surface) of the sublimable substance to the upper surface of the pattern The liquid layer is solidified first, and the molten liquid of the sublimation substance located between the patterns does not solidify but remains in the form of liquid. In this case, sometimes an interface between a solid (solidified body of sublimable substance) and liquid (melted liquid of sublimable substance) is formed in the vicinity of the pattern, resulting in a collapsing force that causes the pattern to collapse. If the pattern becomes more fragile due to the miniaturization of the pattern, the weaker collapsing force will cause the pattern to collapse.

In addition, there are cases where the pattern collapses in a state where the molten liquid of the sublimable substance located between the patterns is not solidified, the front ends of two adjacent patterns are in contact with each other. In this case, even if the solidified body of the sublimable substance is sublimed, the state where the front ends of the pattern are in contact with each other is maintained, and the pattern does not return to the vertical state. Therefore, even if the sublimation drying is performed, depending on the strength of the pattern, there are cases where the collapse of the pattern cannot be sufficiently prevented.

Therefore, one of the objects of the present invention is to provide a substrate processing method and a substrate processing apparatus that can reduce the collapse of the pattern generated when the substrate is dried by sublimation drying and reduce the collapse rate of the pattern. [Technical means to solve the problem]

An embodiment of the present invention provides a substrate processing method, which includes: a pre-drying treatment liquid supply step of supplying the pre-drying treatment liquid containing the adsorbing substance to be adsorbed to the surface of the pattern formed on the substrate to the above-mentioned maintaining level The surface of the substrate allows the adsorbed substance to be adsorbed on the surface of the pattern; the liquid removal step includes a spin-off step, the spin-off step is to pass a portion of the pre-drying treatment liquid on the surface of the substrate that is kept horizontal The substrate is removed by rotating around a vertical axis of rotation, whereby an adsorption film containing the adsorption substance adsorbed on the surface of the pattern is formed along the surface of the pattern; and the adsorption film removal step is performed by making the adsorption film The adsorption film is removed from the surface of the substrate by changing into a gas.

According to this configuration, the pre-drying treatment liquid containing the adsorbent is supplied to the surface of the substrate that is kept level. The adsorption material contained in the treatment solution before drying is adsorbed on the surface of the pattern formed on the substrate. Moreover, in the state where the adsorbed substance is adsorbed on the surface of the pattern, the substrate is kept horizontal while rotating around the vertical axis of rotation. Thereby, the pre-drying treatment liquid is discharged from the surface of the substrate by centrifugal force, and the pre-drying treatment liquid on the surface of the substrate is reduced.

When the substrate is rotated at a certain degree of rotation speed, although most of the pre-drying treatment liquid is removed from the surface of the substrate, the adsorbed substance adsorbed on the surface of the pattern remains on the substrate. Thereby, an adsorption film containing the adsorption material adsorbed on the surface of the pattern is formed along the surface of the pattern. That is, the space between two adjacent patterns is not filled with the adsorption film without gaps, but the surface of the pattern is coated with the adsorption film in such a way that the space between the surfaces of the adsorption film faces each other in the width direction of the pattern. cover.

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

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

The pattern may be a structure formed of a single material, or a structure including a plurality of layers laminated in the thickness direction of the substrate. The surface of the pattern includes a side surface perpendicular or substantially perpendicular to the plane of the substrate orthogonal to the thickness direction of the substrate, and an upper surface parallel or substantially parallel to the plane of the substrate. The adsorption film is, for example, a film having a surface parallel or substantially parallel to the surface of the pattern. When the adsorption film is formed on the entire area of the surface of the pattern, the surface of the adsorption film includes the upper surface parallel or approximately parallel to the upper surface of the pattern, and the side surface parallel or approximately parallel to the side surface of the pattern. It is also possible that not the entire area of the surface of the pattern but only a part of the surface of the pattern is covered by the adsorption film. For example, only the upper end of the side surface of the pattern and the upper end of the pattern on the upper surface of the pattern may be included, or only the upper surface of the pattern may be covered by the adsorption film.

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

The adsorption film removal step includes a pattern recovery step. The pattern recovery step is to remove the adsorption film between the two collapsed patterns that are connected by the adsorption film, and use the restoring force of the pattern to make the collapsed The shape of the above pattern is restored.

According to this structure, as described above, even if two adjacent patterns collapse in the direction of approaching each other, the two patterns do not directly contact each other, but are connected via the adsorption film. Therefore, if the pattern does not undergo plastic deformation or breakage, when the adsorption film is removed, the collapsed pattern recovers with elastic restoring force. Thereby, even when the strength of the pattern is low, the collapse rate of the final pattern can be improved.

Before removing the adsorption film, a part of the adsorption film is interposed between the two collapsed patterns. As long as the shape of the collapsed pattern is restored after the adsorption film is removed, part of the two collapsed patterns can also be directly connected before the adsorption film is removed. Even in this case, when the adsorption film is removed, the adhesive force that maintains the two patterns in a collapsed state is weakened. Therefore, if the pattern does not undergo plastic deformation or damage, the collapsed pattern will also be restored by the restoring force of the pattern. Vertical state.

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

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

The step of supplying the pre-drying treatment liquid includes an adsorption promotion step that stops the rotation of the substrate before forming the adsorption film or makes the substrate rotate at a speed lower than that of the substrate when the adsorption film is formed. The rotation speed rotates to make the pre-drying treatment liquid contact the surface of the pattern.

According to this configuration, before forming the adsorption film, the rotation of the substrate is stopped or the rotation speed of the substrate is maintained at a low value (adsorption acceleration speed), and the pre-drying treatment liquid is brought into contact with the surface of the pattern. Since the rotation speed of the substrate is zero or small, the flow of the pre-drying treatment liquid at the interface between the pre-drying treatment liquid and the surface of the pattern becomes slow, which promotes the adsorption of the adsorbed substance to the surface of the pattern. Thereby, more adsorbed substances can be adsorbed on the surface of the pattern.

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

According to this structure, 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, which can reduce the energy consumption required to remove the adsorption film. When the adsorption film is removed by heating, since the heating time of the substrate can be shortened, the change of the surface of the substrate such as oxidation can be suppressed. Furthermore, even if excess materials such as residues are generated on the substrate when the adsorption film is changed to a gas, since the volume of the adsorption film is small, the amount of excess materials generated is also small. Therefore, the excess can be removed in a short time. Depending on the situation, the excess may not be removed.

The pre-drying treatment liquid is a solution containing the adsorption material and a solvent fused with the adsorption material.

According to this configuration, the pre-drying treatment liquid, which is a solution obtained by uniformly fusing the adsorbent and the solvent, is supplied to the substrate. In the case of supplying the molten liquid of the adsorption material to the substrate, if the freezing point of the adsorption material is above room temperature, the adsorption material must be heated to maintain the adsorption material as a liquid. If the adsorption material is dissolved in a solvent, even if the freezing point of the adsorption material is above room temperature, as long as the freezing point of the treatment solution before drying can be lowered below room temperature by the freezing point reduction caused by the mixing of the adsorption material and the solvent, it can be The treatment liquid before drying is maintained as a liquid at room temperature. Therefore, the consumption of energy required for the processing of the substrate can be reduced.

When the freezing point of the adsorption material is above room temperature, the freezing point of the treatment solution before drying may also be lower than room temperature. In this case, the pre-drying treatment liquid at room temperature may also be supplied to the surface of the substrate. The above-mentioned solvent may be a single substance or a mixture of two or more substances. In either case, the above-mentioned solvent may contain a high vapor pressure substance with a higher vapor pressure than the above-mentioned adsorbed substance.

The liquid removal step further includes a gas supply step in which when a part of the pre-drying treatment liquid on the surface of the substrate is removed by the rotation of the substrate, the gas is sprayed toward the surface 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 the rotation of the substrate, the gas is sprayed toward the surface of the substrate. The pre-drying treatment liquid on the substrate is discharged from the substrate by the pressure of the gas. At the same time, a part of the pre-drying treatment liquid on the substrate is evaporated by the supply of gas. Thereby, the excess pre-drying treatment liquid can be quickly removed from the surface of the substrate.

The liquid removing step further includes a liquid heating step of removing a part of the pre-drying treatment liquid on the surface of the substrate by rotating the substrate, and then removing the pre-drying treatment liquid on the surface of the substrate heating.

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

The liquid heating step may also include at least one of the following steps: a heating gas supply step, which directs the heating gas of the pre-drying treatment liquid at a higher temperature than the surface of the substrate toward at least one of the front and back of the substrate Spraying; heating liquid supply step, which is to spray the heating liquid of the pre-drying treatment liquid on the surface of the substrate with a temperature higher than that on the back of the substrate; approach the heating step, which is to make the temperature higher than that on the surface of the substrate One side of the heating member of the pre-drying treatment liquid is separated from the substrate, and the other side is arranged on the front side or the back side of the above-mentioned substrate; the contact heating step is to make the temperature higher than the heating member of the pre-drying treatment liquid on the surface of the substrate Contacting the back surface of the substrate; and a light irradiation step of irradiating light to the pre-drying treatment liquid on the surface of the substrate. The light irradiation step may include an overall irradiation step of simultaneously irradiating light to the entire area of the surface of the substrate, or irradiating light only to an irradiation area representing a part of the surface of the substrate and placing the irradiation area in the surface of the substrate The moving partial irradiation step may also include both the above-mentioned overall irradiation step and the partial irradiation step.

The adsorption film removal step may also include at least one of the following steps: a sublimation step, which sublimates the adsorption film; a decomposition step, which decomposes the adsorption film (such as thermal decomposition or photolysis) to make the adsorption film From a solid or liquid to a gas; a reaction step, which is to change the adsorption film from a solid or a liquid to a gas by the reaction of the adsorption film (such as an oxidation reaction); and a plasma irradiation step, which is to irradiate the adsorption film Plasma.

