Substrate processing apparatus and substrate processing method

Abstract

A substrate processing apparatus (1) is provided with: a water flow path that guides water toward a substrate (W); and a solvent flow path (33x) that guides an organic solvent, which is a liquid having a lower surface tension than water, to the substrate (W). The water flow path includes a concave-convex surface (72) having a concave portion (72u), at least a part of which is filled with air, and a convex portion (72 h), which is in contact with water in contact with the air in the concave portion (72u). The solvent flow path (33x) includes a mirror surface (71) in contact with the organic solvent.

Description

[0001] Related applications

[0002] This application claims priority based on Japanese Patent Application No. 2023-159045, filed on September 22, 2023, and Japanese Patent Application No. 2024-043839, filed on March 19, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to a substrate processing apparatus and a substrate processing method. Substrates include, for example, semiconductor wafers, substrates for FPD (Flat Panel Display) devices such as liquid crystal display devices or organic EL (electroluminescence) display devices, substrates for optical discs, substrates for magnetic disks, substrates for magneto-optical discs, substrates for photomasks, ceramic substrates, substrates for solar cells, etc. Background Technology

[0004] Patent document 1 discloses that the piping is cleaned with a cleaning solution before the use of the substrate processing device installed in the factory is started.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2020-155649 Summary of the Invention

[0008] [The problem the invention aims to solve]

[0009] During the piping cleaning process, the substrate cannot be processed by the substrate processing apparatus. Therefore, it is preferable to keep the cleaning time for components that form flow paths, such as piping, as short. In addition, a lower cleaning frequency is preferable.

[0010] One embodiment of the present invention provides a substrate processing apparatus and a substrate processing method that can shorten the time for cleaning the flow path of the processing liquid to be supplied to the substrate.

[0011] In addition, one embodiment of the present invention provides a substrate processing apparatus and a substrate processing method that can reduce the frequency of the flow path of the cleaning guide to supply the processing liquid to the substrate.

[0012] [Technical means to solve the problem]

[0013] An embodiment of the present invention provides a substrate processing apparatus comprising: a substrate holder for holding a substrate; a water flow path for guiding water toward the substrate held in the substrate holder; and a solvent flow path for guiding an organic solvent, which is a liquid with a lower surface tension than the water, toward the substrate held in the substrate holder; wherein the water flow path includes a concave-convex surface having a recess and a protrusion, at least a portion of the recess being filled with air, and the protrusion contacting the water in contact with the air in the recess; and the solvent flow path includes a mirror surface in contact with the organic solvent.

[0014] In the above embodiments, the substrate processing apparatus may also include at least one of the following features.

[0015] The aforementioned uneven surfaces are made of fluororesin.

[0016] The aforementioned water flow path includes a water tank for storing the aforementioned water and a water pipe for guiding the aforementioned water supplied from the aforementioned water tank, and the aforementioned uneven surface is provided on the inner surface of the aforementioned water tank.

[0017] The solvent flow path includes a solvent tank for storing the organic solvent and a solvent piping for guiding the organic solvent supplied from the solvent tank, and the mirror is disposed on the inner surface of the solvent tank.

[0018] The aforementioned uneven surfaces are provided at the bends in the aforementioned water flow path.

[0019] The aforementioned substrate processing apparatus further includes a high-temperature liquid flow path, which guides a high-temperature liquid with a temperature higher than room temperature to the substrate held in the aforementioned substrate holder; and the aforementioned high-temperature liquid flow path includes a concave-convex surface having a recess and a convex portion, at least a portion of the recess being filled with air, and the convex portion contacting the aforementioned high-temperature liquid that is in contact with the air in the aforementioned recess.

[0020] The aforementioned uneven surfaces of the high-temperature liquid flow path are made of fluororesin.

[0021] The aforementioned high-temperature liquid flow path includes a high-temperature liquid tank for storing the aforementioned high-temperature liquid and a high-temperature liquid piping for guiding the aforementioned high-temperature liquid supplied from the aforementioned high-temperature liquid tank, and the aforementioned uneven surface of the aforementioned high-temperature liquid flow path is provided on the inner surface of the aforementioned high-temperature liquid tank.

[0022] The aforementioned high-temperature liquid flow path includes a high-temperature liquid piping that guides the high-temperature liquid, and a high-temperature liquid nozzle that sprays out the high-temperature liquid guided by the high-temperature liquid piping, and the aforementioned uneven surface of the high-temperature liquid flow path is provided on the inner surface of the high-temperature liquid nozzle.

[0023] The aforementioned uneven surfaces are provided at the bends in the aforementioned high-temperature liquid flow path.

[0024] Another embodiment of the present invention provides a substrate processing method, comprising: a water supply step in which, with at least a portion of the recess of an uneven surface filled with air and the convex portion of the uneven surface in contact with water in contact with the air in the recess, the water is guided to a substrate held in a substrate holder through a water flow path including the uneven surface; and a solvent supply step in which, before or after the water supply step, the organic solvent, which is an organic solvent having a lower surface tension than the water, is guided to the substrate held in the substrate holder through a solvent flow path including the mirror surface, while the mirror surface is in contact with an organic solvent. The following features can be added to this embodiment to further enable the substrate processing method to include at least one of the features associated with a substrate processing apparatus.

[0025] The above-described substrate processing method further includes a high-temperature liquid supply step, in which a high-temperature liquid with a temperature higher than room temperature is guided to the substrate held in the substrate holder; and the high-temperature liquid supply step includes the following steps: with at least a portion of the concave part of the concave-convex surface filled with air, and the convex part of the concave-convex surface in contact with the high-temperature liquid in contact with the air in the concave part, the high-temperature liquid is allowed to flow through the high-temperature liquid flow path including the concave-convex surface.

[0026] Another embodiment of the present invention provides a substrate processing apparatus comprising: a substrate holder for holding a substrate; and a high-temperature liquid flow path for guiding a high-temperature liquid with a temperature higher than room temperature to the substrate held in the substrate holder; wherein the high-temperature liquid flow path includes a concave-convex surface having a recess and a convex surface, at least a portion of the recess being filled with air, and the convex surface contacting the high-temperature liquid in contact with the air in the recess.

[0027] In the above embodiments, the substrate processing apparatus may also include at least one of the following features.

[0028] The aforementioned substrate processing apparatus further includes a solvent flow path that guides an organic solvent, which is a liquid with a lower surface tension than the aforementioned high-temperature liquid, to the substrate held in the aforementioned substrate holder; and the aforementioned solvent flow path includes a mirror surface in contact with the aforementioned organic solvent.

[0029] The aforementioned uneven surfaces are made of fluororesin.

[0030] The aforementioned high-temperature liquid flow path includes a high-temperature liquid tank for storing the aforementioned high-temperature liquid and a high-temperature liquid piping for guiding the aforementioned high-temperature liquid supplied from the aforementioned high-temperature liquid tank, and the aforementioned uneven surface is provided on the inner surface of the aforementioned high-temperature liquid tank.

[0031] The aforementioned high-temperature liquid flow path includes a high-temperature liquid piping that guides the high-temperature liquid and a high-temperature liquid nozzle that sprays out the high-temperature liquid guided by the high-temperature liquid piping, and the aforementioned uneven surface is provided on the inner surface of the high-temperature liquid nozzle.

[0032] The aforementioned uneven surfaces are provided at the bends in the aforementioned high-temperature liquid flow path.

[0033] Another embodiment of the present invention provides a substrate processing method comprising a high-temperature solution supply step, wherein a high-temperature solution with a temperature higher than room temperature is guided to a substrate held in a substrate holder; and the high-temperature solution supply step comprises the following steps: with at least a portion of the recess of an uneven surface filled with air, and the convex portion of the uneven surface in contact with the high-temperature solution in contact with the air in the recess, the high-temperature solution is allowed to flow through a high-temperature solution flow path including the uneven surface. The following features may be added to this embodiment, and the substrate processing method may also include at least one of the features related to a substrate processing apparatus.

[0034] The above-described substrate processing method further includes a solvent supply step, in which, with the mirror in contact with an organic solvent that has a lower surface tension than the above-described high-temperature liquid, the organic solvent is guided to the substrate held in the substrate holder through a solvent flow path including the mirror before or after the above-described high-temperature liquid supply step.

[0035] The above-mentioned or other objects, features and effects of the present invention will become clear from the following description of the embodiments with reference to the accompanying drawings. Attached Figure Description

[0036] Figure 1A This is a schematic top view showing the layout of a substrate processing apparatus according to an embodiment of the present invention.

[0037] Figure 1B This is a schematic side view of the substrate processing apparatus.

[0038] Figure 2 It is a schematic diagram of the interior of the processing unit in the substrate processing device viewed horizontally.

[0039] Figure 3 This is a block diagram showing the electrical configuration of the substrate processing device.

[0040] Figure 4 This is a step diagram illustrating an example of processing a substrate using a substrate processing apparatus.

[0041] Figures 5A-5B This is a schematic diagram of the processing liquid supply system of a substrate processing apparatus that supplies processing liquid to the substrate.

[0042] Figure 6 This is a schematic cross-sectional view showing an example of a droplet in contact with a smooth surface.

[0043] Figure 7 This is a schematic cross-sectional view showing an example of a droplet in a Wenzel state in contact with a rough surface.

[0044] Figure 8 This is a schematic cross-sectional view showing an example of a droplet in Cassie-Baxter form in contact with a rough surface.

[0045] Figure 9 This is a schematic cross-sectional view showing an example of the interface between the wetted part and the liquid.

[0046] Figure 10 This is a schematic diagram showing an example of a cross-section of a bend in a pharmaceutical piping system.

[0047] Figure 11 It means along Figure 10 A schematic diagram of an example of a cross-section of the bend in the XI-XI line.

[0048] Figure 12 This is a schematic diagram showing an example of a cross-section of a mold used for manufacturing pharmaceutical piping.

[0049] Figure 13 It means along Figure 12 A schematic diagram of an example cross-section of the mold for line XIII-XIII shown.

[0050] Figure 14 This is a schematic cross-sectional view illustrating a substrate processing apparatus according to another embodiment of the present invention.

[0051] Figure 15 This is a schematic diagram showing another configuration example of the processing unit included in the substrate processing apparatus.

[0052] Figure 16 It is used to explain the use Figure 15 The diagram shows the steps of substrate processing in the processing unit.

[0053] Figure 17 This is a schematic diagram of the supply system for the treatment liquid, including high-temperature chemical solutions.

[0054] Figure 18 This is a cross-sectional view used to illustrate a construction example of a high-temperature liquid piping system. Detailed Implementation

[0055] Figure 1A This is a schematic top view showing the layout of a substrate processing apparatus 1 according to an embodiment of the present invention. Figure 1B This is a schematic side view of the substrate processing apparatus 1.

[0056] The substrate processing apparatus 1 is a monolithic device that processes wafer-shaped substrates W, such as semiconductor wafers, one by one. The substrate processing apparatus 1 includes: a loading port LP, which holds a carrier CA that houses the substrates W; a plurality of processing units 2, which process the substrates W transported from the carrier CA on the loading port LP by means of a processing fluid such as a processing liquid or a processing gas; a transport system TS, which transports the substrates W between the carrier CA on the loading port LP and the plurality of processing units 2; and a control device 3, which controls the substrate processing apparatus 1.

[0057] A plurality of processing units 2 form a plurality of towers TW. Figure 1A An example of forming four towers (TW) is shown. For example... Figure 1B As shown, a plurality of processing units 2 are stacked vertically within a single tower TW. (As...) Figure 1A As shown, a plurality of towers TW, viewed from above, form two rows extending along the depth direction of the substrate processing apparatus 1. The two rows face each other across the transport path TP.

[0058] The transfer system TS includes: a transfer robot IR, which transfers substrate W between a carrier CA on the loading port LP and a plurality of processing units 2; and a central robot CR, which transfers substrate W between the transfer robot IR and the plurality of processing units 2. The transfer robot IR is positioned between the loading port LP and the central robot CR in a top view. The central robot CR is positioned on the transfer path TP.

[0059] The transfer robot IR includes one or more hands Hi that horizontally support the substrate W. Hands Hi can move parallel to each other in either the horizontal or vertical direction. Hands Hi can rotate about a vertical line. Hands Hi can load and unload the substrate W onto the carrier CA on any loading port LP, and can exchange substrate W with the central robot CR.

