Substrate processing method

Abstract

In a substrate processing method and a substrate processing apparatus for drying a substrate having a liquid film of an organic solvent formed in a liquid pool state on a surface using a supercritical state processing fluid, the drying time is shortened. In a process of supplying the processing fluid to a processing chamber to increase the pressure of the processing chamber from the atmospheric pressure to a first pressure at which the processing fluid becomes a subcritical state, a part of the processing fluid is mixed into the liquid film. Thus, the surface tension of the liquid film becomes small, and a part of a mixed liquid (= the organic solvent + the processing fluid) constituting the liquid film drops from the substrate, and the film thickness of the liquid film becomes thin. Here, by applying vibration to the substrate at the stage at which the surface tension becomes small, a part of the mixed liquid further drops from the substrate, and the liquid film further becomes thin. After this thinning process, substrate drying is performed with the supercritical state processing fluid.

Description

Technical Field

[0001] This invention relates to a technique for drying a substrate within a processing chamber, and more particularly to a process for processing a substrate covered by a liquid film using a supercritical processing fluid.

[0002] The following is a description, drawings, and claims of a Japanese patent application, the entire contents of which are incorporated herein by reference:

[0003] JP Special Entry 2023-138192 (applied on August 28, 2023). Background Technology

[0004] Processing steps for various substrates, such as semiconductor substrates and glass substrates for display devices, include treating the substrate surface using various processing fluids. Historically, wet processing using liquids such as chemical solutions or rinsing solutions as processing fluids has been widely employed. In recent years, processing using supercritical fluids has become practical for drying substrates after wet processing. This is particularly advantageous in drying substrates with patterned surfaces containing fine patterns. This is because supercritical fluids, compared to liquids, have lower surface tension and penetrate deep into the gaps between patterns. Using such processing fluids allows for efficient drying. Furthermore, it reduces the risk of pattern collapse due to surface tension during drying.

[0005] For example, in the substrate processing apparatus described in JP Patent Application Publication No. 2022-103636, a substrate having a liquid film formed of IPA (isopropyl alcohol), which is an example of an "organic solvent" of the present invention, is dried using supercritical carbon dioxide (processing fluid). This liquid film is in a state where IPA is deposited on the surface of the substrate. Therefore, the surface of the substrate remains wetted by IPA. Then, while maintaining the liquid-deposited state, the substrate is conveyed to a substrate drying apparatus, which is an example of a "substrate processing apparatus" of the present invention, to perform a drying process based on the supercritical processing fluid. Summary of the Invention

[0006] In the aforementioned substrate processing apparatus, the IPA covering the substrate is replaced by a supercritical processing fluid by filling the processing chamber. IPA detached from the substrate surface is discharged from the processing chamber along with the processing fluid while dissolved in it. In this way, the substrate undergoes supercritical drying. Therefore, it is advantageous to thin the liquid film before contacting the supercritical processing fluid in order to shorten the time required for supercritical drying. However, conventional methods have not achieved a reduction in processing time.

[0007] The present invention was made in view of the above-mentioned problems, and its object is to shorten the drying time in a substrate processing method and substrate processing apparatus for drying a substrate on which an organic solvent liquid film is formed on the surface in a liquid state using a supercritical processing fluid.

[0008] One aspect of the present invention is a substrate processing method for drying a substrate on which an organic solvent liquid film is formed in a liquid-pile state on the surface using a supercritical processing fluid. The substrate processing method is characterized by comprising: (a) a step of housing the substrate in a processing chamber; (b) a step of supplying processing fluid to the processing chamber to pressurize the processing chamber from atmospheric pressure to a first pressure that becomes subcritical; (c) a step of supplying processing fluid to the processing chamber pressurized to the first pressure to pressurize the processing chamber to a second pressure that becomes supercritical; and (d) a step of maintaining the liquid-pile state and reducing the thickness of the liquid film by applying vibration to the substrate during the pressurization period from the start of step (b) until the processing chamber becomes supercritical.

[0009] Another aspect of the present invention is a substrate processing apparatus for drying a substrate on which an organic solvent liquid film is formed on the surface in a liquid-pile state using a supercritical processing fluid. The substrate processing apparatus is characterized by comprising: a processing chamber for housing the substrate; a fluid supply unit for supplying processing fluid to the processing chamber; a vibration addition unit for adding vibration to the substrate housed in the processing chamber; and a control unit that controls the fluid supply unit in such a way that the processing chamber is pressurized from a first pressure (becoming subcritical) to a second pressure (becoming supercritical) by supplying processing fluid to the processing chamber at atmospheric pressure, and controls the vibration addition unit in such a way that vibration is added to the substrate during the pressurization period from the start of supplying processing fluid until the processing chamber becomes supercritical, thereby adding vibration to the substrate during the period when the processing chamber is pressurized from atmospheric pressure to the first pressure.

[0010] In this invention, during the pressurization period when the processing fluid is supplied to the processing chamber and pressurized, the processing fluid dissolves into a liquid film, and the surface tension of the liquid film decreases. Therefore, a portion of the liquid film flows off the substrate, and the film thickness decreases to a certain extent. Here, by applying vibration to the substrate during this pressurization period, the reduction in film thickness is significantly increased, promoting thin-film formation. Subsequently, the supercritical processing fluid comes into contact with the thin-film liquid film, thereby drying the substrate.

[0011] Invention Effects

[0012] As described above, the drying time can be shortened by adding vibration to the substrate during the pressurization period according to the present invention.

[0013] All or all of the above-described inventions, or some or all of the effects described in this specification, can be achieved by appropriately modifying, removing, or replacing some of the constituent elements of the plurality of constituent elements with new other constituent elements, or deleting some of the limiting content. Furthermore, in order to solve some or all of the above-described problems, or to achieve some or all of the effects described in this specification, some or all of the technical features included in one aspect of the invention can be combined with some or all of the technical features included in other aspects of the invention to form an independent embodiment of the invention. Attached Figure Description

[0014] Figure 1 This is a diagram showing a schematic configuration of a substrate processing system according to a first embodiment of the present invention, which includes a substrate processing apparatus.

[0015] Figure 2A This is a side view showing the overall structure of the wet processing unit.

[0016] Figure 2B This is a diagram used to illustrate the operation of a wet processing device.

[0017] Figure 3 This is a side view showing the configuration of a supercritical processing unit.

[0018] Figure 4 This is a perspective view showing the structure of the support tray.

[0019] Figure 5 This is a schematic diagram illustrating the structure and operation of the support pin.

