Substrate processing system and substrate processing method

Abstract

To provide a substrate processing system and a substrate processing method capable of reducing excess and deficiency of the film thickness of a protective film by using an appropriate amount of material, thereby reducing the amount of material used and the cost.SOLUTION: The substrate processing system 100 includes a defect measuring device 110 that measures a defect size on a back surface of a substrate W, a substrate processing device 120, and an exposure device 130. The substrate processing apparatus 120 includes a processing liquid preparing unit 121 that prepares a processing liquid having a composition corresponding to the measured defect size, a protective film forming unit that forms a protective film by applying the prepared processing liquid to the back surface of the substrate W, and a removal processing unit that removes the protective film from the back surface of the substrate W. The exposure device 130 performs the exposure processing on the front surface of the substrate with the protective film formed on the back surface of the substrate W. The removal processing section removes the protective film from the back surface of the substrate W after the exposure processing.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a substrate processing system and a substrate processing method. Substrates to be processed include, for example, semiconductor wafers, substrates for liquid crystal display devices, substrates for FPDs (Flat Panel Displays) such as organic EL (Electroluminescence) display devices, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells. [Background technology]

[0002] In the manufacturing process of a semiconductor device, a substrate (specifically, a semiconductor wafer) is subjected to multiple photolithography processes, which include the steps of forming a resist film on the substrate, exposing the resist film to a predetermined pattern using an exposure device (pattern exposure), and developing the exposed resist film.

[0003] When a substrate is held by a vacuum chuck or electrostatic chuck on its backside for processing, relatively large scratches (e.g., on the order of microns) can occur on the backside of the substrate. Furthermore, relatively large fragments (e.g., on the order of microns) can break off from the backside of the substrate and adhere to the backside of the same or another substrate, becoming contaminants. These scratches and contaminants are defects on the backside of the substrate, which can affect subsequent processing steps. For example, if the defects increase the roughness of the backside of the substrate, this can cause defocusing in subsequent exposure processing, potentially reducing the quality of the exposure process.

[0004] Patent Document 1 discloses a substrate processing method in which a planarizing film is formed on the back surface of a substrate, an exposure process is performed, and then the planarizing film is removed. The planarizing film is formed by a spin coating method in which a processing liquid for forming the planarizing film is ejected onto the back surface of the substrate while the substrate is held on a spin chuck and rotated with the back surface facing up. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2024-48593 [Patent Document 2] Japanese Patent Publication No. 2022-73303 Summary of the Invention [Problem to be solved by the invention]

[0006] By forming a protective film (planarizing film in Patent Document 1) on the back surface of the substrate with a thickness sufficient to compensate for unevenness due to defects on the back surface of the substrate, a surface (surface of the protective film) with sufficient flatness can be provided.

[0007] However, because the sizes of defects observed on the backside of a substrate vary, determining the thickness of a protective film based on the expected maximum defect size may result in a film thickness that is excessively large compared to the actual defect size. This results in unnecessary consumption of expensive materials used in the processing solution for forming the protective film. On the other hand, determining the thickness of a protective film based on the expected average defect size may result in a film thickness that is excessive or insufficient compared to the actual defect size, resulting in problems such as defocusing and wasted materials used in the processing solution for forming the protective film.

[0008] Therefore, one embodiment of the present invention provides a substrate processing system and a substrate processing method that use an appropriate amount of material to reduce the thickness of the protective film, thereby reducing the amount of material used and reducing costs. [Means for solving the problem]

[0009] A substrate processing system according to one embodiment of the present invention includes a defect measurement unit that measures the size of defects on the back surface of a substrate having a front surface and a back surface. The substrate processing system includes a processing liquid preparation unit that prepares a processing liquid with a composition corresponding to the defect size measured by the defect measurement unit. The substrate processing system includes a protective film formation unit that applies the processing liquid prepared by the processing liquid preparation unit to the back surface of the substrate to form a protective film. The substrate processing system includes a substrate processing unit that performs a predetermined process on the front surface of the substrate with the protective film formed on the back surface of the substrate. The substrate processing system includes a removal processing unit that removes the protective film from the back surface of the substrate.

[0010] In one embodiment, the processing liquid preparation unit prepares a processing liquid having a composition that allows the protective film to be formed on the rear surface of the substrate with a thickness corresponding to the defect size.

[0011] In one embodiment, the processing liquid is a solution containing a solute and a solvent, and the processing liquid preparation unit prepares the solution having a concentration according to the defect size as the processing liquid.

[0012] In one embodiment, the solute comprises a polymer.

[0013] In one embodiment, the substrate processing system includes a flatness measurement unit that measures flatness of the protective film formed by the protective film formation unit.

[0014] In one embodiment, the substrate processing system includes an additional protective film forming unit that supplies an additional processing liquid onto the protective film to further form an additional protective film on the protective film when the flatness measured by the flatness measuring unit exceeds a reference value.

[0015] In one embodiment, the protective film forming unit applies a first polymer solution as the treatment liquid to the back surface of the substrate, and the additional protective film forming unit applies a second polymer solution, which is incompatible with the first polymer solution, as the additional treatment liquid onto the protective film.

[0016] In one embodiment, the solvent for the first polymer solution is PGMEA (propylene glycol monomethyl ether acetate), and the solvent for the second polymer solution is IPA (isopropyl alcohol).

[0017] In one embodiment, the predetermined process includes an exposure process for the surface of the substrate.

[0018] A substrate processing method according to one embodiment of the present invention includes a defect measurement step of measuring the size of defects on the back surface of a substrate having a front surface and a back surface. The substrate processing method also includes a processing liquid preparation step of preparing a processing liquid having a composition corresponding to the defect size measured in the defect measurement step. The substrate processing method also includes a protective film formation step of forming a protective film by applying the processing liquid prepared in the processing liquid preparation step to the back surface of the substrate. The substrate processing method also includes a substrate processing step of performing a predetermined process on the front surface of the substrate with the protective film formed on the back surface of the substrate. The substrate processing method also includes a removal step of removing the protective film from the back surface of the substrate.

[0019] In one embodiment, the processing liquid preparation step prepares a processing liquid having a composition that allows the protective film to be formed on the rear surface of the substrate with a film thickness corresponding to the defect size.

[0020] In one embodiment, the processing liquid is a solution containing a solute and a solvent, and the processing liquid preparation step prepares the solution having a concentration according to the defect size as the processing liquid.

[0021] In one embodiment, the solute comprises a polymer.

[0022] In one embodiment, the substrate processing method includes a flatness measurement step of measuring flatness of the protective film formed in the protective film formation step, and an additional protective film formation step of supplying an additional processing liquid onto the protective film to further form an additional protective film on the protective film when the flatness measured in the flatness measurement step is less than a reference value.

[0023] In one embodiment, the protective film forming step applies a first polymer solution as the treatment liquid to the rear surface of the substrate, and the additional protective film forming step applies a second polymer solution, which is incompatible with the first polymer solution, as the additional treatment liquid onto the protective film.

[0024] In one embodiment, the solvent for the first polymer solution is PGMEA (propylene glycol monomethyl ether acetate), and the solvent for the second polymer solution is IPA (isopropyl alcohol).

[0025] In one embodiment, the predetermined process includes an exposure process for the surface of the substrate. [Brief explanation of the drawings]

[0026] [Figure 1] FIG. 1 is a block diagram illustrating an example of the configuration of a substrate processing system according to an embodiment of the present invention. [Figure 2] FIG. 2 is a schematic plan view for explaining an example of the configuration of the substrate processing apparatus. [Figure 3] FIG. 3 is a schematic side view of a plurality of liquid processing apparatuses provided in the substrate processing apparatus. [Figure 4] FIG. 4 is a schematic cross-sectional view for explaining a configuration example of a coating / removal treatment apparatus. [Figure 5] FIG. 5 is a system diagram illustrating an example of the configuration of the treatment liquid preparation unit. [Figure 6] FIG. 6 is a block diagram for explaining an example of a configuration relating to control of the substrate processing apparatus. [Figure 7] FIG. 7 is a flowchart illustrating an example of substrate processing by the substrate processing system. [Figures 8A-8C] 8A to 8C are schematic diagrams for explaining the state of a substrate when an example of substrate processing is being performed. [Figure 8D-8F]8D to 8F are schematic diagrams for explaining the state of the substrate when an example of substrate processing is being performed. [Figure 8G-8I] 8G to 8I are schematic diagrams for explaining the state of a substrate when an example of substrate processing is being performed. [Figure 9] FIG. 9 is a diagram for explaining another embodiment of the present invention, showing an example of a coating / peeling treatment apparatus and its related configuration. [Figure 10] FIG. 10 is a flowchart for explaining an example of substrate processing according to the other embodiment. [Figure 11] 11A to 11C are schematic views for explaining the additional protective film forming step in the other embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0027] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0028] FIG. 1 is a block diagram illustrating an example of the configuration of a substrate processing system according to an embodiment of the present invention.

[0029] The substrate processing system 100 is a system for processing a substrate W such as a semiconductor wafer. The substrate W has two main surfaces, one of which is a front surface and the other of which is a back surface. Typically, the front surface of the substrate W is a device surface on which devices such as transistors are formed, and the back surface of the substrate W is a non-device surface on which devices are not formed. However, there are also cases where devices are formed on both of the two main surfaces (front surface and back surface) of the substrate W.

[0030] The substrate processing system 100 includes a defect measurement device 110 that measures the size of defects on the back surface of the substrate W, and a substrate processing device 120 that performs processing on the substrate W. The defect measurement device 110 is an example of a defect measurement unit. In this example, an exposure device 130 that performs exposure processing can be coupled to the substrate processing device 120. The exposure processing is an example of a predetermined process for the substrate W, and the exposure device 130 is an example of a substrate processing unit. The substrate processing device 120 also includes a processing liquid preparation unit 121 that prepares a processing liquid.

[0031] The defect measurement apparatus 110 and the substrate processing apparatus 120 are communicatively connected (for example, connected via a communication network) to a host computer 140. A transport mechanism 150 is also provided to transport substrates W between the defect measurement apparatus 110 and the substrate processing apparatus 120, and the transport mechanism 150 is controlled by commands from the host computer 140. The transport mechanism 150 is typically a carrier transport mechanism that transports carriers C, which are containers that accommodate multiple substrates W.

[0032] The host computer 140 is a computer that includes a processor 140a (CPU (central processing unit)) and a storage device 140b. The processor 140a executes programs stored in the storage device 140b (storage), allowing the host computer 140 to perform various processes.

[0033] Fig. 2 is a schematic plan view for explaining an example of the configuration of the substrate processing apparatus 120. Fig. 3 is a schematic side view of a plurality of liquid processing apparatuses 4 provided in the substrate processing apparatus 120.

[0034] The substrate processing apparatus 120 includes a plurality of liquid processing apparatuses 4, a plurality of temperature adjustment apparatuses 70 that adjust the temperature of the substrates W by heating and cooling, a carrier holding unit LP1 that holds a plurality of carriers C, and an indexer robot IR1.

[0035] The substrate processing apparatus 120 further includes a first main transport robot CR1 that transfers substrates W to and from the indexer robot IR1 and transports substrates W to and from a plurality of liquid processing apparatuses 4 and temperature adjustment apparatuses 70, and a second main transport robot CR2 that transfers substrates W to and from the first main transport robot CR1 and transports substrates W to and from a plurality of liquid processing apparatuses 4 and temperature adjustment apparatuses 70.