[0060] The central robotic arm CR includes one or more hands Hc that horizontally support the substrate W. The hands Hc can move parallel to each other in either the horizontal or vertical direction. The hands Hc can rotate about a vertical line. The hands Hc can transfer the substrate W to the transfer robotic arm IR, and can move the substrate W into and out of any processing unit 2.

[0061] Next, the processing unit 2 will be described.

[0062] Figure 2This is a schematic diagram of the interior of the processing unit 2 included in the substrate processing apparatus 1, viewed horizontally. The processing unit 2 includes: a box-shaped chamber 4 having an internal space; a rotating chuck 10 that holds a substrate W horizontally within the chamber 4 while rotating the substrate W about a vertical axis of rotation A1 passing through the center of the substrate W; and a cylindrical processing cup 21 that surrounds the rotating chuck 10 about the axis of rotation A1.

[0063] The chamber 4 includes: a box-shaped partition wall 5 with an inlet / outlet 5b for the substrate W to pass through; and a door 7 that opens or closes the inlet / outlet 5b. An FFU 6 (fan filter unit) is disposed on an air outlet 5a, which is located on the upper part of the partition wall 5. The FFU 6 continuously supplies clean air (filtered air) into the chamber 4 from the air outlet 5a. Gas within the chamber 4 is discharged from the chamber 4 through an exhaust pipe 8 connected to the bottom of the processing cup 21. This ensures a continuous downward flow of clean air within the chamber 4. The exhaust flow rate to the exhaust pipe 8 varies depending on the opening degree of the exhaust valve 9 disposed within the exhaust pipe 8.

[0064] The rotary chuck 10 includes: a circular plate-shaped rotary base 12, which is held horizontally; a plurality of chuck pins 11, which hold the substrate W horizontally above the rotary base 12; a rotary shaft 13, which extends downward from the center of the rotary base 12; and a rotary motor 14, which rotates the rotary base 12 and the plurality of chuck pins 11 by rotating the rotary shaft 13.

[0065] The rotary chuck 10 is not limited to a clamping chuck that contacts the end faces of the substrate W with a plurality of chuck pins 11, but can also be a vacuum chuck that holds the substrate W horizontally by adsorbing the back side (lower surface) of the substrate W, which is a non-component forming surface, onto the upper surface 12u of the rotating base 12. When the rotary chuck 10 is a clamping chuck, the plurality of chuck pins 11 function as substrate holders. When the rotary chuck 10 is a vacuum chuck, the rotating base 12 function as a substrate holder.

[0066] The processing cup 21 includes: a plurality of baffles 24 for receiving processing liquid discharged from the substrate W to the outside; a plurality of cups 23 for receiving processing liquid guided downward by the plurality of baffles 24; and a cylindrical outer wall member 22 surrounding the plurality of baffles 24 and the plurality of cups 23. Figure 2 An example is shown with four baffles 24 and three cups 23, and the outermost cup 23 is integrated with the third baffle 24 from top to bottom.

[0067] The baffle 24 includes: a cylindrical portion 25 surrounding the rotating chuck 10; and an annular top wall 26 extending obliquely upward from the upper end of the cylindrical portion 25 toward the rotation axis A1. A plurality of top walls 26 overlap vertically, and a plurality of cylindrical portions 25 are arranged concentrically. The annular upper end of the top wall 26 corresponds to the upper end 24u of the baffle 24 surrounding the substrate W and the rotating base 12 when viewed from above. A plurality of cups 23 are respectively disposed below the plurality of cylindrical portions 25. The cups 23 form annular grooves for receiving the processing liquid guided downward by the baffle 24.

[0068] Processing unit 2 includes a baffle lifting unit 27 that independently raises and lowers a plurality of baffles 24. The baffle lifting unit 27 positions the baffles 24 at any position within the range from an upper position to a lower position. Figure 2 The diagram shows two baffles 24 positioned in the upper position and the remaining two baffles 24 positioned in the lower position. The upper position refers to the position where the upper end 24u of the baffle 24 is positioned higher than the holding position of the base plate W held in the rotary chuck 10. The lower position refers to the position where the upper end 24u of the baffle 24 is positioned lower than the holding position.

[0069] The processing unit 2 includes a plurality of nozzles for spraying processing fluid onto the substrate W held in the rotating chuck 10. The plurality of nozzles includes a liquid nozzle 31 for spraying a liquid medicine onto the upper surface of the substrate W, and a rinsing nozzle 32 for spraying a rinsing liquid onto the upper surface of the substrate W. The plurality of nozzles also includes a solvent nozzle 33 for spraying an organic solvent onto the upper surface of the substrate W. Figure 2 An example is shown where rinsing fluid nozzle 32 sprays DIW (Deionized Water) and solvent nozzle 33 sprays IPA (Isopropyl Alcohol). DIW represents pure water (deionized water). Unless otherwise specified, organic solvents refer to liquid organic solvents. The same applies to IPA.

[0070] The liquid nozzle 31 is connected to the liquid pipe 31p that guides the liquid. After the liquid valve 31v installed on the liquid pipe 31p is opened, the liquid is continuously sprayed downward from the spray outlet 31d of the liquid nozzle 31. The liquid can be a liquid containing at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, ammonia, hydrogen peroxide, organic acid (e.g., citric acid, oxalic acid, etc.), organic base (e.g., TMAH (tetramethylammonium hydroxide), surfactant, and preservative), or other liquids.

[0071] Although not illustrated, the liquid medicine valve 31v includes: a valve body having an annular valve seat for the passage of liquid medicine; a valve body movable relative to the valve seat; and an actuator that moves the valve body between a closed position (valve body in contact with valve seat) and an open position (valve body away from valve seat). Other valves are similar. The actuator can be a pneumatic actuator, an electric actuator, or other types of actuator. The control device 3 opens or closes the liquid medicine valve 31v, etc., by controlling the actuator.

[0072] The flushing fluid nozzle 32 is connected to the flushing fluid piping 32p that guides the flushing fluid. After the flushing fluid valve 32v installed on the flushing fluid piping 32p is opened, the flushing fluid is continuously sprayed downwards from the spray outlet 32d of the flushing fluid nozzle 32. The flushing fluid can be any of the following: pure water, carbonated water, electrolyzed ionized water, hydrogen water, ozone water, and hydrochloric acid water with a dilution concentration (e.g., about 10 to 100 ppm), or other liquids.

[0073] Solvent nozzle 33 is connected to solvent piping 33p, which guides organic solvent. When solvent valve 33v, installed on solvent piping 33p, is opened, the organic solvent is continuously sprayed downwards from the outlet 33d of solvent nozzle 33. The organic solvent can be an alcohol other than IPA, or an organic solvent other than alcohols such as HFE (hydrofluoroether). IPA has a higher vapor pressure and lower surface tension than water.

[0074] The liquid nozzle 31 can be a scanning nozzle that moves the impact position of the liquid on the substrate W within the upper surface of the substrate W, or it can be a fixed nozzle that cannot move the impact position of the liquid on the substrate W. The same applies to other nozzles. Figure 2 An example is shown where the drug nozzle 31 and solvent nozzle 33 are scanning nozzles, and the rinsing fluid nozzle 32 is a fixed nozzle.

[0075] The liquid medicine nozzle 31 is connected to a nozzle moving unit 31m that moves the liquid medicine nozzle 31 in at least one of the vertical and horizontal directions. The nozzle moving unit 31m positions the liquid medicine nozzle 31 at a processing position where liquid medicine sprayed from the liquid medicine nozzle 31 is supplied to the upper surface of the substrate W. Figure 2 The position shown is horizontally moved between the position indicated and the standby position located around the treatment cup 21 when viewed from above by the liquid nozzle 31.

[0076] The solvent nozzle 33 is connected to a nozzle moving unit 33m that moves the solvent nozzle 33 in at least one of the vertical and horizontal directions. The nozzle moving unit 33m positions the solvent nozzle 33 at a processing position where organic solvent ejected from the solvent nozzle 33 is supplied to the upper surface of the substrate W. Figure 2 The position shown is horizontally moved between the standby position around the processing cup 21 when viewed from above by the solvent nozzle 33.

[0077] Next, the electrical configuration of the substrate processing apparatus 1 will be explained.

[0078] Figure 3 This is a block diagram showing the electrical configuration of the substrate processing apparatus 1. The control device 3 includes at least one computer. The computer includes a computer body 3a and peripheral devices 3d connected to the computer body 3a. The computer body 3a includes a CPU 3b (central processing unit) that executes various commands and a memory 3c that stores information. The peripheral devices 3d include a memory 3e that stores information such as a program P that should be transmitted and received between the memory 3c and the CPU 3b, a reader 3f that reads information from a removable medium RM, and a communication device 3g that communicates with other devices such as the host computer. The memory 3c and the memory 3e are examples of memory devices that store information that should be transmitted and received between the CPU 3b and the CPU 3b.

[0079] 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 maintenance personnel, inputs information into the board processing device 1. The information is displayed on the screen of the display device. The input device can be any of a keyboard, pointing device, and touch panel, or other devices. A touch panel display that serves as both an input device and a display device can also be provided on the board processing device 1.

[0080] CPU 3b executes program P stored in memory 3e. Program P in memory 3e may be pre-installed in control device 3, may be transferred from removable medium RM to memory 3e via reader 3f, or may be transferred to memory 3e by external device such as autonomous computer via communication device 3g.

[0081] Memory 3c is a volatile memory that retains its storage only when powered. Memory 3e and removable medium RM are non-volatile memories that retain their storage even when no power is supplied. Memory 3e is, for example, a magnetic storage device such as a hard disk drive. Removable medium RM is, for example, a compact optical disc or a semiconductor memory such as a memory card. Removable medium RM is an example of a recording medium that records a program P and can be read by a computer. Removable medium RM is a non-transitory tangible recording medium.

[0082] Storage 3e stores a plurality of procedures. Each procedure specifies the processing content, processing conditions, and processing flow of the substrate W. The plurality of procedures differ from each other in at least one aspect of the processing content, processing conditions, and processing flow of the substrate W. Control device 3 controls substrate processing device 1 to process the substrate W according to the procedures specified by the host computer. Control device 3 is programmed to perform the following steps.

[0083] Next, an example of the processing of substrate W will be described.

[0084] Figure 4 This is a step diagram illustrating an example of processing substrate W by substrate processing apparatus 1. Hereinafter, refer to... Figure 1A , Figure 2 and Figure 4 .

[0085] When processing substrate W, a transfer robot IR removes substrate W from the carrier CA on any loading port LP. A central robot CR then transfers substrate W, removed by the transfer robot IR, into any processing unit 2 and places it on a rotary chuck 10. Subsequently, a plurality of chuck pins 11 are horizontally pressed against the end face of substrate W, and a rotary motor 14 begins to rotate. Thus, substrate W begins to rotate.

[0086] After the substrate W begins to rotate, the liquid valve 31v opens, and the liquid nozzle 31 sprays liquid onto the upper surface of the rotating substrate W. This forms a liquid film of liquid covering the entire upper surface of the substrate W. Figure 4 Step S1: An example of the water supply step). When the liquid sprays out from the liquid nozzle 31, the nozzle moving unit 31m can move the liquid nozzle 31 through the central part and the outer periphery at the impact position of the liquid on the upper surface of the substrate W, or it can keep the liquid nozzle 31 stationary at the impact position in the central part. The same applies to other processing liquids as to whether or not the impact position needs to be moved.

[0087] After a predetermined time has elapsed since the opening of the chemical solution valve 31v, the chemical solution valve 31v closes, and the rinsing solution valve 32v opens. Correspondingly, the rinsing solution nozzle 32 sprays pure water, as an example of the rinsing solution, onto the upper surface of the rotating substrate W. As a result, the chemical solution on the substrate W is replaced with pure water, forming a pure water film covering the entire upper surface of the substrate W. Figure 4 Step S2: An example of the water supply step). Afterwards, the rinsing fluid valve 32v is closed, and the solvent valve 33v is opened. Correspondingly, the solvent nozzle 33 sprays IPA, an example of an organic solvent, onto the upper surface of the rotating substrate W. As a result, the pure water on the substrate W is replaced with IPA, forming a liquid film of IPA covering the entire upper surface of the substrate W. Figure 4 Step S3: An example of the solvent supply step). Afterwards, solvent valve 33V is closed.