[0020] Figure 6 This is a flowchart illustrating a summary of the processes performed by the substrate processing system of the first embodiment.

[0021] Figure 7 It is a diagram showing the pressure changes within the processing chamber, the movement of the support pins, and the situation inside the pattern.

[0022] Figure 8A This diagram schematically illustrates the problem arising from the liquid film formation process after liquid film formation treatment.

[0023] Figure 8B This diagram schematically illustrates how vibration can help eliminate the aforementioned problems.

[0024] Figure 9 This is a diagram illustrating a second embodiment of the substrate processing apparatus of the present invention.

[0025] Figure 10 This is a diagram illustrating a third embodiment of the substrate processing apparatus of the present invention.

[0026] The reference numerals in the attached figures are explained as follows:

[0027] 4. Supercritical processing apparatus (substrate processing apparatus)

[0028] 97. Supercritical Processing Control Unit (Control Unit)

[0029] 412 processing chamber

[0030] 412a Ultrasonic Transducer (Vibration Attachment)

[0031] 415 support tray

[0032] 415a Vibrator (Vibration Attachment)

[0033] 417 Support Pin (Vibration Addition)

[0034] 417f Pin Drive Unit (Vibration Addition Unit)

[0035] LF liquid film

[0036] PT pattern

[0037] S substrate

[0038] Sa upper surface (pattern forming surface)

[0039] Z vertical direction Detailed Implementation

[0040] Figure 1 This diagram illustrates a schematic configuration of a substrate processing system according to a first embodiment of the present invention, which includes a substrate processing apparatus. This substrate processing system 1 is, for example, a processing system for supplying a processing liquid to the upper surface of various substrates such as semiconductor wafers to perform wet processing on the substrates, and subsequently drying the substrates. It has a system configuration preferred for implementing the substrate processing method of the present invention. The main components of the substrate processing system 1 include a wet processing apparatus 2, a substrate conveying apparatus 3, a supercritical processing apparatus 4, and a control device 9.

[0041] The wet processing apparatus 2 accepts the substrate to be processed and performs a prescribed wet processing. The content of the processing is not particularly limited. Wet processing includes developing or washing processes, but after developing, a liquid state containing organic solvents such as IPA solution is formed on the patterned surface of the substrate. The substrate transport device 3 maintains the liquid state while transporting the substrate from the wet processing apparatus 2 and then into the supercritical processing apparatus 4. The supercritical processing apparatus 4 corresponds to the substrate processing apparatus of the present invention, and performs a drying process (supercritical drying process) using a supercritical state processing fluid on the transported substrate. All of these are installed in a clean room. Therefore, the substrate transport device 3 transports the substrate S under ambient gas and atmospheric pressure.

[0042] The control device 9 controls the operation of these devices to achieve the prescribed processing. For this purpose, the control device 9 includes a CPU 91, a memory 92, a storage unit 93, and an interface 94. The CPU 91 executes various control programs. The memory 92 temporarily stores processing data. The storage unit 93 stores the control programs executed by the CPU 91. The interface 94 exchanges information with the user or external devices. The operation of the devices, described later, is achieved by the CPU 91 executing the control programs pre-written into the storage unit 93, causing each part of the device to perform the prescribed actions.

[0043] By having the CPU 91 execute a prescribed control program, the control device 9 implements functional blocks such as the wet processing control unit 95, which controls the operation of the wet processing apparatus 2; the transport control unit 96, which controls the operation of the substrate transport device 3; and the supercritical processing control unit 97, which controls the operation of the supercritical processing apparatus 4, through software execution. Furthermore, at least a portion of each of these functional blocks can also be constructed using dedicated hardware.

[0044] As the "substrate" in this embodiment, various substrates can be used, such as semiconductor wafers, photomask glass substrates, liquid crystal display glass substrates, plasma display glass substrates, FED (Field Emission Display) substrates, optical disc substrates, magnetic disk substrates, and optical disc substrates. Hereinafter, a substrate processing apparatus primarily using a disk-shaped semiconductor wafer for processing will be described with reference to the accompanying drawings. However, the processing of the various substrates illustrated above can also be applied in the same way. Furthermore, various substrate shapes can also be used.

[0045] Furthermore, in the following explanation, a substrate with a pattern formed only on one of its main surfaces will be used as an example. Here, the side with the pattern formed will be referred to as the "surface," and the opposite side without a pattern will be referred to as the "back surface." Additionally, the main surface of the substrate facing downwards will be referred to as the "lower surface," and the main surface of the substrate facing upwards will be referred to as the "upper surface." Furthermore, the upper surface will be explained as the "surface" below.

[0046] Figure 2A as well as Figure 2B This is a diagram illustrating an example of the configuration of a wet processing apparatus. More specifically, Figure 2A This is a side view showing the overall structure of the wet processing unit. Figure 2B This diagram illustrates the operation of the wet processing apparatus. The wet processing apparatus 2 is a device that supplies processing liquid to the upper surface of the substrate S to process the substrate. The operation of the wet processing apparatus 2 is controlled by the wet processing control unit 95 of the control device 9.

[0047] The wet processing apparatus 2 supplies processing liquid to the surface (pattern forming surface) Sa of the substrate S to perform wet processing such as surface treatment and cleaning of the substrate S. For this purpose, the wet processing apparatus 2 has a substrate holding part 21, a splash guard 22, and processing liquid supply parts 23 and 24 inside the processing chamber 200. These operations are controlled by a wet processing control part 95 provided in the control device 9. The substrate holding part 21 has a circular plate-shaped rotary chuck 211 with a diameter approximately the same as that of the substrate S, and a plurality of chuck pins 212 are provided on the periphery of the rotary chuck 211. The substrate S is supported by the chuck pins 212 abutting against the periphery of the substrate S, and the rotary chuck 211 can hold the substrate S in a horizontal position with its upper surface separated from it.

[0048] The rotary chuck 211 is supported by a rotating spindle 213 extending downward from the center of its lower surface, ensuring its upper surface is horizontal. The rotating spindle 213 is rotatably supported by a rotating mechanism 214 mounted at the bottom of the processing chamber 200. The rotating mechanism 214 contains a rotary motor (not shown), which rotates according to control commands from the control device 9, causing the rotary chuck 211, directly connected to the rotating spindle 213, to rotate about the rotation axis AX, indicated by a dashed line. In Figure 2, the vertical direction is indicated by the up-down direction. Thus, the substrate S maintains a horizontal orientation while rotating about the rotation axis AX.

