Substrate processing system and substrate processing method

Abstract

The present disclosure provides a method for removing residues adhering to a wafer surface after a resist pattern is formed.　A substrate processing system (8) according to the present disclosure supplies a processing fluid, which is a gas or mist composed of an acid or an organic solvent, to a substrate (W) which has formed thereon a resist film that is exposed to light and is exposed to a developing fluid.

Description

Substrate processing system and substrate processing method

[0001] The present disclosure relates to a substrate processing system and a substrate processing method.

[0002] In manufacturing semiconductor devices, photolithography is performed on a semiconductor wafer (hereinafter referred to as a wafer) as a substrate. That is, a resist film is formed on the wafer, and the resist film is exposed to light and then developed. Patent Document 1 discloses a system for performing this photolithography.

[0003] JP 2013-4804 A

[0004] The present disclosure provides a technique for forming a good pattern on a resist film formed on a substrate.

[0005] The substrate processing system of the present disclosure supplies a processing fluid, which is a gas or mist composed of an acid or an organic solvent, to a substrate on which a resist film has been formed by exposure to a developing fluid.

[0006] The present disclosure makes it possible to form a good pattern in a resist film formed on a substrate.

[0007] FIG. 1 is a plan view of a wafer processing system according to a first embodiment of the present disclosure; FIG. 2 is a front view of the wafer processing system; FIG. 3 is a longitudinal sectional side view of a development processing apparatus included in the wafer processing system; FIG. 4 is a longitudinal sectional side view of a cleaning processing apparatus included in the wafer processing system; FIG. 5 is a flow diagram of processing performed in the wafer processing system; FIG. 6 is a schematic view showing a surface of a wafer; FIG. 7 is a schematic view showing a surface of a wafer; FIG. 8 is a longitudinal sectional side view of a development processing apparatus as a first modified example of the first embodiment; FIG. 9 is a longitudinal sectional side view of a cleaning processing apparatus as a third modified example of the first embodiment; FIG. 10 is a longitudinal sectional side view of a development processing apparatus included in a wafer processing system of a second embodiment; FIG. 11 is a process diagram of processing in the second embodiment; FIG. 12 is a process diagram of processing in the second embodiment; FIG. 13 is a schematic view showing a surface of a wafer; FIG. 14 is a schematic view showing a surface of a wafer; FIG. 15 is a longitudinal sectional side view of a development processing apparatus as a first modified example of the second embodiment; FIG. 16 is a longitudinal sectional side view of a development processing apparatus as a second modified example of the second embodiment; 1 is a schematic plan view showing another example of a wafer processing system; 2 is a schematic plan view showing another example of a wafer processing system;

[0008] [First Embodiment] Hereinafter, a wafer processing system as a substrate processing apparatus according to this embodiment will be described with reference to the drawings. In this specification, elements having substantially the same functional configurations are designated by the same reference numerals, and redundant description will be omitted.

[0009] <Wafer Processing System> First, the configuration of a wafer processing system according to this embodiment will be described. Figures 1 and 2 are a plan view and a front view, respectively, that schematically show the overall configuration of a wafer processing system 1. In this embodiment, the wafer processing system 1 will be described as an example of a photolithography processing system that performs a resist film forming process and a development process on wafers W.

[0010] 1, the wafer processing system 1 includes a cassette station 2 into which a cassette C containing a plurality of wafers W is loaded and unloaded, and a processing station 3 equipped with a plurality of various processing devices that perform predetermined processing on the wafers W. The wafer processing system 1 is configured by integrally connecting the cassette station 2 and an interface station 4 that transfers the wafers W between the processing station 3 and an exposure device (not shown) adjacent to the opposite side of the processing station 3. Note that, although two processing stations 3 are installed between the cassette station 2 and the interface station 4 as shown in FIG. 1, one processing station 3 or three or more processing stations may be installed.

[0011] The cassette station 2 is equipped with a plurality of cassette mounting plates 21 and wafer transfer devices 22 and 23. The cassette station 2 uses the wafer transfer device 22 or 23 to transfer wafers between the cassette C mounted on the cassette mounting plate 21 and the processing station 3. To this end, the wafer transfer devices 22 and 23 are each provided with drive mechanisms for the X direction, Y direction, vertical direction, and around the vertical axis (θ direction) as needed, and may also be provided with drive mechanisms for all directions. At least one of the wafer transfer devices 22 and 23 is capable of transferring wafers between the cassette C and the processing station 3. Note that transferring wafers to and from the processing station 3 refers to, for example, transferring wafers between the third block G3, which includes a transfer device accessible by the wafer transfer device 33 in the processing station 3 (described later). The third block G3 may also be equipped with a plurality of transfer devices (not shown) arranged vertically.

[0012] An inspection device (not shown) for inspecting the wafer W may be provided at a position accessible to either the wafer transfer device 22 or 23 .

[0013] The processing station 3 includes multiple blocks, e.g., three blocks G1, G2, and G4 (first, second, and fourth blocks). As shown in FIG. 2, multiple layers 31 each including the first and second blocks G1 and G2 are stacked vertically. For example, the first block G1 is provided on the front side of the processing station 3 (the negative X-direction side in FIG. 1), and the second block G2 is provided on the rear side of the processing station 3 (the positive X-direction side in FIG. 1). The fourth block G4 is provided on the interface station 4 side of the processing station 3 (the positive Y-direction side in FIG. 1) or at a connection point with another adjacent processing station 3. The fourth block G4 may include multiple transfer devices arranged vertically. The aforementioned third block G3 may also be provided within the processing station 3.

[0014] The first block G1 includes a plurality of processing devices, such as a patterning film forming device and a development processing device (both not shown). The patterning film forming device may include, for example, a resist film forming device and an anti-reflection film forming device.

[0015] For example, a plurality of processing devices may be arranged in a horizontal direction, and the number, arrangement, and type of these processing devices may be selected arbitrarily.

[0016] In these patterning film forming apparatuses and developing treatment apparatuses, for example, a predetermined processing liquid or a predetermined gas is supplied onto the wafer W. In this manner, the patterning film forming apparatus forms a resist film used as a mask when forming a pattern on an underlying film, or forms an anti-reflection film for efficiently performing a light irradiation process, such as an exposure process. On the other hand, in the developing treatment apparatus, a portion of the exposed resist film is removed to form the uneven shape that serves as the mask.

[0017] For example, the second block G2 is provided with vertically and horizontally aligned heat treatment devices (not shown) that perform heat treatments such as heating and cooling of the wafers W. The second block G2 also is provided with vertically (Z direction in FIG. 2) and horizontally aligned hydrophobization devices that perform hydrophobization treatment to improve the fixation of the resist liquid to the wafers W, and peripheral exposure devices that expose the peripheral portion of the wafers W, both of which are not shown. The number and arrangement of these heat treatment devices, hydrophobization treatment devices, and peripheral exposure devices can also be selected as desired.

[0018] 1, a wafer transfer area 32 is formed in an area sandwiched between the first block G1 and the second block G2 in a plan view. In the wafer transfer area 32, for example, a wafer transfer device 33 is disposed.

[0019] The wafer transfer device 33 has a transfer arm 33a that is movable in, for example, the Y direction, the front-rear direction, the θ direction, and the up-down direction. The wafer transfer device 33 moves within the wafer transfer area 32 and can transfer the wafer W to predetermined devices in the surrounding first block G1, second block G2, third block G3, and fourth block G4. When there are multiple processing stations 3 as shown in Figure 1, the wafer transfer device 33 provided in the processing station 3 located on the interface station 4 side can transfer the wafer W to predetermined devices in the first, second, and fourth blocks G1, G2, and G3, as well as the fifth block G5 described below.

[0020] A plurality of wafer transfer devices 33 are arranged vertically, for example, as shown in FIG. 2 . One wafer transfer device 33 can transfer wafers W to a predetermined device located at the height of the upper layers 31 among the multiple layers 31 stacked vertically. Another wafer transfer device 33 can transfer wafers W to a predetermined device located at the height of the multiple layers 31 located below the above layers 31. A plurality of wafer transfer areas 32 are provided to enable such transfer of wafers W. Note that the number of wafer transfer devices 33 and the number of layers 31 corresponding to one wafer transfer device 33 can be selected arbitrarily, such as by providing a wafer transfer device 33 for each layer 31.

[0021] The wafer transfer area 32, the first block G1, or the second block G2 may also include a shuttle transfer device (not shown). The shuttle transfer device linearly transfers the wafer W between a space adjacent to one side of the processing station 3 and another space adjacent to the opposite side.

[0022] The interface station 4 includes a fifth block G5 equipped with a plurality of transfer devices, and wafer transfer devices 41 and 42. The interface station 4 uses the wafer transfer device 41 or 42 to transfer the wafer W between the fifth block G5, where the wafer W is transferred by the wafer transfer device 33, and the exposure device. To this end, the wafer transfer devices 41 and 42 are each provided with drive mechanisms for the X direction, Y direction, up / down direction, and around the vertical axis (θ direction) as needed, and may also be provided with drive mechanisms for all directions. At least one of the wafer transfer devices 41 and 42 can support the wafer W and transfer the wafer W between the transfer device in the fifth block G5 and the exposure device.