The sublimation step may also include at least one of the following steps: a substrate rotation step, which is to keep the substrate horizontal while rotating around a vertical axis of rotation; a gas supply step, which is to blow inert gas or air and other gases to the adsorption Film; heating step, which heats the adsorption film; decompression step, which reduces the pressure of the environment in contact with the adsorption film; light irradiation step, which irradiates the adsorption film with light; and ultrasonic vibration imparting The step is to impart ultrasonic vibration to the above-mentioned adsorption film. The decomposition step may include at least one of the heating step, light irradiation step, and ultrasonic vibration imparting step. The reaction step may include an oxidation step of oxidizing the adsorption film by contacting an active gas such as ozone gas with the adsorption film.

Another embodiment of the present invention provides a substrate processing apparatus, which includes: a pre-drying treatment liquid supply unit that supplies the pre-drying treatment liquid containing the adsorbent to be adsorbed to the surface of the pattern formed on the substrate to the above-mentioned maintaining level The surface of the substrate allows the adsorbed substance to be adsorbed on the surface of the pattern; a liquid removal unit, which includes a spin-off unit, the spin-off unit uses a portion of the pre-drying treatment liquid on the surface of the substrate that remains level The substrate is removed by rotating around a vertical axis of rotation, whereby an adsorption film including the adsorption substance adsorbed on the surface of the pattern is formed along the surface of the pattern; and an adsorption film removing unit, which changes the adsorption film The adsorption film is removed from the surface of the substrate for gas. According to this structure, the same effect as the above-mentioned effect can be exhibited.

The above or further objects, features, and effects of the present invention will be clarified by referring to the accompanying drawings in the description of the embodiments described below.

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

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

As shown in FIG. 1A, the substrate processing device 1 is a single-chip device that processes disk-shaped substrates W such as semiconductor wafers one by one. The substrate processing apparatus 1 is provided with: a load port LP, which holds a carrier C accommodating a substrate W; a plurality of processing units 2, which process the substrate W conveyed from the carrier C on the load port LP; and a transport machine The hand, which transports the substrate W between the carrier C on the load port LP and the processing unit 2; and the control device 3, which controls the substrate processing device 1.

The transport robot includes: an indexing robot IR, which carries in and out of the substrate W with respect to the carrier C on the load port LP; and a central robot CR, which carries in and out of the substrate W with respect to the plurality of processing units 2 And move out. The indexing robot IR transfers the substrate W between the load port LP and the center robot CR, and the center robot CR transfers the substrate W between the indexing robot IR and the processing unit 2. The center robot CR includes a hand H1 that supports the substrate W, and the index robot IR includes a hand H2 that supports the substrate W.

The plurality of processing units 2 form a plurality of towers TW arranged around the center robot CR in a plan view. Fig. 1A shows an example of forming four towers TW. The central manipulator CR can be connected to any tower TW. As shown in FIG. 1B, each tower TW includes a plurality of (for example, 3) processing units 2 stacked up and down.

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

FIG. 2 is a schematic diagram obtained by observing the inside of the wet processing unit 2w provided in the substrate processing apparatus 1 horizontally.

The wet processing unit 2w includes: a box-shaped chamber 4 with an internal space; a rotating chuck 10, which in the chamber 4 holds a substrate W horizontally on the other side so that it passes through the center of the substrate W The vertical rotation axis A1 rotates; and the cylindrical processing cup 21 surrounds the rotating 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 baffle 7 which opens and closes the loading/unloading port 5b. The FFU6 (fan filter unit) is arranged on the air outlet 5a provided on the upper part of the partition wall 5. The FFU6 always supplies clean air (air filtered by a filter) into the chamber 4 from the air supply port 5a. The gas in the chamber 4 is discharged from the chamber 4 through the exhaust pipe 8 connected to the bottom of the processing cup 21. Thereby, a downflow of clean air is always formed in the chamber 4. The flow rate of the exhaust gas discharged to the exhaust pipe 8 is changed according to the opening degree of the exhaust valve 9 arranged in the exhaust pipe 8.

The rotating chuck 10 includes: a circular plate-shaped rotating base 12 that is held in a horizontal position; a plurality of chuck pins 11 that hold the substrate W in a horizontal position above the rotating base 12; and a rotating shaft 13, which Extending downward from the central part of the rotating base 12; and a rotating motor 14, which rotates the rotating base 12 and the plurality of chuck pins 11 by rotating the rotating shaft 13. The rotating chuck 10 is not limited to a clamping chuck in which a plurality of chuck pins 11 contact the outer peripheral surface of the substrate W, and may be a non-device forming surface by sucking the back (lower surface) of the substrate W onto the rotating base The upper surface 12u of the seat 12 is a vacuum chuck for keeping the substrate W horizontal.

The processing cup 21 includes: a plurality of shields 24 to receive the processing liquid discharged from the substrate W to the outside; a plurality of cups 23 to receive the processing liquid guided downward by the plurality of shields 24; and a cylinder The outer wall member 22 in a shape of a shape surrounds a plurality of shields 24 and a plurality of cups 23. Fig. 2 shows an example in which four shields 24 and three cups 23 are provided, and the outermost cup 23 is integrated with the third shield 24 from the top.

The shield 24 includes a cylindrical portion 25 that surrounds the rotating chuck 10 and an annular top plate portion 26 that extends diagonally upward from the upper end of the cylindrical portion 25 toward the rotation axis A1. The plurality of top plate portions 26 are stacked up and down, and the plurality of cylindrical portions 25 are arranged in a concentric shape. The annular upper end of the top plate portion 26 corresponds to the upper end 24u of the shield 24 surrounding the substrate W and the rotating base 12 in a plan view. The plurality of cups 23 are respectively arranged below the plurality of cylindrical parts 25. The cup 23 forms an annular liquid receiving groove for receiving the processing liquid guided downward by the shield 24.

The wet processing unit 2w includes a shield raising and lowering unit 27 that individually raises and lowers a plurality of shields 24. The shield lifting unit 27 positions the shield 24 at any position from the upper position to the lower position. FIG. 2 shows a state in which two shields 24 are arranged in the upper position and the remaining two shields 24 are arranged in the lower position. The upper position is that the upper end 24u of the shield 24 is arranged above the holding position where the substrate W held by the spin chuck 10 is arranged. The lower position means that the upper end 24u of the shield 24 is arranged at a position lower than the holding position.

When the processing liquid is supplied to the rotating substrate W, at least one shield 24 is arranged at the upper position. If the processing liquid is supplied to the substrate W in this state, the processing liquid will fall off the substrate W by centrifugal force. The thrown-off processing liquid collides with the inner surface of the shield 24 horizontally facing the substrate W, and is guided to the cup 23 corresponding to the shield 24. Thereby, 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 that spray the processing liquid toward the substrate W held by the spin chuck 10. The plurality of nozzles include: a chemical liquid nozzle 31, which sprays chemical liquid toward the upper surface of the substrate W; a rinse liquid nozzle 35, which sprays a rinse liquid toward the upper surface of the substrate W; and a pre-drying treatment liquid nozzle 39 which is directed above the substrate W The surface sprays the pre-drying treatment liquid; and the replacement liquid nozzle 43, which sprays the replacement liquid toward the upper surface of the substrate W.

The liquid medicine nozzle 31 may be a traveling nozzle that can move horizontally in the chamber 4, or a fixed nozzle that is fixed relative to the partition wall 5 of the chamber 4. The same applies to the rinse liquid nozzle 35, the pre-drying treatment liquid nozzle 39, and the replacement liquid nozzle 43. 2 shows an example in which the chemical liquid nozzle 31, the rinse liquid nozzle 35, the pre-drying treatment liquid nozzle 39, and the replacement liquid nozzle 43 are circulating nozzles and are provided with four nozzle moving units corresponding to the four nozzles.

The chemical liquid nozzle 31 is connected to a chemical liquid pipe 32 that guides the chemical liquid to the chemical liquid nozzle 31. When the chemical liquid valve 33 installed in the chemical liquid pipe 32 is opened, the chemical liquid is continuously ejected downward from the ejection port of the chemical liquid nozzle 31. The chemical liquid sprayed from the chemical liquid nozzle 31 may contain sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, ammonia water, hydrogen peroxide water, organic acid (such as citric acid, oxalic acid, etc.), organic alkali (such as TMAH: A liquid of at least one of tetramethylammonium hydroxide, etc.), a surfactant, and a preservative may be other liquids.

Although not shown, the liquid medicine valve 33 includes: a valve body provided with an internal flow path for the liquid medicine to flow and an annular valve seat surrounding the internal flow path; a valve body, which can move relative to the valve seat; and The actuator moves the valve body between the closed position where the valve body contacts the valve seat and the open position where the valve body is away from the valve seat. The same applies to other valves. The actuator can be a pneumatic actuator or an electric actuator, or an actuator other than these. The control device 3 opens and closes the liquid medicine 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 a vertical direction and a horizontal direction. The nozzle moving unit 34 sets the chemical liquid nozzle 31 between the processing position where the chemical liquid sprayed from the chemical liquid nozzle 31 impinges on the upper surface of the substrate W and the standby position where the chemical liquid nozzle 31 is located around the processing holder 21 in a plan view. Move horizontally between.

The washing liquid nozzle 35 is connected to a washing liquid pipe 36 that guides the washing liquid to the washing liquid nozzle 35. When the flushing liquid valve 37 installed in the flushing liquid pipe 36 is opened, the flushing liquid is continuously ejected downward from the ejection port of the flushing liquid nozzle 35. The rinse liquid sprayed from the rinse liquid nozzle 35 is, for example, pure water (DIW (Deionized Water)). The rinsing liquid can be any of carbonated water, electrolyzed ionized water, hydrogen water, ozone water, and hydrochloric acid water with a dilution concentration (for example, about 10-100 ppm).