[0036] The substrate processing apparatus 120 further includes a first inversion unit 5A that receives a substrate W from the indexer robot IR1 and the first main transport robot CR1 and inverts the substrate W, if necessary, so that one of the front and back surfaces of the substrate W faces upward, and a second inversion unit 5B that receives a substrate W from the first main transport robot CR1 and the second main transport robot CR2 and inverts the substrate W, if necessary, so that one of the front and back surfaces of the substrate W faces upward.

[0037] The indexer robot IR1, the first main transport robot CR1, and the second main transport robot CR2 are arranged on a transport path TR extending from the carrier holding unit LP1 to the plurality of liquid processing devices 4. The plurality of liquid processing devices 4 are arranged on one side of the transport path TR. The plurality of temperature adjustment devices 70 are arranged on the opposite side of the transport path TR from the plurality of liquid processing devices 4.

[0038] The liquid processing devices 4 are arranged at four horizontally spaced positions to form four processing towers TW1 to TW4, each including a plurality of liquid processing devices 4 stacked vertically (see also FIG. 3).

[0039] The plurality of temperature adjustment devices 70 form five temperature adjustment towers TW11 to TW15 arranged at five horizontally spaced positions. Each of the temperature adjustment towers TW11 to TW15 includes a plurality of temperature adjustment devices 70 stacked vertically. Each temperature adjustment device 70 includes a plate 72 on which a substrate W is placed to cool or heat the substrate W.

[0040] The first reversing unit 5A is disposed between the indexer robot IR1 and the first main transport robot CR1, and the second reversing unit 5B is disposed between the first main transport robot CR1 and the second main transport robot CR2.

[0041] The first main transport robot CR1 is configured to access the processing towers TW1 and TW2 and the temperature regulation towers TW11 to TW13, and the second main transport robot CR2 is configured to access the processing towers TW3 and TW4 and the temperature regulation towers TW14 and TW15.

[0042] The substrate processing apparatus 120 further includes a first external transfer robot OR1 that transfers the substrate W to and from the second main transport robot CR2, and a third inversion unit 5C that receives the substrate W from the second main transport robot CR2 and the first external transfer robot OR1 and inverts the substrate W, as necessary, so that one of the front and back surfaces of the substrate W faces upward. The substrate processing apparatus 120 further includes a second external transfer robot OR2 that transfers the substrate W to and from the first external transfer robot OR1 and transports the substrate W toward the exposure apparatus 130, and a placement unit 151 on which the substrate W is placed for transfer between the first external transfer robot OR1 and the second external transfer robot OR2. The first external transfer robot OR1, the second external transfer robot OR2, and the placement unit 151 form an interface unit for transferring the substrate W between the substrate processing apparatus 120 and the exposure apparatus 130.

[0043] The indexer robot IR1 has a linearly moving hand H1. In a plan view, the indexer robot IR1 moves horizontally to a position facing either one of the carriers C or the first reversing unit 5A, and by rotating and raising and lowering the hand H1 as necessary, the indexer robot IR1 accesses the carrier C or the first reversing unit 5A corresponding to its horizontal position.

[0044] The first main transport robot CR1 has a linearly moving hand H2. In a plan view, the first main transport robot CR1 moves horizontally to a position facing one of the first reversing unit 5A, the second reversing unit 5B, the plurality of liquid processing devices 4, and the plurality of temperature adjustment devices 70, and by rotating and raising and lowering the hand H2 as necessary, the first main transport robot CR1 can access the first reversing unit 5A, the second reversing unit 5B, the plurality of liquid processing devices 4, and the plurality of temperature adjustment devices 70 that correspond to the horizontal position of the first main transport robot CR1.

[0045] The second main transport robot CR2 has a linearly moving hand H3. In a plan view, the second main transport robot CR2 moves horizontally to a position facing either the second reversing unit 5B, the third reversing unit 5C, the plurality of liquid processing devices 4, or the plurality of temperature adjustment devices 70, and by rotating and raising and lowering the hand H3 as necessary, the second main transport robot CR2 accesses the second reversing unit 5B, the third reversing unit 5C, the plurality of liquid processing devices 4, or the plurality of temperature adjustment devices 70 that correspond to the horizontal position of the first main transport robot CR1.

[0046] For the first reversing unit 5A, the second reversing unit 5B and the third reversing unit 5C, a substrate reversing device having a known configuration such as that described in Patent Document 2 can be used.

[0047] 3, the plurality of liquid treatment devices 4 include a plurality of coating / removal treatment devices 4A, a plurality of coating treatment devices 4D that apply an anti-reflective film or a resist film to the upper surface of the substrate W, and a developing treatment device 4E that develops the upper surface of the substrate W. In this embodiment, the processing towers TW1 and TW2 are composed of a plurality of coating / removal treatment devices 4A and a plurality of coating treatment devices 4D, and the processing towers TW3 and TW4 are composed of a plurality of developing treatment devices 4E.

[0048] The coating treatment device 4D includes an anti-reflection film coating treatment device 4DA that coats the upper surface of the substrate W with an anti-reflection film, and a resist film coating treatment device 4DB that coats the upper surface of the substrate W with a resist film.

[0049] The anti-reflection film coating treatment device 4DA is disposed across the processing towers TW1 and TW2. Similarly, the resist film coating treatment device 4DB is disposed across the processing towers TW1 and TW2. The development treatment device 4E is disposed across the processing towers TW3 and TW4.

[0050] 2, coating processing apparatus 4D includes two spin chucks 6B, two processing cups 7B, and a liquid supply unit 60 that supplies a resist film forming liquid or an anti-reflective coating forming liquid to the substrate W held on each of the two spin chucks 6B, thereby supplying the resist film forming liquid or the anti-reflective coating forming liquid to the upper surface of the substrate W, all of which are housed in chamber 8B. In coating processing apparatus 4D, the two processing cups 7B are arranged side by side without being separated by a partition wall or the like.

[0051] The liquid supply unit 60 includes a plurality of nozzles 61, a gripping portion 62 that grips any one of the plurality of nozzles 61, and a nozzle moving unit 63 that moves the gripping portion 62 while gripping the nozzle 61, thereby moving the nozzle 61 held by the gripping portion 62 between a processing position above the substrate W and a home position that does not face the substrate W.

[0052] Different types of anti-reflection film forming liquids are supplied to the nozzles 61 of the anti-reflection film coating treatment device 4DA. The anti-reflection film forming liquids ejected from the nozzles 61 are supplied to the upper surface of the substrate W in a rotating state, thereby forming an anti-reflection film on the upper surface of the substrate W. In other words, the anti-reflection film is coated on the upper surface of the substrate W.

[0053] Different types of resist film forming liquids are supplied to the nozzles 61 of the resist film coating treatment device 4DB. The resist film forming liquids ejected from the nozzles 61 are supplied to the upper surface of the substrate W in a rotating state, thereby forming a resist film on the upper surface of the substrate W. In other words, a resist film is coated on the upper surface of the substrate W.

[0054] The nozzle moving unit 63 has a first guide rail 65 and a second guide rail 66. The first guide rails 65 are arranged parallel to each other, sandwiching two horizontally arranged processing cups 7B therebetween. The second guide rails 66 are slidably supported by the two first guide rails 65 and are installed above the two processing cups 7B. The gripper 62 is slidably supported by the second guide rails 66. The nozzle moving unit 63 further includes an actuator (not shown), such as an electric motor, that slides the second guide rails 66 and slides the gripper 62. When the actuator is driven, the nozzle 61 gripped by the gripper 62 is moved to a position above the two spin chucks 6B, which corresponds to the processing position.

[0055] Each development processing device 4E includes two rotary holders 80 that rotatably hold a substrate W, and two cups 81 that surround the two rotary holders 80, respectively. The two cups 81 are arranged side by side without being separated by a partition wall or the like. The development processing device 4E further includes a supply unit 82 that supplies a developer. The supply unit 82 includes two slit nozzles 82a that discharge the developer, and a movement mechanism 82b that moves the slit nozzles 82a. This allows each slit nozzle 82a to move above the corresponding rotary holder 80.

[0056] 4 is a schematic cross-sectional view for explaining an example of the configuration of the coating / removal treatment device 4 A. In FIG. 4, the chamber 8 A (see FIG. 3) is not shown.

[0057] The coating / removal processing device 4A includes a spin chuck 6A, a blocking plate 25, a processing cup 7A, a moving nozzle 9, a central nozzle 10, a lower nozzle 11, etc., which are housed in a chamber 8A (see FIG. 3).

[0058] The spin chuck 6A is an example of a holding and rotating unit that rotates the substrate W around a rotation axis A1 while holding the substrate W in a horizontal position.

[0059] The spin chuck 6A includes a holding unit 20 that holds the substrate W, a rotating shaft 22 that extends vertically along the rotation axis A1 and is configured to rotate integrally with the holding unit 20, a spin motor 23 that rotates the rotating shaft 22 around the rotation axis A1, and a motor housing 24 that accommodates the rotating shaft 22 and the spin motor 23.

[0060] The holding unit 20 includes a plurality of chuck pins 20A that grip the peripheral edge of the substrate W, and a spin base 20B that supports the plurality of chuck pins 20A. The spin base 20B has a horizontally extending disk shape. The plurality of chuck pins 20A are arranged on the upper surface of the spin base 20B at intervals in the circumferential direction of the spin base 20B. The holding unit 20 is also referred to as a substrate holder.

[0061] An opening / closing unit 28 is provided to drive the multiple chuck pins 20A to open and close. The multiple chuck pins 20A grip the substrate W when closed by the opening / closing unit 28. The multiple chuck pins 20A release their grip on the substrate W when opened by the opening / closing unit 28. In the open state, the multiple chuck pins 20A release their grip on the substrate W while supporting the peripheral portion of the lower surface of the substrate W from below. The opening / closing unit 28 includes, for example, a link mechanism (not shown) and a drive source (not shown). The drive source includes, for example, an electric motor.

[0062] The chuck pins 20A are an example of a gripping member that grips the peripheral edge of the substrate W to hold the substrate W at a predetermined substrate holding position (the position of the substrate W shown in FIG. 4). The spin base 20B is an example of a support base that supports the multiple chuck pins 20A and is arranged at intervals from the substrate holding position.

[0063] The upper end of the rotary shaft 22 protrudes from the motor housing 24 and is coupled to the spin base 20B.

[0064] The spin motor 23 rotates the rotation shaft 22, thereby rotating the spin base 20B. This causes the substrate W to rotate around the rotation axis A1 together with the spin base 20B. The spin motor 23 is an example of a substrate rotation unit that rotates the substrate W around the rotation axis A1.

[0065] A shield plate 25 is provided above the spin base 20B to shield the atmosphere in the space between the spin chuck 6A and the upper surface of the substrate W held by the spin chuck 6A from the atmosphere outside the space.

[0066] The shielding plate 25 has a facing surface 25a that faces from above the upper surface of the substrate W held by the spin chuck 6A. The shielding plate 25 is formed in a circular plate shape having a diameter that is approximately the same as or greater than that of the substrate W. A support shaft 26 is fixed to the shielding plate 25 on the side opposite to the facing surface 25a.

[0067] The shielding plate 25 is connected to a shielding plate lifting unit 27 that raises and lowers the shielding plate 25. The shielding plate lifting unit 27 includes, for example, an actuator (not shown) such as an electric motor or an air cylinder that drives the support shaft 26 to raise and lower. The shielding plate 25 may be rotatable around a rotation axis A1.