[0023] A cleaning treatment device for cleaning the surface of the wafer W and the aforementioned peripheral exposure device may be provided in the interface station 4 at a position accessible to either of the wafer transfer devices 41 and 42 .

[0024] The inspection device may be provided in the cassette station 2 as described above, but it may also be provided in the processing station 3 and the interface station 4 at a position accessible to any of the transport arms (33, 41, 42 in Figure 1 or Figure 2) provided inside each station.

[0025] The wafer processing system 1 described above is provided with a control device 100. The control device 100 is, for example, a computer, and has a program storage unit (not shown). The program storage unit stores a program for controlling the processing of wafers W in the wafer processing system 1. The program storage unit also stores a program for controlling the operation of drive systems such as the various processing devices and transfer devices described above to realize wafer processing in the wafer processing system 1. The program may be recorded on a computer-readable storage medium H and installed into the control device 100 from the storage medium H.

[0026] <Operation of Wafer Processing System> The wafer processing system 1 is configured as described above. Next, an example of wafer processing performed using the wafer processing system 1 configured as described above will be described.

[0027] First, a cassette C containing a plurality of wafers W is carried into the cassette station 2 of the wafer processing system 1 and placed on the cassette mounting plate 21. Next, each wafer W in the cassette C is sequentially removed by the wafer transfer device 22 or 23 and transferred to the delivery device in the third block G3.

[0028] The wafer W transferred to the transfer device in the third block G3 is supported by the wafer transfer device 33 and transferred to the hydrophobization treatment device provided in the second block G2, where it is subjected to hydrophobization treatment. The wafer W is then transferred by the wafer transfer device 33 to the resist film forming device, where a resist film is formed on the wafer W, and then transferred to the heat treatment device, where it is pre-baked, and then transferred to the transfer device in the fifth block G5. When there are multiple processing stations 3 as shown in FIGS. 1 and 2 , the wafer W is temporarily placed in the transfer device in the fourth block G4 before being transferred to the transfer device in the fifth block G5, and then transferred between the multiple wafer transfer devices 33. If necessary, the wafer W may also be transferred by the wafer transfer device 33 to a peripheral exposure device, where the peripheral edge of the wafer is exposed.

[0029] The wafer W transferred to the transfer device in the fifth block G5 is transferred to the exposure device by wafer transfer devices 41 and 42, and is exposed to a predetermined pattern. The wafer W may be cleaned in a cleaning device before the exposure process.

[0030] The exposed wafer W is transferred to a transfer device in the fifth block G5 by the wafer transfer devices 41 and 42. Thereafter, the wafer W is transferred to a heat treatment device by the wafer transfer device 33 and subjected to post-exposure baking.

[0031] The wafer W that has been subjected to post-exposure baking is transferred by the wafer transfer device 33 to a developing treatment device and developed. After development is completed, the wafer W is transferred by the wafer transfer device 33 to a heat treatment device and subjected to post-baking.

[0032] The wafer W is then transferred by wafer transfer device 33 to the transfer device in third block G3, and then transferred by wafer transfer device 22 or 23 in cassette station 2 to a cassette C on a predetermined cassette mounting plate 21. This completes the photolithography process. Any unnecessary processing equipment listed above may not be provided, or processing in that equipment may not be performed.

[0033] To describe in more detail the processing in the wafer processing system 1, which is a substrate processing system, after the development processing is completed and before the post-bake processing, the wafer W, which is a circular substrate, is subjected to a cleaning processing in a cleaning processing device 8 to remove residues D2 generated during the development processing. As described above, the fluid used in the development processing may be a liquid or a gas, but for convenience of explanation, it will be assumed to be a liquid, and the development processing device provided in the first block G1 and which performs processing using such a developer will be described below as a development processing device 5.

[0034] If the processing station 3 is divided into two, upper and lower, into divided bodies each consisting of a plurality of layers 31, then, for example, each layer 31 constituting the upper divided body is provided with a development processing device 5. That is, in Fig. 2, dotted lines surrounding the plurality of layers 31 are shown stacked one above the other, and the development processing device 5 is provided in each layer 31 surrounded by the upper dotted line frame.

[0035] The developing treatment device 5 performs a developing process by supplying a developer to the resist film R on the wafer W, and a cleaning process for the surface of the wafer W by supplying a cleaning liquid (rinse liquid) to the wafer W in a state in which the developer has been supplied. The cleaning liquid (rinse liquid) may be any liquid capable of removing the developer from the surface of the wafer W, such as pure water. The cleaning process for removing the developer using this rinse liquid will hereinafter be referred to as a rinse process to distinguish it from a cleaning process for removing post-development residues D2 using an organic solvent.

[0036] A longitudinal side view of the development processing device 5 is shown in FIG. In the figure, reference numeral 51 denotes a spin chuck, which suction-holds the central portion of the backside of a horizontally placed wafer W. Reference numeral 52 denotes a rotation mechanism, which rotates the wafer W together with the spin chuck 51 around a vertical axis. Reference numeral 53 denotes a cup with an open top, which stores the wafer W placed on the spin chuck 51 and catches liquid that splashes or drops from the wafer W during processing. The area surrounded by the cup 53 is a processing space 54 for the wafer W. Reference numeral 55 denotes a drain port opening at the bottom of the cup 53 for removing liquid, and a member is provided within the cup 53 to guide the liquid caught in the cup 53 to the drain port 55. Reference numeral 56 denotes an exhaust port opening at the bottom of the cup 53.

[0037] In the figure, reference numeral 57 denotes a gas supply unit equipped with a filter. The gas supply unit 57 is provided directly above the cup 53 and above the movement area of ​​each nozzle, which will be described later, and supplies gas that has passed through a filter provided therein and been purified toward the cup 53. The gas is indicated by arrows in the figure. This gas may be, for example, atmospheric air. During wafer processing, the gas is supplied from the gas supply unit 57 and exhausted from the exhaust port 56, forming a downward air current toward the cup 53 and suppressing the scattering of each liquid from the wafer W.

[0038] In the figure, reference numeral 61 denotes a developing nozzle. In the figure, reference numeral 62 denotes a developer supply unit that supplies developer to the developing nozzle 61 and causes it to be discharged from the developing nozzle 61. In the figure, reference numeral 63 denotes a standby unit where the developing nozzle 61 waits outside the cup 53. In the figure, reference numeral 64 denotes a rinse nozzle. In the figure, reference numeral 65 denotes a rinse liquid supply unit that supplies rinse liquid to the rinse nozzle 64 and causes it to be discharged from the rinse nozzle 64. In the figure, reference numeral 66 denotes a standby unit where the rinse nozzle 64 waits outside the cup 53. Note that the developer supply unit 62 and the rinse liquid supply unit 65 each include, for example, a liquid storage unit, a pump, a valve, etc., and supply the liquid stored in the storage unit to the nozzle to which the liquid is to be sent by operating the pump and opening and closing the valve. Other liquid supply units described below also have the same configuration as, for example, the developer supply unit 62 and the rinse liquid supply unit 65.

[0039] The developing nozzle 61 and the rinsing nozzle 64 are each connected to a moving mechanism (not shown) and can be moved up and down and horizontally by the moving mechanism. More specifically, the developing nozzle 61 and the rinsing nozzle 64 can be moved between their respective waiting positions and above the wafer W in the cup 53, and the positions on the wafer W from which the respective solutions are ejected by these nozzles can be moved along the diameter of the wafer W.

[0040] A wafer W having a resist film R formed on its surface (top surface) is transported to the developing treatment device 5. This resist film R has been exposed by an exposure device. In the developing treatment device 5, a developing nozzle 61 discharging developer D moves from one side of the center or the periphery of the rotating wafer W to the other, forming a liquid film D1 of developer D so as to cover the entire surface of the resist film R, exposing the resist film R to the developer D. This dissolves portions R2 of the resist film R that are soluble in the developer D, forming a pattern in the resist film R. Specifically, unevenness is formed by the partially dissolved resist film R and the underlayer film R1 formed below the resist film R, and the underlayer film R1 is exposed on the surface of the wafer W so as to form the bottom surfaces of the recesses in the unevenness. Note that portions R2 are unexposed and exposed by the exposure device, respectively, when the resist forming the resist film R is a negative-type resist and a positive-type resist, respectively.

[0041] After the pattern is formed, a rinse liquid is supplied to the center of the rotating wafer W from a rinse nozzle 64 located above the center, and the rinse liquid spreads over the entire wafer W, thereby removing the developer D from the wafer W. After the supply of the rinse liquid is stopped, the wafer W continues to rotate, and the rinse liquid is shaken off, completing the processing in the developing treatment device 5. Reference numerals 71 to 74 in Fig. 3, which are not mentioned in the above description of the operation, are members for performing a cleaning process in the developing treatment device 5, and will be described in the description of the second modified example.