The washing liquid nozzle 35 is connected to a nozzle moving unit 38 that moves the washing liquid nozzle 35 in at least one of a vertical direction and a horizontal direction. The nozzle moving unit 38 makes the rinse liquid nozzle 35 reach the processing position on the upper surface of the substrate W with the rinse liquid sprayed from the rinse liquid nozzle 35 and the rinse liquid nozzle 35 is located at the standby position around the processing cup 21 in a plan view. Move horizontally between.

The pre-drying treatment liquid nozzle 39 is connected to the 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 installed in the pre-drying treatment liquid piping 40 is opened, the pre-drying treatment liquid is continuously ejected downward from the nozzle 39 of the pre-drying treatment liquid. 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 installed in the replacement liquid piping 44 is opened, the replacement liquid is continuously ejected downward from the ejection port of the replacement liquid nozzle 43.

The pre-drying treatment liquid includes an adsorbent adsorbed on the surface of the pattern P1 (refer to FIG. 6A) and a dissolved substance fused with the adsorbent. The pre-drying treatment liquid is a solution obtained by uniformly fusing the adsorbed material and the dissolved material. The adsorbed substance is equivalent to the solute, and the dissolved substance is equivalent to the solvent. The treatment liquid before drying can also be a molten liquid of the adsorbed substance.

The freezing point of the treatment solution before drying (the freezing point at 1 atmosphere, the same below) is lower than the freezing point of the adsorbent. Similarly, the freezing point of dissolved substances is lower than the freezing point of adsorbed substances. The freezing point of the treatment solution before drying is lower than room temperature (23°C or its vicinity). The substrate processing apparatus 1 is arranged in a clean room maintained at room temperature. Therefore, even if the pre-drying treatment liquid is not heated, the pre-drying treatment liquid can be maintained as a liquid. However, the freezing point of the treatment solution before drying may be above room temperature, and the freezing point of the dissolved substance may be higher than the freezing point of the adsorbed substance.

The dissolved substance can be a single substance or a mixture of two or more substances. The vapor pressure of the dissolved substance is higher than the vapor pressure of the adsorbed substance. Therefore, dissolved substances are easier to evaporate than adsorbed substances. The vapor pressure of the dissolved substance can be higher than the vapor pressure of water, or below the vapor pressure of water. In addition, the vapor pressure of the dissolved substance may be lower than the vapor pressure of the adsorbed substance.

The adsorbed substance can also be a substance chemically adsorbed on the surface of the pattern P1. That is, the adsorbing substance may also be a substance adsorbed on the surface of the pattern P1 by a chemical reaction between the adsorbing substance and the surface of the pattern P1. Alternatively, the adsorbed substance may also be a substance physically adsorbed on the surface of the pattern P1. That is, the adsorbed substance may also be a substance adsorbed on the surface of the pattern P1 by the electric attraction or 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 under normal temperature or pressure, or it may be a substance other than the sublimable substance. For example, the adsorbent may also be an iodine compound, a chlorine compound, or a brominated compound. Iodine compounds include diiodomethane, iodomethane, and 1-iodopropane. The chlorine compound includes methylene chloride. The brominated compound includes ammonium bromide. The adsorbent may also be a thermally decomposable polymer such as acrylic resin or an inorganic compound. The adsorbent can also be an amphiphilic molecule containing both a hydrophilic group and a hydrophobic group.

As with the adsorbed 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 pre-drying treatment liquid may be two or more types. That is, it is also possible that both of the adsorbing substance and the dissolved substance are sublimable substances, and the sublimable substance different from the adsorbing substance and the dissolved substance may be included in the pre-drying treatment liquid.

The sublimation substance can be, for example, 2-methyl-2-propanol (alias: tertiary butanol, tert-butanol, tertiary butanol) or alcohols such as cyclohexanol, hydrofluorocarbons, 1,3,5 -Any of trioxane (alias: trioxane), camphor (alias: camphor liquid, camphor), naphthalene, iodine, and cyclohexane, and may be other substances.

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

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

As described below, the replacement liquid is supplied to the upper surface of the substrate W covered by the liquid film of the rinse liquid, and the pre-drying treatment liquid is supplied to the upper surface of the substrate W covered by the liquid film of the replacement liquid. The replacement liquid is a liquid that is fused with both the rinse liquid and the pre-drying treatment liquid. The replacement liquid is, for example, IPA. IPA is a liquid that is fused with both water and hydrofluorocarbon. The replacement fluid can also be a mixture of IPA and HFE.

When supplying a mixture of IPA and HFE to the substrate W, connect the first solvent pipe leading to IPA as the first organic solvent and the second solvent pipe leading to HFE as the second organic solvent to the replacement liquid pipe 44 is fine. When one of the first solvent valve installed in the first solvent pipe and the second solvent valve installed in the second solvent pipe is opened, IPA or HFE is supplied to the replacement liquid pipe 44, and when the first solvent valve and When both of the second solvent valves are opened, the mixed liquid of IPA and HFE is supplied to the replacement liquid piping 44. It is also possible to spray HFE from a nozzle different from the replacement liquid nozzle 43.

When the replacement liquid is supplied to the upper surface of the substrate W covered by the liquid film of the rinse liquid, most of the rinse liquid on the substrate W is washed away by the replacement liquid and discharged from the substrate W. The remaining trace amount of flushing fluid is dissolved in the replacement fluid and diffused in the replacement fluid. The diffused rinse liquid is discharged from the substrate W together with the replacement liquid. Therefore, it is possible to efficiently replace the rinse liquid on the substrate W 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 rinse liquid contained in the pre-drying treatment liquid on the substrate W can be reduced.

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 a vertical direction and a horizontal direction. The nozzle moving unit 42 causes the pre-drying treatment liquid nozzle 39 to be sprayed from the pre-drying treatment liquid nozzle 39 at the processing position where the pre-drying treatment liquid impinges on the upper surface of the substrate W and the pre-drying treatment liquid nozzle 39 is located in the processing substrate in a plan view. The standby positions around the cup 21 move horizontally.

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 sets the replacement liquid nozzle 43 at a processing position where the replacement liquid sprayed from the replacement liquid nozzle 43 impinges on the upper surface of the substrate W and the replacement liquid nozzle 43 is located at a standby position around the processing cup 21 in a plan view. Move horizontally between.

The wet processing unit 2w includes a blocking member 51 disposed above the rotating 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 circular plate portion 52 horizontally arranged above the rotating chuck 10. The blocking member 51 is horizontally supported by a cylindrical support shaft 53 extending upward from the central portion of the circular plate portion 52. The center line of the disc portion 52 is arranged on the rotation axis A1 of the substrate W. The lower surface of the disc portion 52 corresponds to the lower surface 51L of the blocking member 51. The lower surface 51L of the blocking member 51 is the opposite 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 greater than the diameter of the substrate W.

The blocking member 51 is connected to a blocking member elevating unit 54 that vertically raises and lowers the blocking member 51. The blocking member lifting unit 54 positions the blocking member 51 at any position from the upper position (the position shown in FIG. 2) to the lower position. The lower position is a close position where the lower surface 51L of the blocking member 51 approaches the upper surface of the substrate W to a height where the circulating nozzles such as the chemical liquid nozzle 31 cannot enter between the substrate W and the blocking member 51. The upper position is the separation position where the blocking member 51 is retracted to the height between the blocking member 51 and the substrate W where the traveling nozzle can enter.

The plurality of nozzles includes a center nozzle 55 that sprays a processing fluid such as a processing liquid or a processing gas downward through the central opening 61 above the central opening of the lower surface 51L of the blocking member 51. The center nozzle 55 extends up and down along the rotation axis A1. The center nozzle 55 is arranged in a through hole that penetrates the center portion of the blocking member 51 up and down. The inner peripheral surface of the blocking member 51 surrounds the outer peripheral surface of the center 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 ejection port of the central nozzle 55 for ejecting the processing liquid is arranged above the central opening 61 of the blocking member 51.

The center nozzle 55 is connected to a gas piping 56 that guides the inert gas onto the center nozzle 55. The substrate processing apparatus 1 may include an upper temperature regulator 59 for heating or cooling the inert gas sprayed from the center nozzle 55. When the gas valve 57 installed on the upper gas piping 56 is opened, the inert gas is continuously ejected downward from the ejection port of the center nozzle 55 at a flow rate corresponding to the opening of the flow adjustment valve 58 that changes the flow rate of the inert gas. The inert gas sprayed from the central nozzle 55 is nitrogen. The inert gas may also be a gas other than nitrogen such as helium or argon.

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 flow path 62 is connected to a 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 also include an upper temperature regulator 66 for heating or cooling the inert gas sprayed from the central opening 61 on the blocking member 51. When the gas valve 64 installed on the upper gas piping 63 is opened, the inert gas continues downward from the upper central opening 61 of the blocking member 51 at a flow rate corresponding to the opening of the flow adjustment valve 65 that changes the flow rate of the inert gas. Spit out. The inert gas sprayed from the central opening 61 on the blocking member 51 is nitrogen. The inert gas may also be a gas other than nitrogen such as helium or argon.

The plurality of nozzles includes a lower surface nozzle 71 that ejects the processing liquid toward the center of the lower surface of the substrate W. The lower surface nozzle 71 includes: a nozzle disc portion disposed between the upper surface 12u of the rotating base 12 and the lower surface of the substrate W; and a nozzle cylindrical portion extending downward from the nozzle disc portion. The ejection port of the lower surface nozzle 71 opens in the center of the upper surface of the nozzle disc. When the substrate W is held by the spin chuck 10, the ejection port of the nozzle 71 on the lower surface and the center of the lower surface of the substrate W face vertically.

The lower surface nozzle 71 is connected to a heating fluid pipe 72 that guides warm water (pure water with a temperature higher than room temperature) as an example of the heating fluid to the lower surface nozzle 71. The pure water supplied to the lower surface nozzle 71 is heated by a heater 75 installed under the heating fluid pipe 72. When the heating fluid valve 73 installed in the heating fluid piping 72 is opened, the warm water is continuously sprayed upward from the spray outlet of the nozzle 71 on the lower surface at a flow rate corresponding to the opening of the flow adjustment valve 74 that changes the flow rate of the warm water. . Thereby, warm water is supplied to the lower surface of the substrate W.