[0049] A splash guard 22 is provided to surround the substrate holding portion 21 from the side. The splash guard 22 has a generally cylindrical cup portion 221 that covers the periphery of the rotating chuck 211, and a liquid receiving portion 222 located below the outer periphery of the cup portion 221. The cup portion 221 moves up and down according to control commands from the control device 9. The cup portion 221 moves up and down between a lower position and an upper position, such as the lower position... Figure 2A The upper end of the cup portion 221 is lowered to a position below the periphery of the substrate S held in the rotating chuck 211, as shown in the figure. Figure 2B The upper end of the cup portion 221 is located above the periphery of the substrate S.

[0050] When the cup portion 221 is in the lower position, such as Figure 2A As shown, the substrate S held by the rotary chuck 211 is in a state where it protrudes outward toward the cup portion 221. For this purpose, for example, it is to prevent the cup portion 221 from causing an obstruction when the substrate S is being moved into and out of the rotary chuck 211.

[0051] Additionally, when the cup portion 221 is in the upper position, such as Figure 2BAs shown, the peripheral portion of the substrate S, held by the rotating chuck 211, is surrounded. This prevents the processing liquid ejected from the peripheral portion of the substrate S during the liquid supply process (described later) from splashing into the chamber 200, allowing for reliable recovery of the processing liquid. Specifically, droplets of processing liquid ejected from the peripheral portion of the substrate S by rotating the substrate S adhere to the inner wall of the cup portion 221 and flow downwards, where they are collected and recovered by the liquid receiving portion 222 located below the cup portion 221. Multiple cup portions are provided concentrically for the independent recovery of various processing liquids.

[0052] The processing fluid supply unit 23 has a structure in which a nozzle 234 is mounted at the front end of an arm 233 that extends horizontally from a rotating main shaft 232 rotatably mounted relative to a base 231 fixed to the processing chamber 200. By rotating the rotating main shaft 232 according to a control command from the control device 9, the arm 233 is rocked, and the nozzle 234 at the front end of the arm 233... Figure 2A The retraction position shown is the one that retracts laterally from the top of the substrate S, and as shown in the figure. Figure 2B The processing position above the substrate S shown moves between different locations.

[0053] Nozzle 234 is connected to processing liquid supply source 238. When appropriate processing liquid is supplied from processing liquid supply source 238, processing liquid is sprayed from nozzle 234 toward substrate S. Figure 2B As shown, while rotating the rotating chuck 211 at a relatively low speed to rotate the substrate S, a processing liquid L1 is supplied from a nozzle 234 positioned above the center of rotation of the substrate S, thereby treating the surface Sa of the substrate S with the processing liquid L1. The processing liquid L1 can be any liquid with various functions such as developing solution, etching solution, cleaning solution, and rinsing solution, and its composition is arbitrary. Furthermore, multiple processing liquids can be combined to perform the processing.

[0054] Another set of processing liquid supply units 24 also has a configuration corresponding to the first processing liquid supply unit 23 described above. That is, the second processing liquid supply unit 24 has a base 241, a rotating spindle 242, an arm 243, a nozzle 244, etc., which are the same as the configuration corresponding to the first processing liquid supply unit 23. The rotating spindle 242 rotates according to the control command from the control device 9, thereby causing the arm 243 to rock. The nozzle 244 at the front end of the arm 243 supplies processing liquid relative to the surface Sa of the substrate S.

[0055] In this embodiment, the second processing liquid supply unit 24 is used for the purpose of forming a liquid film to prevent drying relative to the substrate S after wet processing. That is, the substrate S after wet processing is transported to the supercritical processing apparatus 4 to undergo supercritical drying processing, but in order to prevent the surface of the substrate S from being exposed and oxidized during transport, or the collapse of the fine patterns formed on the surface, the substrate S is transported with its surface covered by a paddle-shaped liquid film.

[0056] The liquid constituting the liquid film is an organic solvent such as isopropanol (IPA) or acetone, which has a lower surface tension than water, the main component of the treatment liquid used in the cleaning process. These organic solvents are supplied from organic solvent supply source 248.

[0057] Here, the wet processing apparatus 2 is provided with two sets of processing liquid supply units, but the number, structure, and function of the processing liquid supply units are not limited to this. For example, there may be only one set of processing liquid supply units, or there may be three or more sets. In addition, a processing liquid supply unit may have multiple nozzles. For example, multiple nozzles may be provided at the front end of an arm. Furthermore, this can include not only a form in which the nozzle sprays the processing liquid in a state where it is positioned at a predetermined position, but also a form in which the nozzle scans and moves along the surface Sa of the substrate S while spraying the processing liquid.

[0058] return Figure 1 Continuing the explanation, the substrate conveying device 3 includes a conveying robot 30 with a hand 31 at the front end of a telescopic / rotatable arm. The hand 31 can support the substrate by partially abutting against the lower surface of the substrate, such as... Figure 1 As shown by the dashed lines, the hand 31 can move freely forward and backward relative to both the wet processing unit 2 and the supercritical processing unit 4. This allows for the loading and unloading of substrates relative to both the wet processing unit 2 and the supercritical processing unit 4. The operation of the transport robot 30 is controlled by the transport control unit 96 of the control device 9. Many known technologies exist for this type of transport robot, and it can be appropriately selected and used in this embodiment; therefore, detailed descriptions are omitted.

[0059] Figure 3 This is a side view showing the configuration of the supercritical processing apparatus. The supercritical processing apparatus 4 corresponds to the first embodiment of the substrate processing apparatus of the present invention, and is an apparatus for performing drying treatment using a supercritical processing fluid on a substrate S after wet processing. More specifically, the supercritical processing apparatus 4 is an apparatus that receives the substrate S after wet processing, displaces the liquid remaining on the substrate S using a supercritical processing fluid, and then discharges the processing fluid, thereby ultimately bringing the substrate S to a dry state.

[0060] The supercritical processing apparatus 4 includes a processing unit 41, a transfer unit 43, and a supply unit 45. The processing unit 41 is the main body for performing the supercritical drying process. The transfer unit 43 receives the wet-processed substrate S transported by the substrate transfer device 3 and transfers it into the processing unit 41, and then delivers the processed substrate S from the processing unit 41 to an external transfer device. The supply unit 45 supplies the chemical substances, power, and energy required for processing to the processing unit 41 and the transfer unit 43. These operations are controlled by the control device 9, particularly by the supercritical processing control unit 97.