[0042] Next, the cleaning treatment device 8 that performs the above-mentioned cleaning treatment will be described with reference to the vertical side view of Fig. 4. If the treatment station 3 is divided into two, upper and lower, into partitions each consisting of a plurality of layers 31, this cleaning treatment device 8 is provided in each layer 31 that forms the upper partition, similar to the development treatment device 5, and is arranged, for example, in the second block G2.

[0043] The cleaning processing device 8 supplies a cleaning gas composed of an organic solvent as a cleaning fluid to the wafer W. The cleaning processing device 8 includes a wafer mounting unit 81 and an elevator 91, and the wafer mounting unit 81 and elevator 91 together form a processing vessel 82 that is circular in plan view and that houses the wafer W. The wafer mounting unit 81 includes a hot plate 83 equipped with a heater (not shown) therein, and a support member 84. The wafer W is placed on a number of protrusions 85 that are distributed on the upper surface of the hot plate 83, and is heated to a desired temperature.

[0044] The support member 84 is formed concave in vertical cross section and includes a side wall 84A that surrounds the lateral periphery of the hot plate 83 and a bottom wall 84B that supports the hot plate 83 from below. Three pins 86 are provided that penetrate the bottom wall 84B and the hot plate 83. The pins 86 are moved above and below the hot plate 83 by an elevator mechanism 87 provided outside the processing vessel 82, thereby transferring wafers W between the hot plate 83 and a transfer device that moves the wafer W onto the hot plate 83. A plurality of exhaust ports 88 are provided on the upper surface of the side wall 84A, which is formed in an annular shape in plan view. The exhaust ports 88 open along the periphery of the side wall 84A and at different positions in the radial direction of the side wall 84A.

[0045] The lifting body 91 forms a lid for the processing vessel 82, which is composed of an upper wall 91A and a side wall 91B extending downward from the periphery of the upper wall 91A, and can be raised and lowered by a lifting mechanism 90 provided outside the processing vessel 82. When processing the wafer W, the lifting body 91 is located at a lower position where the lower surface of the side wall 91B is close to the exhaust port 88, and when transferring the wafer W to the heating plate 83, the lifting body 91 is located at an upper position above the lower position. Figure 4 shows the state in which the lifting body 91 is located at the lower position.

[0046] When the lifting body 91 is in the lower position, exhaust is performed through the exhaust port 88, and the gas inside the processing vessel 82 is exhausted through the exhaust port 88, and the gas in the atmosphere outside the processing vessel 82 is exhausted through the exhaust port 88 via the gap between the lifting body 91 and the wafer loading unit 81. At this time, the gas flow formed by the atmosphere outside the processing vessel 82 prevents the gas inside the processing vessel 82 from leaking outside the processing vessel 82. In the figure, the flow of each gas is indicated by arrows.

[0047] A plate 93 is provided to divide the space surrounded by the top wall 91A and the side wall 91B into upper and lower sections, thereby forming a gas diffusion space 92 on the upper side and a processing space 80 for the wafer W on the lower side. Numerous through-holes 94 are formed in the plate 93, and the cleaning gas supplied to the diffusion space 92 is discharged into the processing space 80 in a shower-like manner, thereby being supplied to the entire surface of the wafer W. Therefore, the plate 93 forms a ceiling when viewed from the processing space 80, and the lower surface of the plate 93 is a surface on which gas discharge ports are formed. The downstream end of a gas supply path 95 is connected to the top wall 91A and opens into the diffusion space 92. The upstream end of the gas supply path 95 is connected to a cleaning gas supply unit 96.

[0048] The cleaning gas supply unit 96 generates cleaning gas by bubbling and supplies the cleaning gas to the diffusion space 92. Specifically, the cleaning gas supply unit 96 includes a storage unit 102 that stores a heatable liquid L1 made of an organic solvent, an inert gas supply unit 103 that supplies an inert gas to the storage unit 102 to volatilize the liquid L1, and a valve V1 that switches between supplying and cutting off the cleaning gas, which is a mixed gas of the volatilized liquid L1 and an inert gas, to the downstream side of the gas supply path 95. An inert gas supply unit 97 is connected to the gas supply path 95, and the inert gas can be supplied to the processing space 80 via the diffusion space 92 as a purge gas. The inert gas supply units 97 and 103 may be, for example, N ２ The inert gas supply unit 97 includes a mass flow controller for adjusting the flow rate of the inert gas (such as nitrogen gas) from its supply source downstream to a desired amount, a valve for switching on and off the supply of the inert gas to the downstream side, etc. The other inert gas supply units described later also have the same configuration as the inert gas supply units 97 and 103, for example.

[0049] To further explain the cleaning gas, let us assume that the resist film R formed on the wafer W is composed of a negative resist. An example of a negative resist is a metal oxide resist (MOR), which is a type of metal-containing resist. The MOR contains a metal, such as tin (Sn), and is exposed to extreme ultraviolet (EUV). Note that "containing a metal" refers to the inclusion of a metal as a constituent component, not as an impurity. To develop a negative resist film R such as this MOR, a developer D is used, for example, in which acetic acid, an organic acid with polar molecules, is added to PGMEA (propylene glycol methyl ether acetate), an organic solvent with nonpolar molecules. Therefore, the developer D is primarily composed of nonpolar molecules. Note that the nonpolar molecules include low-polarity molecules with relatively low polarity in addition to nonpolar molecules. To further explain MOR, in a resist film, ligands coordinated to Sn atoms are released from the Sn atoms in areas exposed by an exposure device, and the numerous Sn atoms from which the ligands have been released bond to each other via oxygen (O) atoms. In other words, Sn is oxidized to form a crosslinked structure, and a structure of -Sn-O-Sn-O-Sn-O- is formed in the exposed areas of the resist film. Note that the ratio of Sn atoms to O atoms in the crosslinked structure is not limited to 1:1. The formation of this crosslinked structure renders the exposed areas insoluble in the developer fluid, and PEB promotes the formation of this crosslinked structure. During development, the unexposed areas where no crosslinked structure is formed are removed.

[0050] In terms of the Hansen solubility parameter, compounds in the portion R2 of the resist film R that should be dissolved have a value relatively far from that of the nonpolar molecules that make up the majority of the developer D, and may remain on the surface of the wafer W as residue D2 after development. That is, residue D2 is composed of compounds that are difficult to dissolve in organic solvents with nonpolar molecules (nonpolar solvents). The solubility parameter value of such compounds is close to that of organic solvents with polar molecules (polar solvents). That is, compounds that make up residue D2 tend to have relatively high solubility in polar solvents. Therefore, in order to effectively remove residue D2, a polar solvent such as ethyl acetate or butyl acetate is used as liquid L1, which is the raw material for the cleaning gas.

[0051] On the other hand, if the resist film R is composed of a positive resist, a solution of polar molecules such as an aqueous solution of TMAH (tetramethyl ammonium hydroxide) is used as the developer D. Therefore, contrary to when the resist film R is a negative resist, the residue D2 tends to be more soluble in nonpolar solvents than in polar solvents. Therefore, in order to effectively remove the residue D2, a nonpolar solvent is used as the liquid L1. Specifically, for example, the developer D for the negative resist film R described above, which is PGMEA with acetic acid added, is used as the liquid L1 to generate the cleaning gas.

[0052] As described above, in this example, the molecules constituting the developer D and the molecules constituting the cleaning gas have an opposite relationship in terms of polarity. In other words, if the molecules constituting the developer D are either nonpolar or polar molecules, the molecules constituting the cleaning gas are the other one of nonpolar and polar molecules.

[0053] The processing performed on the wafer W will be explained below in order with reference to Fig. 5, which is a flow chart of the processing performed in the developing processing unit 5 and the cleaning processing unit 8, and Figs. 6 to 9, which schematically show changes in the surface of the wafer W. It is assumed that the wafer W has a negative resist film R formed thereon, as described above.

[0054] First, developer D is supplied to the surface of wafer W in developing treatment device 5. As described above, developer D is composed of nonpolar molecules if resist film R is negative-type, and is composed of polar molecules if resist film R is positive-type. This developer D then forms a liquid film D1 over the entire surface of wafer W (FIG. 6), dissolving portions R2 of resist film R that are soluble in developer D to form a pattern (step S1). Thereafter, a rinse liquid is supplied to wafer W to remove liquid film D1, and then the rinse liquid is removed from wafer W (FIG. 7).

[0055] Next, the wafer W is transferred to the processing vessel 82 of the cleaning processing device 8, placed on the hot plate 83, and heated to a predetermined temperature. Meanwhile, the lifting body 91 moves from an upper position to a lower position. Then, while exhaust is being performed from the exhaust port 88, cleaning gas generated from the organic solvent is discharged into the processing space 80 and supplied to the resist film R exposed on the surface of the wafer W (step S2, FIG. 8). In FIG. 8, the cleaning gas is indicated by arrows. As described above, the polarity of the molecules constituting the cleaning gas is opposite to the polarity of the molecules constituting the developer D.