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

The outer peripheral surface of the lower surface nozzle 71 and the inner peripheral surface of the rotating base 12 form a cylindrical lower gas flow path 82 extending vertically. The lower gas flow path 82 includes a central opening 81 below the central opening of the upper surface 12 u of the rotating base 12. The lower gas flow path 82 is connected to a gas pipe 83 that guides the inert gas to the lower central opening 81 under the spin base 12. The substrate processing apparatus 1 may also include a lower temperature regulator 86 for heating or cooling the inert gas sprayed from the central opening 81 under the rotating susceptor 12. When the gas valve 84 installed under the lower gas piping 83 is opened, the inert gas continues upward from the central opening 81 under the rotating base 12 at a flow rate corresponding to the opening of the flow adjustment valve 85 that changes the flow rate of the inert gas. Spit out.

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

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

The dry processing unit 2d includes a box-shaped chamber 4 having an internal space, and a heating unit 91 that heats the substrate W in the chamber 4. The heating unit 91 includes: a heating plate 92, which supports the substrate W horizontally while heating; a plurality of jacking pins 97, which support the substrate W horizontally above the heating plate 92; and a jacking-up and lifting unit 98, which A plurality of jacking pins 97 are raised and lowered.

The heating plate 92 is an example of a heating member that heats the substrate W. The heating plate 92 includes a heating element 93 that generates Joule heat by energization, and a housing 94 that supports the substrate W horizontally and houses the heating element 93. The heating element 93 and the housing 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 heats the heating element 93, it heats the entire substrate W uniformly.

The housing 94 of the heating plate 92 includes: a disc-shaped base portion 95 disposed under 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 greater than the outer diameter of the substrate W. The plurality of protrusions 96 are in contact with the lower surface of the substrate W at positions away from the upper surface of the base portion 95 upward. The plurality of protruding portions 96 are arranged at a plurality of positions in the upper surface of the base portion 95 in such a manner that the substrate W is horizontally supported. The substrate W is horizontally supported in a state where the lower surface of the substrate W is separated upward from the upper surface of the base portion 95.

The plurality of jack-up pins 97 are respectively inserted into the plurality of through holes penetrating the heating plate 92. The jack-up pin 97 includes a hemispherical upper end contacting the lower surface of the substrate W. The upper ends of the plural jack-up pins 97 are arranged at the same height. The jack-up lifting unit 98 is to make the plurality of jack-up pins 97 above the plurality of jack-up pins 97 are located at a position higher than the heating plate 92 (the position shown by the two-dot chain line in FIG. 3) and a plurality of The upper end of the jack-up pin 97 moves in the vertical direction between the retreat to the lower position inside the heating plate 92 (the position shown by the solid line in FIG. 3).

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

The control device 3 is a computer including a computer body 3a and a peripheral device 3d connected to the computer body 3a. The computer body 3a includes: a CPU 3b (central processing unit), which executes various commands; and a main memory device 3c, which stores information. The peripheral device 3d includes: an auxiliary memory device 3e, which stores information such as a program P; a reading device 3f, which reads information from the removable medium M; and a communication device 3g, which communicates with other devices 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 one of a keyboard, a pointing device, and a touch panel, or may be other devices. The substrate processing apparatus 1 can also be provided with a touch panel display that also serves as an input device and a display device.

The CPU 3b executes the program P stored in the auxiliary memory device 3e. The program P in the auxiliary memory device 3e can be pre-installed in the control device 3, or can be sent from the removable medium M to the auxiliary memory device 3e via the reading device 3f, or can be communicated from an external device such as a host computer The device 3g is sent to the auxiliary memory device 3e.

The auxiliary memory device 3e and the removable medium M are non-volatile memories that retain memory even if they are not supplied with power. The auxiliary memory device 3e is, for example, a magnetic memory device such as a hard disk drive. The removable medium M is, for example, an optical disc such as a compact disc 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 memory device 3e memorizes a plurality of process recipes. The process recipe specifies the processing content, processing conditions, and processing sequence of the substrate W. The plurality of process recipes are different from each other in at least one of the processing content, processing conditions, and processing sequence of the substrate W. The control device 3 controls the substrate processing device 1 in a manner of processing the substrate W according to the process 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 the 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 front surface of the substrate W is equivalent to the device forming surface for forming devices such as transistors or capacitors. The substrate W may be a substrate W on which the pattern P1 (see FIG. 6A) is formed on the front surface of the substrate W as a pattern forming surface, or may be a substrate W on which the pattern P1 is not formed on the front surface of the substrate W. In the latter case, the pattern P1 may also be formed in the following chemical liquid supply step.

FIG. 5 is a step diagram for explaining an example of the processing of the substrate W 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 performed. Hereinafter, refer to FIG. 2, FIG. 3, and FIG. 5. Refer to FIGS. 6A to 6D as appropriate.

When the substrate W is processed by the substrate processing apparatus 1, the carrying-in step of carrying the substrate W into the wet processing unit 2w (step S1 in FIG. 5) is performed.

Specifically, when the blocking member 51 is at the upper position, all the shields 24 are at the lower position, and all the traveling nozzles are at the standby position, the center robot CR (see FIG. 1A) supports the substrate W with the hand H1. While making the hand H1 enter the wet processing unit 2w. Then, the central robot CR places the substrate W on the hand H1 on the plurality of chuck pins 11 with the front side of the substrate W facing up. After that, a plurality of chuck pins 11 are pressed against the outer peripheral surface of the substrate W, and the substrate W is held. After the center robot CR places the substrate W on the spin chuck 10, the hand H1 is retracted from the inside of 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 rotating base 12 start to spray nitrogen gas. Thereby, the space between the substrate W and the blocking member 51 is filled with nitrogen gas. Similarly, the space between the substrate W and the spin base 12 is filled with nitrogen. On the other hand, the shield lifting unit 27 raises at least one shield 24 from the lower position to the upper position. After that, the rotation motor 14 is driven to start the rotation of the substrate W (step S2 in FIG. 5). Thereby, the substrate W rotates at the liquid supply speed.

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

Specifically, in a state where the blocking member 51 is at the upper position and at least one shield 24 is at the upper position, the nozzle moving unit 34 moves the liquid chemical nozzle 31 from the standby position to the processing position. After that, the chemical liquid valve 33 is opened, and the chemical liquid nozzle 31 starts to discharge the chemical liquid. When a certain time has passed after the liquid medicine valve 33 is opened, the liquid medicine valve 33 is closed to stop the discharge of the liquid medicine. After that, the nozzle moving unit 34 moves the chemical liquid nozzle 31 to the standby position.

After the chemical liquid sprayed from the chemical liquid nozzle 31 reaches the upper surface of the substrate W rotating at the liquid supply speed, it flows outward along the upper surface of the substrate W by centrifugal force. Therefore, the chemical liquid is supplied to the entire area of the upper surface of the substrate W, and a liquid film of the chemical liquid covering the entire area of the upper surface of the substrate W is formed. When the chemical liquid nozzle 31 ejects the chemical liquid, the nozzle moving unit 34 can move the impingement position of the chemical liquid on the upper surface of the substrate W through the center and the outer periphery, or make the impingement position in the center. Department is still.

Then, a rinsing liquid supply step of supplying pure water as an example of the rinsing liquid to the upper surface of the substrate W to rinse the chemical liquid on the substrate W is performed (step S4 in FIG. 5).

Specifically, in a state where the blocking member 51 is located at the upper position and at least one shield 24 is located at the upper position, the nozzle moving unit 38 moves the rinse liquid nozzle 35 from the standby position to the processing position. After that, the rinsing liquid valve 37 is opened, and the rinsing liquid nozzle 35 starts to spray the rinsing liquid. Before starting to spray pure water, the shield lifting unit 27 can also move at least one shield 24 vertically to switch the shield 24 that receives the liquid discharged from the substrate W. When a certain time elapses after the flushing liquid valve 37 is opened, the flushing liquid valve 37 is closed to stop the spraying of the flushing liquid. After that, the nozzle moving unit 38 moves the rinse liquid nozzle 35 to the standby position.

The pure water sprayed from the rinse liquid nozzle 35 is deposited 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 liquid on the substrate W is replaced with pure water sprayed from the rinse liquid nozzle 35. Thereby, a liquid film of pure water covering the entire area of the upper surface of the substrate W is formed. When the flushing liquid nozzle 35 sprays pure water, the nozzle moving unit 38 can move the impingement position of pure water relative to the impingement position of the upper surface of the substrate W through the center and the outer periphery, or the impingement position may be in the center. Department is still.

Next, a replacement liquid supply step of supplying a replacement liquid fused with both the rinse liquid and the pre-drying treatment liquid to the upper surface of the substrate W to replace the pure water on the substrate W with the replacement liquid is performed (step S5 in FIG. 5) ).

Specifically, in a state where the blocking member 51 is at the upper position and at least one shield 24 is at the upper position, the nozzle moving unit 46 moves the replacement liquid nozzle 43 from the standby position to the processing position. After that, the replacement liquid valve 45 is opened, and the replacement liquid nozzle 43 starts to discharge the replacement liquid. Before starting to spray the replacement liquid, the shield lifting unit 27 can also move at least one shield 24 vertically to switch the shield 24 that receives the liquid discharged from the substrate W. When a certain time elapses after the replacement liquid valve 45 is opened, the replacement liquid valve 45 is closed to stop the discharge of the replacement liquid. After that, the nozzle moving unit 46 moves the replacement liquid nozzle 43 to the standby position.