[0068] The processing cup 7A includes a plurality of guards 30 that catch liquid splashed from the substrate W held on the spin chuck 6A of the spin base 20B, a plurality of cups 31 that catch liquid guided downward by the plurality of guards 30, and an exhaust bucket 32 ​​that surrounds all of the guards 30 and cups 31 in a planar view.

[0069] 4 shows an example in which three guards 30 and three cups 31 are provided. Each guard 30 corresponds to one cup 31, and each cup 31 receives the liquid guided downward by the corresponding guard 30.

[0070] A guard lifting unit 37 is connected to the multiple guards 30, which raises and lowers the multiple guards 30 individually. The guard lifting unit 37 raises and lowers the multiple guards 30 individually between a lower position and an upper position. The guard lifting unit 37 includes multiple actuators (not shown) that drive the raising and lowering of each of the multiple guards 30. The actuators may be electric motors or air cylinders.

[0071] The guard lifting unit 37 positions the guard 30 at any position within a range from the lower position to the upper position. The upper position of each guard 30 is a position where the upper end of the guard 30 is located above the position of the substrate W held by the multiple chuck pins 20A (substrate holding position). The lower position of each guard 30 is a position where the upper end of the guard 30 is located below the substrate holding position.

[0072] By placing at least one of the multiple guards 30 in the upper position, the guard 30 can receive liquid splashed from the substrate W. By placing all of the guards 30 in the lower position, the first main transport robot CR1 (see FIG. 2) can access the spin chuck 6A.

[0073] The coating / removal processing device 4A includes a plurality of nozzles that supply fluid to the substrate W held on the spin chuck 6A. The plurality of nozzles includes a plurality of mobile nozzles 9 (first mobile nozzle 9A and second mobile nozzle 9B) that move horizontally and vertically to supply fluid to the substrate W from above, a central nozzle 10 that supplies fluid to the center of the substrate W from above, and a bottom nozzle 11 that supplies fluid to the substrate W from below.

[0074] The multiple movable nozzles 9 are connected to multiple nozzle movement units 36 (first nozzle movement unit 36A and second nozzle movement unit 36B) that move the nozzles 9 horizontally and vertically. Each movable nozzle 9 can move horizontally between a central position and a home position (retracted position). When positioned at the central position, each movable nozzle 9 faces the central region of the upper surface of the substrate W.

[0075] When positioned at the home position, each movable nozzle 9 does not face the upper surface of the substrate W, and is positioned outside the processing cup 7A in a plan view. Each movable nozzle 9 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0076] Each nozzle moving unit 36 ​​includes an arm (not shown) connected to the corresponding moving nozzle 9 and extending horizontally, a rotary shaft (not shown) connected to the arm and extending vertically, an elevation actuator (not shown) such as an electric motor or air cylinder that raises and lowers the rotary shaft, and a horizontal actuator (not shown) such as an electric motor or air cylinder that rotates the rotary shaft to move the arm horizontally. Each moving nozzle 9 is a rotary nozzle, but unlike this embodiment, it may also be a linear nozzle.

[0077] The first movable nozzle 9A has a discharge port 9a at its tip. The discharge port 9a is provided above the substrate holding position. When the first movable nozzle 9A is positioned above the substrate W, the discharge port 9a faces the upper surface of the substrate W from above. The first movable nozzle 9A is configured to supply (discharge) the protective film formation liquid and the removal liquid toward the upper surface of the substrate W held by the spin chuck 6A.

[0078] The first moving nozzle 9A is an example of a protective film forming liquid nozzle that supplies a protective film forming liquid to the upper surface of the substrate W. The first moving nozzle 9A is also an example of a removing liquid nozzle that supplies a removing liquid such as ammonia water to the upper surface of the substrate W. The outlet 9a is an example of a protective film forming liquid outlet that discharges a protective film forming liquid, and is also an example of a removing liquid outlet that discharges a removing liquid.

[0079] The protective film forming liquid is a liquid (processing liquid) that is applied to the main surface of the substrate W and then solidifies or hardens to form a protective film that protects the main surface of the substrate W. The protective film forming liquid contains a solute and a solvent. The protective film forming liquid solidifies or hardens when at least a portion of the solvent contained in the protective film forming liquid volatilizes (evaporates).

[0080] Here, "solidification" refers to the solidification of a solute due to forces acting between molecules or atoms, for example, as the solvent evaporates. "Hardening" refers to the solidification of a solute due to chemical changes such as polymerization or crosslinking. Therefore, "solidification or hardening" refers to the "solidification" of a solute due to various factors.

[0081] The solute of the protective film forming liquid includes, for example, a polymer, and the solvent of the protective film forming liquid is, for example, an organic solvent such as PGMEA (propylene glycol monomethyl ether acetate) or IPA (isopropyl alcohol).

[0082] The protective film forming solution may contain, as solutes, a low-solubility component and a high-solubility component having a higher solubility in the remover than the low-solubility component. The low-solubility component and the high-solubility component may be substances having different solubilities in the remover, as described below. The low-solubility component is, for example, novolak. The high-solubility component is, for example, 2,2-bis(4-hydroxyphenyl)propane.

[0083] The solvent contained in the protective film-forming liquid may be any liquid that dissolves the low-solubility component and the high-solubility component. The solvent contained in the protective film-forming liquid is preferably a liquid that is compatible (miscible) with the removal liquid. Compatibility refers to the property of two types of liquids dissolving and mixing with each other.

[0084] The protective film forming solution may contain a corrosion inhibitor, such as BTA (benzotriazole), which will be described in detail later.

[0085] The protective film is mainly composed of a low-solubility component in a solid state (low-solubility solid) and a high-solubility component in a solid state (high-solubility solid). The solvent may remain in the protective film. Details of each component (solvent, low-solubility component, high-solubility component, and corrosion-preventing component) contained in the protective film-forming solution will be described later.

[0086] The removal liquid is a liquid for peeling off the protective film and removing it from the main surface of the substrate W. The removal liquid may be an alkaline aqueous solution (alkaline liquid) other than ammonia water. Specific examples of alkaline aqueous solutions other than ammonia water include a TMAH (tetramethylammonium hydroxide) aqueous solution, a choline aqueous solution, and any combination thereof. The removal liquid may be pure water (preferably DIW), or a neutral or acidic aqueous solution (non-alkaline aqueous solution).

[0087] A common pipe 40 that guides the protective film forming liquid and the removing liquid to the first moving nozzle 9A is connected to the first moving nozzle 9A. A protective film forming liquid pipe 41 that guides the protective film forming liquid to the common pipe 40 and a removing liquid pipe 42 that guides the removing liquid to the common pipe 40 are connected to the common pipe 40.

[0088] When the protective film formation liquid valve 51 installed in the protective film formation liquid pipe 41 is opened, the protective film formation liquid is discharged downward in a continuous flow from the discharge port 9a of the first moving nozzle 9A. When the removal liquid valve 52 installed in the removal liquid pipe 42 is opened, the removal liquid is discharged downward in a continuous flow from the discharge port 9a of the first moving nozzle 9A.

[0089] The first moving nozzle 9A, the common pipe 40, and the protective film forming liquid pipe 41 constitute a protective film forming liquid supply unit 13A (protective film forming section) that supplies and applies the protective film forming liquid from the discharge port 9a toward the upper surface of the substrate W. The first moving nozzle 9A, the common pipe 40, and the removing liquid pipe 42 constitute a removing liquid supply unit 13B (removal processing section) that supplies the removing liquid from the discharge port 9a toward the upper surface of the substrate W.

[0090] A rinse liquid pipe 43 that guides the rinse liquid to the second moving nozzle 9B is connected to the second moving nozzle 9B. When a rinse liquid valve 53 provided in the rinse liquid pipe 43 is opened, the rinse liquid is discharged downward from the second moving nozzle 9B in a continuous flow.

[0091] The second moving nozzle 9B and the rinse liquid pipe 43 constitute a rinse liquid supply unit that supplies (discharges) a rinse liquid such as carbonated water toward the upper surface of the substrate W held on the spin chuck 6A. The second moving nozzle 9B is an example of a rinse liquid nozzle.

[0092] The rinse liquid is not limited to carbonated water, but may be a liquid containing at least one of DIW (Deionized Water), carbonated water, electrolytic ionized water, diluted hydrochloric acid water (for example, 1 ppm or more and 100 ppm or less), diluted ammonia water (for example, 1 ppm or more and 100 ppm or less), and reduced water (hydrogen water).

[0093] The central nozzle 10 is housed in a support shaft 26 of the shielding plate 25. A discharge port 10a provided at the tip of the central nozzle 10 is exposed from a communication hole 25b formed in the shielding plate 25, and faces the central region of the upper surface of the substrate W from above.

[0094] The central nozzle 10 includes a plurality of tubes that discharge fluid downward and a cylindrical casing 33 that surrounds the plurality of tubes. The plurality of tubes and the casing 33 extend vertically along the rotation axis A1. The plurality of tubes includes a residue removing liquid tube 34 that supplies a residue removing liquid such as IPA to the upper surface of the substrate W. The residue removing liquid is a liquid that dissolves and removes residue of the protective film that remains on the upper surface of the substrate W after it has been peeled off and removed from the upper surface of the substrate W by the removing liquid. In addition to the residue removing liquid tube 34, the plurality of tubes may also include a rinse liquid tube and a gas tube.

[0095] The residue removing liquid tube 34 is connected to a residue removing liquid pipe 44 that guides the residue removing liquid to the residue removing liquid tube 34. When a residue removing liquid valve 54 installed in the residue removing liquid pipe 44 is opened, the residue removing liquid is discharged in a continuous flow from the residue removing liquid tube 34 (central nozzle 10) toward the central region of the upper surface of the substrate W. The residue removing liquid tube 34 (central nozzle 10) and the residue removing liquid pipe 44 constitute a residue removing liquid supply unit. The central nozzle 10 is an example of a residue removing liquid nozzle.

[0096] The residue removal liquid is preferably compatible with the rinse liquid and the protective film forming liquid. The residue removal liquid dissolves the residue of the protective film. Therefore, the residue removal liquid is also called a residue dissolving liquid. The residue removal liquid may be, for example, an organic solvent, and may be a liquid containing at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, PGEE (propylene glycol monoethyl ether), and trans-1,2-dichloroethylene.

[0097] The lower surface nozzle 11 is inserted through an insertion hole 21a that opens in the center of the upper surface of the spin base 20B. The outlet 11a of the lower surface nozzle 11 is exposed from the upper surface of the spin base 20B. The outlet 11a of the lower surface nozzle 11 faces a central region of the lower surface (lower main surface) of the substrate W from below. The central region of the lower surface of the substrate W is a region on the lower surface of the substrate W that includes the center of rotation of the substrate W.

[0098] The lower surface nozzle 11 is configured to eject fluids such as a rinse liquid such as carbonated water, a chemical liquid such as hydrofluoric acid (HF: hydrofluoric acid), and a heat transfer medium such as hot water. A fluid pipe 46 that guides liquid to the lower surface nozzle 11 is connected to the lower surface nozzle 11. The fluid pipe 46 may be configured to be able to selectively guide a rinse liquid such as carbonated water, a chemical liquid such as hydrofluoric acid, and a heat transfer medium such as hot water. A fluid valve 56 that opens and closes the flow path of the fluid pipe 46 is installed in the fluid pipe 46.