[0056] Residue D2 adhering to the surface of the wafer W is dissolved by exposure to this cleaning gas and vaporized by heat transfer from the wafer W ( FIG. 9 ). The vaporized residue D2 is carried by the gas flow formed in the processing space 80 and flows into the exhaust port 88, where it is removed. Thereafter, the supply of cleaning gas to the processing space 80 is stopped, and a purge gas is supplied to the processing space 80, thereby purging the cleaning gas remaining in the processing space 80. Thereafter, the wafer W is unloaded from the processing vessel 82.

[0057] As described above, according to the wafer processing system 1, the supply of a cleaning gas containing an organic solvent removes residue D2 adhering to the uneven pattern formed by the resist film R and the underlayer film R1 after development, thereby improving the quality of the pattern. However, suppose that instead of supplying the cleaning fluid to the wafer W as a gas, a liquid is ejected from a nozzle to form a liquid flow between the nozzle and the wafer W. In this case, there is a concern that the convex portions of the pattern formed by the resist film R may collapse due to the effects of the pressure of the liquid flow and the surface tension of the liquid. However, by supplying the cleaning fluid as a gas, the convex portions of the pattern are prevented from being affected by the pressure and surface tension of the liquid flow, preventing the convex portions from collapsing, and more reliably achieving the desired uneven shape of the pattern. Therefore, the fact that the cleaning fluid is supplied to the wafer W as a gas also contributes to improving the quality of the pattern.

[0058] [First Modification of First Embodiment] While the developer fluid used to develop the resist film R has been described as developer D, it may also be a developing gas. As a first modification of the first embodiment, a configuration example of a wafer processing system 1A that performs processing using such a developing gas will be described. The difference between this wafer processing system 1A and the wafer processing system 1 is that a developing processing device 5A is provided in the position where the cleaning processing device 8 is described above, and a vertical cross-sectional side view of the developing processing device 5A is shown in FIG.

[0059] The developing treatment device 5A includes each of the components constituting the cleaning treatment device 8 and a developing gas supply unit 111 for supplying a developing gas. The developing gas supply unit 111 has a configuration generally similar to that of the cleaning gas supply unit 96 for supplying a cleaning gas, but the developing solution D is stored in a reservoir 102, and the vaporized developing solution D (developing gas) is supplied to the treatment container 82 via a gas supply path 95. As a result, the developing gas is sprayed onto the wafer W in a shower-like manner.

[0060] The processing of a wafer W in the developing treatment device 5A will be described step by step. First, the wafer W is transferred to the processing chamber 82, placed on the heating plate 83, and heated to a predetermined temperature. The lifting body 91 moves to a lower position, and a developing gas is supplied to the processing space 80 while exhaust is being performed through the exhaust port 88. Due to the action and heating of the developing gas, the portion R2 of the resist film R that is soluble in the developing gas is dissolved and vaporized, and then removed through the exhaust port 88. As a result, a pattern is formed on the resist film R as shown in FIG. 7 . After the supply of the developing gas is stopped, a cleaning gas and a purge gas are supplied in sequence, as in the process described for the cleaning treatment device 8. As shown in FIGS. 8 and 9 , residue D2 is removed from the surface of the wafer W, and then the cleaning gas remaining in the processing space 80 is purged. Therefore, in the developing treatment device 5A of the first modified example, the cleaning gas is supplied to the pattern formed by the exposed portion of the resist film R that is not covered with the liquid, as in the cleaning treatment device 8 of the first embodiment, thereby removing the residue D2.

[0061] As described above, in the wafer processing system 1 of the first embodiment, the developing and cleaning processes are performed in distinct processing spaces, namely, the processing space 54 (first processing space) in the cup 53 of the developing processing device 5 and the processing space 80 (second processing space) in the processing container 82 of the cleaning processing device 8, which are separate from each other and require transport by a wafer transport device. In contrast, in the wafer processing system 1A of the first modified example, the developing and cleaning processes are performed in the same processing space 80. By performing the processes in the same processing space 80 in this manner, the wafer processing system 1A can reduce the number of wafer W transport steps required to complete photolithography within the system compared to the wafer processing system 1, thereby improving throughput.

[0062] It is also possible to supply a purge gas into the processing space 80 after the supply of the developing gas is stopped and before the supply of the cleaning gas is started, so that the developing gas is removed from the processing space 80 and then the cleaning gas is supplied to the processing space 80. Furthermore, the supply of the cleaning gas does not necessarily have to be started after the supply of the developing gas into the processing space 82 is stopped, and the supply of the cleaning gas may be started before the supply of the developing gas is stopped.

[0063] [Second Modification of First Embodiment] The cleaning fluid may be mist instead of gas. In a wafer processing system 1B according to the second modification of the first embodiment, the developing treatment, rinsing treatment, and cleaning treatment (residue D2 removal treatment) are performed in the developing treatment device 5 described in FIG. 3 , and mist is used in the cleaning treatment. The cleaning nozzle 71 shown in FIG. 3 is a nozzle for discharging mist and is connected to a movement mechanism, similar to the developing nozzle 61 and the rinsing nozzle 64. The movement mechanism allows the cleaning nozzle 71 to move between a waiting section 73 provided outside the cup 53 and above the wafer W, and the position from which the mist is discharged (the position of the nozzle discharge port projected onto the wafer W in the discharge direction) can be moved along the diameter of the wafer W.

[0064] The cleaning nozzle 71 is connected to a cleaning liquid supply unit 72, and liquid L1, which is an organic solvent, is supplied to the cleaning nozzle 71 from a reservoir in the cleaning liquid supply unit 72. The cleaning nozzle 71 is also connected to an inert gas supply unit 74, and when the liquid L1 is supplied to the cleaning nozzle 71, an inert gas is supplied from the inert gas supply unit 74 to the cleaning nozzle 71. The liquid flow of the liquid L1 supplied to the cleaning nozzle 71 is broken up and atomized by the inert gas, and the liquid L1 is ejected downward as a mist.

[0065] The processing steps for wafer W in developing treatment device 5 in this second modified example will now be described. After the developing treatment and rinsing treatment are performed as described with reference to Figures 6 and 7 and the rinsing liquid is removed from wafer W, a mist of liquid L1 is ejected from cleaning nozzle 71 positioned above rotating wafer W. While ejecting the cleaning mist, cleaning nozzle 121 moves from one side of the center or the periphery of rotating wafer W to the other, supplying the cleaning mist to the entire surface of wafer W and dissolving residue D2. The dissolved residue D2 is exposed to gas flowing into cup 53 and volatilizes, and is removed from wafer W.

[0066] Because the liquid L1 is discharged as a mist, it quickly volatilizes and is removed from the surface of the wafer W after being supplied to the wafer W. This reduces stress on the convex portions of the pattern on the resist film R compared to when the liquid L1 is supplied as a liquid flow from a nozzle, just like when the liquid L1 is supplied as a gas. This prevents the convex portions from collapsing, allowing for a good pattern shape to be obtained. Furthermore, in this second modification, the development and cleaning processes are performed in the same processing space 54, so, like the first modification, the number of wafer W transfer steps required to complete photolithography within the system is reduced. This improves throughput.

[0067] [Third Modification of First Embodiment] A wafer processing system 1C according to a third modification of the first embodiment differs from the wafer processing system 1 in that a cleaning processing device 8A is provided instead of the cleaning processing device 8. This cleaning processing device 8A will be described with reference to the vertical cross-sectional side view of Figure 11, focusing on the differences from the cleaning processing device 8. The cleaning processing device 8A supplies cleaning gas only to the peripheral portion of the wafer W, out of the central portion and the peripheral portion.

[0068] The diffusion space 92 in the cleaning processing apparatus 8A, which is circular in plan view, is radially divided by a partition 121, which is annular in plan view and disposed between the plate 93 and the upper wall 91A, to form a central region 92A and a peripheral region 92B, which respectively overlap the central and peripheral portions of the hot plate 83 in plan view. The central region 92A and the peripheral region 92B also overlap the central and peripheral portions of the wafer W when the wafer W is placed on the hot plate 83 and when a cleaning gas is supplied. The downstream end of a gas supply path 95 opens in the peripheral region 92B, so that cleaning gas and a purge gas, which is an inert gas, are supplied to the peripheral region 92B, similar to the diffusion space 92 in the cleaning processing apparatus 8. The downstream end of a gas supply path 122 opens in the central region 92A. The upstream end of the gas supply path 122 is connected to an inert gas supply unit 123, and an inert gas is supplied to the central region 92A as a purge gas.

[0069] The processing steps performed in the cleaning processing apparatus 8A will now be described. With the lifting body 91 in its upper position, a wafer W is placed on pins 86 whose tips protrude above the heating plate 83, and the wafer W is heated by radiant heat from the heating plate 83. As the lifting body 91 moves to its lowered position, the wafer W approaches the plate 93 and moves away from the protrusions 85. With exhaust from the exhaust port 88, a purge gas is supplied to the central region 92A, and a cleaning gas is supplied to the peripheral region 92B.