The replacement liquid ejected from the replacement liquid nozzle 43 impinges on the upper surface of the substrate W rotating at the liquid supply speed, and 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 sprayed from the replacement liquid nozzle 43. Thereby, a liquid film of the replacement liquid covering the entire area of the upper surface of the substrate W is formed. When the replacement liquid nozzle 43 ejects the replacement liquid, the nozzle moving unit 46 can move the imposition position of the replacement liquid phase on the upper surface of the substrate W through the center and the outer periphery, or make the imposition position in the center. Department is still.

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

Specifically, in a state where the blocking member 51 is at the upper position and at least one shield 24 is at the upper position, the nozzle moving unit 42 moves the pre-drying treatment liquid nozzle 39 from the standby position to the treatment position. Thereafter, the pre-drying treatment liquid valve 41 is opened, and the pre-drying treatment liquid nozzle 39 starts to spray the pre-drying treatment liquid. Before starting to spray the pre-drying treatment liquid, the shield lifting unit 27 can also move at least one shield 24 vertically to switch the shield 24 that receives the liquid discharged from the substrate W.

After the pre-drying treatment liquid sprayed from the pre-drying treatment liquid nozzle 39 reaches the upper surface of the substrate W rotating at the liquid supply speed, it 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 treatment liquid ejected from the pre-drying treatment liquid nozzle 39. Thereby, a liquid film of the pre-drying treatment liquid covering the entire area of the upper surface of the substrate W is formed. When the pre-drying treatment liquid nozzle 39 sprays the pre-drying treatment liquid, the nozzle moving unit 42 can move the impingement position of the pre-drying liquid on the upper surface of the substrate W through the central part and the outer peripheral part, or Make the landing position at the center of the static.

FIG. 6A shows an example of a cross section of a substrate W supplied with a pre-drying treatment liquid. When the pre-drying treatment liquid is in contact with the upper surface of the substrate W (the front surface of the substrate W) including the surface of the pattern P1, the adsorbent contained in the pre-drying treatment liquid is adsorbed on the upper surface of the substrate W. The same phenomenon occurs in all parts of the upper surface of the substrate W, and the adsorbed material contained in the treatment solution before drying is adsorbed on each part of the upper surface of the substrate W. FIG. 6A shows an example in which one molecule of the adsorbed substance is adsorbed on each part of the upper surface of the substrate W and a monomolecular film of the adsorbed substance is formed along the upper surface of the substrate W. In this example, it is depicted that there is a boundary between the pre-drying treatment liquid adsorbed on the upper surface of the substrate W and the pre-drying treatment liquid not adsorbed on the upper surface of the substrate W, but there is actually no such boundary.

After the liquid film of the pre-drying treatment liquid is formed, the adsorption promotion step (step S7 in FIG. 5) is carried out. The adsorption promotion step is to promote while maintaining the entire area of the upper surface of the substrate W covered by the liquid film of the pre-drying treatment liquid. The adsorption of the adsorbed substance to the upper surface of the substrate W.

Specifically, in a state where the pre-drying treatment liquid nozzle 39 sprays the pre-drying treatment liquid, the rotation motor 14 reduces the rotation speed of the substrate W. At this time, the rotation motor 14 can stop the rotation of the substrate W, and can also rotate the substrate W at an adsorption promotion speed (for example, a speed exceeding 0 to 20 rpm or less) that is less than the liquid supply speed. After the rotation speed of the substrate W is reduced, the pre-drying treatment liquid valve 41 is closed to stop the discharge of the pre-drying treatment liquid. Furthermore, 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.

When the rotation speed of the substrate W decreases, the centrifugal force of the pre-drying treatment liquid applied to the substrate W decreases, and the flow rate of the pre-drying treatment liquid discharged from the substrate W decreases. Furthermore, since the centrifugal force of the pre-drying treatment liquid applied to 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, after the ejection of the pre-drying treatment liquid is stopped, the entire area of the upper surface of the substrate W is maintained in the state covered by the liquid film of the pre-drying treatment liquid. Since the rotation speed of the substrate W is zero or small, the flow of the pre-drying treatment liquid at the interface between the pre-drying treatment liquid and the pattern P1 becomes slow, which promotes the adsorption of the adsorbed substance to the surface of the pattern P1.

Then, a liquid removal step of removing a part of the pre-drying treatment liquid on the upper surface of the substrate W by rotating the substrate W at a liquid removal speed (step S8 in FIG. 5) is performed to form an adsorption film 101 ( Refer to Figure 6B).

Specifically, in a state where the blocking member 51 is at the lower position and nitrogen is ejected from the central opening 61 above the blocking member 51, the rotation motor 14 increases the rotation speed of the substrate W to a liquid removal speed greater than the adsorption promotion speed, and maintains Is the liquid removal rate. The liquid removal rate can 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 treatment liquid discharged from the substrate W increases, and the pre-drying treatment 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 treatment liquid is removed from the upper surface of the substrate W. However, the adsorption material adsorbed on the surface of the pattern P1 remains on the substrate W by the force acting between the adsorption material and the substrate W. The surface layer of the pre-drying treatment liquid remaining on the upper surface of the substrate W including the surface of the pattern P1 is concentrated by drying and changed into a solid thin film. As a result, as shown in FIG. 6B, an adsorption film 101 including an adsorption material adsorbed on the surface of the pattern P1 is formed along the surface of the pattern P1. The pre-drying treatment liquid remaining on the upper surface of the substrate W may be changed into a solid only on the surface layer, or may be changed into a solid as a whole. Alternatively, the pre-drying treatment liquid remaining on the upper surface of the substrate W may be changed into a gel state.

The adsorption film 101 corresponds to a sacrificial film that is finally removed from the substrate W. The adsorption film 101 may be a cured film obtained by curing the treatment liquid before 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, a surface film 101u covering the upper surface Pu of the pattern P1, and a bottom surface covering the substrate W (plane Ws of the substrate W) The bottom mask 101b. The upper end portion of the side film 101s and the upper surface film 101u constitute the front end film of the front end of the cover pattern P1. The thickness T1 of the adsorption film 101 is smaller than the height Hp of the pattern P1. The thickness T1 of the adsorption film 101 may be smaller than the width Wp of the pattern P1, or may be smaller than the interval G1 between two adjacent patterns P1. The adsorption film 101 can also be a monomolecular film for adsorbing substances. In this case, the thickness T1 of the adsorption film 101 is several nanometers or several angstroms.

Fig. 6B shows the state just after two adjacent patterns P1 collapse in the direction of approaching each other. When the pre-drying treatment liquid on the substrate W is reduced to a certain extent, the upper surface (liquid surface) of the pre-drying treatment liquid moves between two adjacent convex patterns P1. That is, the interface between the gas and the liquid (treatment liquid before drying) moves between the patterns P1, and the collapse force caused by the surface tension of the treatment liquid before drying is applied to the patterns P1 via the adsorption film 101. At this time, even if the two adjacent patterns P1 collapse toward each other, since at least a part of the surface of the pattern P1 is coated by the adsorption film 101, the two patterns P1 do not directly contact but interpose the adsorption film 101. Meet.

The collapsed pattern P1 is restored to a vertical state relative to the bottom surface of the substrate W (the plane Ws of the substrate W) by the restoring force (elastic force) of the pattern P1. On the other hand, if the two side films 101s respectively covering the front ends of the two collapsed patterns P1 contact 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 maintains the 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 passed after two adjacent patterns P1 collapse in the direction of 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 vaporizes and flows in all directions. The pre-drying treatment liquid vaporized near the base of the two collapsed patterns P1 adheres to the adsorption film 101 interposed between the front ends of the two patterns P1. Therefore, as shown by the dotted circle in FIG. 6C, near the front end of the two collapsed patterns P1, the adsorption film 101 becomes thicker than other positions.

Furthermore, when a part of the pre-drying treatment liquid on the upper surface of the substrate W is removed by the rotation of the substrate W in order to form the adsorption film 101 containing the adsorbed substance, the pre-drying treatment liquid on the upper surface of the substrate W can also be removed. heating. For example, the heating fluid valve 73 can be opened to cause the lower surface nozzle 71 to spray warm water, or the central opening 81 under the rotating base 12 can spray nitrogen heated by the lower temperature regulator 86. If the pre-drying treatment liquid on the upper surface of the substrate W is heated, the time required to form the adsorption film 101 can be shortened.

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

Specifically, the rotation motor 14 is stopped, and the rotation of the substrate W is stopped (step S9 in FIG. 5). Furthermore, the shielding member raising and lowering unit 54 raises the shielding member 51 to the upper position, and the shield raising and lowering unit 27 lowers all the shields 24 to the lower position. Furthermore, 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 rotating base 12 stop spraying nitrogen gas. After that, the central robot CR moves the hand H1 into the wet processing unit 2w. After the plurality of chuck pins 11 release the holding of the substrate W, the central robot CR uses the hand H1 to support the substrate W on the rotating chuck 10. After that, while supporting the substrate W with the hand H1, the center robot CR retracts the hand H1 from the inside of the wet processing unit 2w. Thereby, the board|substrate W is carried out from the wet processing unit 2w.

After unloading the substrate W from the wet processing unit 2w, with the plurality of lift-up pins 97 in the upper position, the center manipulator CR supports the substrate W with the hand H1 while allowing the hand H1 to enter the dry processing unit 2d . Then, the center robot CR places the substrate W on the hand H1 on the plurality of lifting pins 97 with the front side of the substrate W facing up. After that, the jack-up lifting unit 98 lowers the plurality of jack-up pins 97 to the lower position. Thereby, the substrate W on the plurality of lifting pins 97 is placed on the heating plate 92. After the center robot CR places the substrate W on the plurality of lift-up pins 97, the hand H1 is retracted from the inside of the dry processing unit 2d.