[0088] After solvent valve 33V is closed, rotary motor 14 causes the substrate W, held by a plurality of chuck pins 11, to rotate at a high rotational speed (e.g., several thousand rpm). As a result, liquid is removed from the substrate W, and the substrate W dries. Figure 4(Step S4). After the substrate W is dried, the rotary motor 14 stops, and the plurality of chuck pins 11 leave the end face of the substrate W. Thus, the substrate W stops rotating, and the holding of the substrate W is released. Afterwards, the central robot CR removes the substrate W from the processing unit 2. The transfer robot IR moves the substrate W removed by the central robot CR into the carrier CA on any loading port LP.

[0089] Thus, one substrate W is processed with a treatment solution such as a chemical solution or rinsing solution. The control device 3 controls the transfer and conveying robot IR, etc., to make the substrate processing device 1 repeat the above series of actions. In this way, multiple substrates W are processed one by one.

[0090] Next, the processing liquid supply system of the substrate processing apparatus 1 will be described.

[0091] Figure 5A This is a schematic diagram of the liquid supply system of the substrate processing apparatus 1, which supplies liquid medicine to the substrate W. In addition to the liquid medicine nozzle 31, liquid medicine piping 31p, and liquid medicine valve 31v, the substrate processing apparatus 1 also includes a liquid medicine tank 31t for storing the liquid medicine to be supplied to the liquid medicine nozzle 31. The substrate processing apparatus 1 further includes a liquid medicine pump 31P for conveying the liquid medicine in the liquid medicine tank 31t to the liquid medicine nozzle 31, and a liquid medicine filter 31F for removing foreign matter from the liquid medicine discharged from the liquid medicine tank 31t. The upstream end of the liquid medicine piping 31p is connected to the liquid medicine tank 31t. The downstream end of the liquid medicine piping 31p is connected to the liquid medicine nozzle 31.

[0092] Figure 5B This is a schematic diagram of the solvent supply system of a substrate processing apparatus 1 that supplies organic solvent to a substrate W. In addition to the solvent nozzle 33, solvent piping 33p, and solvent valve 33v, the substrate processing apparatus 1 also includes a solvent tank 33t for storing the organic solvent to be supplied to the solvent nozzle 33. The substrate processing apparatus 1 further includes a solvent pump 33P for conveying the organic solvent in the solvent tank 33t to the solvent nozzle 33, and a solvent filter 33F for removing foreign matter from the organic solvent discharged from the solvent tank 33t. The upstream end of the solvent piping 33p is connected to the solvent tank 33t. The downstream end of the solvent piping 33p is connected to the solvent nozzle 33.

[0093] A medicinal solution is an aqueous solution of a medicine. Figure 5A In this context, "H2O" indicates the presence of water in the solution. The surface tension of the solution is the same as or approximately the same as that of water (H2O). The surface tension of the solution is higher than that of organic solvents such as IPA. Unless otherwise specified, "water" in the following description refers to a liquid with a water (H2O) concentration of 100% or approximately 100%, or a liquid with a surface tension equal to or approximately equal to that of water (H2O). Water may also contain substances other than water (H2O), provided the above conditions are met. Pure water and other rinsing solutions are examples of water. The solution itself is another example of water.

[0094] Organic solvents are liquids with a lower surface tension than water (H2O). An organic solvent can be a liquid containing only one substance or a liquid containing multiple substances, as long as its surface tension is lower than that of water (H2O). In the latter case, the organic solvent may also contain water (H2O). An organic solvent can also be a liquid in which, when the organic solvent is brought into contact with the aforementioned uneven surface 72, the concave portion 72u is filled with organic solvent, and the convex portion 72h is in contact with the organic solvent. Hereinafter, water and organic solvents will sometimes be collectively referred to as processing liquids.

[0095] The path that the liquid medicine travels before exiting the outlet 31d of the liquid medicine nozzle 31 corresponds to a liquid medicine flow path 31x extending from the starting position to the ending position. The path that the organic solvent travels before exiting the outlet 33d of the solvent nozzle 33 corresponds to a solvent flow path 33x extending from the starting position to the ending position. Although not shown, the path that the rinsing fluid travels before exiting the outlet 32d of the rinsing fluid nozzle 32 corresponds to a rinsing fluid flow path extending from the starting position to the ending position.

[0096] The chemical solution flow path 31x is an example of a water flow path that extends from the starting point to the ending point. The rinsing fluid flow path is also an example of a water flow path. The rinsing fluid flow path is identical to the chemical solution flow path 31x in construction, except that it is supplied with pure water from a common piping installed in the factory where the substrate processing device 1 is located, rather than from a tank such as the chemical solution tank 31t. Therefore, the description of the rinsing fluid flow path will be omitted below.

[0097] The liquid tank 31t corresponds to the starting point of the liquid flow path 31x. The nozzle outlet 31d of the liquid nozzle 31 corresponds to the ending point of the liquid flow path 31x. Similarly, the solvent tank 33t corresponds to the starting point of the solvent flow path 33x. The nozzle outlet 33d of the solvent nozzle 33 corresponds to the ending point of the solvent flow path 33x. When the processing liquid is supplied to the liquid flow path 31x or the solvent flow path 33x from the common piping provided in the factory where the substrate processing apparatus 1 is installed, the starting point may not be the liquid tank 31t or the solvent tank 33t, but the upstream end of the liquid piping 31p or the solvent piping 33p, or it may be the joint connecting the liquid piping 31p or the solvent piping 33p to the common piping.

[0098] The starting point can be a single point or multiple points on a single liquid flow path 31x. Similarly, the ending point can be a single point or multiple points on a single liquid flow path 31x. For example, the treatment liquid supplied from a single starting point can be sprayed from multiple ending points. When spraying a mixture of the first and second component liquids, the liquid flow path 31x can also include a starting point for the first component liquid, a starting point for the second component liquid, and one or more ending points for the mixed first and second component liquids sprayed downstream from the two starting points. The same applies to the starting and ending points of the solvent flow path 33x.

[0099] The liquid flow path 31x includes a liquid nozzle 31 with a spray outlet 31d for dispensing liquid, and a liquid piping 31p for guiding liquid to the liquid nozzle 31. The liquid flow path 31x may also include fluid devices other than the liquid nozzle 31 and the liquid piping 31p.

[0100] Specifically, the liquid flow path 31x may also replace at least one of the following components: liquid valve 31v, liquid tank 31t, liquid pump 31P, and liquid filter 31F, or, in addition to the above components, include a circulation pipe upstream of the liquid pipe 31p that circulates the liquid in the liquid tank 31t, a flow regulating valve that changes the flow rate of the liquid supplied to the liquid nozzle 31, a flow meter that measures the flow rate of the liquid supplied to the liquid nozzle 31, a connector that connects two or more pipes, a manifold that connects three or more pipes, a heater that heats the liquid, and a cooler that cools the liquid.

[0101] Similar to the liquid flow path 31x, the solvent flow path 33x includes a solvent nozzle 33 with an outlet 33d for dispensing organic solvent, and a solvent piping 33p for guiding the organic solvent to the solvent nozzle 33. The solvent flow path 33x may also include fluid devices other than the solvent nozzle 33 and solvent piping 33p, such as a solvent valve 33v. Specific examples of fluid devices are the same as described above.

[0102] The liquid flow path 31x includes an internal space for distributing flowing or stationary liquid medicine, and a cylindrical inner surface 31y surrounding the entire circumference of the internal space. The internal space of the liquid flow path 31x is a closed space that is only open at the end point of the liquid flow path 31x. In other words, the internal space of the liquid flow path 31x only connects to the space outside the liquid flow path 31x at the end point of the liquid flow path 31x.

[0103] Similar to the drug flow path 31x, the solvent flow path 33x includes an internal space for disposing of flowing or stationary organic solvent, and a cylindrical inner surface 33y surrounding the entire circumference of the internal space. The internal space of the solvent flow path 33x is a closed space that opens only at the end point of the solvent flow path 33x. In other words, the internal space of the solvent flow path 33x only connects to the space outside the solvent flow path 33x at the end point of the solvent flow path 33x.

[0104] The inner surface 31y of both the drug flow path 31x and the solvent flow path 33x is made of resin such as fluoropolymer. The fluoropolymer can be PTFE (Polytetrafluoroethylene) or PFA (Perfluoroalkoxyalkane), or other materials. The inner surface 31y of the drug flow path 31x can be entirely made of the same material, or a portion of the inner surface 31y of the drug flow path 31x and the remainder can be made of different materials. The inner surface 33y of the solvent flow path 33x is similarly made of the same material.

[0105] like Figure 5B As shown in the enlarged view on the right, the inner surface 33y of the solvent flow path 33x includes a mirror surface 71 that is in contact with the organic solvent within the solvent flow path 33x. The mirror surface 71 is a surface that has undergone mirror finishing to reduce surface roughness. Mirror finishing can be grinding or other finishing processes.

[0106] like Figure 5A As shown in the enlarged view on the right, the inner surface 31y of the liquid flow path 31x includes a concave-convex surface 72 that contacts the liquid within the liquid flow path 31x. The concave-convex surface 72 is a rough surface with a larger surface roughness than the mirror surface 71. In other words, the mirror surface 71 is a smooth surface with a smaller surface roughness than the concave-convex surface 72.

[0107] The inner surface 31y of the liquid flow path 31x can be entirely uneven 72, or only a portion of the inner surface 31y of the liquid flow path 31x can be uneven 72. The mirror surface 71 is the same. Figure 5A An example is shown where the inner surface of the medicine tank 31t is wholly or partially uneven 72. Figure 5B An example is shown where the inner surface of the solvent tank 33t is entirely or partially mirrored 71.

[0108] The uneven surface 72 is a water-repelling surface that has undergone a water-repelling process to increase the contact angle of water such as liquid medicine or rinsing fluid. The water-repelling process can be at least one of the following: cutting, laser processing, plastic processing, extrusion molding, sandblasting, and etching, or other processing methods.

[0109] Cutting can be at least one of machine tool processing and milling, or other processing methods. Sandblasting is a process in which solid particles are impacted onto the surface of an object (shot peening, etc.). Etching is a process in which chemicals are used to corrode the surface of an object. Water repellency can also be a process in which the contours of a mold surface are transferred to an object. In this case, water repellency can be at least one of plastic forming and extrusion molding, or other processing methods.

[0110] like Figure 5A As shown, the uneven surface 72 is a solid surface provided with a plurality of recesses 72u and a plurality of protrusions 72h. The recesses 72u are recessed from the front end 72d of the protrusions 72h. The protrusions 72h protrude from the bottom 72b of the recesses 72u. The bottom 72b of the recesses 72u corresponds to the root of the protrusions 72h. The front end 72d of the protrusions 72h corresponds to the opening end of the recesses 72u. The front ends 72d of two adjacent protrusions 72h form the entrance to the recesses 72u located between them.

[0111] The convex portion 72h can be a line with a greater depth than its width, or a point with a depth equal to or approximately equal to its width, or other shapes. The concave portion 72u is similarly shaped. The cross-section of the convex portion 72h can be any of the following: rectangular, square, triangular, inverted triangular, trapezoidal, inverted trapezoidal, and semicircle, or other shapes. The cross-section of the concave portion 72u is similarly shaped. Figure 5A An example is shown where both the convex portion 72h and the concave portion 72u have rectangular cross-sections. The height of the convex portion 72h ( Figure 5A The length (in the left-right direction) can be uniform or non-uniform. The depth of the concave portion 72u is similarly uniform. The height of the convex portion 72h can be the same as the width of the convex portion 72h (…). Figure 5A The length of the recess 72u (in the vertical direction) is equal to or different from the width of the recess 72u.