[0070] The cleaning gas discharged to the peripheral portion of the wafer W from the through holes 94 communicating with the peripheral region 92B flows over the peripheral portion of the wafer W toward the outer periphery of the wafer W due to exhaust from the exhaust port 88 and is removed through the exhaust port 88. The purge gas discharged to the central portion of the wafer W from the through holes 94 communicating with the central region 92A flows over the peripheral portion of the wafer W toward the outer periphery of the wafer W due to exhaust from the exhaust port 88 and is removed through the exhaust port 88. The flow of the purge gas prevents the cleaning gas supplied to the surface of the wafer W from flowing toward the central portion of the wafer W, and dissolves and removes residue D2 on the peripheral portion of the wafer W. Furthermore, since the wafer W is close to the plate 93 on which the gas discharge ports (through holes 94) are formed, diffusion of the cleaning gas toward the central portion of the wafer W is suppressed. Therefore, the area of ​​the wafer W to which the cleaning gas is supplied is kept at the periphery by the support of the pins 86 in addition to the action of the purge gas.

[0071] Thereafter, the supply of cleaning gas to the peripheral region 92B is stopped, and instead, an inert gas is supplied to the peripheral region 92B as a purge gas. That is, purge gas is supplied from the central region 92A and the peripheral region 92B, and the cleaning gas remaining in the processing space 80 is purged. Then, the pins 86 are lowered, and the wafer W is placed on the heating plate 83, and the temperature of the wafer W is increased. As a result, the dissolved residue D2 remaining on the surface of the wafer W is vaporized, flows toward the exhaust port 88, and is removed. Thereafter, the wafer W is unloaded from the processing vessel 82.

[0072] If the adhesion of residue D2 to the central portion of the wafer W after the development process is suppressed while the adhesion of residue D2 to the peripheral portion is relatively large, the above-described cleaning processing device 8A can be used to remove residue D2 while avoiding the supply of cleaning gas to the central portion of the wafer W where the supply of cleaning gas is not necessary. Suppose that the supply of cleaning gas may cause a slight change in the shape of the pattern of the resist film R. In this case, the cleaning processing device 8A can limit the area where the shape change may occur to the peripheral portion of the wafer W. Furthermore, the cleaning gas can be supplied only to the area of ​​the peripheral portion of the wafer W where semiconductor devices are not formed (non-device formation area), i.e., the cleaning gas is not supplied to the pattern. For these reasons, processing in the cleaning processing device 8A is preferable for forming a good pattern.

[0073] Alternatively, the wafer W may be placed on the heating plate 83, the temperature of which is rapidly increased, and then the pins 86 may be raised to bring the wafer W close to the plate 93, and purge gas and cleaning gas may be supplied to the center and peripheral edge of the wafer W. Thereafter, for example, the gas supplied from the peripheral region 92B may be switched to purge gas while the pins 86 are kept raised, and the cleaning gas in the processing space 80 may be purged.

[0074] [Regarding cleaning fluids] Ethyl acetate and butyl acetate are given as examples of cleaning fluids when using a negative resist, and PGMEA with added acetic acid is given as an example of cleaning fluid when using a positive resist. In other words, cleaning fluids for each resist are exemplified as those derived from acids. More specifically, these examples are carboxylic acids or ester compounds obtained by condensation reaction of carboxylic acids. However, cleaning fluids are not limited to those derived from acids.

[0075] As described above, a developing fluid consisting of non-polar molecules is used for a negative resist, so it is preferable to use an organic solvent consisting of polar molecules as the cleaning fluid. Examples of organic solvents with polar molecules include methanol, ethanol, isopropyl alcohol, glycerin, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, methylene chloride, trichloroethylene, perchloroethylene, chlorobenzene, methyl formate, dimethyl sulfoxide, ethylene carbonate, and N-methyl-2-pyrrolidone.

[0076] As described above, since a developing fluid consisting of polar molecules is used for a positive resist, it is preferable to use an organic solvent consisting of nonpolar molecules as the cleaning fluid. Examples of organic solvents consisting of nonpolar molecules include hexane, cyclohexane, liquid paraffin, benzene, toluene, and xylene. Each of the organic solvents listed above may be supplied as a cleaning gas or a cleaning mist. The cleaning gas and cleaning mist correspond to the gas and mist of the processing fluid, respectively.

[0077] In the above example, a compound in which acetic acid is added to PGMEA (i.e., a polar compound is added to a nonpolar compound) is used to clean a wafer W having a positive resist film R formed thereon. Conversely to the case of cleaning a wafer W having a negative resist film R formed thereon, a compound in which a polar compound is added to a nonpolar compound may be used. However, when adding a polar compound to one of the polar and nonpolar compounds (i.e., adding a compound of opposite polarity) in this manner, if the amount added is too large, the dissolving effect of the residue D2 decreases. Therefore, it is preferable that the amount added be, for example, 20% by mass or less of the total. Therefore, when PGMEA to which acetic acid is added is used as the liquid L1 that generates the cleaning gas or cleaning mist, the content of the acetic acid is preferably 20% by mass or less of the liquid L1.

[0078] Although it has been described above that it is preferable to use an organic solvent of a compound having an opposite polarity to the compound constituting the developer fluid as the cleaning fluid, the cleaning fluid is not limited to having an opposite polarity to that of the developer fluid. A different compound having a polarity not opposite to that of the developer fluid may be used as the cleaning fluid, or the same compound as the developer fluid may be used as the cleaning fluid. The reason why the polarity does not need to be reversed is that even if residue D2 remains undissolved in one of the polar and nonpolar compounds during the development process, the other compound may have solubility in residue D2, and the supply of the other compound during the cleaning process may be sufficient to completely dissolve residue D2. In other words, if the other compound is supplied in the cleaning process as in the development process, the cleaning process extends the time of exposure to the other compound, thereby dissolving residue D2.

[0079] In the development process and cleaning process, if the location where the fluid is supplied or the type of fluid (mist or gas) supplied is changed, as in the example in which the development processing device 5 of the first embodiment supplies the developer and the cleaning processing device 8 supplies the cleaning gas, the period before the change and the period after the change correspond to the development processing, respectively. Even if the location where the fluid is supplied or the type of fluid supplied is not changed, as in the development processing device 5A of the first modified example, if the compound of the supplied fluid or the concentration of the compound is changed, the period before the change and the period after the change correspond to the development processing, respectively. To give a specific example of changing the concentration of the compound, for example, in the development processing device 5A of the first modified example described in FIG. 10, the same liquid L1 is stored in the gas supply units 96 and 111 and processing is performed, but the temperatures of the liquid L1 stored in the gas supply units 96 and 111 are made different to generate differences in the vaporization efficiency of the liquid L1. During development, a gas having a high concentration of the compounds constituting the liquid L1 is supplied to the wafer W from one of the gas supply units 96, 111, and during cleaning, a gas having a low concentration of the compounds constituting the liquid L1 is supplied to the wafer W from the other gas supply unit 96, 111 so as to minimize the impact on the pattern shape.

[0080] [Other Matters Related to the First Embodiment and Its Modifications] The development process may be performed using either the developer D or the developer mist as the developing fluid, and the wafer W that has been developed using either of these developing fluids may be cleaned using either a cleaning gas or a cleaning mist. Therefore, although an example has been shown in which a cleaning mist is supplied to the wafer W in the development processing device 5 to which the developer D is supplied as the developing fluid, a cleaning gas may be supplied instead of the cleaning mist. Furthermore, although the description has been given of a device including a processing container 82 such as the cleaning processing device 8 in which a cleaning gas is supplied to the wafer W, a cleaning mist may be supplied instead of the cleaning gas.

[0081] Furthermore, as exemplified in the wafer processing system 1 of the first embodiment, a system configuration may be adopted in which the development process and the cleaning process are performed in different apparatuses, and the wafer is transported between the apparatuses by a wafer transport mechanism. In such a system configuration, for example, the wafer W transported from the development process is prevented from passing through a heat treatment device equipped with a hot plate before being transported to the cleaning process device 8, thereby preventing the residue D2 from being solidified by heating in the heat treatment device and becoming difficult to remove. Note that the above-mentioned hot plate heats the wafer W placed thereon, similar to the hot plate 83 of the development process device 5.

[0082] The cleaning processing devices 8 and 8A may also be used to clean the surface of the wafer W before the formation of a patterning film, including a resist film R. By cleaning in this manner and removing foreign matter adhering to the surface of the wafer W, the occurrence of processing defects due to the foreign matter can be prevented. Although the positions of the cleaning processing devices 8 and 8A within the system have been illustrated, they may be disposed in any position depending on the role of the cleaning processing devices 8 and 8A. In this case, when cleaning the surface of the wafer W before the formation of a patterning film, for example, instead of being disposed within the upper dotted frame in FIG. 2, the cleaning processing devices 8 and 8A may be disposed within the lower dotted frame in FIG. 2, as with the patterning film forming device.

[0083] Second Embodiment A wafer processing system 1D of the second embodiment will be described, focusing on the differences from the wafer processing system 1 of the first embodiment. The wafer processing system 1D is provided with a developing treatment device 5B that forms a positive resist film R by a patterning film forming device and develops the resist film R using a developer D. The developing treatment device 5B has a configuration generally similar to that of the developing treatment device 5 described in FIG. 3, but in order to develop the resist film R, an aqueous solution of, for example, TMAH is supplied to the wafer W as the developer D. Therefore, the developer D is alkaline.