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

Specifically, the heating plate 92 intervenes the substrate W to heat the adsorption film 101 on the substrate W at a removal temperature (for example, a temperature higher than 100° C.). When the adsorption material contained in the adsorption film 101 is a sublimable material, if the adsorption film 101 is heated at the removal temperature, the adsorption film 101 on the substrate W will change into a gas without passing through a liquid. When the adsorption material contained in the adsorption film 101 is a substance other than the sublimation material, if the adsorption film 101 is heated at the removal temperature, the adsorption film 101 on the substrate W is transformed 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 pipe 8. Thereby, the adsorption film 101 is removed from the upper surface of the substrate W.

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 front ends of the two collapsed patterns P1. Thereby, the adhesive force that maintains the two patterns P1 in a collapsed state is weakened. If the pattern P1 is not plastically deformed or damaged, the collapsed pattern P1 is restored to the vertical state by the restoring force of the pattern P1 (refer to the black arrow in FIG. 6D). Therefore, even if the pattern P1 collapses when the remaining pre-drying treatment liquid is removed, after the adsorption film 101 is removed, the pattern P1 returns to a vertical state. Thereby, even when the strength of the pattern P1 is low, the collapse rate of the final pattern P1 can be improved.

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

Specifically, the jack-up lifting unit 98 raises the plurality of jack-up pins 97 from the lower position to the upper position. Thereby, the substrate W on the heating plate 92 is lifted by a plurality of push-up pins 97 and is separated from the heating plate 92 upward. After that, the central robot CR moves the hand H1 into the dry processing unit 2d. In this state, the jack-up lifting unit 98 lowers the plurality of jack-up pins 97 to the lower position. Thereby, the substrate W on the plurality of lifting pins 97 is placed on the hand H1. After the center robot CR places the substrate W on the hand H1, the hand H1 is retracted from the inside of the dry processing unit 2d. Thereby, the processed substrate W is carried out from the dry processing unit 2d.

As described above, in this embodiment, the pre-drying treatment liquid containing the adsorbent is supplied to the surface of the substrate W which is kept level. The adsorption material contained in the treatment solution before drying is adsorbed on the surface of the pattern P1 formed on the substrate W. Then, in a state where the adsorbed substance is adsorbed on the surface of the pattern P1, the substrate W is kept horizontal while rotating around the vertical axis of rotation A1. Thereby, the pre-drying treatment liquid is discharged from the surface of the substrate W by centrifugal force, and the pre-drying treatment liquid on the surface of the substrate W is reduced.

When the substrate W is rotated at a certain degree of rotation speed, although most of the pre-drying treatment liquid is removed from the surface of the substrate W, the adsorbed substance adsorbed on the surface of the pattern P1 remains on the substrate W. As a result, an adsorption film 101 containing an adsorbing substance adsorbed on the surface of the pattern P1 is formed along the surface of the pattern P1. That is, the space between two adjacent patterns P1 is not filled up by the adsorption film 101 without gaps, but the surface of the adsorption film 101 faces each other in the width direction of the pattern P1. The surface is coated with the adsorption film 101.

On the other hand, when the pre-drying treatment liquid on the substrate W is reduced to a certain extent, the upper surface (liquid surface) of the pre-drying treatment liquid moves between two adjacent convex patterns P1. That is, the interface between the gas and the liquid (treatment liquid before drying) moves between the patterns P1, and the collapse force caused by the surface tension of the treatment liquid before drying is applied to the patterns P1 via the adsorption film 101. At this time, even if the two adjacent patterns P1 collapse toward each other, since at least a part of the surface of the pattern P1 is coated by the adsorption film 101, the two patterns P1 do not directly contact but interpose the adsorption film 101. Meet.

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. When the pre-drying treatment liquid is removed, when two adjacent patterns P1 collapse in a direction close to each other, the adsorption film 101 is removed from between the two patterns P1. If the pattern P1 is not plastically deformed or damaged, when the adsorption film 101 is removed, the collapsed pattern P1 is restored to a vertical state by the restoring force of the pattern P1. In other words, even if the pattern P1 collapses during the period before the adsorption film 101 is removed, after the adsorption film 101 is removed, the pattern P1 returns to the vertical state. Thereby, not only when the strength of the pattern P1 is high, but also when the strength of the pattern P1 is low, the collapse rate of the final pattern P1 can be improved. The sample in which the pattern P1 was formed was subjected to the same treatment as an example of the above-mentioned substrate W treatment. As a result, it was confirmed that the collapse rate of the pattern P1 was actually improved.

In this embodiment, before forming the adsorption film 101, while stopping the rotation of the substrate W or maintaining the rotation speed of the substrate W at a low value (adsorption acceleration speed), the pre-drying treatment liquid is brought into contact with the surface of the pattern P1 . Since the rotation speed of the substrate W is zero or small, 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 slow, which promotes the adsorption of the adsorbed substance to the surface of the pattern P1. Thereby, more adsorbed substances can be adsorbed on the surface of the pattern P1.

In this embodiment, a thin adsorption film 101 is formed on the surface of the pattern P1. That is, the thickness T1 (refer to FIG. 6B) of the adsorption film 101 is smaller than the height Hp of the pattern P1 (refer to FIG. 6A). Since the adsorption film 101 is relatively thin, the adsorption film 101 can be removed in a short time, and the energy consumption required to remove the adsorption film 101 can be reduced. When the adsorption film 101 is removed by heating, since the heating time of the substrate W can be shortened, it is possible to suppress changes in the surface of the substrate W such as oxidation. Furthermore, when the adsorption film 101 is changed to a gas, even if excess materials such as residues are generated on the substrate W, since the volume of the adsorption film 101 is small, the generation amount of the excess materials is also small. Therefore, the excess can be removed in a short time. Depending on the situation, the excess may not be removed.

In this embodiment, the pre-drying treatment liquid, which is a solution obtained by uniformly dissolving the adsorption material and the solvent, is supplied to the substrate W. In the case of supplying the molten liquid of the adsorption material to the substrate W, if the freezing point of the adsorption material is above room temperature, the adsorption material must be heated to maintain the adsorption material as a liquid. If the adsorption material is dissolved in the solvent, even if the freezing point of the adsorption material is above room temperature, as long as the freezing point of the treatment solution before drying can be lowered below room temperature by the lowering of the freezing point caused by the mixing of the adsorption material and the solvent, The treatment liquid before drying is maintained as a liquid at room temperature. Therefore, the consumption of energy required for processing the substrate W can be reduced.

In this embodiment, when a part of the pre-drying treatment liquid on the surface of the substrate W is removed by the rotation of the substrate W, nitrogen gas, which is an example of the gas, is sprayed toward the surface of the substrate W. The pre-drying treatment liquid on the substrate W is discharged from the substrate W under the pressure of gas. At the same time, a part of the pre-drying treatment liquid on the substrate W is evaporated by the supply of gas. Thereby, the excess pre-drying treatment liquid can be quickly removed from the surface of the substrate W.

Next, the second embodiment will be described.

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

Fig. 7A is a schematic view obtained by observing the rotating chuck 10, the blocking member 51 and the heating plate 92 of the second embodiment of the present invention horizontally. FIG. 7B is a schematic view of the rotating chuck 10 and the heating plate 92 viewed from above. In FIG. 7A, FIG. 7B, FIG. 8A, and FIG. 8B, the same reference numerals as those in FIG. 1 and the like are attached to the same structures as those shown in FIG. 1 to FIG. 6D, and their description is omitted.

As shown in FIG. 7A, the built-in heater 111 is arranged inside the circular plate 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 under the built-in heater 111. The built-in heater 111 is, for example, a heating element that generates Joule heat by energization. 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 heating plate 92 is arranged above the rotating base 12. As shown in FIG. 7B, the center line of the heating plate 92 is arranged on the rotation axis A1 of the substrate W. Even if the rotating chuck 10 rotates, the heating plate 92 does not rotate. The outer diameter of the heating plate 92 is smaller than the diameter of the substrate W. The plurality of chuck pins 11 are arranged around the heating plate 92. The substrate W is arranged above the heating plate 92.

As shown in FIG. 7A, the heating plate 92 is horizontally supported by a support shaft 113 extending downward from the central portion of the heating plate 92. The heating plate 92 can move up and down with respect to the rotating base 12. The heating plate 92 is connected to the plate lifting unit 114 via a support shaft 113. The plate lifting unit 114 vertically lifts the heating plate 92 between the upper position (the position shown by the solid line in FIG. 7A) and the lower position (the position shown by the two-dot chain line in FIG. 7A). The upper position is the contact position where the heating plate 92 contacts the lower surface of the substrate W. The lower position is the close position between the lower surface of the substrate W and the upper surface 12u of the spin base 12 when the heating plate 92 is away from the substrate W.

The plate lifting unit 114 positions the heating plate 92 at any position from the upper position to the lower position. When the substrate W is supported by the plurality of chuck pins 11 and the holding of the substrate W is released, and the heating plate 92 is raised to the upper position, the plurality of protrusions 96 of the heating plate 92 contact the lower surface of the substrate W, and the substrate W is supported by the heating plate 92. After that, the substrate W is lifted by the heating plate 92 and separated upward from the plurality of chuck pins 11. When the heating plate 92 is lowered to the lower position in this state, the substrate W on the heating plate 92 is placed on the plurality of chuck pins 11, and the heating plate 92 is separated from the substrate W downward. Thereby, the substrate W is transferred between the plurality of chuck pins 11 and the heating plate 92.

FIG. 8A is a schematic view obtained by observing the rotating chuck 10, the blocking member 51 and the heating plate 92 horizontally when the liquid removal step is performed.

In FIG. 8A, the blocking member 51 and the heating plate 92 are arranged at respective lower positions. In the liquid removal step (step S8 in FIG. 5), the control device 3 removes a portion of the pre-drying treatment liquid on the upper surface of the substrate W by the rotation of the substrate W, and can also use the built-in heater 111 and the heating plate 92 At least one of them generates heat 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 to form the adsorption film 101 can be shortened.

FIG. 8B is a schematic view obtained by horizontally observing the rotating chuck 10, the blocking member 51, and the heating plate 92 when the adsorption film removal step is performed.