[0061] The processing unit 41 has a structure in which a processing chamber 412 is mounted on a base 411. The processing chamber 412 is composed of a combination of several metal blocks, and its interior is hollow, forming a processing space SP. The substrate S to be processed is moved into the processing space SP and processed. A slit-like opening 421 extending elongatedly in the X direction is formed on the (-Y) side of the processing chamber 412. The processing space SP communicates with the external space through the opening 421. The cross-sectional shape of the processing space SP is approximately the same as the opening shape of the opening 421. That is, the processing space SP has a cross-sectional shape that is long in the X direction and short in the Z direction, and is a hollow extending in the Y direction.

[0062] On the (-Y) side of the processing chamber 412, a cover member 413 is provided to close the opening 421. The cover member 413 closes the opening 421 of the processing chamber 412, thereby forming an airtight processing container. Thus, high-pressure processing can be performed relative to the substrate S within the internal processing space SP. On the (+Y) side of the cover member 413, a flat support tray 415 is mounted horizontally. The upper surface of the support tray 415 serves as a support surface for placing the substrate S. The cover member 413 is supported by a support mechanism (not shown) that allows it to move freely horizontally in the Y direction.

[0063] The cover member 413 can move forward and backward relative to the processing chamber 412 via the forward and backward mechanism 453 provided in the supply unit 45. Specifically, the forward and backward mechanism 453 is, for example, a direct-acting mechanism having a linear motor, a direct-acting guide rail, a ball screw mechanism, a solenoid valve, a cylinder, etc. This direct-acting mechanism moves the cover member 413 in the Y direction. The forward and backward mechanism 453 operates according to control commands from the control device 9.

[0064] The cover member 413 separates from the processing chamber 412 by moving in the (-Y) direction, as shown by the dashed line. If the support tray 415 is pulled outward from the processing space SP through the opening 421, it can be brought into contact with the support tray 415. That is, the substrate S can be placed on the support tray 415 and removed from the support tray 415. On the other hand, by moving the cover member 413 in the (+Y) direction, the support tray 415 is housed within the processing space SP. When the support tray 415 carries the substrate S, the substrate S and the support tray 415 are moved together into the processing space SP.

[0065] Figure 4 This is a perspective view showing the structure of the support tray. The support tray 415 has a tray member 416 and a plurality of support pins 417. The tray member 416 has, for example, a structure in which a recess 418 is provided on the horizontal and flat upper surface of the flat plate-shaped structure. The recess 418 has a diameter corresponding to the planar dimensions of the substrate S, and more specifically, a diameter slightly larger than the diameter of the circular substrate S.

[0066] The recess 418 extends partially to the side of the tray member 416. That is, the sidewall of the recess 418 is not circular, but rather partially cut out. Therefore, in this cut-out portion, a portion of the bottom surface 418a of the recess 418 is directly connected to the side surface. In this example, such cut-out portions are provided at both ends of the X side and the (+Y) side of the supporting tray 415, in which the bottom surface 418a is directly connected to the side surface.

[0067] Additionally, a through hole 419 is provided in the bottom surface 418a at a position corresponding to the lifting pin 437 of the transfer unit 43 for the lifting pin 437 to pass through. By allowing the lifting pin 437 to pass through the through hole 419 and move up and down, the substrate S is housed in the recess 418 and in the state of being lifted upwards.

[0068] A plurality of support pins 417 are disposed on the periphery of the recess 418. The number of support pins 417 is arbitrary, but from the viewpoint of stabilizing the support base plate S, it is preferable to have three or more. In this embodiment, three support pins 417 are mounted on the tray member 416 in such a way that they surround the bottom surface 418a when viewed from above.

[0069] Multiple support pins 417 have the same configuration. Therefore, the configuration of one support pin 417 will be described below, while the same reference numerals will be used to label the parts of the other support pins 417 and descriptions will be omitted. Support pin 417 as... Figure 5The diagram shows a pallet abutment surface 417a. This pallet abutment surface 417a is movable radially D on the upper surface of the pallet member 416. A lower abutment surface 417b is provided above the pallet abutment surface 417a of the support pin 417. The lower abutment surface 417b slopes downward as it moves toward the centerline BX side (+D). Here, as... Figure 4 As shown, “center line BX” refers to a vertical line passing through the center of the recess 418. As will be explained later, when the substrate S is clamped by multiple support pins 417, “center line BX” passes through the center of the substrate S.

[0070] A curved abutment surface 417c is provided upward from the end of the lower abutment surface 417b in the (-D) direction. This curved abutment surface 417c completes a curved surface approaching the centerline BX. Furthermore, an upper abutment surface 417d extends upward from the upper end of the curved abutment surface 417c. This upper abutment surface 417d tilts upward as it advances in the direction (+D) towards the centerline BX. More specifically, as... Figure 5 As shown, the curved abutment surface 417c, positioned between the upper abutment surface 417d and the lower abutment surface 417b, is directly connected to both. Therefore, if the substrate abutment portion 417e, which consists of the upper abutment surface 417d, the curved abutment surface 417c, and the lower abutment surface 417b connected together and abutting against the substrate S, is viewed from a horizontal direction orthogonal to the radial direction D, this substrate abutment portion 417e has a generally C-shaped form. In other words, the support pin 417 can move back and forth along the radial direction D with the substrate abutment portion 417e facing the centerline BX.

[0071] The support pin 417 is connected to the pin drive unit 417f. The pin drive unit 417f moves the support pin 417 radially D according to instructions from the supercritical processing control unit 97. For example, during the transfer of substrate S between the substrate transport device 3 and the substrate transfer unit 3, as... Figure 5 As shown in (b), the pin drive 417f moves the support pin 417 in the direction (-D) and positions it in a non-clamped position (an example of the "released position" of the present invention). At this time, the curved abutment surface 417c and the upper abutment surface 417d are separated from the center line BX by a distance slightly larger than the radius of the substrate S. On the other hand, the lower abutment surface 417b is located below the substrate S. Therefore, as shown in Figure (b), the substrate S is supported only by the lower abutment surface 417b, and only at the position in the lower abutment surface 417b separated from the curved abutment surface 417c in the (+D) direction.

[0072] On the other hand, when clamping the substrate S, such as Figure 5As shown in (a), the pin drive 417f moves the support pin 417 in the direction (+D) and positions it in the clamping position (an example of the "clamping position" of the present invention). By moving the support pin 417 from the non-clamping position to the clamping position, the support position of the substrate S, supported by the lower abutment surface 417b, is displaced in the direction (-D). When the support pin 417 has finished moving to the clamping position, the substrate S is supported by the lower abutment surface 417b, the curved abutment surface 417c, and the upper abutment surface 417d. In other words, clamping of the substrate is completed.