[0084] When developing the wafer W with this developer D, the progress of the development reaction (the dissolution reaction of the portion R2 soluble in the developer D, as described in FIG. 6 ) varies across the wafer W, resulting in variations in the CD (Critical Dimension) of the resist pattern. In this example, the progress is higher in the central portion of the wafer W than in the peripheral portion. The development processing unit 5B supplies a processing gas containing acid (hereinafter referred to as acid gas) exclusively to the central portion to neutralize the developer D and slow down the rate of progress of the development reaction. This increases the uniformity of the progress of development across the wafer W and suppresses the above-mentioned CD variations.

[0085] 12, which is a longitudinal side view of the development processing device 5B, the differences from the development processing device 5 in FIG. 3 will be mainly described. In the development processing device 5B, an acidic gas nozzle 131 for ejecting acidic gas is provided instead of the cleaning nozzle 71 for ejecting cleaning mist, and a standby unit 73 is used to standby the acidic gas nozzle 131. The acidic gas nozzle 131 is connected to a moving mechanism in the same manner as the cleaning nozzle 71. Therefore, the position on the wafer W from which the acidic gas is ejected (the position when the nozzle outlet is projected onto the wafer W in the ejection direction) can be moved along the diameter of the wafer W.

[0086] An acidic gas is supplied to the acidic gas nozzle 131 from an acidic gas supply unit 132. This acidic gas supply unit 132 stores an acid-containing liquid L2 instead of the organic solvent liquid L1. The acidic gas supply unit 132 has a configuration similar to that of the cleaning gas supply unit 96 of the first embodiment, except that the acidic gas is generated by vaporizing the liquid L2. If the neutralization reaction proceeds excessively, the development process of the resist film R may become impossible or a large amount of salt may be generated, resulting in residue D2. To prevent such problems, an aqueous solution containing a weakly acidic compound, such as various carboxylic acids such as acetic acid or phosphoric acid, is used as the liquid L2, and the pH is adjusted to be lower than 7 and higher than 5, for example. When acetic acid is used, the neutralization reaction with the developer D generates salts such as calcium acetate, sodium acetate, potassium acetate, zinc acetate, and magnesium acetate. However, these salts are highly soluble in the developer D, which prevents the salts from becoming residue D2, making this preferable.

[0087] The processing in the development processing unit 5B will be described with reference to the process diagrams in FIGS. 13 to 15 and the schematic diagrams in FIGS. 16 to 19 showing the surface of the central portion of the wafer W. W0 in the figures indicates the semiconductor device formation region on the wafer W, and therefore the region where the uneven pattern is formed. Within the semiconductor device formation region W0, the region where the development reaction is suppressed by the acidic gas is referred to as the neutralization region W1. As described above, in this example, the neutralization region W1 is the central portion of the wafer W. Within the semiconductor device formation region W0, the region outside the neutralization region W1 is referred to as the outer region W2. In FIGS. 16 to 19, the neutralization region W1 is shown on the left and the outer region W2 is shown on the right. In some of FIGS. 16 to 19, the acidic gas is indicated as G and the rinse liquid is indicated as L3.

[0088] First, as shown in Fig. 6 of the first embodiment, a liquid film D1 of the developer D is formed on the wafer W by the rotation of the wafer W and the discharge of the developer D from the developing nozzle 61 that moves along the diameter of the wafer W, and the dissolution of the portion R2 of the resist film R that is soluble in the developer D progresses. Meanwhile, the acidic gas nozzle 131 is positioned above the wafer W so that the position from which the acidic gas is discharged is located at the peripheral edge of the neutralization region W1 (Figs. 13 and 16).

[0089] While the wafer W is rotating at a relatively low rotational speed so as not to remove the liquid film D1 of the developer D by centrifugal force (i.e., so that the resist film R is continuously covered with the liquid film D1 and exposed to the developer D), acidic gas is discharged from the acidic gas nozzle 131 toward the peripheral edge of the neutralization region W1. Then, while the wafer W continues to rotate and the discharge of acidic gas continues, the acidic gas nozzle 131 moves toward the center of the wafer W (FIG. 14). When the acidic gas nozzle 131 reaches the center of the wafer W and the acidic gas is supplied to the entire neutralization region W1, the discharge of acidic gas from the acidic gas nozzle 131 stops (FIG. 15).

[0090] In the neutralization region W1, the acidic gas G supplied to the surface penetrates into the liquid film D1, and the developer D in the neutralization region W1 is neutralized (the concentration of TMAH decreases), thereby decreasing the dissolution rate of the resist film R ( FIG. 17 ). Note that this decrease in the dissolution rate may also mean that the dissolution rate becomes zero, i.e., the dissolution reaction stops, and the dissolution reaction may stop in this way.

[0091] In this way, the dissolution rate decreases in the neutralization region W1, while the dissolution rate is maintained in the outer region W2, and the CD of the pattern of the resist film R is aligned between the neutralization region W1 and the outer region W2 (FIG. 18). Thereafter, as described in the first embodiment, rinse liquid L3 is supplied to the wafer W, and the liquid film D1 of the developer D is removed from the wafer W (FIG. 19). That is, upon completion of the development process, a rinse process is initiated. Thereafter, the rinse liquid L3 is shaken off by the rotation of the wafer W, and the process in the development processing unit 5B is completed.

[0092] Suppose that, when neutralizing the developer D as described above, acid-containing liquid L2 is supplied to the liquid film D1 of the developer D by ejecting it from a nozzle to form a liquid flow. In this case, the liquid flow causes relatively large agitation of the developer D and the liquid L2, which could result in the acid spreading over a relatively wide area from the position where the liquid L2 is ejected onto the wafer W. However, in the development processing apparatus 5B, an acidic gas generated from the liquid L2 is supplied to the liquid film D1 of the developer D, eliminating such agitation due to the liquid flow and preventing the acid from spreading over a wide area from the position where the acidic gas is supplied. Furthermore, since the acid is supplied as a gas to the liquid film D1 of the developer D, some of the acid penetrates from the surface of the liquid film D1 into the interior of the liquid film D1 and causes a neutralization reaction, while the other part does not penetrate and is removed from the periphery of the wafer W by exhausting the gas from the cup 53. Therefore, compared to when the acid is supplied by forming a liquid flow from a nozzle, the amount of acid supplied can be kept to a small amount, making it easier to prevent excessive suppression of the development reaction. As described above, in the developing treatment device 5B, unnecessary spread of acid from the neutralization region W1 where acid is supplied can be suppressed, and the amount of acid supplied in the neutralization region W1 can be made appropriate. Therefore, as described above, it is possible to improve the CD uniformity of the pattern of the resist film R within the surface of the wafer W. In other words, it is possible to make the pattern excellent.

[0093] Although the neutralization region W1 has been described as being set at the center of the wafer W, this is not a limitation, and the neutralization region W1 may be set at, for example, the peripheral edge of the wafer W. In this case, the acidic gas nozzle 131, which is discharging acidic gas above the peripheral edge of the rotating wafer W, may be moved along the radial direction of the wafer W so that the acidic gas is supplied only to the peripheral edge of the wafer W. Alternatively, the neutralization region W1 may be set at an intermediate region between the peripheral edge and the center of the wafer W. When supplying acidic gas to a portion of the wafer W as described above, the acidic gas nozzle 131 discharging acidic gas is not limited to being moved from the peripheral edge to the center of the wafer W, but may be moved from the center to the peripheral edge.

[0094] Incidentally, a nozzle that ejects a mist containing acid may be provided instead of the acid gas nozzle 131 to perform the same process as in the above-described example. This nozzle (hereinafter referred to as the acid mist nozzle) may have a configuration similar to that of the cleaning nozzle 71 (see FIG. 3 ) in the second modified example of the first embodiment. That is, the acid-containing liquid L2 and the inert gas may be supplied from their respective supply units to the acid mist nozzle, and the liquid L2 converted into a mist by the inert gas may be ejected as a mist.

[0095] In this way, when the acid is supplied as a mist, as in the case of supplying the acid as a gas, compared to when a liquid flow of the acid is formed from a nozzle, the spread of the acid from the discharge position is suppressed and a small amount of acid can be supplied, so that the development reaction can be suppressed to a desired degree in a desired region on the surface of the wafer W. As a result, the uniformity of the pattern on the surface of the wafer W can be improved.

[0096] [First Modification of Second Embodiment] Next, a wafer processing system 1E, which is a first modification of the second embodiment, will be described. This wafer processing system 1E includes a development processing device 5C instead of the development processing device 5B described in FIG. 12, and FIG. 20 is a vertical cross-sectional side view of the development processing device 5C. This development processing device 5C has the same configuration as the development processing device 5B, except that it does not include the acidic gas nozzle 131 and instead ejects an acidic gas from a gas supply unit 57. In this example, the central portion of the wafer W will also be described as being set as the neutralization region W1.