In FIG. 8B, the blocking member 51 is arranged in the lower position, and the heating plate 92 is arranged in the upper position. The heating plate 92 can also be arranged at a position below the heating plate 92 far away from the substrate W instead of a position above the heating plate 92 and the substrate W being connected. The control device 3 may also heat at least one of the built-in heater 111 and the heating plate 92 in the adsorption film removal step (step S11 in FIG. 5) to heat the adsorption film 101 on the substrate W at the removal temperature. In this case, the adsorption film 101 on the substrate W can be removed in the wet processing unit 2w. Furthermore, if both the built-in heater 111 and the heating plate 92 are heated, the time required to remove the adsorption film 101 can be shortened.

Furthermore, instead of heating the adsorption film 101 on the substrate W by the built-in heater 111 and the heating plate 92 by spraying the heating gas whose temperature is higher than room temperature toward the upper surface of the substrate W, the adsorption film 101 on the substrate W can be adsorbed. The film 101 is heated at the removal temperature. For example, the central nozzle 55 can spray nitrogen heated by the upper temperature regulator 59 (refer to FIG. 2), or the central opening 61 on the blocking member 51 can be sprayed and heated by the upper temperature regulator 66 (refer to FIG. 2).的nitrogen.

When removing part of the pre-drying treatment liquid on the surface of the substrate W, if at least one of the built-in heater 111, the heating plate 92 and the heating gas is used to heat the pre-drying treatment liquid on the substrate W, the formation and adsorption of the adsorption film 101 The removal of the film 101 can be performed simultaneously. In this case, instead of removing a part of the pre-drying treatment liquid on the surface of the substrate W, it is possible to remove a part of the pre-drying treatment liquid on the surface of the substrate W while changing the adsorption film 101 into a gas.

When the adsorption film 101 on the substrate W is removed in the wet processing unit 2w, the duration of the collapse during which the pattern P1 is maintained in the collapsed state is shortened compared with the case of removing it in the dry processing unit 2d. If the collapse duration is longer, the shape of the collapsed pattern P1 may be memorized and the elastic restoring force of the shape recovery may be weakened. If the adsorption film 101 on the substrate W is removed in the wet processing unit 2w, the collapse duration can be shortened. Therefore, the pattern P1 that remains in the collapsed state after the adsorption film 101 is removed can be reduced.

Other implementation forms The present invention is not limited to the content of the above-mentioned embodiment, and various modifications can be made.

For example, instead of performing the adsorption promotion step (step S7 in FIG. 5), the liquid removal step (step S8 in FIG. 5) may be performed.

When the rinsing liquid on the substrate W such as pure water can be replaced with the pre-drying treatment liquid, it is also possible to use the pure water as an example of the rinsing liquid as an example of the replacement liquid as shown in the processing example 1 in FIG. The replacement liquid supply step of IPA replacement, and the pre-drying treatment liquid supply step.

The five steps are shown in the top section of Figure 9. The pure water as an example of the rinse liquid is described as DIW. Spinning off refers to removing part of the pre-drying treatment liquid by the rotation of the substrate W. The circular mark in Figure 9 means that the steps shown in the top paragraph are executed, and the blank column in Figure 9 means that the steps shown in the top paragraph are not executed. The processing example 2 of FIG. 9 corresponds to an example of the processing of the substrate W shown in FIG. 5.

As shown in processing example 3 of 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 of FIG. 9, IPA may be supplied to the substrate W not only before supplying the pre-drying treatment liquid, but also after spinning off. When the adsorption film 101 is formed by spin-off, there is a case where excess materials such as residues are generated on the substrate W. Even in this case, if the IPA is supplied to the substrate W after the spin-off, the IPA can also be used to rinse the excess on the substrate W.

Moreover, as shown in processing example 5 of FIG. 9, after supplying IPA, HFE may be supplied to the substrate W, and thereafter, the pre-drying treatment liquid may be supplied to the substrate W. That is, the replacement liquid supply step may include a first replacement liquid supply step of supplying IPA as an example of the first replacement liquid to the substrate W, and a second replacement step of supplying HFE as an example of the second replacement liquid to the substrate W. Liquid supply step. Although not shown, in the processing example 5 of FIG. 9, IPA may be supplied to the substrate W after the spin-off.

In the first embodiment, an example in which the concentration of the adsorbent contained in the pre-drying treatment liquid is less than 1 wt% and the main components of the pre-drying treatment liquid are IPA and pure water has been described. In the processing example 5 of FIG. 9, the pure water on the substrate W is replaced with IPA, and thereafter, the IPA on the substrate W is replaced with HFE. After that, the HFE on the substrate W is replaced with a pre-drying treatment liquid. The density of HFE is greater than that of water and greater than that of IPA.

When the density of HFE is greater than the density of the treatment solution before drying, that is, when there is a difference in specific gravity between HFE and the treatment solution before drying, as shown in Figure 10, only the surface layer of HFE is replaced with the treatment solution before drying. The case where the bottom layer of HFE remains on the substrate W. In this case, the adsorbent is only adsorbed to the front end of the pattern P1. If the spin-off is performed in this state, the adsorption film 101 is formed only at the front end of the pattern P1. In this case, compared with the case where the adsorption film 101 covering the entire surface area of the pattern P1 is formed, the adsorption film 101 has a smaller volume. Therefore, the adsorption film 101 can be removed in a short time and the removal of the adsorption film 101 can be reduced. The amount of energy consumed.

In processing example 1 to processing example 5 in FIG. 9, the substrate W may be heated in parallel with at least one step shown in the uppermost stage of FIG. 9. For example, the heating fluid valve 73 shown in FIG. 2 may be opened to cause the lower surface nozzle 71 to spray warm water. Alternatively, at least one of the built-in heater 111 and the heating plate 92 of the blocking member 51 shown in FIG. 7A may be heated. If the substrate W is heated when the liquid on the substrate W is replaced with another liquid, the efficiency of liquid replacement can be improved.

It is also possible to form the adsorption film 101 which is only in contact with the upper surface Pu of the pattern P1 as shown in FIG. 11A. FIG. 11A shows an example in which the space between two adjacent patterns P1 and the adsorption film 101 is recessed downward and not in contact with the pattern P1. Such an adsorption film 101 is obtained by supplying a pre-drying treatment liquid having a higher viscosity than the pre-drying treatment liquid used in the first embodiment to the substrate W, and the substrate in the adsorption promotion step (step S7 in FIG. 5) The rotation speed of W (adsorption promotion speed) rises.

If the substrate W is heated from the lower surface side of the substrate W while the IPA is present on the upper surface of the substrate W, the IPA on the substrate W is heated through the substrate W. If the IPA is heated at a temperature above the boiling point of the IPA, the IPA located between the two adjacent patterns P1 will evaporate, and at least a part of the space between the two adjacent patterns P1 will be filled with the vapor of the IPA. Even if the pre-drying treatment liquid is supplied to the substrate W in this state, the adsorbing substance contained in the pre-drying treatment liquid is not adsorbed on the surface of the pattern P1 excluding the upper surface Pu of the pattern P1. The reason is that the surface of the pattern P1 except the upper surface Pu of the pattern P1 is in contact with the steam of the IPA. Thereby, the adsorption film 101 which only contacts the upper surface Pu of the pattern P1 is formed.

Furthermore, if the interface between the liquid of IPA and the vapor of IPA reaches 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 weak. Therefore, when the adsorption material contained in the adsorption film 101 is a thermally decomposable polymer, the removal temperature required for thermal decomposition can be lowered, and the adsorption film 101 can be removed in a short time. Thereby, the consumption of energy required to remove the adsorption film 101 can be reduced.

In the case of forming the adsorption film 101 as shown in FIG. 11A, only the upper end of the surface of the pattern P1 definitely contacts the adsorption film 101, and therefore, the stress generated in the pattern P1 can be reduced. That is, even if two adjacent patterns P1 collapse in the direction of approaching each other, as shown in FIG. 11B, a part of the adsorption film 101 is sandwiched between the two patterns P1 to serve as a buffer. Therefore, the surface of the pattern P1 can be prevented from being damaged.

Instead of the heating plate 92 or in addition to the heating plate 92, the electromagnetic wave generating device 115 shown in FIG. 12A or FIG. 12B may be installed in the dry processing unit 2d. Alternatively, in place of the heating plate 92 or in addition to the heating plate 92, the active gas supply device 116 shown in FIG. 12C may be installed in the dry processing unit 2d (refer to FIG. 3). The electromagnetic wave generating device 115 and the active gas supply device 116 may also be installed in the wet processing unit 2w instead of the dry processing unit 2d.

The electromagnetic wave generator 115 shown in FIGS. 12A and 12B changes the adsorption film 101 into a gas by irradiating the adsorption film 101 on the substrate W with electromagnetic waves. The active gas supply device 116 shown in FIG. 12C changes the adsorption film 101 into a gas by contacting the adsorption film 101 with an active gas such as ozone gas or a gas containing hydrogen fluoride. When the hot plate 92 is used to change the adsorption film 101 into a gas, when the residue and the like remain on the substrate W, electromagnetic waves or active gas may be used to remove the excess by thermal decomposition, oxidation or ashing.

The electromagnetic wave emitted by the electromagnetic wave generating device 115 may be any of visible light, infrared light, and ultraviolet light, or may be other than these. That is, the electromagnetic wave generating device 115 may be a lamp heater that emits visible light and infrared rays, or a UV lamp that emits ultraviolet rays. In addition, the electromagnetic wave generating device 115 may be a local irradiation device 115A that only irradiates electromagnetic waves to an irradiation area representing a partial area on the upper surface of the substrate W as shown in FIG. 12A, or may be a local irradiation device 115A that irradiates the substrate W as shown in FIG. 12B The whole area of the upper surface is simultaneously irradiated with the whole irradiation device 115B of electromagnetic waves. In the former case, the local irradiation device 115A can be moved in such a way that the irradiation area moves within the upper surface of the substrate W.