[0073] When the substrate S is released from clamping, the support pin 417 is moved in the reverse order described above, and the support position of the substrate S supported by the lower abutment surface 417b is displaced in the (+D) direction.

[0074] Furthermore, by using the lower abutment surface 417b to support the substrate S, the support position moves radially D, and the height position of the substrate S in the vertical direction Z is only displaced by a distance dz. Therefore, if the supercritical processing control unit 97 sends a reciprocating movement command to the pin drive unit 417f, the support pin 417 moves reciprocally in the radial direction D, and the substrate S is raised and lowered repeatedly in sync. In other words, it is possible to add vertical vibration relative to the substrate S. In this embodiment, the object of the present invention is achieved by using this added vibration. This will be explained in detail later along with the description of the operation of the substrate processing system 1.

[0075] The cover member 413 blocks the opening 421 by moving in the (+Y) direction, thus sealing the processing space SP. A sealing member 422 is provided between the (+Y) side of the cover member 413 and the (-Y) side of the processing chamber 412 to maintain the airtight state of the processing space SP. The sealing member 422 is, for example, made of rubber. In addition, the cover member 413 is fixed relative to the processing chamber 412 by a locking mechanism (not shown). Thus, in this embodiment, the cover member 413 switches between a closed state (solid line) in which the opening 421 is closed to seal the processing space SP, and a separated state (dashed line) in which the substrate S can enter and exit by a large distance from the opening 421.

[0076] While ensuring the airtightness of the processing space SP, processing of the substrate S is performed within the processing space SP. In this embodiment, the fluid supply unit 457 provided in the supply unit 45 supplies a processing fluid, such as carbon dioxide, which is a substance usable in supercritical processing, to further pressurize the processing fluid within the processing chamber 412, thereby achieving a supercritical state. The processing fluid is supplied to the processing unit 41 in a gaseous or liquid state. Carbon dioxide is a preferred chemical substance for supercritical drying processing because it reaches a supercritical state at relatively low temperature and low pressure, and also has the property of effectively dissolving organic solvents commonly used in substrate processing. The critical point for carbon dioxide to reach a supercritical state is a gas pressure (critical pressure) of 7.38 MPa and a temperature (critical temperature) of 31.1 °C.

[0077] Processing fluid is filled into the processing space SP. When the processing space SP reaches the appropriate temperature and pressure, it becomes completely filled with supercritical processing fluid. Thus, the substrate S is processed within the processing chamber 412 using supercritical processing fluid. A fluid recovery unit 455 is provided in the supply unit 45, and the processed fluid is recovered by the fluid recovery unit 455. The fluid supply unit 457 and the fluid recovery unit 455 are controlled by the supercritical processing control unit 97.

[0078] The processing space SP has a shape and volume capable of receiving a support tray 415 and a substrate S supported by the support tray 415. Specifically, the processing space SP has a generally rectangular cross-sectional shape that is larger in the horizontal direction than the width of the support tray 415 and larger in the vertical direction than the combined height of the support tray 415 and the substrate S, and a depth capable of receiving the support tray 415. Thus, the processing space SP has a shape and volume capable only of receiving the support tray 415 and the substrate S. However, the gap between the support tray 415 and the substrate S and the inner wall surface of the processing space SP is very small. Therefore, the amount of processing fluid required to fill the processing space SP is relatively small and sufficient.

[0079] The fluid supply unit 457 supplies processing fluid to the processing space SP from the (+Y) side, which is further to the (+Y) side end of the substrate S. On the other hand, the fluid recovery unit 55, located further to the (-Y) side than the (-Y) side end of the substrate S, discharges the processing fluid flowing in the processing space SP in the space above the substrate S and in the space below the support tray 415. Thus, laminar flow of processing fluid flowing from the (+Y) side to the (-Y) side is formed in the processing space SP above the substrate S and below the support tray 415, respectively.

[0080] The supercritical processing control unit 97 of the control device 9 determines the pressure and temperature within the processing space SP based on the detection results of a detection unit (not shown), and controls the fluid supply unit 457 and the fluid recovery unit 455 based on these results. Thus, the supply of processing fluid to the processing space SP and the discharge of processing fluid from the processing space SP are appropriately managed, and adjustments are made according to the processing procedure to achieve the specified pressure and temperature within the processing space SP.

[0081] The transfer unit 43 is responsible for the transfer of substrate S between the substrate transport device 3 and the support tray 415. To achieve this, the transfer unit 43 includes a main body 431, a lifting member 433, a base member 435, and a plurality of lifting pins 437. The lifting member 433 is a columnar member extending in the Z direction and is supported relative to the main body 431 in the Z direction by a support mechanism (not shown). A base member 435 with a generally horizontal upper surface is mounted on the upper part of the lifting member 433. A plurality of lifting pins 437 are erected upward from the upper surface of the base member 435. The lifting pins 437 support the substrate S in a horizontal position from below by abutting their upper ends against the lower surface of the substrate S. To stably support the substrate S in a horizontal position, it is preferable to provide three or more lifting pins 437 with equal upper end heights.

[0082] The lifting member 433 can be raised and lowered using the lifting mechanism 451 provided in the supply unit 45. Specifically, the lifting mechanism 451 is, for example, a linear motor, a direct-acting guide rail, a ball screw mechanism, a solenoid valve, a cylinder, etc., which causes the lifting member 433 to move in the Z direction. The lifting mechanism 451 operates according to control commands from the control device 9.

[0083] The lifting member 433 moves the base member 435 up and down, causing multiple lifting pins 437 to move up and down integrally with it. This enables the transfer of the base plate S between the transfer unit 43 and the support tray 415. More specifically, as... Figure 4As shown in dashed lines, the substrate S is transferred when the support tray 415 is pulled out of the cavity. To achieve this, the support tray 415 is provided with a through hole 419 for the insertion of the lifting pin 437. When the base member 435 rises, the upper end of the lifting pin 437 passes through the through hole 419 and reaches above the upper surface of the support tray 415. In this state, the substrate S transferred by the transfer robot 30 is transferred from the hand 31 of the transfer robot 30 relative to the lifting pin 437. By lowering the lifting pin 437, the substrate S is transferred from the lifting pin 437 to the support tray 415. The removal of the substrate S can be performed in the reverse order described above. Furthermore, in this embodiment, when the substrate S is being moved in or out, the plurality of support pins 417 are positioned in the released position. On the other hand, in addition to this, the plurality of support pins 417 are positioned in the clamping position. In the thin-film processing described below, the positions of the released and clamping positions are repeatedly switched.