[0097] The interior of the gas supply unit 57 of the development processing apparatus 5C is partitioned into a central region 141 and a peripheral region 142 located above the center and peripheral region of the wafer W, respectively. To the central region 141, an acidic gas is supplied from an acidic gas supply unit 132, and a gas, such as atmospheric air, is supplied from a gas supply mechanism 143 equipped with a fan or the like. To the peripheral region 142, atmospheric air is supplied from the gas supply mechanism 143. The gas supplied to the central region 141 flows toward the center of the wafer W on the spin chuck 51, i.e., toward the neutralization region W1, and the gas supplied to the peripheral region 142 flows toward the outer region W2.

[0098] During processing of the wafer W, atmospheric air is constantly supplied from the central region 141 and the peripheral region 142, forming a downward air current from the gas supply unit 57 toward the cup 53. During the period described in the second embodiment in which an acidic gas is supplied to the wafer W, the acidic gas is supplied from the central region 141 together with atmospheric air. During this supply of the acidic gas, the wafer W may be stationary and not rotated. In the developing treatment device 5C described above, similar to the developing treatment device 5B, the acidic gas is supplied only to the neutralization region W1 in the center of the wafer W, thereby neutralizing the developer D and aligning the CD of the pattern of the resist film R within the surface of the wafer W.

[0099] In the gas supply unit 57 of this first modified example, the arrangement of the members that divide the interior and the connection position of the acidic gas supply part 132 can be set appropriately, so that the region on the wafer W to which the acidic gas is supplied can be set at any position. Therefore, in this first modified example as well, the neutralization region W1 is not limited to being set at the center of the wafer W, and can be set at any position. The configuration of the gas supply unit 57 of this first modified example may also be applied to the development processing apparatus 5B of the second embodiment. In other words, the apparatus may be configured so that the acidic gas is supplied from both the gas supply unit 57 and the acidic gas nozzle 131 to a desired region set as the neutralization region W1 within the surface of the wafer W.

[0100] [Deviation in Acid Supply Amount] In the second embodiment and its first modification, acid gas or acid mist is supplied only to the neutralized region W1 in order to suppress the development reaction in the neutralized region W1 more than the development reaction in the outer region W2. However, the supply of acid gas or acid mist to suppress CD variations within the surface of the wafer W is not limited to this limited supply. Specifically, acid gas or acid mist is supplied to both the neutralized region W1 and the outer region W2 that constitute the semiconductor device formation region W0, but the amount of acid supplied per unit area to the neutralized region W1 may be greater than that to the outer region W2.

[0101] A specific method for providing such a deviation in the amount of acid supplied will be described below, assuming that the central portion of the wafer W is the neutralization region W1. The acid gas nozzle 131 of the development processing device 5B (see FIG. 12 ) is moved from the peripheral edge of the wafer W, which is rotating at a constant speed, to the center of the wafer W while discharging acid gas. While the discharge position of the acid gas from the acid gas nozzle 131 on the wafer W (the position of the nozzle discharge port projected onto the wafer W in the discharge direction) is located in the outer region W2, the acid gas nozzle 131 is moved at a first speed. Then, while the discharge position of the acid gas is located in the neutralization region W1, the acid gas nozzle 131 is moved at a second speed slower than the first speed. In this manner, the amount of acid supplied per unit area may be greater in the neutralization region W1 than in the outer region W2. In addition, instead of keeping the movement speed of the acid gas nozzle 131 constant, the rotation speed of the wafer W may be changed so that the amount of acid supplied per unit area is different between the neutralization region W1 and the outer region W2.

[0102] Furthermore, in the development processing apparatus 5C of the first modified example (see FIG. 20 ), the central region 141 and the peripheral region 142 of the gas supply unit 57 are each connected to a separately provided acidic gas supply part 132. The acid concentration contained in the liquid L2 of the acidic gas supply part 132 connected to the central region 141 is set to be higher than the acid concentration contained in the liquid L2 of the acidic gas supply part 132 connected to the peripheral region 142. In other words, by setting the acid concentration to be higher in the acidic gas supplied to the neutralization region W1 in the center of the wafer W than in the acidic gas supplied to the outer region W2, the amount of acid supplied per unit area to the neutralization region W1 may be greater than that to the outer region W2.

[0103] As described above, the development reaction within the surface of the wafer W can be adjusted by providing a deviation in the supply time of the processing fluid (acid gas or acid mist) per unit area or the concentration of acid in the processing fluid supplied per unit area between the neutralization region W1 and the outer region W2.

[0104] [Second Modification of Second Embodiment] Next, a wafer processing system 1F, which is a second modification of the second embodiment, will be described. This wafer processing system 1F is configured similarly to the wafer processing system 1A, which is the first modification of the first embodiment, except that it includes a development processing device 5D instead of the development processing device 5A (see FIG. 10). FIG. 21 is a vertical cross-sectional side view of the development processing device 5D. The development processing device 5D is configured generally similarly to the development processing device 5A, but in addition to the development gas, the acidic gas described in the second embodiment is supplied. In this second modification, the acidic gas is supplied to the entire surface of the wafer W after the development gas has been supplied, thereby stopping the development reaction on the entire surface.

[0105] The development treatment device 5D differs from the development treatment device 5A in that an acidic gas supply unit 151 is provided instead of the cleaning gas supply unit 96. The acidic gas supply unit 151 has the same configuration as the cleaning gas supply unit 96, except that an acid-containing liquid L2 is stored in place of the organic solvent liquid L1, and an acidic gas generated from the liquid L2 is supplied to the treatment container 82.

[0106] The process performed in the developing treatment device 5D will now be described. First, as in the developing treatment device 5A, a developing process is performed in a treatment container 82 that has been evacuated through an exhaust port 88 by supplying a developing gas to a wafer W heated by a heating plate 83, thereby forming a pattern on a resist film R. Then, when the supply of the developing gas into the treatment container 82 is stopped, an acidic gas is supplied into the treatment container 82 while the heating and evacuation of the wafer W continues.

[0107] A neutralization reaction occurs over the entire surface of the wafer W between the molecules of the acidic gas and the molecules of the developing gas adsorbed to the wafer W, thereby stopping the developing reaction. The developing gas remaining in the processing vessel 82 without adhering to the wafer W is also neutralized. The product of the neutralization reaction is vaporized by heat transfer and radiant heat from the wafer W. Thereafter, the supply of the acidic gas into the processing vessel 82 is stopped, and a purge gas is supplied into the processing vessel 82, thereby removing the acidic gas and reaction product gas remaining in the processing vessel 82.

[0108] In this way, in the developing treatment device 5D, the action of the acidic gas can stop the development reaction more reliably and more quickly than when the developing gas is removed from around the wafer W only by exhausting the processing vessel 82 without supplying the acidic gas. Therefore, excessive development reaction can be suppressed, and the CD of the pattern on the resist film R can be more reliably set to a desired value. Therefore, the pattern can be made good. Note that, as shown in the second embodiment and the second modified example, supplying an acidic processing fluid to a resist film exposed to an alkaline developing fluid includes supplying the processing fluid to the resist film while it is exposed to the processing fluid, as well as supplying the processing fluid to the resist film after it has been exposed.

[0109] It should be noted that the development reaction may be stopped in this development processing apparatus 5D by introducing an acid mist instead of an acid gas into the processing vessel 82 and supplying the acid mist instead of the acid gas to the wafer W. In stopping the development reaction in this manner, supplying an acid as a gas or mist is advantageous over supplying a liquid flow of acid to the wafer W, since it can suppress collapse of the convex portions of the formed pattern.

[0110] [Other Matters Related to the Second Embodiment] Incidentally, in the developing treatment device 5B of the second embodiment (see FIG. 12) and the developing treatment device 5C of its first modified example (see FIG. 20), the development reaction may be stopped, as in the second modified example, by supplying an acidic gas to the entire surface of the wafer W. In other words, the development treatment may be stopped by supplying an acidic gas before supplying a rinse liquid to the wafer W.

[0111] When stopping the development process in this manner, in the development processing apparatus 5B, the acidic gas nozzle 131 may be moved and the wafer W may be rotated so that the acidic gas is supplied to the entire semiconductor device formation region W0. The acidic gas nozzle 131 may have a long outlet that is long in a plan view, so that the acidic gas is supplied to the entire semiconductor device formation region W0 without rotating the wafer W. As described above, the nozzle may discharge an acidic mist instead of the acidic gas. In the development processing apparatus 5C, the acidic gas supply unit 132 may be connected to both the central region 141 and the peripheral region 142 of the gas supply unit 57, so that the acidic gas is supplied from the central region 141 and the peripheral region 142.

[0112] [Supplementary Notes on the First and Second Embodiments and Each Modification] The post-exposure bake (PEB) and development treatment of the resist film may be repeated any number of times. For example, the number of repetitions may be set to two, and the treatments may be performed in the order of PEB, development, PEB, and development. When repeated twice in this manner, the first PEB and development treatment is a treatment performed to form the general shape of the pattern, and the second PEB and development treatment is a treatment performed to modify the shape of the pattern to the desired shape.