[0112] When the water contact angle is less than 90 degrees, the solid surface is considered hydrophilic. When the water contact angle is 90 degrees or more, the solid surface is considered hydrophobic or water-repellent. When the water contact angle is 150 degrees or more, the solid surface is considered superhydrophobic. The water contact angle relative to a smooth surface made of fluoropolymer resin can be greater than 90 degrees or less than 90 degrees. The water contact angle relative to a smooth surface made of PTFE is generally considered to be 104 to 114 degrees. The water contact angle relative to a smooth surface made of PFA is generally considered to be 105 to 118 degrees. The water contact angle relative to the uneven surface 72 is 119 degrees or more, preferably 150 degrees or more. The water contact angle relative to the mirror surface 71 may be less than 100 degrees.

[0113] Next, the contact between the droplet and the uneven surface 72 and the mirror surface 71 will be explained.

[0114] Figure 6 This is a schematic cross-sectional view showing an example of a droplet in contact with a smooth surface. Figure 7 This is a schematic cross-sectional view showing an example of a droplet in contact with a rough surface in a Wenzel state. Figure 8 This is a schematic cross-sectional view showing an example of a droplet in contact with a rough surface in the Cassie-Baxter state. Figure 9 This is a schematic cross-sectional view showing an example of the interface between the wetted part and the liquid.

[0115] like Figure 8 As shown, the uneven surface 72 is a surface in which, when a water droplet is placed on a horizontal uneven surface 72 under normal temperature and pressure conditions (room temperature and 1 atmosphere), the bottom 72b of the concave portion 72u is separated from the water droplet, while the front end 72d of the convex portion 72h is in contact with the water droplet. In other words, the uneven surface 72 is a surface that becomes a Cassie-Baxter state when a water droplet is placed on a horizontal uneven surface 72 under normal temperature and pressure conditions. Room temperature is, for example, a constant or approximately constant temperature in the range of 10 to 30°C.

[0116] The Cassie-Baxter model and the Wenzel model are models used to describe the wettability of rough surfaces. For example... Figure 7 As shown, in the Wenzel state (hereinafter also referred to as the W state), water droplets on a horizontally rough surface will enter the pits. Conversely, as... Figure 8 As shown, in the Cassie-Baxter state (hereinafter also referred to as the CB state), the recess 72u is filled with air, and the water droplet is supported by the front end 72d of the protrusion 72h.

[0117] The state (W or CB) of a water droplet on a rough surface is influenced by factors such as the surface tension of the liquid, the surface free energy of the rough surface (solid), and the surface texture. It can be assumed that the higher the surface tension of the liquid and the lower the surface free energy of the rough surface (the higher the water repellency of the rough surface), the more likely the water droplet on the rough surface is to be in the CB state.

[0118] The inner surface 31y of the liquid flow path 31x is made of a water-repellent material with a water contact angle exceeding 90 degrees relative to a horizontal smooth surface. Therefore, as long as the surface properties of the concave-convex surface 72 meet the conditions, the water droplet will contact the horizontal concave-convex surface 72 in a CB state. That is, if a water droplet is placed on the horizontal concave-convex surface 72 under normal temperature and pressure, the bottom 72b of the concave portion 72u is separated from the water droplet while the front end 72d of the convex portion 72h contacts the water droplet. If the water droplet contacts the horizontal concave-convex surface 72 in a CB state under normal temperature and pressure, the liquid in the liquid flow path 31x can also contact all or part of the concave-convex surface 72 in a W state.

[0119] Compare Figure 7 and Figure 8 It can be seen that, compared to the case where the water droplet contacts the horizontal uneven surface 72 in the CB state, the contact area between the water droplet and the uneven surface 72 is smaller when the water droplet contacts the horizontal uneven surface 72 in the W state. Furthermore, the contact angle of the water relative to the uneven surface 72 is larger when the water droplet contacts the horizontal uneven surface 72 in the CB state.

[0120] Solvent flow path 33x is the flow path that comes into contact with organic solvents such as IPA. The inner surface 33y of solvent flow path 33x is made of a water-repellent material with a contact angle exceeding 90 degrees relative to a smooth horizontal surface. However, organic solvents have low surface tension; therefore, even if the inner surface 33y of solvent flow path 33x is rough, the organic solvent within solvent flow path 33x will still contact the inner surface 33y of solvent flow path 33x in a W-state. (Comparison) Figure 6 and Figure 7 It can be seen that, compared with the case where the inner surface 33y of the solvent flow path 33x is a mirror surface 71, the contact area between the organic solvent droplets and the inner surface 33y of the solvent flow path 33x is smaller when the inner surface 33y of the solvent flow path 33x is a mirror surface 71.

[0121] Figure 9 A schematic example of the interface between the liquid receiving part and the liquid is shown. Figure 9 The large circle in the diagram represents a fluoropolymer molecule. Figure 9 The small black dots in the image represent impurities. Figure 9 An example is shown where the impurity is smaller than the fluoropolymer molecule. The size of the impurity is not limited to this.

[0122] The inner surface 31y of the drug flow path 31x (refer to) Figure 8 ) and the inner surface 33y of the solvent flow path 33x (refer to Figure 6 The wetted part (or contacting part) is the portion that comes into contact with the liquid. The inner surface of the flushing fluid flow path is also considered a wetted part. The wetted part is made of resin such as fluoropolymer. Figure 9 As shown, fluoropolymers sometimes contain impurities that are different from those in fluoropolymers. Figure 9 (Small black spots). This type of impurity can dissolve from the contact area into the liquid. To prevent this, when the substrate processing apparatus 1 is started, that is, when preparing to use the substrate processing apparatus 1 in a factory such as a semiconductor manufacturing plant, the contact area is cleaned with a cleaning solution. This cleaning is also called flushing.

[0123] However, even after cleaning, impurities will still move from the interior of the fluororesin to its surface. If the substrate processing apparatus 1 does not process the substrate W for an extended period (the period during which the liquid does not flow along the contact portion), a large amount of impurities will accumulate in the contact portion. When processing of the substrate W resumes, these impurities will dissolve into the liquid from the contact portion. Therefore, when the substrate processing apparatus 1 does not process the substrate W for an extended period, cleaning must be performed before resuming processing of the substrate W.

[0124] Cleaning requires not only cleaning fluid but also energy, such as electricity. If the cleaning process takes a long time, the energy consumption and the amount of cleaning fluid used will increase. The same applies to frequent cleaning operations. To reduce cleaning costs and environmental impact, it is desirable to reduce the cleaning time and the number of cleaning sessions.

[0125] However, even when the substrate processing apparatus 1 continuously processes the substrate W, or when the substrate processing apparatus 1 does not process the substrate W for a short period of time, impurities and other contaminants can still leach from the contact area into the liquid. For example, in areas where the liquid has low flowability (areas where the liquid accumulates or stagnates), it is foreseeable that a large amount of impurities will accumulate in the contact area and dissolve into the liquid at unexpected times. It is also foreseeable that foreign matter contained in the liquid will accumulate in areas where the liquid has low flowability and flow downstream with the liquid at unexpected times.

[0126] The uneven surface 72 of the liquid flow path 31x is the surface where the liquid and water, separated from the bottom 72b of the concave portion 72u, contact the front end 72d of the convex portion 72h. Therefore, compared to the case where water contacts the bottom 72b of the concave portion 72u, the contact area between water and the uneven surface 72 can be reduced. Furthermore, since water does not contact or has difficulty contacting the bottom 72b of the concave portion 72u, the contact area between water and the uneven surface 72 can be limited. As a result, the area to be cleaned is reduced, thus shortening the cleaning time. Furthermore, if the contact area between water and the liquid flow path 31x is reduced, the amount of impurities dissolved from the liquid flow path 31x into the water per unit time is reduced, thus lowering the impurity concentration in the water. The amount of foreign matter transferred from water to the uneven surface 72 is also reduced, so even if such foreign matter peels off from the uneven surface 72, the foreign matter concentration in the water can still be reduced.

[0127] The mirror surface 71 of the solvent flow path 33x is a surface with reduced contact area with the organic solvent. That is, the inner surface 33y of the solvent flow path 33x is as follows: Figure 6 The situation of mirror 71 shown is as follows: Figure 7Compared to the case where the inner surface 33y of the solvent flow path 33x is a mirror surface 71, the contact area between the organic solvent and the solvent flow path 33x is smaller when the surface is rough. If the contact area between the organic solvent and the solvent flow path 33x is reduced, the amount of impurities dissolved from the solvent flow path 33x into the organic solvent per unit time decreases, thus lowering the impurity concentration in the organic solvent. Furthermore, compared to the case where the inner surface 33y of the solvent flow path 33x is rough, foreign matter contained in the organic solvent is less likely to adhere to the solvent flow path 33x, reducing the amount of foreign matter transferred from the organic solvent to the solvent flow path 33x. Therefore, even if foreign matter adhering to the solvent flow path 33x peels off, the concentration of foreign matter in the organic solvent can still be reduced.

[0128] Next, the liquid flow at the bend 74 of the liquid flow path 31x will be explained.

[0129] Figure 10 This is a schematic diagram showing an example of the cross-section of the bend 74 of the liquid medicine pipe 31p. Figure 11 It means along Figure 10 A schematic diagram of an example of the cross-section of the bend 74 of the XI-XI line shown. Figure 12 This is a schematic diagram of an example of a cross-section of the mold 75 used to manufacture the liquid medicine piping 31p. Figure 13 It means along Figure 12 A schematic diagram of an example cross-section of mold 75 for line XIII-XIII shown.

[0130] like Figure 11 As shown, the inner circumferential surface of the liquid medicine pipe 31p includes a textured surface 73. The textured surface 73 includes a plurality of linear protrusions 73h and a plurality of linear grooves 73u forming a textured pattern extending along the axial direction of the liquid medicine pipe 31p (along the direction of the center line 31L of the liquid medicine pipe 31p). The textured surface 73 is a concave-convex surface 72 (see reference). Figure 8 One of the forms. Linear protrusion 73h is the convex part 72h (refer to...). Figure 8 One of the forms of ), the linear groove 73u is the concave portion 72u (refer to) Figure 8 One of the forms of ).

[0131] A plurality of linear protrusions 73h are spaced apart along the circumference of the liquid pipe 31p (around the center line 31L of the liquid pipe 31p). The same applies to a plurality of linear grooves 73u. One linear groove 73u is formed between every two nearest linear protrusions 73h along the circumference of the liquid pipe 31p. Figure 11 An example is shown where the textured surface 73 is an annular shape surrounding the centerline 31L of the liquid medicine pipe 31p. Alternatively, the textured surface 73 may only be the inner circumferential surface of the liquid medicine pipe 31p in the circumferential direction.

[0132] The linear groove 73u and the linear protrusion 73h extend in a direction parallel to the center line 31L of the liquid medicine pipe 31p. Where the center line 31L of the liquid medicine pipe 31p is straight, the linear groove 73u and the linear protrusion 73h are also straight. Where the center line 31L of the liquid medicine pipe 31p is curved, the linear groove 73u and the linear protrusion 73h are also curved. The width of the linear groove 73u is shorter than its length. The width of the linear protrusion 73h is shorter than its length. The width of the linear protrusion 73h may be equal to or different from the width of the linear groove 73u.

[0133] Figure 12 and Figure 13 An example of a cross-section of a die 75 for manufacturing a pharmaceutical tubing 31p by melt extrusion, one type of extrusion molding, is shown. The die 75 is a mold for forming resin tubing such as the pharmaceutical tubing 31p. The die 75 can be a mold or die head used to shape molten tubing raw material, or a shaping mold used to finish the shape of the tubing passing through the mold or die head. The die 75 includes a core 75c for shaping the inner circumferential surface of the tubing and a ring 75r for shaping the outer circumferential surface of the tubing. Figure 13 The appearance of the core 75c is shown.

[0134] Raw materials for resin-based tubing, such as the liquid tubing 31p, are supplied into a cylindrical space 75s between the core 75c and the ring 75r, and then continuously extruded from this space 75s. This forms the tubing. At this time, a textured surface 73 is formed on the inner circumferential surface of the tubing, with a shape identical or substantially the same as the textured surface on the outer circumferential surface of the core 75c. The tubing extruded from the die 75 is straight. If a bend 74 is required in the tubing, the straight tubing can be temporarily softened by heating to bend it. If the tubing is flexible, it can be bent without heating.