[0084] Figure 6 This is a flowchart illustrating an overview of the processing performed using the substrate processing system of the first embodiment. The substrate processing system 1 receives a substrate S to be processed and sequentially performs wet processing using a processing liquid and supercritical drying processing using a supercritical processing fluid. Specifically, the following steps S101 to S114 are performed. The substrate S to be processed is housed in the wet processing apparatus 2 constituting the substrate processing system 1 (step S101). The substrate S can be moved in directly using an external transport device, or it can be moved in from an external transport device using a transport robot 30.

[0085] The wet processing apparatus 2 performs wet processing on the substrate S using a prescribed processing solution (step S102). In this wet processing, after a prescribed treatment with a developer, a cleaning solution, etc., a rinsing solution such as DIW (deionized water) is supplied to the surface Sa of the substrate S. Therefore, immediately after the wet processing is completed, the rinsing solution, as an example of the "liquid" of the present invention, adheres to the surface Sa of the substrate S. Then, after the wet processing, an organic solvent such as IPA is supplied to the substrate S, thereby replacing the rinsing solution adhering to the surface Sa of the substrate S with the organic solvent, and forming a liquid pile state with organic solvent. That is, a liquid film LF is formed on the surface Sa of the substrate S (step S103: liquid film formation process).

[0086] The technical significance of the liquid film formation process is as follows. When a DIW (distilled water) is present inside a pattern PT formed, for example, on the surface Sa of a substrate S, there is a concern that the surface tension of the DIW may cause the pattern PT to collapse. Furthermore, watermarks may sometimes remain on the surface Sa of the substrate S due to incomplete drying. Moreover, the surface Sa of the substrate S may sometimes undergo oxidation or other deterioration due to contact with external air. To prevent these problems, an organic solvent is used to cover the surface Sa of the substrate S. As the organic solvent, a liquid with lower surface tension than the DIW and lower corrosivity to the substrate S is preferred, such as IPA, acetone, or other solvents that are compatible with the DIW. The following describes the case where DIW is used as the rinsing solution and IPA is used as the organic solvent.

[0087] A liquid film LF is formed on the surface Sa of the substrate S using a liquid film formation process. The substrate S is then transported from the wet processing apparatus 2 to the supercritical processing apparatus 4 using a substrate transport device 3 while maintaining the liquid film. (Step S104)

[0088] The substrate S, transported to the supercritical processing apparatus 4, is contained within the processing chamber 412 while maintaining a liquid-packed state. Specifically, the substrate S is transported with its patterned surface (surface Sa) as its upper surface, and this patterned surface is covered by a very thin liquid film LF. Figure 3 As shown by the dashed line, with the cover member 413 moving towards the (-Y) side and the support tray 415 pulled out, the lifting pin 437 rises. The conveying device transfers the substrate S to the lifting pin 437. When the lifting pin 437 descends, the substrate S is placed on the support pin 417, which is positioned in the release position. Thereafter, the support pin 417 moves to the clamping position and holds the substrate S. In this way, the reception of the substrate S by the support tray 415 is completed (step S105).

[0089] When the support tray 415 and the cover member 413 move together in the (+Y) direction, the support tray 415 of the support substrate S is housed in the processing space SP within the processing chamber 412, and the opening 421 is closed by the cover member 413.

[0090] When the acceptance of the substrate S is confirmed (determined as "yes" in step S106), carbon dioxide, as a processing fluid, is introduced into the processing space SP in a gaseous state while maintaining the liquid state. That is, the processing fluid is introduced into the processing chamber 412 (step S107). When the substrate S is moved in, external air enters the processing space SP, but it is replaced by the introduced gaseous processing fluid. Furthermore, by injecting the gaseous processing fluid, the pressure inside the processing chamber 412 rises from atmospheric pressure, bringing the interior of the processing chamber 412 to an atmospheric pressure state.

[0091] Furthermore, during the introduction of the processing fluid, the processing fluid from the processing space SP continues to be discharged. That is, while the processing fluid is introduced using the fluid supply unit 457, the fluid recovery unit 455 also discharges the processing fluid from the processing space SP. As a result, the processing fluid supplied to the process is discharged without remaining in the processing space SP, preventing impurities such as residues that have entered the processing fluid from re-adhering to the substrate S.

[0092] If the supply of the processing fluid is greater than the discharge, the density of the processing fluid in the processing space SP increases, and the pressure inside the chamber rises. Conversely, if the supply of the processing fluid is less than the discharge, the density of the processing fluid in the processing space SP decreases, and the pressure inside the chamber is reduced. The supply of processing fluid to and from the processing chamber 412 is based on a pre-established supply and discharge process. That is, the control device 9 controls the fluid supply unit 457 and the fluid recovery unit 455 based on the supply and discharge process, thereby adjusting the timing and flow rate of the processing fluid supply / discharge. Furthermore, based on the pressure changes within the processing chamber 412, the support pin 417 is moved back and forth to perform diaphragm treatment.

[0093] Figure 7 This diagram illustrates the pressure changes within the processing chamber, the movement of the support pins, and the internal conditions. When the processing fluid is carbon dioxide, the critical temperature remains essentially unchanged from room temperature; therefore, the temperature changes during processing are also minimal. Here, we focus on the pressure changes within the chamber to explain the phenomenon, which makes the changes more pronounced. Starting from a state where the processing space SP is open to the atmosphere, resulting in an internal pressure of atmospheric pressure (Pa), the processing fluid is introduced at time T1 after the processing space SP is sealed, and the internal pressure begins to rise.

[0094] The pressure of the processing fluid within the processing space SP continues to rise. In this embodiment, the pressure within the processing chamber 412 continues to be increased until it reaches a subcritical pressure (hereinafter referred to as "subcritical pressure") Ps and exceeds the critical pressure Pc. Carbon dioxide is supplied as the processing fluid, and it is mixed with the IPA constituting the liquid film LF. As a result, the liquid film LF increases, but the surface tension of the mixture (=IPA + carbon dioxide) decreases. For example, when the pressure within the processing chamber 412 reaches near the subcritical pressure Ps, a portion of the mixture constituting the liquid film LF drips from the substrate S, and the thickness of the liquid film LF becomes thinner. Here, if vibration is applied to the substrate S during the stage when the surface tension decreases, a portion of the mixture drips further from the substrate S, and further thinning of the liquid film LF can be achieved.