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

The blocking member 51 may also rotate around the rotation axis A1 together with the rotating chuck 10. For example, the blocking member 51 may also be placed on the rotating base 12 in a manner that does not contact the substrate W. In this case, since the blocking member 51 is connected to the rotating base 12, the blocking member 51 and the rotating base 12 rotate in the same direction and 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 to provide a blocking member 51. The reason is that the droplets that flow back from the lower surface of the substrate W to the upper surface of the substrate W along the outer peripheral surface of the substrate W, or the droplets that splash inward from the processing cup 21 can be blocked by the blocking member 51 , And can reduce the liquid of the pre-drying treatment liquid mixed on the substrate W.

The wet processing unit 2w and the dry processing unit 2d can also be installed in different substrate processing apparatuses instead of being installed in the same substrate processing apparatus. That is, the substrate processing apparatus 1 equipped with the wet processing unit 2w and the substrate processing apparatus equipped with the dry processing unit 2d may be installed in the same substrate processing system, and the substrate W may be removed from the substrate processing apparatus before the adsorption film 101 is removed. 1 Transport to another substrate processing device.

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

It is also possible to combine two or more of all the above configurations. It is also possible to combine 2 or more of all the above steps.

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

The embodiments of the present invention have been described in detail, but these are only specific examples used to clarify the technical content of the present invention. The present invention should not be limited to these specific examples for interpretation. The spirit and scope of the present invention are only The scope of the attached patent application is limited.

1: Substrate processing equipment 2: processing unit 2d: Dry processing unit 2w: wet processing unit 3: control device 3a: Computer body 3b: CPU 3c: Main memory device 3d: peripheral devices 3e: auxiliary memory device 3f: reading device 3g: communication device 4: chamber 5: next wall 5a: Air outlet 5b: Moving in and out 6: FFU 7: bezel 8: Exhaust pipe 9: Exhaust valve 10: Rotating chuck 11: Chuck pin 12: Rotating base 12u: upper surface 13: Rotation axis 14: Rotating motor 21: Handling the cup 22: Outer wall components 23: Cup 24: Guard 24u: upper end 25: Cylinder 26: Top plate 27: Shield lifting unit 31: Liquid Nozzle 32: Liquid piping 33: Liquid valve 34: Nozzle moving unit 35: flushing fluid nozzle 36: flushing fluid piping 37: Flushing fluid valve 38: Nozzle moving unit 39: Treatment liquid nozzle before drying 40: Pretreatment liquid piping before drying 41: Treatment liquid valve before drying 42: Nozzle moving unit 43: Replacement fluid nozzle 44: Replacement fluid piping 45: Replacement fluid valve 46: Nozzle moving unit 51: Interrupting member 51L: lower surface 52: Disc Department 53: Pivot 54: Interrupting member lifting unit 55: Center nozzle 56: Upper gas piping 57: Upper gas valve 58: Flow adjustment valve 59: Upper temperature regulator 61: Upper central opening 62: Upper gas flow path 63: Upper gas piping 64: Upper gas valve 65: Flow adjustment valve 66: Upper temperature regulator 71: bottom surface nozzle 72: Heating fluid piping 73: Heating fluid valve 74: Flow adjustment valve 75: Lower heater 76: Cooling fluid piping 77: Cooling fluid valve 78: Flow adjustment valve 79: cooler 81: Lower central opening 82: Lower gas flow path 83: Lower gas piping 84: Lower gas valve 85: Flow adjustment valve 86: Lower temperature regulator 91: heating unit 92: heating plate 93: heating element 94: Shell 95: Base 96: protrusion 97: jack pin 98: jack up the lifting unit 101: Adsorption film 101b: bottom mask 101s: side film 101u: Upper surface film 111: Built-in heater 113: Pivot 114: Plate lifting unit 115: Electromagnetic wave generator 115A: partial irradiation device 115B: Overall irradiation device 116: Active gas supply device A1: Rotation axis C: Vehicle CR: Central robot G1: interval H1: Hand H2: Hands Hp: height IR: Indexing robot LP: Load port M: removable media P: program P1: Pattern Ps: side Pu: upper surface S1: Step S1: Step S2: Step S3: steps S4: Step S5: Step S6: Step S7: steps S8: steps S9: steps S10: steps S11: steps S12: steps T1: thickness TW: Tower W: substrate Wp: width Ws: plane

Fig. 1A is a schematic view of the substrate processing apparatus of the first embodiment of the present invention viewed from above. Fig. 1B is a schematic view of the substrate processing apparatus viewed from the side. Fig. 2 is a schematic view obtained by observing the inside of the wet processing unit equipped in the substrate processing apparatus horizontally. Fig. 3 is a schematic diagram obtained by observing the inside of the dry processing unit equipped in the substrate processing apparatus horizontally. Figure 4 is a block diagram showing the hardware of the control device. FIG. 5 is a step diagram for explaining an example of substrate processing by the substrate processing apparatus. FIG. 6A is a schematic diagram showing the state of the substrate when the processing shown in FIG. 5 is performed. FIG. 6B is a schematic diagram showing the state of the substrate when the processing shown in FIG. 5 is performed. FIG. 6C is a schematic diagram showing the state of the substrate when the processing shown in FIG. 5 is performed. FIG. 6D is a schematic diagram showing the state of the substrate when the processing shown in FIG. 5 is performed. Fig. 7A is a schematic view obtained by observing the rotating chuck, the blocking member and the heating plate of the second embodiment of the present invention horizontally. Fig. 7B is a schematic view of the rotating chuck and the heating plate of the second embodiment of the present invention viewed from above. Fig. 8A is a schematic view obtained by horizontally observing the rotating chuck, the blocking member, and the heating plate during the liquid removal step. Fig. 8B is a schematic view obtained by horizontally observing the rotating chuck, the blocking member and the heating plate during the step of removing the adsorbed film. FIG. 9 is a table for explaining processing example 1 to processing example 5. FIG. 10 is a schematic diagram showing the state of the substrate when the HFE on the substrate is replaced with the pre-drying treatment liquid. Fig. 11A is a schematic view showing a cross-section of the adsorption film only in contact with the upper end of the pattern surface. Fig. 11B is a schematic diagram showing the state of the adsorption film when the pattern shown in Fig. 11A collapses. Fig. 12A is a schematic diagram showing a state in which the electromagnetic wave generator only irradiates electromagnetic waves to a part of the upper surface of the substrate. Fig. 12B is a schematic diagram showing a state where the electromagnetic wave generator simultaneously irradiates the entire area of the upper surface of the substrate with electromagnetic waves. Fig. 12C is a schematic diagram showing a state in which the active gas supply device supplies active gas to the substrate.

S1: Step

S1: Step

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S12: steps

Claims (10)

A substrate processing method, comprising: a pre-drying treatment liquid supply step of supplying a pre-drying treatment liquid containing an adsorbing substance to be adsorbed to the surface of a pattern formed on a substrate to the surface of the above-mentioned substrate that is kept level, so that the above-mentioned The adsorbed substance is adsorbed on the surface of the pattern; the liquid removal step includes a spin-off step, the spin-off step is to rotate a portion of the pre-drying treatment liquid on the surface of the substrate that remains horizontal through the substrate to rotate vertically The axis is rotated and removed, whereby an adsorption film is formed along the surface of the pattern, the adsorption film including the adsorption material whose surface of the pattern is dried and changed into a solid or gel state; and the step of removing the adsorption film, which is The adsorption film is removed from the surface of the substrate by changing the adsorption film into a gas. The substrate processing method of claim 1, wherein the adsorption film removing step includes a pattern recovery step, and the pattern recovery step is to remove the adsorption film between the two collapsed patterns connected by the adsorption film, The restoring force of the above pattern is used to restore the collapsed shape of the above pattern. The substrate processing method of claim 1 or 2, wherein the adsorbent is a substance chemically adsorbed on the surface of the pattern. The substrate processing method of claim 1 or 2, wherein the adsorbent is a substance physically adsorbed on the surface of the pattern. The substrate processing method of claim 1 or 2, wherein the step of supplying the treatment solution before drying includes an adsorption promotion step, which is performed before the formation of the adsorption film, while stopping the rotation of the substrate or making the substrate more When the adsorption film is formed, the substrate is rotated at a low rotation speed, while the pre-drying treatment liquid is brought into contact with the surface of the pattern. The substrate processing method of claim 1 or 2, wherein the thickness of the adsorption film is smaller than the height of the pattern. The substrate processing method of claim 1 or 2, wherein the pre-drying treatment liquid is a solution containing the adsorbent and a solvent fused with the adsorbent. The substrate processing method of claim 1 or 2, wherein the liquid removing step further includes a gas supply step, and the gas supply step is when a portion of the pre-drying treatment liquid on the surface of the substrate is removed by the rotation of the substrate, The gas is sprayed toward the surface of the substrate. The substrate processing method of claim 1 or 2, wherein the liquid removing step further includes a liquid heating step, and the liquid heating step is performed when a portion of the pre-drying treatment liquid on the surface of the substrate is removed by the rotation of the substrate, The pre-drying treatment liquid on the surface of the substrate is heated. A substrate processing device, which includes: Pre-drying treatment liquid supply unit, which supplies the pre-drying treatment liquid containing the adsorption material to be adsorbed to the surface of the pattern formed on the substrate to the surface of the substrate that is kept level, so that the adsorption material is adsorbed on the surface of the pattern; liquid A removing unit, which includes a rotating removal unit that removes a portion of the pre-drying treatment liquid on the surface of the substrate that is kept horizontal by rotating the substrate around a vertical axis of rotation, thereby, along An adsorption film is formed on the surface of the pattern, and the adsorption film includes the adsorption material whose surface of the pattern is dried and changed into a solid or gel state; and an adsorption film removal unit, which is freed by changing the adsorption film into a gas The adsorption film is removed from the surface of the substrate.

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