[0099] A gas flow path 12 is formed by the space between the lower surface nozzle 11 and the insertion hole 21a of the spin base 20B. The gas flow path 12 is connected to a lower gas pipe 47 that is inserted into the space between the inner circumferential surface of the rotation shaft 22 and the lower surface nozzle 11. When a lower gas valve 57 installed in the lower gas pipe 47 is opened, a gas such as nitrogen gas (N2) is discharged from the gas flow path 12 toward the area around the rotation center of the lower surface of the substrate W. Discharging the gas from the gas flow path 12 can prevent liquid adhering to the upper surface of the substrate W from moving to the lower surface of the substrate W. Furthermore, it can prevent mist from entering between the lower surface of the substrate W and the spin base 20B.

[0100] The gas discharged from the gas flow path 12 is not limited to nitrogen gas. The gas discharged from the gas flow path 12 may be air. The gas discharged from the gas flow path 12 may also be an inert gas other than nitrogen gas. The inert gas is not limited to nitrogen gas, but refers to a gas that is inert to the upper surface of the substrate W. Examples of the inert gas include nitrogen gas and rare gases such as argon.

[0101] 5 is a system diagram illustrating an example of the configuration of the treatment liquid preparation unit 121. The treatment liquid prepared in the treatment liquid preparation unit 121 is supplied as a protective film formation liquid to the protective film formation liquid piping 41. In other words, the protective film formation liquid is a treatment liquid for forming a protective film.

[0102] The processing liquid preparation unit 121 includes a solvent tank 75, a low-solubility component tank 76, and a high-solubility component tank 77. The solvent tank 75 stores a solvent for the protective film formation liquid. The low-solubility component tank 76 stores a low-solubility component liquid in which a low-solubility component is dissolved in the solvent for the protective film formation liquid at a predetermined concentration (preferably a saturated concentration). The high-solubility component tank 77 stores a high-solubility component liquid in which a high-solubility component is dissolved in the solvent for the protective film formation liquid at a predetermined concentration (preferably a saturated concentration).

[0103] The processing liquid preparation unit 121 further includes a mixing unit 90 that mixes the solvent, the low-solubility component liquid, and the high-solubility component liquid. The mixing unit 90 is supplied with the solvent from the solvent tank 75 via a solvent pipe 85, with the low-solubility component liquid from the low-solubility component tank 76 via a low-solubility component pipe 86, and with the high-solubility component liquid from the high-solubility component tank 77 via a high-solubility component pipe 87. The mixing unit 90 may have manifolds connected to the pipes 85, 86, and 87. A solvent pump 91, a low-solubility component pump 92, and a high-solubility component pump 93 are respectively provided in the solvent pipe 85, the low-solubility component pipe 86, and the high-solubility component pipe 87. Furthermore, a solvent flow control valve 95, a low-solubility component flow control valve 96, and a high-solubility component flow control valve 97 are respectively provided in the solvent pipe 85, the low-solubility component pipe 86, and the high-solubility component pipe 87.

[0104] The solvent stored in the solvent tank 75 is pumped out by a solvent pump 91 and sent to a solvent pipe 85, and flows into the mixing section 90 at a flow rate adjusted by a solvent flow rate adjustment valve 95. The low-solubility component liquid stored in the low-solubility component tank 76 is pumped out by a low-solubility component pump 92 and sent to a low-solubility component pipe 86, and flows into the mixing section 90 at a flow rate adjusted by a low-solubility component flow rate adjustment valve 96. The high-solubility component liquid stored in the high-solubility component tank 77 is pumped out by a high-solubility component pump 93 and sent to a high-solubility component pipe 87, and flows into the mixing section 90 at a flow rate adjusted by a high-solubility component flow rate adjustment valve 97.

[0105] Thus, the solvent, low-solubility component liquid, and high-solubility component liquid flow into mixing section 90 at the flow rate ratio (flow rate ratio) set by flow rate adjustment valves 95, 96, and 97, and are mixed in mixing section 90 to prepare a protective film formation liquid (treatment liquid). This protective film formation liquid contains the solvent, low-solubility component, and high-solubility component in a composition ratio that corresponds to the above-mentioned flow rate ratio. The protective film formation liquid prepared in this manner is supplied from mixing section 90 to protective film formation liquid piping 41.

[0106] 6 is a block diagram illustrating an example of a configuration related to control of the substrate processing apparatus 120. The controller 3 is a computer including a computer main body 3a and a peripheral device 3d connected to the computer main body 3a. The computer main body 3a includes a CPU 3b (central processing unit) that executes various instructions and a main memory device 3c that stores information. The peripheral device 3d includes an auxiliary memory device 3e that stores information such as a program P, a reading device 3f that reads information from removable media RM, and a communication device 3g that communicates with other devices such as the host computer 140.

[0107] The controller 3 is connected to an input device 3A, a display device 3B, and an alarm device 3C. The input device 3A is operated when an operator such as a user or a maintenance technician inputs information into the substrate processing apparatus 120. The information is displayed on the screen of the display device 3B. The input device 3A may be any of a keyboard, a pointing device, and a touch panel, or may be a device other than these. A touch panel display that serves as both the input device 3A and the display device 3B may be provided in the substrate processing apparatus 120. The alarm device 3C issues an alarm using one or more of light, sound, characters, and figures. If the input device 3A is a touch panel display, the input device 3A may also serve as the alarm device 3C.

[0108] The CPU 3b executes a program P stored in the auxiliary storage device 3e. The program P in the auxiliary storage device 3e may be pre-installed in the controller 3, may be sent from a removable medium RM to the auxiliary storage device 3e via a reader 3f, or may be sent to the auxiliary storage device 3e from an external device such as a host computer 140 via a communication device 3g.

[0109] The auxiliary storage device 3e and the removable medium RM are non-volatile memories that retain their memory even when power is not supplied. The auxiliary storage device 3e is, for example, a magnetic storage device such as a hard disk drive. The removable medium RM is, for example, an optical disk such as a compact disk or a semiconductor memory such as a memory card. The removable medium RM is an example of a computer-readable recording medium on which the program P is recorded. The removable medium RM is a non-transitory tangible recording medium.

[0110] The auxiliary storage device 3e stores a plurality of recipes R. The recipes R are information that defines the processing content, processing conditions, and processing procedure for the substrate W. The plurality of recipes R differ from each other in at least one of the processing content, processing conditions, and processing procedure for the substrate W.

[0111] The controller 3 reads out the recipe R from the auxiliary storage device 3e and controls the liquid processing device 4, the reversing units 5A, 5B, 5C, the indexer robot IR1, the main transport robots CR1, CR2, the external transport robots OR1, OR2, the processing liquid preparer 121, etc. so that the substrate W is processed in accordance with the recipe R. The controller 3 controls the pumps 91, 92, 93, the flow rate adjustment valves 95, 96, 97, etc. included in the processing liquid preparer 121.

[0112] The following steps are executed by controlling these components with the controller 3. In other words, the controller 3 is programmed to execute the steps described below.

[0113] Fig. 7 is a flowchart illustrating an example of substrate processing by the substrate processing system 100. Figs. 8A to 8I are schematic views illustrating the state of the substrate W when the example of substrate processing is being performed.

[0114] Before a carrier C containing an unprocessed substrate W is loaded into the substrate processing apparatus 120, the defect size of the back surface Wb (non-device surface) of the substrate W contained in the carrier C is measured by the defect measuring apparatus 110 (step S1: defect measurement step). Data representing the measurement results is provided to and stored in the host computer 140.

[0115] The host computer 140 calculates the thickness of the protective film necessary and sufficient to make the rear surface Wb of the substrate W a surface with the desired flatness based on the measured defect size, and calculates the composition of the protective film (more specifically, the concentration (especially the concentration of the low-solubility component)) to achieve that thickness.The host computer 140 then determines the flow rate ratio of the solvent, low-solubility component liquid, and high-solubility component liquid corresponding to that composition, and transmits a processing liquid preparation command to the controller 3 of the substrate processing apparatus 120 to prepare a protective film forming liquid (processing liquid) using that flow rate ratio (step S2).

[0116] The host computer 140 does not necessarily need to determine the thickness or composition of the protective film, but may determine a command value (in this embodiment, a flow rate ratio) for instructing the controller 3 on the composition of the protective film according to the defect size. For example, a table correlating the defect size with the command value (in this embodiment, a flow rate ratio) according to the appropriate thickness of the protective film may be stored in advance in the storage device 140b of the host computer 140, and the host computer 140 may determine the command value by referring to the table. The processing liquid preparation command (here, the command value representing the flow rate ratio) transmitted from the host computer 140 to the controller 3 is stored in the auxiliary storage device 3e and is read out and used when necessary.

[0117] The processing liquid preparation command preferably includes a command value for each individual substrate W. However, when the sizes of defects on the rear surfaces Wb of multiple substrates W, for example, multiple substrates W accommodated in one carrier C, are expected to be substantially equal, a processing liquid preparation command including a command value commonly applied to the multiple substrates W may be transmitted from the host computer 140 to the controller 3.

[0118] In the substrate processing apparatus 120, an unprocessed substrate W is carried out from a carrier C by the indexer robot IR1 and carried into the first reversing unit 5A. The substrate W carried into the first reversing unit 5A is then reversed by the first reversing unit 5A so that the back surface Wb faces upward (step S3: pre-reversing step).

[0119] The substrate W inverted by the first inversion unit 5A is transported into the coating / removal processing device 4A by the first main transport robot CR1 and handed over to the spin chuck 6A. Specifically, the substrate W is placed on the plurality of chuck pins 20A in the open state. In this state, the opening / closing unit 28 closes the plurality of chuck pins 20A, whereby the substrate W is held horizontally by the spin chuck 6A with the back surface Wb facing up (substrate holding step).

[0120] The controller 3 reads from the auxiliary storage device 3e a processing liquid preparation command previously received from the host computer 140 in order to form a protective film of an appropriate (necessary and sufficient) thickness on the rear surface of the substrate W (step S4). The processing liquid preparation command includes a command value representing the mixing ratio of the solvent, the low-solubility component liquid, and the high-solubility component liquid, i.e., the flow rate ratio. In accordance with this command value, the controller 3 controls the apertures of the solvent flow control valve 95, the low-solubility component flow control valve 96, and the high-solubility component flow control valve 97 (step S5: processing liquid preparation step). Therefore, when the protective film formation liquid valve 51 is opened, the solvent, the low-solubility component liquid, and the high-solubility component liquid flow into the mixer 90 at the commanded flow rate ratio and are mixed therein. A protective film formation liquid containing the solvent, the low-solubility component, and the high-solubility component mixed at a composition ratio corresponding to the flow rate ratio is prepared and supplied to the protective film formation liquid pipe 41.

[0121] After the first main transport robot CR1 retreats to the outside of the coating / removal treatment device 4A, the protective film formation liquid supplying step (step S6: protective film forming step) is started. In the protective film formation liquid supplying step, first, the spin motor 23 (see FIG. 4) rotates the spin base 20B. This causes the substrate W held horizontally by the holding unit 20 to rotate (substrate rotation step).

[0122] Thereafter, the first nozzle movement unit 36A moves the first movable nozzle 9A to the processing position. The processing position of the first movable nozzle 9A is, for example, the central position. With the first movable nozzle 9A positioned at the processing position, the protective film formation liquid valve 51 is opened. As a result, as shown in FIG. 8A , the protective film formation liquid is supplied (discharged) from the discharge port 9a of the first movable nozzle 9A, i.e., from above, toward the central region of the upper surface (rear surface Wb) of the rotating substrate W (protective film formation liquid supply step, protective film formation liquid discharge step). The protective film formation liquid supplied to the rear surface Wb of the substrate W is spread and applied over the entire rear surface Wb of the substrate W by centrifugal force. As a result, a liquid film 201 of the protective film formation liquid (protective film formation liquid film) is formed on the rear surface Wb of the substrate W (liquid film forming step).