[0095] Therefore, in this embodiment, when the pressure inside the processing chamber 412 reaches the subcritical pressure Ps (determined as "yes" in step S108: time T2), a reciprocating movement command is given to the pin drive unit 417f from the supercritical processing control unit 97. Thus, as... Figure 7 As shown in the mid-section diagram, the pin drive 417f causes the support pin 417 to move back and forth in the radial direction D. Simultaneously, the substrate S repeatedly rises and falls, adding vertical vibration relative to the substrate S. This maintains the liquid film LF in a liquid-packed state, and the thickness dz of the liquid film LF is reduced (step S109: thin film processing). Furthermore, if the pressure inside the processing chamber 412 exceeds the time T3 when it reaches the subcritical pressure Ps, the processing fluid becomes supercritical within the chamber. Therefore, the end point of the additional vibration period (i.e., the vibration additional period) needs to be set to less than (less than) time T3. Conversely, the start point of the vibration additional period is not limited to time T2, as long as it is set to a time when the surface tension of the liquid film LF is sufficiently low. Additionally, the number of reciprocating movements of the support pin 417 during the vibration additional period (i.e., the number of vibrations) is arbitrary.

[0096] After performing the thin-film treatment as described above, the pressure is further increased. Therefore, at the moment T3 when the critical pressure Pc is reached within the chamber, the processing fluid becomes supercritical within the chamber. That is, due to the phase change within the processing space SP, the processing fluid changes from the gas phase to the supercritical state. By filling the processing space SP with the supercritical processing fluid, the IPA covering the substrate S is replaced by the supercritical processing fluid. IPA and the like, freed from the surface of the substrate S, are dissolved in the processing fluid and discharged from the processing chamber 412 along with the processing fluid, thus being removed from the substrate S. In other words, the supercritical processing fluid has the function of replacing the IPA adhering to the substrate S as a replacement fluid and discharging it outside the processing chamber 412.

[0097] After the processing fluid reliably transitions to a supercritical state at moment T3, by maintaining the processing space SP filled with the supercritical processing fluid for a predetermined time (steps S110, S111), the replacement fluid adhering to the substrate S can be completely replaced and discharged out of the chamber. Furthermore, in Figure 7 The diagram shows that after continuous pressurization up to time T4, which exceeds time T3, the pressure Pm in the chamber under supercritical conditions is constant, but there can also be pressure variations within a range that does not fall below the critical pressure Pc.

[0098] At time T4, if the replacement of the target liquid based on the supercritical state processing fluid in the processing chamber 412 is completed (step S112), the processing fluid in the processing space SP is discharged to dry the substrate S. Specifically, by increasing the discharge amount of fluid from the processing space SP, the pressure in the processing chamber 12 filled with the supercritical state processing fluid is reduced (step S113).

[0099] In the decompression process, the supply of the processing fluid can be stopped, or a small amount of processing fluid can be continued to be supplied. By decompressing the processing space SP from a state filled with supercritical processing fluid, the processing fluid undergoes a phase transition from the supercritical state to the gas phase. By discharging the vaporized processing fluid to the outside, the substrate S becomes dry. At this time, the decompression rate is adjusted in a way that prevents the formation of solid and liquid phases due to a rapid temperature drop. That is, after decompression begins at time T5, decompression is performed at a relatively low rate until the pressure reliably drops to the critical pressure Pc at time T6. As a result, the processing fluid in the processing space SP directly vaporizes from the supercritical state and is discharged to the outside.

[0100] After the moment T6 when the processing fluid is completely vaporized, the decompression rate is increased, thereby enabling the decompression to atmospheric pressure Pa in a short time. In this way, during the entire period from the moment T4 when the decompression begins until T7 when the pressure in the chamber drops to atmospheric pressure Pa, the processing fluid will not liquefy, thus preventing the formation of a gas-liquid interface on the substrate S exposed on the dried surface.

[0101] In this supercritical drying process, after the processing space SP is filled with a supercritical fluid, the gas phase undergoes a phase change and is discharged. This efficiently replaces the liquid adhering to the substrate S, preventing residue from remaining on the substrate S. Furthermore, the substrate can be dried without problems such as contamination caused by impurities, pattern collapse, or the formation of a gas-liquid interface.

[0102] The processed substrate S is moved to the next process (step S114). That is, by moving the cover member 413 in the (-Y) direction, the support tray 415 is pulled out from the processing chamber 412 and transferred to the external transport device via the transfer unit 43. At this time, the substrate S is in a dry state. The content of the next process is arbitrary. The processing of one substrate S is completed in this way. If there is a substrate to be processed next, return to step S101 to receive a new substrate S, and repeat the above processing.

[0103] As described above, according to the first embodiment, after the liquid film LF is thinned, the substrate is dried using a supercritical processing fluid, thus enabling a reduction in drying time.

[0104] In addition, the following effects are achieved by utilizing additional vibration. (Refer to the following...) Figure 8A as well as Figure 8B Please provide an explanation.

[0105] Figure 8A This diagram schematically illustrates the problems arising from the liquid film after liquid film formation treatment. Additionally, Figure 8B This diagram schematically illustrates how vibration can be applied to eliminate the aforementioned problems. After the liquid film formation process (step S103), as... Figure 8A As shown, sometimes a portion of the rinsing fluid (DIW) remains on the inner bottom surface of the pattern PT. When the substrate S is subjected to drying processing based on a supercritical state processing fluid while such residual liquid (hereinafter referred to as "residual liquid") remains, the following problem sometimes occurs. That is, the replacement of the liquid components constituting the liquid film with the supercritical state processing fluid is prone to incompleteness. Therefore, in order to address this problem, measures such as increasing the amount of processing fluid used have been considered. However, this would lead to increased operating costs and impose a significant environmental burden on society.

[0106] In contrast, in this embodiment, vibration is applied to the substrate S by performing a thin-film treatment. Therefore, the residual liquid (DIW) in the pattern PT migrates and diffuses, mixing with the mixture (=IPA + carbon dioxide) constituting the liquid film LF. Thus, drying of the processing fluid based on a supercritical state is performed in a state where there is no residual liquid on the inner bottom surface of the pattern, i.e., a so-called residue-free state. As a result, the consumption of processing fluid can be reduced and the yield increased.

[0107] Furthermore, sometimes a portion of the mixture that drips from the substrate S during the pressurization process adheres to the through-holes 419, which may adversely affect the drying performance. However, in this embodiment, by adding vibration to the substrate S during the thin-film forming process, the mixture adhering to the through-holes 419 can be made to fall down and be removed. As a result, the drying performance can be improved.

[0108] Furthermore, in the first embodiment, the reciprocating movement of the support pin 417 on the radial direction D is utilized to add vibration to the substrate S. That is, in addition to the function of holding the substrate S by clamping the side end of the support pin 417, it also performs the function of adding vibration. Therefore, it is not necessary to add a component specifically responsible for the function of adding vibration, thereby reducing the cost of the device.