[0135] Figure 10 An example is shown where the turning portion 74 includes a straight upstream portion 74u, a straight downstream portion 74d inclined at a certain angle relative to the upstream portion 74u, and an arc-shaped corner portion 74c extending from the upstream portion 74u to the downstream portion 74d. In this example, the turning portion 74 is bent at 90 degrees. In other words, the upstream portion 74u and the downstream portion 74d are arranged on two orthogonal straight lines. The upstream portion 74u, the corner portion 74c, and the downstream portion 74d are all cylindrical. The linear grooves 73u and linear protrusions 73h of the textured surface 73 bend at the turning portion 74.

[0136] Figure 10The vortex-like curves in the diagram represent areas where liquid accumulates or stagnates. Because a textured surface 73 is provided on the inner circumferential surface of the bend 74, the contact area between water and the bend 74 is reduced, thereby limiting the contact area between water and the bend 74. Furthermore, the resistance exerted on the water by the inner circumferential surface of the bend 74 is reduced, thus minimizing the decrease in water velocity at the bend 74, thereby reducing the area where accumulation or stagnation occurs. Therefore, impurities and foreign matter accumulated in this area are reduced, and contaminants moving from the inner circumferential surface of the bend 74 through the water flowing through it are reduced.

[0137] Next, the effects of this implementation method will be explained.

[0138] In this embodiment, water is guided to the substrate W via a water flow path, and an organic solvent, which has a lower surface tension than water, is guided to the substrate W via a solvent flow path 33x. The drug flow path 31x and the rinsing liquid flow path are examples of water flow paths, and the drug and rinsing liquid are examples of water. The water flow path includes an uneven surface 72 that contacts the water. The solvent flow path 33x includes a mirror surface 71 that contacts the organic solvent.

[0139] The uneven surface 72 of the liquid flow path 31x includes: a recess 72u, at least a portion of which is filled with air; and a protrusion 72h, which contacts water that is in contact with the air inside the recess 72u. Because at least a portion of the recess 72u is filled with air, the contact area between water and the uneven surface 72 is reduced compared to when the recess 72u is completely filled with water. Furthermore, since water does not contact or has difficulty contacting the inner surface of the recess 72u, the contact area between water and the uneven surface 72 is limited. Therefore, the area to be cleaned by the cleaning solution is reduced, thus shortening the cleaning time.

[0140] The mirror surface 71 of the solvent flow path 33x is a smooth surface in contact with the organic solvent. Because the organic solvent has a low surface tension, even if the inner surface 33y of the solvent flow path 33x is rough, the organic solvent within the flow path 33x will still enter the grooves of the rough surface. In this case, if the surface roughness of the rough surface is reduced, the contact area between the organic solvent and the solvent flow path 33x will also decrease. If the surface roughness is made extremely small, the rough surface will become the mirror surface 71. Therefore, by providing the mirror surface 71 on the inner surface 33y of the solvent flow path 33x, compared to the case where the inner surface 33y of the solvent flow path 33x is rough, the area that needs to be cleaned with the cleaning solution can be reduced, thereby shortening the cleaning time.

[0141] In this embodiment, all or part of the uneven surface 72 is made of fluoropolymer resin. Fluoropolymer resin is a material with high water repellency. Whether the droplets on the rough surface exhibit a Wenzel state or a Cassie-Baxter state is affected by factors such as the surface tension of the liquid, the surface free energy of the rough surface (solid), and the surface properties of the rough surface. By making the uneven surface 72 with a material with high water repellency, at least a portion of the recess 72u can be kept filled with air. Thus, the contact area between water and the uneven surface 72 can be limited, and the contact area between water and the uneven surface 72 can be reduced.

[0142] In this embodiment, the liquid medicine is guided from the liquid medicine tank 31t to the liquid medicine pipe 31p. The liquid medicine tank 31t and the liquid medicine pipe 31p are equivalent to a water tank and a water pipe. A concave-convex surface 72 is provided on the inner surface of the liquid medicine tank 31t. The time the liquid medicine is in contact with the liquid medicine tank 31t is longer than the time the liquid medicine is in contact with the liquid medicine pipe 31p. Therefore, by reducing the contact area between the liquid medicine and the liquid medicine tank 31t, the amount of pollutants transferred from the liquid medicine tank 31t to the liquid medicine can be effectively reduced.

[0143] In this embodiment, the organic solvent is guided from the solvent tank 33t to the solvent piping 33p. A mirror 71 is disposed on the inner surface of the solvent tank 33t. The time the organic solvent is in contact with the solvent tank 33t is longer than the time it is in contact with the solvent piping 33p. Therefore, by reducing the contact area between the organic solvent and the solvent tank 33t, the amount of pollutants transferred from the solvent tank 33t to the organic solvent can be effectively reduced.

[0144] In this embodiment, an uneven surface 72 is provided on the inner surface of the bend 74 of the liquid flow path 31x, which is an example of a water flow path. Sometimes, areas of low liquid flow (areas where liquid accumulates or stagnates) occur in the bend 74. In such cases, it is foreseeable that contaminants such as particulate matter will accumulate in the bend 74 and flow along with the liquid at unexpected times. By providing the uneven surface 72 on the inner surface of the bend 74, the resistance exerted on the liquid by the inner surface of the bend 74 is reduced, thus minimizing the decrease in liquid velocity at the bend 74 and reducing the area where liquid accumulates or stagnates. Therefore, impurities and foreign matter accumulated in this area can be reduced, and contaminants moving from the inner surface of the bend 74 into the liquid flowing through the bend 74 can be reduced.

[0145] Next, another implementation method will be described.

[0146] Alternatively, the uneven surface 72 or textured surface 73 may not be provided on both the liquid tank 31t and the turning part 74, but may be provided only on the liquid tank 31t or only on the turning part 74.

[0147] Alternatively, a textured surface 73 may be provided on a portion of the inner surface 31y of the liquid flow path 31x, other than the inner circumferential surface of the liquid pipe 31p, on the inner surface of the liquid tank 31t. In this case, the directions of the plurality of linear protrusions 73h and the plurality of linear grooves 73u may not be parallel to the flow direction of the liquid.

[0148] The substrate processing apparatus 1 is not limited to processing circular substrates W, but can also be a processing apparatus for polygonal substrates W. The substrate processing apparatus 1 can also be a batch processing apparatus that processes multiple substrates W at one time.

[0149] like Figure 14 As shown, the batch substrate processing apparatus 1 includes: a lifter 81 that holds a plurality of substrates W and moves up and down between an upper position and a lower position; and an inner tank 82 that stores a processing liquid for impregnating the plurality of substrates W held by the lifter 81 in the lower position. The batch substrate processing apparatus 1 also includes: a nozzle 87 that supplies processing liquid to the inner tank 82; an outer tank 83 that stores processing liquid overflowing from the inner tank 82; a circulation pipe 84 that guides processing liquid from the outer tank 83 to the nozzle 87; a pump 85 that delivers processing liquid from the outer tank 83 to the nozzle 87 through the circulation pipe 84; and a filter 86 that removes foreign matter from the processing liquid flowing through the circulation pipe 84. The lifter 81 functions as a substrate holder.

[0150] The treatment fluid supplied to the inner tank 82 can be water, such as a medicinal solution or rinsing solution, or an organic solvent. The outer tank 83 corresponds to the starting point of the water flow path or solvent flow path 33x. The inner tank 82 corresponds to the ending point of the water flow path or solvent flow path 33x. When the treatment fluid is water, at least one of the inner tank 82, outer tank 83, circulation piping 84, pump 85, filter 86, and nozzle 87 has an uneven surface 72 on its inner surface. When the treatment fluid is an organic solvent, at least one of the inner tank 82, outer tank 83, circulation piping 84, pump 85, filter 86, and nozzle 87 has a mirror surface 71 on its inner surface.

[0151] Figure 15 This is a schematic diagram showing another configuration example of processing unit 2, and... Figure 2 Similarly, this indicates a horizontal view of the internal structure of processing unit 2. In Figure 15 In China, Figure 2 The corresponding parts are labeled with the same reference numerals as those in the attached drawings, and their structure and operation are the same as those in the attached drawings. Figure 2 The situation is essentially the same, therefore the explanation is omitted.

[0152] The contents of the processing liquid supply system and substrate processing in this embodiment are similar to those of the previous one. Figure 2 The constituent examples are different, so this will be the main focus of the explanation.

[0153] The processing unit 2 includes a plurality of nozzles for spraying processing fluid onto the substrate W held in the rotary chuck 10. The plurality of nozzles includes a first liquid nozzle 131 for spraying a first liquid onto the upper surface of the substrate W, a second liquid nozzle 132 for spraying a second liquid onto the upper surface of the substrate W, and a rinsing liquid nozzle 134 (first rinsing liquid nozzle) for spraying rinsing liquid onto the upper surface of the substrate W. Additionally, the plurality of nozzles includes a third liquid nozzle 133 for spraying a third liquid onto the upper surface of the substrate W. Figure 15 This illustrates a scenario where the first solution is DHF (dilute hydrofluoric acid), an example of an acid; the second solution is a sulfuric acid-hydrogen peroxide mixture (SPM), which removes organic matter and is an antioxidant; and the third solution is an ammonia-hydrogen peroxide mixture (SC1: Standard Clean 1), an example of an alkali. Additionally, Figure 15 This illustration shows the case where the flushing fluid ejected from the flushing fluid nozzle 134 is DIW (Deionized Water). As mentioned above, the flushing fluid can also be a liquid other than DIW.

[0154] and Figure 2 Similarly, in the configuration example, the plurality of nozzles also include a rinsing fluid nozzle 32 (second rinsing fluid nozzle) for spraying rinsing fluid onto the upper surface of the substrate W, and a solvent nozzle 33 for spraying organic solvent onto the upper surface of the substrate W. Figure 2 In the same situation, Figure 15 An example is shown where DIW (distilled liquid) is ejected from the rinsing fluid nozzle 32 and IPA (isopropyl alcohol) is ejected from the solvent nozzle 33. The types of rinsing fluid ejected from the rinsing fluid nozzle 32 and the types of organic solvent ejected from the solvent nozzle 33 are as described above. Furthermore, the configurations of the rinsing fluid supply system to the rinsing fluid nozzle 32 and the organic solvent supply system to the solvent nozzle 33 are also as described above. Figure 2 The situation is the same as the case of the constituent examples.

[0155] although Figure 15 The illustration is omitted, but a baffle plate facing upwards can also be provided and held on the upper surface of the substrate W in the rotating chuck 10. In this case, the rinsing fluid nozzle 32 and the solvent nozzle 33 can also be installed on the baffle plate and configured to spray liquid from the center of the baffle plate to the center of the substrate W.

[0156] The first liquid nozzle 131, the second liquid nozzle 132, and the rinsing nozzle 134 are connected to the nozzle moving unit 38. The nozzle moving unit 38 causes the liquid ejected from the first liquid nozzle 131, the second liquid nozzle 132, and the rinsing nozzle 134 to vary the radial (radial direction centered on the rotation axis A1) landing position (i.e., the distance of the landing position from the rotation axis A1) on the substrate W. Thus, the first liquid nozzle 131, the second liquid nozzle 132, and the rinsing nozzle 134 have the shape of scanning nozzles whose landing positions vary radially on the substrate W. For example, the nozzle moving unit 38 may also be a rotary unit that causes the first liquid nozzle 131, the second liquid nozzle 132, and the rinsing nozzle 134 to rotate along an arc-shaped horizontal path passing near the rotation axis A1. The third liquid nozzle 133 is connected to the nozzle moving unit 133m. The nozzle moving unit 133m changes the radial landing position of the liquid ejected from the third liquid nozzle 133 on the substrate W. Thus, the third liquid nozzle 133 has the shape of a scanning nozzle whose landing position changes radially on the substrate W. For example, the nozzle moving unit 133m can also be a rotary unit that rotates the third liquid nozzle 133 along an arc-shaped horizontal path passing near the rotation axis A. One or more of the first liquid nozzle 131, the second liquid nozzle 132, the third liquid nozzle 133, and the rinsing liquid nozzle 134 can also be fixed nozzles fixed within the processing unit 2.