[0123] The supply of the protective film formation liquid from the first moving nozzle 9A continues for a predetermined time, for example, 2 to 4 seconds. In the protective film formation liquid supplying step, the substrate W is rotated at a predetermined protective film formation liquid rotation speed, for example, 10 to 1500 rpm.

[0124] Next, a solidification step (step S7: protective film forming step) is performed. In the solidification step, the protective film forming liquid on the rear surface Wb of the substrate W is solidified or hardened, and a protective film 200 (see FIG. 8C) is formed on the rear surface Wb of the substrate W.

[0125] Prior to the solidification step, the thickness of the liquid film 201 of the protective film formation liquid on the substrate W may be thinned (thinning step, spin-off step). Specifically, the protective film formation liquid valve 51 is closed. This stops the supply of the protective film formation liquid to the substrate W, as shown in FIG. 8B. Then, the first nozzle movement unit 36A moves the first moving nozzle 9A to the home position.

[0126] 8B, in the thinning step, the substrate W is rotated with the supply of the protective film formation liquid to the rear surface Wb of the substrate W stopped, and thus a portion of the protective film formation liquid is removed from the rear surface Wb of the substrate W. This causes the liquid film 201 on the substrate W to have an appropriate thickness. This thickness depends on the composition of the protective film formation liquid, more specifically, its concentration (even more specifically, the concentration of low-solubility components in particular).

[0127] The centrifugal force caused by the rotation of the substrate W not only expels the protective film formation liquid from the back surface Wb of the substrate W, but also acts on the gas in contact with the liquid film 201. The centrifugal force forms an airflow that directs the gas from the center toward the periphery of the upper surface (back surface Wb) of the substrate W. This airflow expels the gaseous solvent in contact with the liquid film 201 from the atmosphere in contact with the substrate W. This promotes evaporation (volatilization) of the solvent from the protective film formation liquid on the substrate W, and as shown in FIG. 8C, the protective film formation liquid solidifies to form the protective film 200 (solvent evaporation process, protective film formation process). In the solidification process, the spin motor 23 functions as an evaporation unit (evaporation promotion unit) that evaporates the solvent in the protective film formation liquid.

[0128] In the thinning process (see FIG. 8B), the spin motor 23 changes the rotation speed of the substrate W to a predetermined thinning speed. The thinning speed is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W may be kept constant within the range of 300 rpm to 1500 rpm, or may be changed as appropriate within the range of 300 rpm to 1500 rpm during the thinning process. The thinning process is performed for a predetermined time, for example, 30 seconds.

[0129] 8A, before the thinning process is started, the protective film formation liquid valve 51 may be closed in a state in which the protective film formation liquid is present only in the central region of the back surface Wb of the substrate W. In this case, the centrifugal force caused by the rotation of the substrate W causes the protective film formation liquid to spread over the entire back surface Wb of the substrate W, thinning the liquid film 201. Therefore, the amount of protective film formation liquid removed from the back surface Wb of the substrate W can be reduced.

[0130] With the protective film 200 formed on the back surface Wb, the substrate W is unloaded from the coating / removal processing device 4A by the first main transport robot CR1. Specifically, after the rotation of the substrate W is stopped and the multiple chuck pins 20A are opened, the first main transport robot CR1 receives the substrate W from the spin chuck 6A. The substrate W unloaded from the coating / removal processing device 4A is loaded into the first reversal unit 5A or the second reversal unit 5B by the first main transport robot CR1. The substrate W loaded into the first reversal unit 5A or the second reversal unit 5B is then inverted by the first reversal unit 5A or the second reversal unit 5B so that the front surface Wf (device surface) faces upward (step S8: first inversion step).

[0131] The substrate W inverted by the first inversion unit 5A or the second inversion unit 5B is then carried out of the first inversion unit 5A or the second inversion unit 5B by the first main transport robot CR1 and carried into the resist film coating treatment device 4DB. As a result, the substrate W is held on the spin chuck 6B with its front surface Wf facing upward. The spin chuck 6B is configured to hold the substrate W in a horizontal position and rotate the substrate W about a vertical rotation axis A2 passing through its center. The spin chuck 6B may be of a suction type that holds the substrate W by suction on the underside. After transferring the substrate W to the spin chuck 6B, the first main transport robot CR1 retreats to the outside of the resist film coating treatment device 4DB.

[0132] Next, a resist film coating process (step S9) is started in which a resist film is coated on the front surface Wf of the substrate W. In the resist film coating process, as shown in Fig. 8D, a resist film forming liquid is supplied from the nozzle 61 located at the processing position toward the front surface Wf of the substrate W in a rotating state. As a result, a resist film 180 (see Fig. 8E) is formed on the front surface Wf of the substrate W. That is, a resist film coating process is performed on the front surface Wf of the substrate W.

[0133] The substrate W, with the resist film 180 coated on its front surface Wf, is carried out of the resist film coating treatment apparatus 4DB by the first main transport robot CR1 and carried into the anti-reflective film coating treatment apparatus 4DA. As a result, the substrate W is held by the spin chuck 6B of the anti-reflective film coating treatment apparatus 4DA with its back surface Wb facing downward. After transferring the substrate W to the spin chuck 6B, the first main transport robot CR1 retreats to the outside of the anti-reflective film coating treatment apparatus 4DA.

[0134] Next, an anti-reflection film coating process (step S10) is started, in which an anti-reflection film is coated on the front surface Wf of the substrate W. In the anti-reflection film coating process, as shown in FIG. 8E, an anti-reflection film forming solution is supplied from the nozzle 61 located at the processing position while the substrate W is rotated around the rotation axis A2 by the spin chuck 6B. As a result, an anti-reflection film 181 is coated on the front surface Wf of the substrate W, as shown in FIG. 8F. That is, the anti-reflection film coating process is performed on the front surface Wf of the substrate W. In this substrate processing, the anti-reflection film 181 is formed on the resist film 180.

[0135] The substrate W whose front surface Wf has been subjected to the anti-reflection film coating treatment is carried out from the anti-reflection film coating treatment apparatus 4DA by the first main transport robot CR1.

[0136] This substrate W is handed over to the second main transport robot CR2 via the second reversing unit 5B. At this time, the second reversing unit 5B does not turn over the substrate W, and the second main transport robot CR2 transports the substrate W with its front surface Wf facing up. The second main transport robot CR2 hands over the substrate W to the third reversing unit 5C. This substrate W is then transported towards the exposure device 130 by the first external transport robot OR1, the placement unit 151 and the second external transport robot OR2.

[0137] In the exposure device 130, a light beam is irradiated onto the surface Wf of the substrate W through a photomask (not shown) having a predetermined mask pattern, thereby exposing the surface Wf of the substrate W (step S11: exposure step, substrate processing step, predetermined processing).

[0138] After the exposure process, the substrate W is transported to the third reversing unit 5C by the second external transport robot OR2, the first external transport robot OR1, etc. The second main transport robot CR2 transports the substrate W into the developing treatment device 4E for development (step S12: developing step). After the development process, the substrate W is transported out by the second main transport robot CR2 and handed over to the second reversing unit 5B. The second reversing unit 5B turns the substrate W over so that the back surface Wb faces upward (step S13: second reversing step). After this reversal process, the first main transport robot CR1 transports the substrate W into the coating / removal treatment device 4A and hands it over to the spin chuck 6A. Alternatively, the third reversing unit 5C may turn over the substrate W (step S13), and the turned substrate W may be handed over to the second reversing unit 5B by the second main transport robot CR2. In this case, the second reversing unit 5B does not turn over the substrate W.

[0139] Thereafter, the coating / peeling treatment device 4A performs a protective film removing step (step S14) to a drying step (step S17).

[0140] Specifically, after the first main transport robot CR1 retreats to the outside of the coating / removal processing apparatus 4A, the protective film removal step (step S14: removal step) is started. In the protective film removal step, first, the spin motor 23 rotates the spin base 20B. This causes the substrate W, which is held horizontally, to rotate.

[0141] Thereafter, the first nozzle movement unit 36A moves the first movable nozzle 9A to the processing position (center position). With the first movable nozzle 9A positioned at the processing position, the removing liquid valve 52 is opened. As a result, as shown in FIG. 8G, the removing liquid is supplied (discharged) from the discharge port 9a of the first movable nozzle 9A, i.e., from above (one side in the vertical direction), toward the central region of the back surface Wb of the rotating substrate W (removing liquid supplying step, removing liquid discharging step). The removing liquid supplied to the back surface Wb of the substrate W spreads over the entire back surface Wb of the substrate W due to centrifugal force. As a result, the protective film 200 on the back surface Wb of the substrate W is peeled off and discharged outside the substrate W together with the removing liquid.

[0142] The supply of the removal liquid to the back surface Wb of the substrate W continues for a predetermined time, for example, 60 seconds. In the protective film removing step, the substrate W is rotated at a predetermined removal rotation speed, for example, 800 rpm.

[0143] After the protective film removal process (step S14), a rinsing process (step S15) is performed in which the removing liquid is washed away from the back surface Wb of the substrate W with a rinsing liquid. Specifically, the removing liquid valve 52 is closed. This stops the supply of the removing liquid to the back surface Wb of the substrate W. After the supply of the removing liquid is stopped, the first nozzle movement unit 36A moves the first moving nozzle 9A to the home position.

[0144] After the first movable nozzle 9A is retracted, the second nozzle movement unit 36B moves the second movable nozzle 9B to the processing position. The processing position of the second movable nozzle 9B is, for example, the central position. With the second movable nozzle 9B positioned at the processing position, the rinse liquid valve 53 is opened. As a result, as shown in FIG. 8H, rinse liquid is supplied (discharged) from the second movable nozzle 9B toward the central region of the back surface Wb of the rotating substrate W (rinse liquid supply process, rinse liquid discharge process). The rinse liquid supplied to the back surface Wb of the substrate W spreads over the entire back surface Wb of the substrate W due to centrifugal force. As a result, the removing liquid on the back surface Wb of the substrate W is washed away by the rinse liquid.

[0145] In the rinsing step, the rinsing liquid is continuously discharged from the second moving nozzle 9B for a predetermined time, for example, 30 seconds. In the rinsing step, the substrate W is rotated at a predetermined rinsing rotation speed, for example, 800 rpm.

[0146] After the rinsing step (step S15), a residue removal step (step S16) is performed in which residues of the protective film 200 are removed from the back surface Wb of the substrate W using a residue removal liquid. Even after the protective film is peeled off from the substrate W by the removal liquid and removed from the substrate W, residues of the protective film 200 may remain on the back surface Wb of the substrate W. The residue removal liquid supplied to the back surface Wb of the substrate W dissolves such residues of the protective film.

[0147] Specifically, the second nozzle moving unit 36B moves the second moving nozzle 9B to the retracted position, and the shielding plate lifting unit 27 moves the shielding plate 25 to the processing position.

[0148] Then, with the blocking plate 25 in the processing position, the residue removing liquid valve 54 is opened. As a result, as shown in Fig. 8I, the residue removing liquid is supplied (discharged) from the central nozzle 10 toward the central region of the back surface Wb of the rotating substrate W (residue removing liquid supplying step, residue removing liquid discharging step).