[0109] As described above, in the first embodiment, DIW and IPA correspond to examples of "liquid" and "organic solvent" of the present invention, respectively. Furthermore, subcritical pressure Ps and critical pressure Pc correspond to examples of "first pressure" and "second pressure" of the present invention, respectively. Additionally, the surface Sa of the substrate S corresponds to the "patterning surface" of the present invention. Furthermore, steps S105 and S106 correspond to examples of "process (a)" of the present invention, steps S107 and S108 correspond to examples of "process (b)" of the present invention, steps S110 and S111 correspond to examples of "process (c)" of the present invention, and step S109 corresponds to an example of "process (d)" of the present invention. Furthermore, the liquid film formation process (step S103) corresponds to an example of the "liquid film formation process" of the present invention. Furthermore, the period from time T1 to time T4 corresponds to an example of the "pressure boosting period" of the present invention. Furthermore, the supercritical processing control unit 97 corresponds to an example of the "control unit" of the present invention.

[0110] Furthermore, in the first embodiment, the support pin 417 is moved back and forth in the D direction to perform the thin-film treatment. That is, the support pin 417 and the pin drive portion 417f function as a "vibration addition portion" of the present invention, but the configuration of the vibration addition portion is not limited to this. For example, vibration can be added to Z along the vertical direction using the support pin 417 (hereinafter referred to as "vertical vibration addition"), but vibration can be added to the substrate S using an additional configuration. For example, it can also be configured to use a vibrator 415a ( Figure 9 ) or ultrasonic transducer ( Figure 10 The support tray 415 is vibrated directly or indirectly by means of the vibration of the support tray 415, and the substrate S is vibrated by means of the vibration of the support tray 415.

[0111] Figure 9 This figure illustrates a second embodiment of the substrate processing apparatus of the present invention. In this second embodiment, a vibrator 415a is mounted on a support tray 415. The vibrator 415a vibrates according to a vibration command from the supercritical processing control unit 97. In this second embodiment, the vibrator 415a corresponds to an example of the "vibration attachment" of the present invention. Here, the mounting position of the vibrator 415a is not limited to the support tray 415, but may also be mounted on the cover member 413.

[0112] Figure 10 This figure illustrates a third embodiment of the substrate processing apparatus of the present invention. In this third embodiment, an ultrasonic transducer 412a is mounted in the processing chamber 412 opposite to the lower surface of the support tray 415. The ultrasonic transducer 412a vibrates according to a vibration command from the supercritical processing control unit 97. In this third embodiment, the ultrasonic transducer 412a corresponds to an example of the "vibration attachment" of the present invention.

[0113] As described above, in the second or third embodiment, similar to the first embodiment, a thin-film treatment (step S109) is performed before the drying treatment using the supercritical processing fluid. Therefore, the effect of shortening the drying time is achieved.

[0114] Furthermore, the present invention is not limited to the embodiments described above, and various modifications other than those described can be made without departing from its spirit. Each time supercritical drying is performed relative to a substrate S, only one thin-film treatment is performed, but multiple thin-film treatments may also be performed.

[0115] Furthermore, the examples of various chemical substances used in the processing of the above embodiments are shown in part. Various chemical substances can be used instead, provided they conform to the technical concept of the present invention.

[0116] The invention has been described above along specific embodiments, but these descriptions are not intended to be interpreted in a limiting sense. Various modifications of the disclosed embodiments will become apparent to those skilled in the art, as with other embodiments of the invention, upon reference to the description of the invention. Therefore, the appended claims should be considered to include such modifications or embodiments without departing from the spirit and scope of the invention.

[0117] This invention can be applied to all techniques for drying substrates using supercritical processing fluids within a chamber.

Claims

1. A substrate processing method for drying a substrate having a liquid film of an organic solvent formed in a puddle state on a surface thereof with a processing fluid in a supercritical state, the substrate processing method characterized by comprising: (a) a step of housing the substrate in a processing chamber; (b) a step of supplying the processing fluid to the processing chamber to increase a pressure of the processing chamber from an atmospheric pressure to a first pressure at which the processing fluid becomes a subcritical state; (c) a step of supplying the processing fluid to the processing chamber increased to the first pressure to increase a pressure of the processing chamber to a second pressure at which the processing fluid becomes the supercritical state; and (d) a step of reducing a film thickness of the liquid film while maintaining the puddle state by applying vibration to the substrate in a state where a surface tension of the liquid film is reduced by dissolution of the processing fluid during a pressure increase period from the start of the step (b) to the processing chamber becoming the supercritical state.

2. The substrate processing method according to claim 1, wherein the step (a) includes: (a-1) a step of sandwiching and holding the substrate from a horizontal direction with a plurality of supporting pins provided to a supporting tray after supporting a peripheral portion of the substrate from below with the plurality of supporting pins, and moving the plurality of supporting pins toward the substrate while continuously supporting the substrate with the plurality of supporting pins; and (a-2) a step of moving the supporting tray into the processing chamber while holding the substrate with the plurality of supporting pins, wherein in the step (d), the vibration is applied to the substrate by moving the plurality of supporting pins to and from between a sandwiching position sandwiching the substrate and a release position separated from the sandwiching position.

3. The substrate processing method according to claim 1, wherein the step (a) includes: (a-3) a step of placing the substrate on a supporting tray; and (a-4) a step of moving the supporting tray into the processing chamber while the substrate is placed thereon, wherein in the step (d), the vibration is applied to the substrate by operating a vibrator installed to the supporting tray.

4. The substrate processing method according to claim 1, wherein the step (a) includes: (a-3) a step of placing the substrate on a supporting tray; and (a-4) a step of moving the supporting tray into the processing chamber while the substrate is placed thereon, wherein in the step (d), the vibration is applied to the substrate by operating an ultrasonic transducer installed to the processing chamber.

5. The substrate processing method according to any one of claims 1 to 4, wherein the vibration is applied to the substrate in the step (d) in the subcritical state.

6. The substrate processing method according to any one of claims 1 to 4, wherein the surface of the substrate is a pattern formation surface on which a pattern is formed. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ Before the process (a) is performed, a liquid film formation process of forming the liquid film on the pattern formation surface is performed after the liquid adhered to the pattern formation surface is replaced with the organic solvent by supplying the organic solvent to the pattern formation surface to which the liquid is adhered, In the process (d), the liquid remaining in the pattern is mixed with the organic solvent in parallel with the thinning of the liquid film by applying the vibration to the substrate.

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