[0157] The first chemical nozzle 131 is connected to a first chemical pipe 131p that supplies DHF to the first chemical nozzle 131. The rinsing fluid nozzle 134 is connected to a rinsing fluid pipe 134p that supplies pure water to the rinsing fluid nozzle 134. When the first chemical valve 131v installed on the first chemical pipe 131p is opened, DHF is supplied from the first chemical pipe 131p to the first chemical nozzle 131, and then continuously sprayed downwards from the first chemical nozzle 131. When the rinsing fluid valve 134v installed on the rinsing fluid pipe 134p is opened, pure water is supplied from the rinsing fluid pipe 134p to the rinsing fluid nozzle 134, and then continuously sprayed downwards from the rinsing fluid nozzle 134. The temperature of the pure water sprayed from the rinsing fluid nozzle 134 can be room temperature or higher than room temperature.

[0158] The second chemical nozzle 132 is connected to a sulfuric acid pipe 132p that directs sulfuric acid to the second chemical nozzle 132, and a hydrogen peroxide water pipe 135p that directs hydrogen peroxide water to the second chemical nozzle 132. A sulfuric acid valve 132v and a flow regulating valve 132f are installed on the sulfuric acid pipe 132p. A hydrogen peroxide water valve 135v and a flow regulating valve 135f are installed on the hydrogen peroxide water pipe 135p.

[0159] After the sulfuric acid valve 132v is opened, sulfuric acid is supplied from the sulfuric acid pipe 132p to the second chemical nozzle 132 at a flow rate corresponding to the opening degree of the flow regulating valve 132f. After the hydrogen peroxide water valve 135v is opened, hydrogen peroxide water is supplied from the hydrogen peroxide water pipe 135p to the second chemical nozzle 132 at a flow rate corresponding to the opening degree of the flow regulating valve 135f. After the sulfuric acid valve 132v and the hydrogen peroxide water valve 135v are opened, the sulfuric acid and hydrogen peroxide water mix to generate SPM. Then, this SPM is continuously sprayed downwards from the second chemical nozzle 132 toward the upper surface of the substrate W.

[0160] The flow rate of SPM ejected from the second chemical nozzle 132 and the mixing ratio of sulfuric acid to hydrogen peroxide water (the ratio of sulfuric acid flow rate to hydrogen peroxide water flow rate) are changed by flow control valves 132f and 135f. The temperature of the SPM ejected from the second chemical nozzle 132 is changed according to the mixing ratio of sulfuric acid to hydrogen peroxide water, the temperature of sulfuric acid before mixing, and the temperature of hydrogen peroxide water before mixing.

[0161] The mixing ratio of sulfuric acid to hydrogen peroxide solution (the ratio of sulfuric acid flow rate to hydrogen peroxide solution flow rate) is, for example, 2 or more. When sulfuric acid and hydrogen peroxide solution are mixed, high-temperature SPM is generated due to the heat of dilution of the sulfuric acid. The temperature of the SPM ejected from the second chemical nozzle 132 is, for example, higher than 100°C. The temperature of the sulfuric acid before mixing with the hydrogen peroxide solution is higher than room temperature, for example, higher than 100°C. The substrate processing apparatus 1 is equipped with a heater 34h for heating the sulfuric acid supplied to the second chemical nozzle 132. The temperature of the hydrogen peroxide solution before mixing with the sulfuric acid is, for example, room temperature (e.g., 20–30°C). The temperature of the hydrogen peroxide solution before mixing with the sulfuric acid may also be higher than room temperature.

[0162] The third liquid nozzle 133 is connected to the third liquid pipe 133p, which guides SC1 to the third liquid nozzle 133. After the third liquid valve 133v installed on the third liquid pipe 133p is opened, SC1 is supplied from the third liquid pipe 133p to the third liquid nozzle 133, and then continuously sprayed downward from the third liquid nozzle 133.

[0163] Next, an example of the processing of substrate W will be described.

[0164] Figure 16 This is a step diagram illustrating an example of processing a substrate W by a substrate processing apparatus 1. Figure 16 An example is shown in which these processing solutions are supplied to the substrate W in the order of DHF, pure water, SPM, pure water, SCI, IPA.

[0165] The substrate W being processed is, for example, a semiconductor wafer such as a silicon wafer. The front side of the substrate W corresponds to the device formation surface for forming devices such as transistors or capacitors. Hereinafter, an example of resist removal will be described, in which SPM, serving as both a resist remover and a resist stripping solution, is supplied to the upper surface of the substrate W, thereby removing excess resist masking from the substrate W. The processing of the substrate W can also be other than resist removal.

[0166] When processing substrate W, a transfer robot IR removes substrate W from the carrier CA on any loading port LP. A central robot CR then transfers substrate W, removed by the transfer robot IR, into any processing unit 2 and places it on a rotary chuck 10. Subsequently, a plurality of chuck pins 11 are horizontally pressed against the end face of substrate W, and a rotary motor 14 begins to rotate. Thus, substrate W begins to rotate.

[0167] After the substrate W begins to rotate, the first chemical valve 131v opens, and the first chemical nozzle 131 sprays DHF onto the upper surface of the rotating substrate W. Thus, the entire upper surface of the substrate W is treated with DHF (an example of step S11: water supply step). This treatment can also be a pre-cleaning process to remove foreign matter by lightly etching the front side of the substrate W (e.g., etching of the natural oxide film). When the first chemical nozzle 131 sprays DHF, the nozzle moving unit 38 can move the first chemical nozzle 131 through the central portion and the outer periphery of the impact position of the DHF on the upper surface of the substrate W, or it can keep the first chemical nozzle 131 stationary at the central portion of the impact position. The same applies to other treatment solutions (pure water, SPM, SCI, IPA) as to whether or not the impact position needs to be moved.

[0168] After a predetermined time has elapsed since the first chemical solution valve 131v opened, the first chemical solution valve 131v closes, and the rinsing solution valve 134v opens. Correspondingly, the rinsing solution nozzle 134 sprays pure water, as an example of the rinsing solution, onto the upper surface of the rotating substrate W. As a result, the DHF on the substrate W is replaced with pure water, thereby removing the DHF from the entire upper surface of the substrate W (step S12: an example of the water supply step). Alternatively, a solvent rinsing step can be performed before rinsing with pure water, i.e., IPA is supplied to the substrate W from the solvent nozzle 33 (an example of the solvent supply step).

[0169] After a specified period of pure water rinsing, the rinsing fluid valve 134V is closed. Then, SPM treatment begins (step S13: an example of the high-temperature chemical supply step). That is, the sulfuric acid valve 132V and the hydrogen peroxide water valve 135V are opened, thereby mixing sulfuric acid and hydrogen peroxide water in the second chemical nozzle 132 to generate SPM, which is then sprayed from the second chemical nozzle 132 onto the substrate W. Thus, the entire upper surface of the substrate W is treated with SPM. Through this SPM treatment, the resist on the upper surface of the substrate W is stripped and removed from the substrate W.

[0170] After a specified time, the sulfuric acid valve 132V and the hydrogen peroxide water valve 135V are closed, and the SPM treatment ends. Then, the rinsing fluid valve 134V is opened. Correspondingly, the rinsing fluid nozzle 134 sprays pure water, as an example of the rinsing fluid, onto the upper surface of the rotating substrate W. As a result, the SPM on the substrate W is replaced with pure water, thereby removing the SPM from the entire upper surface of the substrate W (step S14: an example of the water supply step).

[0171] After a specified period of pure water rinsing, the rinsing fluid valve 134v is closed. Then, treatment with SC1 solution begins (step S15). That is, the third solution valve 133v is opened, and the third solution nozzle 133 sprays SC1 onto the upper surface of the rotating substrate W. Thus, the entire upper surface of the substrate W is treated with SC1. This treatment can also be used to remove residues remaining on the substrate after SPM treatment and rinsing.

[0172] After a specified time, the third chemical solution valve 133v closes, and the chemical treatment using SC1 ends. Then, the solvent valve 33v opens. Correspondingly, the solvent nozzle 33 sprays IPA, an example of an organic solvent, onto the upper surface of the rotating substrate W. As a result, the SC1 on the substrate W is replaced with IPA, forming a liquid film of IPA covering the entire upper surface of the substrate W (step S16: an example of the solvent supply step). Afterward, the solvent valve 33v closes. Alternatively, a pure water rinsing process can be performed after chemical treatment with SC1 and before IPA supply begins.

[0173] After the solvent valve 33V is closed, the rotary motor 14 rotates the substrate W, held by a plurality of chuck pins 11, at a high rotational speed (e.g., several thousand rpm). As a result, liquid is removed from the substrate W, and the substrate W dries (step S17). After the substrate W is dried, the rotary motor 14 stops, and the plurality of chuck pins 11 disengage from the end face of the substrate W. Thus, the substrate W stops rotating, and the holding of the substrate W is released. Then, the central robot CR removes the substrate W from the processing unit 2. The transfer robot IR moves the substrate W removed by the central robot CR into a carrier CA on any loading port LP.

[0174] Thus, one substrate W is processed with a treatment solution such as a chemical solution or rinsing solution. The control device 3 controls the transfer and conveying robot IR, etc., to make the substrate processing device 1 repeat the above series of actions. In this way, multiple substrates W are processed one by one.

[0175] Secondly, the treatment fluid supply system will be explained.

[0176] DHF (dilute hydrofluoric acid), the first liquid, has an HF / H2O composition ratio of approximately 1 / 1000 to 1 / 100 by volume, and its surface tension is equal to or approximately equal to that of water (H2O). Therefore, it can be considered a liquid similar to water. Consequently, the path that DHF takes before reaching the nozzle 131d of the first liquid nozzle 131 is a liquid flow path 131x extending from the starting point to the ending point, which is an example of a water flow path. Furthermore, the structure of the liquid flow path 131x through which DHF passes is similar to that of a water flow path. Figure 5A The structure of the liquid flow path 31x described above is essentially the same. Therefore, the term "liquid" in the above description related to the structure of the liquid flow path 31x will be replaced with "DHF" and used to describe the flow path structure of the liquid flow path 131x through which DHF passes.

[0177] Furthermore, SC1 (a mixture of ammonia and hydrogen peroxide) as the third liquid is, for example, a liquid with a volume ratio of 1 part ammonia (28-30 wt%), 1 part hydrogen peroxide (30 wt%), and 5 parts water, and whose surface tension is equal to or approximately equal to that of water (H2O). Therefore, the path SC1 takes before reaching the nozzle 133d of the third liquid nozzle 133 is a liquid flow path 133x extending from the starting point to the ending point, which is an example of a water flow path. Moreover, the structure of the liquid flow path 133x through which SC1 passes is similar to that of a water flow path. Figure 5A The structure of the liquid flow path 31x described above is essentially the same. Therefore, the term "liquid" in the above description related to the structure of the liquid flow path 31x will be replaced with "SC1" and then referenced to describe the flow path structure of the liquid flow path 133x through which SC1 passes.

[0178] Secondly, the path that the flushing fluid travels before exiting the nozzle 134d of the flushing fluid nozzle 134 corresponds to a flushing fluid flow path 134x extending from the starting position to the ending position. The construction of this flushing fluid flow path 134x is similar to... Figure 2 The flushing fluid flow path described for the flushing fluid nozzle 32 in the configuration example of the processing unit 2 is the same, so the description is omitted.

[0179] The path that the flushing fluid travels before exiting the flushing fluid nozzle 32 through the outlet 32d, i.e., the structure of the flushing fluid flow path 32x. Figure 2The configuration of the processing unit 2 is the same as in the example. Furthermore, the structure of the solvent flow path 33x, the path the organic solvent travels before being ejected from the outlet 33d of the solvent nozzle 33, is also the same. Figure 2 The configuration of processing unit 2 is the same as in the case of the example.