[0149] The residue removing liquid supplied from the central nozzle 10 to the back surface Wb of the substrate W spreads radially due to centrifugal force and reaches the entire back surface Wb of the substrate W. The centrifugal force causes the residue removing liquid to dissolve the residue of the protective film, and the residue removing liquid is discharged from the periphery of the back surface Wb of the substrate W. This removes the residue of the protective film from the substrate W.

[0150] In the residue removing liquid supplying step, the discharge of the residue removing liquid from the central nozzle 10 continues for a predetermined time, for example, 30 seconds. In the residue removing step (step S9), the substrate W is rotated at a predetermined residue removal rotation speed, for example, 300 rpm.

[0151] After the residue removal step, the residue removal liquid valve 54 is closed, and the spin motor 23 accelerates the rotation of the substrate W, rotating the substrate W at a high rotation speed (for example, several thousand rpm) (drying step: step S17). This removes the liquid from the substrate W, and the substrate W is dried. When a predetermined time has elapsed since the high-speed rotation of the substrate W began, the spin motor 23 stops rotating. This stops the rotation of the substrate W.

[0152] The first main transport robot CR1 enters the coating / removal processing apparatus 4A, receives the processed substrate W from the chuck pins 20A of the spin chuck 6A, and transports it out of the coating / removal processing apparatus 4A. The first main transport robot CR1 passes the substrate W transported from the coating / removal processing apparatus 4A to the first reversal unit 5A. The substrate W transported to the first reversal unit 5A is reversed by the first reversal unit 5A so that the front surface Wf faces upward (step S18: third reversal step). Thereafter, the indexer robot IR1 receives the substrate W from the first reversal unit 5A and stores the substrate W in the carrier C (see FIG. 2). The third reversal step (step S18) may be performed by the second reversal unit 5B.

[0153] As described above, according to this embodiment, the defect size on the back surface Wb of the substrate W is measured, and a protective film formation liquid (processing liquid) having a composition (particularly a concentration) corresponding to the measured defect size is prepared. By forming the protective film 200 on the back surface Wb of the substrate W using the protective film formation liquid prepared in this manner, it is possible to form a protective film 200 having a thickness that is neither too thick nor too thin according to the defect size, i.e., a thickness that is sufficient for the defect size. This makes it possible to suppress consumption of the solvent and solute that are materials for the protective film formation liquid. Then, by performing the exposure process in the exposure device 130 in a state in which the protective film 200 having the required thickness has been formed on the back surface Wb of the substrate W, it is possible to perform an appropriate exposure process while suppressing or preventing problems such as defocus.

[0154] This embodiment may be modified so that the anti-reflection film coating step is performed before the resist film coating step, or may be omitted. Furthermore, the protective film 200 may be formed after the anti-reflection film coating step and the resist film coating step. The third reversing unit 5C may be replaced with a mounting unit that does not have a substrate reversing function. Furthermore, the substrate processing apparatus 120 may be provided with at least one reversing unit. For example, the substrate processing apparatus 120 may be provided with only the first reversing unit 5A, and mounting units may be provided instead of the other reversing units (the second reversing unit 5B and the third reversing unit 5C).

[0155] 9 is a diagram for explaining another embodiment of the present invention, and shows a coating / removal processing apparatus 4A and an example of the related configuration in the above-mentioned substrate processing apparatus 120. In explaining this embodiment, reference will again be made to the above-mentioned FIGS. 1 to 8I.

[0156] In this embodiment, the coating / removal processing apparatus 4A includes a flatness measuring unit 160 that measures the flatness (surface flatness) of the protective film 200 formed on the substrate W.

[0157] Specifically, the flatness measuring section 160 includes a film thickness measuring device 161 and a scan unit 165 that moves (scans) the film thickness measuring device 161 above the substrate W held by the spin chuck 6A.

[0158] For example, an optical displacement sensor or the like is used as the film thickness measuring device 161. The film thickness of the protective film 200 can be measured by adjusting the measurement irradiation wavelength of the light irradiated onto the substrate W from the film thickness measuring device 161 according to the constituent material of the protective film 200, which is the film to be measured.

[0159] The scan unit 165 includes a horizontal arm 162 having a film thickness measuring device 161 attached to its tip, a rotation shaft 163 connected to the base end of the horizontal arm 162, and a rotation drive source 164 that rotates the rotation shaft 163. The rotation shaft 163 is aligned in the vertical direction and is rotatable around its axis. The horizontal arm 162 is an arm that extends in the horizontal direction. The rotation drive source 164 includes, for example, an electric motor. The rotation drive source 164 is controlled by the controller 3.

[0160] The horizontal arm 162 can be oscillated horizontally by rotating the rotation shaft 163 with the rotation drive source 164. As a result, the film thickness measuring device 161 attached to the tip of the horizontal arm 162 moves along the upper surface of the substrate W held by the spin chuck 6A, and the measurement position can be moved relative to the rotation axis A1. This makes it possible to measure the film thickness of the protective film 200 at multiple radial positions on the substrate W. Furthermore, by rotating the substrate W with the spin chuck 6A, the film thickness of the protective film 200 can be measured at any position on the substrate W.

[0161] The measurement results from the film thickness measuring instrument 161 are input to the controller 3. The controller 3 creates a film thickness profile of the protective film 200 based on the film thickness measurement results at multiple positions, for example. Then, the controller 3 calculates the flatness of the protective film 200 based on the film thickness profile. For example, the difference between the maximum film thickness value and the minimum film thickness value in the film thickness profile may be taken as the flatness. The smaller the flatness value, the closer it is to flatness (plane).

[0162] On the other hand, in addition to the first protective film forming liquid prepared in the first processing liquid preparation unit 121 having the configuration described in the above-mentioned embodiment (see Figure 5), a second protective film forming liquid can be supplied from the second processing liquid preparation unit 122 to the protective film forming liquid piping 41.

[0163] Specifically, the protective film formation liquid pipe 41 branches into a first branch pipe 411 and a second branch pipe 412 upstream of the protective film formation liquid valve 51. The first branch pipe 411 is connected to a first processing liquid preparation unit 121, and the second branch pipe 412 is connected to a second processing liquid preparation unit 122. Valves 511 and 512 are provided in the first branch pipe 411 and the second branch pipe 412, respectively. The opening and closing of these valves 511 and 512 is controlled by the controller 3, thereby allowing either the first protective film formation liquid prepared in the first processing liquid preparation unit 121 or the second protective film formation liquid supplied from the second processing liquid preparation unit 122 to be supplied to the substrate W from the first moving nozzle 9A via the protective film formation liquid pipe 41.

[0164] The second protective film forming liquid is an example of an additional processing liquid supplied onto the protective film 200. The second processing liquid preparation unit 122, the second branch pipe 412, the protective film forming liquid pipe 41, the common pipe 40, the first moving nozzle 9A, etc. are an example of an additional protective film forming unit for supplying the second protective film forming liquid (additional processing liquid) onto the protective film 200 to form an additional protective film.

[0165] The second processing liquid preparation unit 122 may include a tank for storing a second protective film formation liquid that has been prepared in advance. Similarly to the first processing liquid preparation unit 121, the second processing liquid preparation unit 122 may be configured to prepare the second protective film formation liquid by mixing multiple liquids at an arbitrary flow rate ratio using multiple flow rate adjustment valves controlled by the controller 3.

[0166] For example, the first protective film-forming liquid may be a first polymer solution, and the second protective film-forming liquid may be a second polymer solution that is incompatible with the first polymer solution. Specifically, the solvent of the first polymer solution may be PGMEA (propylene glycol monomethyl ether acetate), and the solvent of the second polymer solution may be IPA (isopropyl alcohol).

[0167] Fig. 10 is a flowchart for explaining an example of substrate processing by the substrate processing system 100 having the configuration shown in Fig. 9. In Fig. 10, steps in which the same processes as those shown in Fig. 7 are performed are denoted by the same reference numerals, and descriptions thereof will be omitted.

[0168] In this embodiment, after a protective film forming step (steps S6 and S7) in which a first protective film formation liquid is supplied and applied to the back surface Wb of the substrate W and the liquid film is solidified or hardened to form the protective film 200, the flatness measurement unit 160 measures the flatness of the protective film 200 (step S21: flatness measurement step). In the protective film formation liquid supply step (step S6), with the first movable nozzle 9A positioned at the processing position, the protective film formation liquid valve 51 is opened and the valve 511 is also opened. As a result, the first protective film formation liquid is supplied (discharged) from the discharge port 9a of the first movable nozzle 9A toward the central region of the upper surface (back surface Wb) of the substrate W in a rotating state.

[0169] The controller 3 compares the flatness measured in the flatness measurement step (step S21) with a predetermined threshold (reference value), and if the flatness exceeds the threshold (step S22: YES), it determines that the surface of the protective film 200 is not sufficiently flat, and executes the additional protective film formation step (steps S23, S24). If the flatness is equal to or less than the threshold (step S22: NO), the controller 3 determines that the surface of the protective film 200 is sufficiently flat, and proceeds to the first reversal step (step S8) without executing the additional protective film formation step (steps S23, S24).

[0170] The additional protective film forming process includes a process of supplying a second protective film forming liquid to the back surface Wb of the substrate W, more precisely, to the surface of the protective film 200, to form a liquid film of the second protective film forming liquid (step S23: second protective film forming liquid supply process), and a process of solidifying or hardening the liquid film to form an additional protective film (step S24: solidification process).

[0171] 11A to 11C are schematic views for explaining the details of the additional protective film forming step.

[0172] When the second protective film formation liquid is supplied (step S23: second protective film formation liquid supplying step), first, the spin motor 23 (see FIG. 4) rotates the spin base 20B. This rotates the substrate W held horizontally by the holding unit 20 (substrate rotation step). Thereafter, the first nozzle moving unit 36A moves the first movable nozzle 9A to a processing position. The processing position of the first movable nozzle 9A is, for example, a central position. With the first movable nozzle 9A positioned at the processing position, the protective film formation liquid valve 51 is opened, and the valve 512 is also opened. As a result, as shown in FIG. 11A, the second protective film formation liquid is supplied (discharged) from the discharge port 9a of the first movable nozzle 9A, i.e., from above (one side in the vertical direction), toward a central region of the upper surface (rear surface Wb) of the substrate W in a rotating state. The second protective film formation liquid supplied to the rear surface Wb of the substrate W, more precisely, to the surface of the protective film 200, spreads by centrifugal force over the entire surface of the protective film 200. As a result, a liquid film 201A (second protective film formation liquid film) of the second protective film formation liquid is formed on the protective film 200 formed on the rear surface Wb of the substrate W (liquid film forming process).

[0173] The supply of the second protective film formation liquid from the first moving nozzle 9A continues for a predetermined time, for example, 2 to 4 seconds. In the second protective film formation liquid supplying step, the substrate W is rotated at a predetermined second protective film formation liquid rotation speed, for example, 10 to 1500 rpm.

[0174] Next, a solidification step (step S24) is performed. In the solidification step, the second protective film formation liquid on the protective film 200 is solidified or hardened, and an additional protective film 200A (see FIG. 11C) is formed on the rear surface Wb of the substrate W, more precisely, on the protective film 200. In other words, the additional protective film 200A is applied on the protective film 200 formed on the rear surface Wb of the substrate W.

[0175] Prior to the solidification step (step S24), the thickness of the liquid film 201A of the second protective film formation liquid on the substrate W may be thinned (thinning step, spin-off step). Specifically, the protective film formation liquid valve 51 is closed. This stops the supply of the second protective film formation liquid to the substrate W, as shown in FIG. 11B. Then, the first nozzle movement unit 36A moves the first movement nozzle 9A to the home position.

[0176] 11B, in the thinning step, the substrate W is rotated with the supply of the second protective film formation liquid to the rear surface Wb of the substrate W stopped, and thus a portion of the second protective film formation liquid is removed from the rear surface Wb of the substrate W. This causes the thickness of the liquid film 201A on the substrate W to become an appropriate thickness. This thickness depends on the composition of the second protective film formation liquid, more specifically, its concentration.

[0177] The centrifugal force caused by the rotation of the substrate W not only expels the second protective film formation liquid from the back surface Wb of the substrate W, but also acts on the gas in contact with the liquid film 201A. The centrifugal force creates an airflow of the gas directed from the center to the periphery of the upper surface (back surface Wb) of the substrate W. This airflow expels the gaseous solvent in contact with the liquid film 201A from the atmosphere in contact with the substrate W. This promotes evaporation (volatilization) of the solvent from the second protective film formation liquid on the substrate W, and as shown in FIG. 11C, the second protective film formation liquid solidifies to form the additional protective film 200A (solvent evaporation step). In the solidification step (step S24), the spin motor 23 functions as an evaporation unit (evaporation promotion unit) that evaporates the solvent in the second protective film formation liquid.

[0178] In the thinning process (see FIG. 11B), the spin motor 23 changes the rotation speed of the substrate W to a predetermined thinning speed. The thinning speed is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W may be kept constant within the range of 300 rpm to 1500 rpm, or may be changed as appropriate within the range of 300 rpm to 1500 rpm during the thinning process. The thinning process is performed for a predetermined time, for example, 30 seconds.

[0179] 11A, before the thinning step is started, the protective film formation liquid valve 51 may be closed in a state in which the second protective film formation liquid is present only in the central region of the back surface Wb of the substrate W. In this case, the centrifugal force caused by the rotation of the substrate W spreads the second protective film formation liquid over the entire back surface Wb of the substrate W, thinning the liquid film 201A. Therefore, the amount of the second protective film formation liquid removed from the back surface Wb of the substrate W can be reduced.

[0180] Thus, according to this embodiment, when the protective film 200 is formed to a necessary and sufficient thickness based on the defect size, if the flatness of the protective film 200 is insufficient, the additional protective film 200A is formed on the surface of the protective film 200. This allows the exposure process in the exposure device 130 to be performed in a state in which the back surface Wb of the substrate W (more precisely, the surface of the additional protective film 200A) has sufficient flatness.

[0181] In particular, when the first protective film forming liquid is a first polymer solution and the second protective film forming liquid is a second polymer solution that is incompatible with the first polymer solution, it is possible to suppress damage to the protective film 200 when the second protective film forming liquid is supplied. As a result, it is possible to reliably increase the flatness by forming the additional protective film 200A.

[0182] After the step of forming the additional protective film 200A (steps S23 and S24), the process may return to the flatness measurement step (step S21). That is, the flatness may be measured again, and if the flatness is insufficient (step S22: YES), a second protective film formation liquid may be supplied and solidified (steps S23 and S24) to coat an additional protective film on the additional protective film 200A, thereby thickening the additional protective film 200A. This ensures that a surface with sufficient flatness (surface of the additional protective film 200A) is provided on the back surface Wb of the substrate W.

[0183] Furthermore, the additional protective film to be coated on the additional protective film 200A may be formed using a third protective film-forming liquid that is incompatible with the second protective film-forming liquid. This third protective film-forming liquid may be the first protective film-forming liquid.

[0184] <Examples of highly soluble ingredients> An example of each component in the protective film forming liquid (first, second and third protective film forming liquid) used in the above-described embodiment will be described below.

[0185] In the following, "C x~y "," "C x~ C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1~6 Alkyl refers to alkyl chains having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0186] When a polymer has multiple types of repeating units, these repeating units are copolymerized. Unless otherwise specified, these copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are represented by structural formulas, the n, m, etc. in parentheses indicate the number of repeating units.

[0187] <Low solubility component> The (A) low-solubility component includes at least one of novolak, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof. Preferably, the (A) low-solubility component may include at least one of novolak, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonate, polymethacrylic acid derivatives, and copolymers of combinations thereof. More preferably, the (A) low-solubility component may include at least one of novolak, polyhydroxystyrene, polycarbonate, and copolymers of combinations thereof. The novolak may be a phenolic novolak.

[0188] The protective film-forming liquid may contain one or a combination of two or more of the above-mentioned preferred examples as the low-solubility component (A). For example, the low-solubility component (A) may contain both novolak and polyhydroxystyrene.

[0189] In a preferred embodiment, the low-solubility component (A) is dried to form a film, and the film is peeled off while retaining the object to be removed without being dissolved in the removal solution for the most part. However, an embodiment in which only a small part of the low-solubility component (A) is dissolved in the removal solution is acceptable.

[0190] Preferably, (A) the low-solubility component does not contain fluorine and / or silicon, more preferably does not contain both.

[0191] The copolymerization is preferably random copolymerization or block copolymerization.

[0192] Although there is no intention to limit the scope of the rights, specific examples of the low-solubility component (A) include the compounds shown in Chemical Formulas 1 to 7 below.

[0193] [ka]

[0194] [ka]

[0195] [ka] (An asterisk * indicates a bond to an adjacent building block.)

[0196] [ka] (R is C 1~4 (The asterisk * indicates a bond to an adjacent structural unit.)

[0197] [ka]

[0198] [ka]

[0199] [ka] (Me means a methyl group. An asterisk * indicates a bond to an adjacent structural unit.)

[0200] The weight average molecular weight (Mw) of the (A) low-solubility component is preferably 150 to 500,000, more preferably 300 to 300,000, even more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

[0201] (A) Low-solubility components can be obtained by synthesis. They can also be purchased. If purchased, examples of suppliers include the following. Suppliers can also synthesize (A) polymers. Novolac: Showa Kasei Co., Ltd., Asahi Organic Materials Co., Ltd., Gunei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd. Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Industry Co., Ltd. Polyacrylic acid derivative: Nippon Shokubai Co., Ltd. Polycarbonate: Sigma-Aldrich Polymethacrylic acid derivatives: Sigma-Aldrich Compared to the total mass of the protective film-forming liquid, the amount of the low-solubility component (A) is 0.1 to 50 mass%, preferably 0.5 to 30 mass%, more preferably 1 to 20 mass%, and even more preferably 1 to 10 mass%. In other words, the total mass of the protective film-forming liquid is taken as 100 mass%, and the amount of the low-solubility component (A) is 0.1 to 50 mass% based on this. In other words, "compared to" can be rephrased as "based on." The same applies hereinafter unless otherwise specified.

[0202] <Highly soluble components> The (B) highly soluble component is the (B') crack-accelerating component. The (B') crack-accelerating component contains a hydrocarbon and further contains a hydroxyl group (-OH) and / or a carbonyl group (-C(=O)-). When the (B') crack-accelerating component is a polymer, one of the constituent units contains a hydrocarbon on a unit-by-unit basis and further contains a hydroxyl group and / or a carbonyl group. Examples of the carbonyl group include carboxylic acid (-COOH), aldehyde, ketone, ester, amide, and enone, with carboxylic acid being preferred.

[0203] Without intending to limit the scope of the invention or being bound by theory, it is believed that when the protective film-forming liquid is dried to form a protective film on the substrate and the remover peels off the protective film, the (B) highly soluble component creates a portion that triggers the protective film to peel off. For this reason, it is preferable that the (B) highly soluble component has a higher solubility in the remover than the (A) low solubility component. Examples of embodiments of the (B') crack-promoting component that contain a ketone as a carbonyl group include cyclic hydrocarbons. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

[0204] In a more specific embodiment, the highly soluble component (B) is represented by at least one of the following (B-1), (B-2), and (B-3). (B-1) is a compound containing 1 to 6 (preferably 1 to 4) structural units of the following chemical formula 8, each of which is linked by a linking group (linker L1). Here, the linker L1 may be a single bond or a C 1~6 It may be alkylene. 1~6 The alkylene acts as a linker to connect the constituent units and is not limited to a divalent group. Preferably, it is a divalent to tetravalent group. 1~6 The alkylene may be either straight-chain or branched.

[0205] [ka]

[0206] Cy1 is C 5~30 Preferably, it is phenyl, cyclohexane, or naphthyl, more preferably phenyl. In a preferred embodiment, the linker L1 connects multiple Cy1s.

[0207] R1 is independently C 1~5 alkyl, preferably methyl, ethyl, propyl, or butyl. 1~5 The alkyl may be either straight-chain or branched.

[0208] n b1 is 1, 2 or 3, preferably 1 or 2, and more preferably 1. b1’ is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0209] The following chemical formula 9 is a chemical formula that uses a linker L9 to represent the structural unit described in chemical formula 8. The linker L9 is preferably a single bond, methylene, ethylene, or propylene.

[0210] [ka]

[0211] Although not intending to limit the scope of the invention, suitable examples of (B-1) include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalenediol, 2,5-di-tert-butylhydroquinone, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. These may be obtained by polymerization or condensation.

[0212] As an example, we will explain 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol shown in the following chemical formula 10. In (B-1), this compound has three structural units of chemical formula 8, and the structural units are linked by a linker L1 (methylene). b1 =n b1’ =1 and R1 is methyl.

[0213] [ka]

[0214] (B-2) is represented by the following chemical formula 11.

[0215] [ka]

[0216] R 21 , R 22 , R 23 , and R 24 are each independently hydrogen or C 1~5 and is preferably hydrogen, methyl, ethyl, t-butyl, or isopropyl, more preferably hydrogen, methyl, or ethyl, and even more preferably methyl or ethyl.

[0217] Linker L 21 and linker L 22 are each independently, C 1~20 Alkylene, C 1~20 Cycloalkylene, C 2~4 Alkenylene, C 2~4 Alkynylene of C 6~20 These groups are arylenes of the formula C 1~5 The linker L may be substituted with an alkyl or hydroxy. Here, alkenylene means a divalent hydrocarbon group having one or more double bonds, and alkynylene means a divalent hydrocarbon group having one or more triple bonds. 21 and linker L 22is preferably C 2~4 alkylene, acetylene (C alkynylene) or phenylene, more preferably C 2~4 or acetylene, more preferably acetylene.

[0218] n b2 is 0, 1 or 2, preferably 0 or 1, more preferably 0.

[0219] Although not intending to limit the scope of the invention, suitable examples of (B-2) include 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol. In another embodiment, suitable examples of (B-2) include 3-hexyne-2,5-diol, 1,4-butynediol, 2,4-hexadiyne-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy-2-butene, and 1,4-benzenedimethanol.

[0220] (B-3) is a polymer containing a constituent unit represented by the following chemical formula 12, and has a weight average molecular weight (Mw) of 500 to 10,000. Mw is preferably 600 to 5,000, and more preferably 700 to 3,000.

[0221] [ka]

[0222] where R 25 is —H, —CH3, or —COOH, preferably —H or —COOH. It is also acceptable for one (B-3) polymer to contain two or more types of constitutional units each represented by Chemical Formula 12.

[0223] Although not intending to limit the scope of the invention, preferred examples of the (B-3) polymer include polymers of acrylic acid, maleic acid, or a combination thereof. More preferred examples include polyacrylic acid and maleic-acrylic acid copolymers.