[0180] Figure 17 This is a schematic diagram of a chemical supply system that supplies SPM, used as the second chemical solution, to substrate W. The substrate processing apparatus 1 includes a sulfuric acid tank 132t for storing sulfuric acid (typically concentrated sulfuric acid) and a hydrogen peroxide water tank 135t for storing hydrogen peroxide water. The sulfuric acid stored in the sulfuric acid tank 132t is, more precisely, a sulfuric acid-containing solution. For example, SPM used for processing substrate W can be recovered, subjected to necessary regeneration treatment, and then introduced into the sulfuric acid tank 132t for use as sulfuric acid (a sulfuric acid-containing solution). The upstream end of a sulfuric acid pipe 132p is connected to the sulfuric acid tank 132t, and the upstream end of a hydrogen peroxide water pipe 135p is connected to the hydrogen peroxide water tank 135t. The downstream ends of the sulfuric acid pipe 132p and the hydrogen peroxide water pipe 135p are connected to the second chemical solution nozzle 132. The sulfuric acid piping 132p is equipped with a sulfuric acid pump 132P that delivers sulfuric acid from the sulfuric acid tank 132t to the second chemical nozzle 132, and a sulfuric acid filter 132F that removes foreign matter from the sulfuric acid discharged from the sulfuric acid tank 132t. The hydrogen peroxide water piping 135p is equipped with a pump 135P that delivers hydrogen peroxide water from the hydrogen peroxide water tank 135t to the second chemical nozzle 132, and a filter 135F that removes foreign matter from the hydrogen peroxide water discharged from the hydrogen peroxide water tank 135t.

[0181] The hydrogen peroxide water supplied to the second liquid nozzle 132, mixed with sulfuric acid, is a liquid with a surface tension similar to that of water (H2O), and can be considered as an example of water when designing the flow path. Therefore, the path that the hydrogen peroxide water takes before reaching the second liquid nozzle 132 is a liquid flow path 135x extending from the starting position to the ending position, which is an example of a water flow path. Furthermore, the construction of the liquid flow path 135x through which the hydrogen peroxide water passes is similar to that of a reference... Figure 5A The structure of the liquid flow path 31x described above is essentially the same. Therefore, the term "liquid" in the above description related to the structure of the liquid flow path 31x will be replaced with "hydrogen peroxide water" and used to describe the flow path structure of the liquid flow path 135x of hydrogen peroxide water.

[0182] On the other hand, sulfuric acid (concentrated sulfuric acid) supplied to the second liquid nozzle 132 and mixed with hydrogen peroxide water, and SPM formed by mixing sulfuric acid and hydrogen peroxide water, are examples of high-temperature liquids with temperatures higher than room temperature. Although the dynamics of sulfuric acid (especially concentrated sulfuric acid) and SPM as liquids are difficult to view in the same way as water, there is a particular concern that impurities (especially plasticizers) in the resin material may leach into the liquid when the high-temperature liquid flow path to which the sulfuric acid and SPM are supplied is made of resin material such as fluoropolymer. Therefore, similar to the water flow path described above, the high-temperature liquid flow path is preferably designed to minimize the contact area with the liquid.

[0183] The path that the high-temperature chemical solution (sulfuric acid or SPM) travels before exiting from the outlet 132d of the second chemical solution nozzle 132 corresponds to a high-temperature chemical solution flow path 132x extending from the starting position to the ending position. The sulfuric acid tank 132t is an example of a high-temperature chemical solution tank, corresponding to the starting position of the high-temperature chemical solution flow path 132x. The second chemical solution nozzle 132 is an example of a high-temperature chemical solution nozzle, and its outlet 132d corresponds to the ending position of the high-temperature chemical solution flow path 132x.

[0184] The high-temperature chemical solution flow path 132x includes a second chemical solution nozzle 132 with an outlet 132d for discharging SPM, and a sulfuric acid pipe 132p that directs sulfuric acid to the second chemical solution nozzle 132. The sulfuric acid pipe 132p is an example of a high-temperature chemical solution pipe. The high-temperature chemical solution flow path 132x may also include fluid equipment other than the second chemical solution nozzle 132 and the sulfuric acid pipe 132p. In this example, the high-temperature chemical solution flow path 132x includes a sulfuric acid valve 132v, a flow regulating valve 132f, a sulfuric acid tank 132t, a sulfuric acid pump 132P, a sulfuric acid filter 132F, and a heater 132h. The high-temperature liquid flow path 132x may also replace at least one of the above components or include, in addition to the above components, at least one of the following: a circulation pipe that circulates sulfuric acid from downstream of the heater 132h to the sulfuric acid tank 132t; a flow meter that measures the flow rate of sulfuric acid supplied to the second liquid nozzle 132; a connector that connects two or more pipes; and a manifold that connects three or more pipes.

[0185] The high-temperature liquid flow path 132x includes an internal space for distributing a flowing or stationary high-temperature liquid (sulfuric acid or SPM), and a cylindrical inner surface 132y surrounding the entire circumference of the internal space. The internal space of the high-temperature liquid flow path 132x is a closed space that opens only at the end point of the high-temperature liquid flow path 132x. In other words, the internal space of the high-temperature liquid flow path 132x only connects to the space outside the high-temperature liquid flow path 132x at the end point of the high-temperature liquid flow path 132x.

[0186] The inner surface 132y of the high-temperature liquid flow path 132x is made of resin such as fluororesin. The fluororesin can be PTFE (Polytetrafluoroethylene) or PFA (Perfluoroalkoxyalkane), or other materials. The entire inner surface 132y of the high-temperature liquid flow path 132x can be made of the same material, or a portion of the inner surface 132y of the high-temperature liquid flow path 132x and the remainder of the inner surface 132y can be made of different materials.

[0187] like Figure 17 As shown in the enlarged view on the right, the inner surface 132y of the high-temperature liquid flow path 132x includes a concave-convex surface 172 that contacts the liquid (sulfuric acid or SPM) within the high-temperature liquid flow path 132x. The concave-convex surface 172 has a surface roughness relatively lower than that of mirror surface 71 (see reference). Figure 5B Large, rough surface.

[0188] The inner surface 132y of the high-temperature liquid flow path 132x can be entirely uneven 172, or only a portion of the inner surface 132y of the high-temperature liquid flow path 132x can be uneven 172. Figure 17 An example is shown where the inner surfaces of the sulfuric acid tank 132t and the second liquid nozzle 132 are wholly or partially irregular surfaces 172.

[0189] The uneven surface 172 is, similarly to the case of the liquid flow path 31x described above, a water-repellent surface after undergoing water-repellent processing. Therefore, it has a larger contact angle with sulfuric acid and a correspondingly smaller contact area with sulfuric acid. The water-repellent processing can be at least one of cutting, laser processing, plastic processing, extrusion molding, sandblasting, and etching, or other processing methods.

[0190] like Figure 17 As shown, the uneven surface 172 is a solid surface provided with a plurality of recesses 172u and a plurality of protrusions 172h. The recesses 172u are recessed from the front end 172d of the protrusions 172h. The protrusions 172h protrude from the bottom 172b of the recesses 172u. The bottom 172b of the recesses 172u corresponds to the root of the protrusions 172h. The front end 172d of the protrusions 172h corresponds to the opening end of the recesses 172u. The front ends 172d of two adjacent protrusions 172h form the entrance to the recesses 172u located between them.

[0191] The convex portion 172h can be a line with a greater depth than width, or a point with a depth equal to or approximately equal to its width, or other shapes. The concave portion 172u is similarly shaped. The cross-section of the convex portion 172h can be any of the following: rectangular, square, triangular, inverted triangular, trapezoidal, inverted trapezoidal, and semicircle, or other shapes. The cross-section of the concave portion 172u is similarly shaped. Figure 17An example is shown where both the convex portion 172h and the concave portion 172u have rectangular cross-sections. The height of the convex portion 172h ( Figure 17 The length in the left-right direction (the middle part) can be uniform or non-uniform. The depth of the concave part 172u is similarly uniform. The height of the convex part 172h can be the same as the width of the convex part 172h (…). Figure 17 The length of the recess 172u (in the vertical direction) is equal to or different from the width of the recess 172u.

[0192] The contact angle of water relative to the uneven surface 172 is 119 degrees or more, preferably 150 degrees or more.

[0193] The inner surface 132y of the high-temperature liquid flow path 132x is the liquid-contacting part. The liquid-contacting part is made of resin such as fluoropolymer. (See reference...) Figure 9 As mentioned above, fluoropolymers sometimes contain impurities that are different from fluoropolymers ( Figure 9 (Small black spots). One example of an impurity is a plasticizer. This type of impurity can leach from the contact area into the high-temperature solution. To prevent this, when the substrate processing apparatus 1 is started, that is, when preparing for its use in a factory such as a semiconductor manufacturing plant, the contact area is cleaned with a cleaning solution. This cleaning is also called washing.

[0194] However, even after cleaning, impurities such as plasticizers will still migrate from the interior of the fluoropolymer to its surface. If the substrate processing apparatus 1 does not process the substrate W for an extended period (the period during which the liquid does not flow along the contact portion), a large amount of impurities will accumulate in the contact portion. When processing of the substrate W resumes, these impurities will dissolve into the liquid from the contact portion. Therefore, when the substrate processing apparatus 1 does not process the substrate W for an extended period, cleaning must be performed before resuming processing of the substrate W.

[0195] Cleaning requires not only cleaning fluid but also energy, such as electricity. If the cleaning process takes a long time, the energy consumption and the amount of cleaning fluid used will increase. The same applies to frequent cleaning operations. To reduce cleaning costs and environmental impact, it is desirable to reduce the cleaning time and the number of cleaning sessions.

[0196] However, even when the substrate processing apparatus 1 continuously processes the substrate W, or when the substrate processing apparatus 1 does not process the substrate W for a short period of time, impurities and other contaminants can still leach from the contact area into the liquid. For example, in areas where the liquid has low flowability (areas where the liquid accumulates or stagnates), it is foreseeable that a large amount of impurities will accumulate in the contact area and dissolve into the liquid at unexpected times. It is also foreseeable that foreign matter contained in the liquid will accumulate in areas where the liquid has low flowability and flow downstream with the liquid at unexpected times.

[0197] The uneven surface 172 of the high-temperature liquid flow path 132x is the surface where the high-temperature liquid contacts the front end 172d of the convex portion 172h, in a state separated from the bottom 172b of the concave portion 172u. Therefore, compared to the case where the high-temperature liquid contacts the bottom 172b of the concave portion 172u, the contact area between the high-temperature liquid and the uneven surface 172 can be reduced. Furthermore, since the high-temperature liquid does not contact or has difficulty contacting the bottom 172b of the concave portion 172u, the contact area between the high-temperature liquid and the uneven surface 172 can be limited. As a result, the area to be cleaned is reduced, and thus the cleaning time can be shortened. Furthermore, if the contact area between the high-temperature liquid and the high-temperature liquid flow path 132x is reduced, the amount of impurities dissolved from the high-temperature liquid flow path 132x into the high-temperature liquid per unit time is reduced, thus lowering the impurity concentration in the high-temperature liquid. The amount of foreign matter transferred from the high-temperature liquid to the uneven surface 172 will also decrease. Therefore, even if such foreign matter peels off from the uneven surface 172, the concentration of foreign matter in the high-temperature liquid can be reduced.

[0198] Figure 18 This is a cross-sectional view showing a construction example of a sulfuric acid pipe 132p, which is an example of a high-temperature chemical solution piping. The inner circumferential surface of the sulfuric acid pipe 132p includes a textured surface 173, which includes a plurality of linear protrusions 173h and a plurality of linear grooves 173u forming a textured pattern extending along the axial direction of the sulfuric acid pipe 132p (along the direction of the centerline 132L of the sulfuric acid pipe 132p). The textured surface 173 is a concave-convex surface 172 (see reference). Figure 17 One of the forms. Linear protrusion 173h is the convex part 172h (refer to...). Figure 17 One of the forms of ), the linear groove 173u is the concave part 172u (refer to) Figure 17 One of the forms of ) . Preferably, the inner surface of the entire section of the sulfuric acid piping 132p, or at least the section including the bend, becomes this textured surface 173.

[0199] A plurality of linear protrusions 173h are spaced apart along the circumference of the sulfuric acid pipe 132p (around the center line 132L of the sulfuric acid pipe 132p). The same applies to a plurality of linear grooves 173u. One linear groove 173u is formed between every two nearest linear protrusions 173h along the circumference of the sulfuric acid pipe 132p. Figure 18 An example is shown where the textured surface 173 is an annular ring surrounding the centerline 132L of the sulfuric acid pipe 132p. Alternatively, the textured surface 173 may only be the inner circumferential surface of the sulfuric acid pipe 132p in the circumferential direction.