[0224] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0225] As an example, the maleic acid acrylic acid copolymer shown in the following chemical formula 13 will be described. This copolymer is included in (B-3) and has two types of structural units shown in chemical formula 12, with R 25 is -H, and in another building block, R 25 is -COOH.

[0226] [ka]

[0227] Needless to say, the protective film-forming liquid may contain one or a combination of two or more of the above preferred examples as the highly soluble component (B). For example, the highly soluble component (B) may contain both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0228] The (B) highly soluble component may have a molecular weight of 80 to 10,000. The (B) highly soluble component preferably has a molecular weight of 90 to 5000, more preferably 100 to 3000. When the (B) highly soluble component is a resin, a polymer, or a polymer, the molecular weight is expressed as a weight average molecular weight (Mw).

[0229] (B) Highly soluble components can be synthesized or purchased from suppliers such as Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., and Nippon Shokubai.

[0230] In the protective film-forming liquid, the amount of the highly soluble component (B) is preferably 1 to 100 mass % and more preferably 1 to 50 mass % of the low solubility component (A).In the protective film-forming liquid, the amount of the highly soluble component (B) is even more preferably 1 to 30 mass % of the low solubility component (A).

[0231] <Solvent> The (C) solvent preferably contains an organic solvent. The (C) solvent may be volatile. Volatile means that it is more volatile than water. For example, the boiling point of the (C) solvent at 1 atmosphere is preferably 50 to 250°C. The boiling point of the solvent at 1 atmosphere is more preferably 50 to 200°C, and even more preferably 60 to 170°C. The boiling point of the solvent at 1 atmosphere is even more preferably 70 to 150°C. The (C) solvent may also contain a small amount of pure water. The amount of pure water contained in the (C) solvent is preferably 30% by mass or less relative to the total amount of the (C) solvent. The amount of pure water contained in the solvent is more preferably 20% by mass or less, and even more preferably 10% by mass or less. The amount of pure water contained in the solvent is even more preferably 5% by mass or less. A suitable embodiment is one in which the solvent does not contain pure water (0% by mass). The pure water is preferably DIW.

[0232] Examples of organic solvents include alcohols such as isopropanol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactic acid esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ-butyrolactone. These organic solvents can be used alone or in combination.

[0233] In a preferred embodiment, the organic solvent contained in the solvent (C) is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. When two organic solvents are combined, the volume ratio is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.

[0234] The content of the (C) solvent is 0.1 to 99.9% by mass relative to the total mass of the protective film-forming liquid. The content of the (C) solvent is preferably 50 to 99.9% by mass, more preferably 75 to 99.5% by mass relative to the total mass of the protective film-forming liquid. The content of the (C) solvent is further preferably 80 to 99% by mass, even more preferably 85 to 99% by mass relative to the total mass of the protective film-forming liquid.

[0235] <Other additives> The protective film-forming liquid of the present invention may further contain (D) other additives. In one embodiment of the present invention, (D) other additives may include a surfactant, an acid, a base, an antibacterial agent, a bactericide, a preservative, or an antifungal agent (preferably a surfactant), or any combination thereof.

[0236] In one embodiment of the present invention, the amount of (D) other additives (if multiple additives are present) relative to the mass of (A) low-solubility component in the protective film-forming liquid is 0 to 100 mass % (preferably 0 to 10 mass %, more preferably 0 to 5 mass %, even more preferably 0 to 3 mass %, and even more preferably 0 to 1 mass %). Another embodiment of the present invention is when the protective film-forming liquid does not contain (D) other additives (0 mass %).

[0237] <Corrosion prevention ingredients> (E) Examples of corrosion inhibitors include, in addition to BTA, uric acid, caffeine, buterin, adenine, glyoxylic acid, glucose, fructose, and mannose.

[0238] The present invention is not limited to the above-described embodiment, and can be embodied in other forms.

[0239] For example, the protective film forming liquid is not limited to those described above. For example, a resist film forming liquid or a reflective film forming liquid can be used as the protective film forming liquid. In this case, a developer can be used as the remover.

[0240] It is also possible to use, as the protective film forming liquid, a liquid containing a water-soluble polymer that forms a water-soluble film by evaporating the solvent.

[0241] The water-soluble polymer may contain at least one of the following: a cellulose-based polymer such as hydroxypropyl methylcellulose phthalate, hydroxypropyl methylcellulose acetate phthalate, hydroxypropyl methylcellulose acetate succinate, hydroxypropyl methylcellulose hexahydrophthalate, hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, cellulose acetate hexahydrophthalate, carboxymethylcellulose, ethyl cellulose, or methylcellulose; an acrylic polymer such as N,N-dimethylacrylamide, dimethylaminopropyl methacrylamide, N,N-dimethylaminopropyl acrylamide, N-methylacrylamide, diacetone acrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, acryloylmorpholine, or acrylic acid; or a vinyl-based polymer such as polyvinyl alcohol or polyvinylpyrrolidone. These water-soluble polymers may be used alone or in combination of two or more.

[0242] When a water-soluble film is used as the protective film, by using DIW as the removing liquid, the protective film is dissolved in the removing liquid and removed from the substrate W (dissolution and removal process). In this case, the supply of a rinse liquid can be omitted. Even when the protective film is composed of a low-solubility solid and a high-solubility solid, the supply of a rinse liquid can be omitted when DIW is used as the removing liquid.

[0243] In the above-described embodiment, an example was shown in which the defect measurement unit was the defect measurement device 110 separate from the substrate processing apparatus 120, but the substrate processing apparatus 120 may also be equipped with the defect measurement unit. In the above-described embodiment, an example was shown in which the processing liquid preparation unit 121 was equipped in the substrate processing apparatus 120, but the processing liquid preparation unit 121 may also be an apparatus separate from the substrate processing apparatus 120.

[0244] In addition, in the above-described embodiment, an example was shown in which the substrate processing unit that performs a predetermined process on the front surface of the substrate with a protective film formed on the back surface of the substrate is the exposure device 130 (exposure processing unit), but the process performed on the front surface of the substrate may be a process other than the exposure process.

[0245] In this specification, when a numerical range is indicated using "~" or "-", it includes both endpoints and has the same units, unless otherwise specified.

[0246] In addition, various design modifications can be made within the scope of the claims. [Explanation of symbols]

[0247] 3: Controller 4A: Coating and peeling treatment equipment 5A: First reversing unit 5B: Second reversing unit 5C: 3rd inversion unit 9A: First moving nozzle 9B: Second moving nozzle 13A: Protective film forming liquid supply unit 13B: Removal liquid supply unit 40: Common piping 41:Protective film forming liquid piping 42:Removal liquid piping 51: Protective film forming liquid valve 52: Removal liquid valve 75: Solvent tank 76: Low solubility component tank 77: Highly soluble component tank 85: Solvent piping 86:Low solubility component piping 87: Highly soluble component piping 90: Mixing section 91: Solvent pump 92: Low solubility component pump 93: Highly soluble component pump 95: Solvent flow control valve 96: Low-solubility component flow control valve 97: Highly soluble component flow control valve 100: Substrate processing system 110: Defect measurement device 120: Substrate processing equipment 121: Processing liquid preparation unit, first processing liquid preparation unit 122: Second processing liquid preparation unit 130: exposure device 140: Host computer 160: Flatness measurement section 161: Film thickness measuring instrument 165: Scan unit 200: Protective film 200A: Additional protective film 201:Liquid film 201A:Liquid film 411: First branch pipe 412: Second branch pipe 511: Valve 512: Valve C: Carrier CR1: First main transport robot CR2: Second main transport robot IR1: Indexer robot W: Substrate Wb: Back side Wf: surface

Claims

1. a defect measurement unit that measures the size of a defect on the back surface of a substrate having a front surface and a back surface; a processing solution preparation unit that prepares a processing solution having a composition according to the defect size measured by the defect measurement unit; a protective film forming unit that applies the treatment liquid prepared by the treatment liquid preparing unit to the rear surface of the substrate to form a protective film; a substrate processing unit that performs a predetermined process on the front surface of the substrate while the protective film is formed on the rear surface of the substrate; a removal processing unit that removes the protective film from the back surface of the substrate; A substrate processing system comprising:

2. 2. The substrate processing system according to claim 1, wherein the processing liquid preparation unit prepares a processing liquid having a composition that allows the protective film to be formed on the rear surface of the substrate, the protective film having a thickness corresponding to the defect size.

3. 2. The substrate processing system according to claim 1, wherein the processing liquid is a solution containing a solute and a solvent, and the processing liquid preparation unit prepares the solution having a concentration according to the defect size as the processing liquid.

4. The substrate processing system of claim 3 , wherein the solute comprises a polymer.

5. 5. The substrate processing system according to claim 1, further comprising a flatness measuring unit that measures flatness of the protective film formed by the protective film forming unit.

6. 6. The substrate processing system of claim 5, further comprising an additional protective film forming unit that supplies an additional processing liquid onto the protective film to further form an additional protective film on the protective film when the flatness measured by the flatness measuring unit exceeds a reference value.

7. the protective film forming unit applies a first polymer solution as the treatment liquid to the rear surface of the substrate; The substrate processing system according to claim 6 , wherein the additional protective film forming unit applies a second polymer solution that is incompatible with the first polymer solution as the additional processing liquid onto the protective film.

8. 8. The substrate processing system of claim 7, wherein the solvent of the first polymer solution is PGMEA (propylene glycol monomethyl ether acetate), and the solvent of the second polymer solution is IPA (isopropyl alcohol).

9. 5. The substrate processing system according to claim 1, wherein the predetermined process includes an exposure process for the surface of the substrate.

10. a defect measuring step of measuring a defect size on the back surface of a substrate having a front surface and a back surface; a processing solution preparation step of preparing a processing solution having a composition according to the defect size measured in the defect measurement step; a protective film forming step of applying the treatment liquid prepared in the treatment liquid preparing step to the back surface of the substrate to form a protective film; a substrate processing step of performing a predetermined process on the front surface of the substrate with the protective film formed on the rear surface of the substrate; a removing step of removing the protective film from the back surface of the substrate; A substrate processing method comprising:

11. 11. The substrate processing method according to claim 10, wherein the processing liquid preparation step prepares a processing liquid having a composition that allows the protective film to be formed on the rear surface of the substrate, the protective film having a thickness corresponding to the defect size.

12. 11. The substrate processing method according to claim 10, wherein the processing liquid is a solution containing a solute and a solvent, and the processing liquid preparation step prepares the solution having a concentration according to the defect size as the processing liquid.

13. The method of claim 12 , wherein the solute comprises a polymer.

14. a flatness measurement step of measuring the flatness of the protective film formed in the protective film formation step; The substrate processing method according to any one of claims 10 to 13, further comprising: an additional protective film forming step of supplying an additional processing liquid onto the protective film to further form an additional protective film on the protective film when the flatness measured by the flatness measuring step is less than a reference value.

15. the protective film forming step includes applying a first polymer solution as the treatment liquid to the rear surface of the substrate; 15. The substrate processing method according to claim 14, wherein the additional protective film forming step applies a second polymer solution, which is incompatible with the first polymer solution, onto the protective film as the additional processing liquid.

16. 16. The substrate processing method according to claim 15, wherein the solvent of the first polymer solution is PGMEA (propylene glycol monomethyl ether acetate), and the solvent of the second polymer solution is IPA (isopropyl alcohol).

17. The substrate processing method according to any one of claims 10 to 13, wherein the predetermined processing includes an exposure processing for the surface of the substrate.

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