[0200] The linear groove 173u and the linear protrusion 173h extend in a direction parallel to the centerline 132L of the sulfuric acid pipe 132p. Where the centerline 132L of the sulfuric acid pipe 132p is straight, the linear groove 173u and the linear protrusion 173h are also straight. Where the centerline 132L of the sulfuric acid pipe 132p is curved, the linear groove 173u and the linear protrusion 173h are also curved. The width of the linear groove 173u is shorter than its length. The width of the linear protrusion 173h is shorter than its length. The width of the linear protrusion 173h may be equal to or different from the width of the linear groove 173u.

[0201] Secondly, for those that are capable of use Figure 15 The effects of this embodiment on the processing unit 2 described above will be explained.

[0202] The effects of the water flow path and solvent flow path are as described above.

[0203] Furthermore, in this embodiment, high-temperature chemicals (sulfuric acid and SPM) are guided to the substrate W through the high-temperature chemical flow path 132x. The high-temperature chemical flow path 132x includes a concave-convex surface 172 in contact with the high-temperature chemical.

[0204] The uneven surface 172 of the high-temperature liquid flow path 132x includes: a recess 172u, at least a portion of which is filled with air; and a protrusion 172h, which contacts the high-temperature liquid that is in contact with the air in the recess 172u. Since at least a portion of the recess 172u is filled with air, the contact area between the high-temperature liquid and the uneven surface 172 is reduced compared to the case where the recess 172u is completely filled with high-temperature liquid. Furthermore, since the high-temperature liquid does not contact or has difficulty contacting the inner surface of the recess 172u, the contact area between the high-temperature liquid and the uneven surface 172 is limited. Therefore, the area to be cleaned by the cleaning liquid is reduced, thus shortening the cleaning time.

[0205] In this embodiment, all or part of the uneven surface 172 is made of fluoropolymer resin. Fluoropolymer resin is a material with high water repellency. Whether the droplets on the rough surface exhibit a Wenzel state or a Cassie-Baxter state is affected by factors such as the surface tension of the liquid, the surface free energy of the rough surface (solid), and the surface properties of the rough surface. By making the uneven surface 172 with a material with high water repellency, at least a portion of the recess 172u can be kept filled with air. Thus, the contact area between the high-temperature liquid and the uneven surface 172 can be limited, and the contact area between the high-temperature liquid and the uneven surface 172 can be reduced.

[0206] In this embodiment, high-temperature chemical solution (high-temperature sulfuric acid) is guided from the sulfuric acid tank 132t to the sulfuric acid piping 132p (high-temperature chemical solution piping). A raised / concave surface 172 is provided on the inner surface of the sulfuric acid tank 132t. The high-temperature sulfuric acid is in contact with the sulfuric acid tank 132t for a longer time than the high-temperature sulfuric acid is in contact with the sulfuric acid piping 132p. Therefore, by reducing the contact area between the high-temperature sulfuric acid and the sulfuric acid tank 132t, the amount of contaminants transferred from the sulfuric acid tank 132t to the high-temperature sulfuric acid can be effectively reduced. In particular, when using a sulfuric acid tank 132t made of fluororesin, the leaching of plasticizers as impurities can be suppressed. Although this problem does not occur when the sulfuric acid tank 132t is made of quartz, it leads to increased costs. Therefore, using a sulfuric acid tank 132t made of fluororesin can both reduce costs and overcome the problem of impurity (plasticizer) leaching, thereby improving the substrate processing quality and thus increasing yield.

[0207] In this embodiment, a textured surface 172 is provided on the inner surface of the second liquid nozzle 132. This second liquid nozzle 132 is used to generate SPM as a high-temperature liquid, and the SPM flows through and is ejected from the nozzle outlet 132d. When the ejection of SPM from the second liquid nozzle 132 stops, the SPM remains inside the second liquid nozzle 132. Impurities (typically plasticizers) dissolve from the fluoropolymer-made second liquid nozzle 132 into the retained SPM. Subsequently, the SPM, along with the dissolved impurities, is ejected from the second liquid nozzle 132. If these impurities are supplied to the substrate W, there is a concern that this could lead to poor processing and a decrease in product yield. Therefore, by reducing the contact area between the SPM and the second liquid nozzle 132, the amount of contaminants transferred from the second liquid nozzle 132 to the SPM can be effectively reduced, thereby reducing poor processing.

[0208] In this embodiment, an uneven surface 172 is provided on the inner surface (at least the inner surface of the bend) of the sulfuric acid pipe 132p constituting the high-temperature liquid flow path 132x. At bends, areas of low liquid flow (areas where liquid stagnates or accumulate) sometimes occur. In such cases, it is anticipated that impurities (typically plasticizers) dissolved from the resin material (PTFE, PFA, or other fluoropolymers) constituting the sulfuric acid pipe 132p) will accumulate in the bend and flow along with the high-temperature liquid at unexpected times. By providing the uneven surface 172 on the inner surface of the bend, the resistance exerted on the high-temperature liquid by the inner surface of the bend is reduced, thus minimizing the decrease in the velocity of the high-temperature liquid at the bend and reducing the area where high-temperature liquid stagnates or accumulates. Therefore, impurities and foreign matter accumulated in this area can be reduced, and contaminants moving from the inner surface of the bend to the high-temperature liquid flowing through the bend can be reduced.

[0209] Furthermore, in addition to sulfuric acid and SPM, other chemicals are supplied to the substrate at higher temperatures than room temperature. Phosphoric acid is another example of a chemical used at high temperatures.

[0210] Alternatively, two or more of the above components can be combined. Alternatively, two or more of the above steps can be combined.

[0211] The embodiments of the present invention have been described in detail, but these are merely specific examples used to clarify the technical content of the present invention. The present invention should not be limited to these specific examples, and the spirit and scope of the present invention are defined only by the appended claims.

Claims

1. A substrate processing apparatus comprising: a substrate holder that holds a substrate; a water flow path that guides water toward the substrate held by the substrate holder; and a solvent flow path that guides an organic solvent, which is a liquid having a lower surface tension than the water, toward the substrate held by the substrate holder; the water flow path includes a concave-convex surface having a concave portion and a convex portion, at least a portion of the concave portion is filled with air, and the convex portion contacts the water in contact with the air in the concave portion; the solvent flow path includes a mirror surface that contacts the organic solvent.

2. The substrate processing apparatus of claim 1, wherein, The concave-convex surface is made of fluororesin.

3. The substrate processing apparatus according to claim 1 or 2, wherein The water flow path includes a water tank that stores the water and a water pipe that guides the water supplied from the water tank, the concave-convex surface is provided to an inner surface of the water tank.

4. The substrate processing apparatus as claimed in claim 1 or 2, wherein The solvent flow path includes a solvent tank that stores the organic solvent and a solvent pipe that guides the organic solvent supplied from the solvent tank, the mirror surface is provided to an inner surface of the solvent tank.

5. The substrate processing apparatus as claimed in claim 1 or 2, wherein The concave-convex surface is provided to a turning portion of the water flow path.

6. The substrate processing apparatus as recited in Claim 1 or 2, wherein, Further comprising a high-temperature chemical liquid flow path that guides a high-temperature chemical liquid, which has a higher temperature than room temperature, toward the substrate held by the substrate holder; the high-temperature chemical liquid flow path includes a concave-convex surface having a concave portion and a convex portion, at least a portion of the concave portion is filled with air, and the convex portion contacts the high-temperature chemical liquid in contact with the air in the concave portion.

7. The substrate processing apparatus of claim 6, wherein, The concave-convex surface of the high-temperature chemical liquid flow path is made of fluororesin.

8. The substrate processing apparatus of claim 6, wherein, The high-temperature chemical liquid flow path includes a high-temperature chemical liquid tank that stores the high-temperature chemical liquid and a high-temperature chemical liquid pipe that guides the high-temperature chemical liquid supplied from the high-temperature chemical liquid tank, the concave-convex surface of the high-temperature chemical liquid flow path is provided to an inner surface of the high-temperature chemical liquid tank.

9. The substrate processing apparatus of claim 8, wherein, The concave-convex surface is provided to a turning portion of the high-temperature chemical liquid flow path.

10. The substrate processing apparatus of claim 6, wherein, The high-temperature chemical liquid flow path includes the high-temperature chemical liquid pipe that guides the high-temperature chemical liquid and a high-temperature chemical liquid nozzle that ejects the high-temperature chemical liquid guided by the high-temperature chemical liquid pipe, the concave-convex surface of the high-temperature chemical liquid flow path is provided to an inner surface of the high-temperature chemical liquid nozzle.

11. The substrate processing apparatus of claim 10, wherein, The concave-convex surface is provided to a turning portion of the high-temperature chemical liquid flow path.

12. A substrate processing method, wherein, Comprising: a water supply step of guiding water toward a substrate held by a substrate holder through a water flow path including a concave-convex surface, in a state where at least a portion of a concave portion of the concave-convex surface is filled with air and a convex portion of the concave-convex surface contacts the water in contact with the air in the concave portion; and a solvent supply step of guiding an organic solvent, which is a liquid having a lower surface tension than the water, toward the substrate held by the substrate holder through a solvent flow path including a mirror surface, in a state where the mirror surface contacts the organic solvent, before or after the water supply step.

13. The substrate processing method of claim 12, wherein, Further comprising a high-temperature chemical liquid supply step of guiding a high-temperature chemical liquid, which has a higher temperature than room temperature, toward the substrate held by the substrate holder; the high-temperature chemical liquid supply step includes a step of circulating the high-temperature chemical liquid through a high-temperature chemical liquid flow path including a concave-convex surface, in a state where at least a portion of a concave portion of the concave-convex surface is filled with air and a convex portion of the concave-convex surface contacts the high-temperature chemical liquid in contact with the air in the concave portion.

14. A substrate processing apparatus, wherein, Comprising: a substrate holder that holds a substrate; and a high-temperature chemical liquid flow path that guides a high-temperature chemical liquid having a temperature higher than room temperature toward the substrate held by the substrate holder; the high-temperature chemical liquid flow path includes a concave-convex surface having a concave portion and a convex portion, at least a portion of the concave portion is filled with air, and the convex portion contacts the high-temperature chemical liquid that contacts the air in the concave portion.

15. The substrate processing apparatus of claim 14, wherein, a solvent flow path that guides an organic solvent that is a liquid having a surface tension lower than the high-temperature chemical liquid toward the substrate held by the substrate holder; the solvent flow path includes a mirror surface that contacts the organic solvent.

16. The substrate processing apparatus of claim 14, wherein, the concave-convex surface is made of a fluororesin.

17. The substrate processing apparatus of claim 14, wherein, the high-temperature chemical liquid flow path includes a high-temperature chemical liquid tank that stores the high-temperature chemical liquid and a high-temperature chemical liquid pipe that guides the high-temperature chemical liquid supplied from the high-temperature chemical liquid tank, the concave-convex surface is provided to an inner surface of the high-temperature chemical liquid tank.

18. The substrate processing apparatus of claim 14, wherein, the high-temperature chemical liquid flow path includes a high-temperature chemical liquid pipe that guides the high-temperature chemical liquid and a high-temperature chemical liquid nozzle that ejects the high-temperature chemical liquid guided by the high-temperature chemical liquid pipe, the concave-convex surface is provided to an inner surface of the high-temperature chemical liquid nozzle.

19. The substrate processing apparatus of claim 17 or 18, wherein, the concave-convex surface is provided to a turning portion of the high-temperature chemical liquid flow path.

20. A substrate processing method, wherein a high-temperature chemical liquid supply step in which a high-temperature chemical liquid having a temperature higher than room temperature is guided toward a substrate held by a substrate holder is included; the high-temperature chemical liquid supply step includes a step in which, in a state in which at least a portion of a concave portion of a concave-convex surface is filled with air and a convex portion of the concave-convex surface contacts the high-temperature chemical liquid that contacts the air in the concave portion, the high-temperature chemical liquid is circulated through a high-temperature chemical liquid flow path that includes the concave-convex surface.

21. The substrate processing method of claim 20, wherein, a solvent supply step in which, in a state in which a mirror surface contacts an organic solvent that is a liquid having a surface tension lower than the high-temperature chemical liquid, the organic solvent is guided toward the substrate held by the substrate holder through a solvent flow path that includes the mirror surface before or after the high-temperature chemical liquid supply step is further included.

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