[0113] The first and second embodiments and their modifications have been described assuming that no pattern is formed on the resist film R at the start of the development process. That is, the first and second embodiments and their modifications have been described assuming that the first development process and the associated cleaning process are performed, but they may also be performed in subsequent development processes or associated cleaning processes. Regarding the developer fluid used in each development process, it is optional whether to form a liquid film D1 of developer D or to supply a developer gas. For example, when performing two development processes, it is preferable to form a liquid film D1 in the first development process by supplying a large amount of developer D components to enable rapid development, and to use a developer gas in the second development process so that a small amount of developer D components can be supplied and the surface shape can be easily controlled.

[0114] [Wafer Processing System in Which Cassettes are Transported Between Apparatuses] For convenience, in the following description, what has been described as a processing apparatus will be referred to as a processing module, and what has been described as a wafer transport apparatus will be referred to as a wafer transport mechanism. The wafer processing system may be configured to perform the above-described photolithography by transporting cassettes C between multiple apparatuses, each of which may include a cassette station 2 and a processing station 3, or by connecting cassette station 2 to an exposure apparatus. In other words, the processing modules (processing apparatuses) described above as being installed in wafer processing systems 1, 1A-1F to perform photolithography may be distributed among multiple apparatuses to which cassettes C are transported, and the wafer processing system may be configured from these multiple apparatuses.

[0115] Any of the multiple devices that make up the wafer processing system is equipped with an interface station 4, and the exposure device is connected to a cassette station 2 or a processing station 3 via the interface station 4. A cassette station 2 is provided in each device, and devices that are not connected to an exposure device are made up of a cassette station 2 and a processing station 3. A control device (controller) 100 is provided for each device. Cassettes C are transported between load ports LP of different devices by a transport mechanism (hereinafter referred to as the factory transport mechanism) installed in the factory where the wafer processing system is installed. The load port LP is made up of a cassette mounting plate 21 installed in the cassette station 2 and an openable / closable wafer W loading / unloading opening that is provided corresponding to the position of the cassette mounting plate 21.

[0116] 22 to 26, which are schematic plan views, will be used to describe an example of the configuration of a wafer processing system comprising the above-described multiple devices. To facilitate understanding of the configuration, each processing module is designated differently in these figures. A patterning film formation module is designated as COT, and a development processing module is designated as DEV. Regarding thermal processing modules, the modules that perform thermal processing (pre-applied bake: PAB) on wafers W after patterning film formation, the modules that perform thermal processing (post-exposure bake: PEB) on wafers W after exposure, and the modules that perform thermal processing (post-bake) on wafers W after development are designated as PAB, PEB, and POST, respectively. In other words, the processes performed in each module are designated as module names.

[0117] By distinguishing between the types of processing modules as described above, the drawings show the types of processing modules arranged in the first block G1 and the second block G2 within the processing station 3 of each device, but the arrangement of the processing modules is not limited to this illustrated example. The processing modules arranged in the first block G1 and the processing modules arranged in the second block G2 may be arranged in the opposite direction to that shown in the drawing, for example.

[0118] Of the processing modules, the cleaning processing module is not shown. As illustrated in the first embodiment, when the development processing and the cleaning processing for removing the residue D2 are performed in different modules, the cleaning processing module may be installed in the same apparatus as the development processing module DEV or in the processing station 3 of the apparatus to which the cassette C is transported next after the development processing module DEV. The cassette station 2 is also appropriately provided with a temporary storage section for temporarily storing the cassette C and a cassette transport mechanism for transporting the cassette C between the load port LP and the temporary storage section. If a temporary storage section is provided, a factory transport mechanism may deliver the cassette C to the temporary storage section instead of the load port LP. The exposure apparatus is shown in the figure as an exposure machine EXP.

[0119] First, a wafer processing system 200 shown in Fig. 22 will be described. The wafer processing system 200 is composed of apparatuses 201 to 203. The apparatus 201 includes a patterning film formation module COT and a thermal treatment module PAB. The apparatus 202 includes a thermal treatment module PEB and an interface station 4, and an exposure machine EXP is connected to the apparatus 202. The apparatus 203 includes a development treatment module DEV and a thermal treatment module POST. A cassette C is transported through the apparatuses 201, 202, and 203 in this order, and the wafers W are processed.

[0120] Next, a wafer processing system 210 shown in FIG. 23 will be described. The wafer processing system 210 is composed of apparatuses 211 to 213. The apparatus 211 includes a patterning film formation module COT, a thermal treatment module PAB, and an interface station 4, and an exposure machine EXP is connected to the apparatus 211. The apparatus 212 includes a thermal treatment module PEB and a development treatment module DEV. The apparatus 213 includes a thermal treatment module PEB and a development treatment module DEV. Cassettes C are transported through the apparatuses 211, 212, and 213 in this order, and wafers W are processed. In the apparatus 212, a first PEB and a development treatment are performed in that order, and in the apparatus 213, a second PEB and a development treatment are performed in that order.

[0121] Next, a description will be given of the wafer processing system 220 shown in Fig. 24. The wafer processing system 220 is made up of apparatuses 221 to 224. The apparatus 221 is equipped with a patterning film formation module COT and a thermal processing module PAB. The apparatus 222 is equipped with an interface station 4, and an exposure machine EXP is connected to the apparatus 222. The apparatus 223 is equipped with thermal processing modules PAB and PEB. The apparatus 224 is equipped with a development processing module DEV. Therefore, PAB is performed in either the apparatus 221 or 223.

[0122] When receiving PAB in apparatus 221, cassette C is transported in the order of apparatus 221, 222, 223, and 224. When receiving PAB in apparatus 223, cassette C is transported in the order of apparatus 221, 223, 222, 223, and 224, and wafers W receive PAB when cassette C is transported to apparatus 223 for the first time, and wafers W receive PEB when cassette C is transported to apparatus 223 for the second time. In this way, the system may be configured such that cassettes C are repeatedly transported to the same apparatus for processing.

[0123] The wafer processing system 230 shown in Figure 25 will now be described. The wafer processing system 230 is composed of apparatuses 231 and 232. The apparatus 231 includes a patterning film formation module COT, thermal treatment modules PAB and PEB, a development processing module DEV, and an interface station 4, and an exposure machine EXP is connected to the apparatus 231. The apparatus 232 includes a thermal treatment module PEB and a development processing module DEV. Cassettes C are transported through the apparatuses 231 and 232 in this order, and wafers W are processed therein. The wafer processing system 230 also performs PEB and development processing twice.

[0124] The wafer processing system 240 shown in Fig. 26 will now be described. The wafer processing system 240 is composed of apparatuses 241 and 242. The apparatus 241 includes a patterning film formation module COT and a thermal treatment module PAB. The apparatus 242 includes a thermal treatment module PEB, a development treatment module DEV, and an interface station 4, and an exposure machine EXP is connected to the apparatus 242. Cassettes C are transported through the apparatuses 241 and 242 in this order, and wafers W are processed.

[0125] As described above, the exposure machine EXP may be configured as a system connected to either an apparatus for forming a patterning film or an apparatus for performing PEB, as shown in FIGS. 22, 23, and 26, or as a system connected to neither of these apparatuses, as shown in FIG. 24. Furthermore, as shown in FIG. 23, etc., the PEB and the subsequent development process may be performed in the same apparatus, or as shown in FIG. 22. Similarly, as shown in FIG. 24, the PAB and the formation of the patterning film may be performed in the same apparatus, or in different apparatuses. Furthermore, when performing the PEB and development process twice, the apparatus for performing the first PEB and development process and the apparatus for performing the second PEB and development process may be different, as shown in FIGS. 23 and 25, or the system may be configured to perform the two PEB and development processes in the same apparatus.

[0126] In addition, when a cleaning processing module for cleaning the wafer W before forming a patterning film is installed, it may be installed in the apparatus in which the patterning film formation module COT is installed, or in the apparatus to which the cassette C is transported immediately before the apparatus in which the patterning film formation module COT is installed. Specifically, for example, in the system 220 of Figure 24, the cleaning module may be installed in the apparatus 221 or the apparatuses 223 and 224. When the cleaning processing module is installed in the apparatus 223 or 224, the cassette C may be transported to the apparatus 223 or 224 and then the cassette C may be transported to the apparatus 221 to form a patterning film.

[0127] [Additional Effects of the Second Embodiment and Modifications in a System Including Multiple Apparatuses] When an acid is supplied to a resist film R made of MOR after the first PEB, the width of the convex portions of the formed pattern becomes larger than when no acid is supplied in this manner. This is because the hydrolysis reaction of the components contained in the resist film R progresses after the PEB.

[0128] On the other hand, when performing PEB and development twice, depending on the transport status of each cassette C in the factory, the wait time from when the cassette C becomes ready to be transported from the apparatus performing the first development process until the factory transport mechanism receives the cassette C for transport to the apparatus performing the subsequent process may vary among cassettes C. Specifically, using the wafer processing system 210 in FIG. 23 as an example, a cassette C containing wafers W that have completed processing in apparatus 212 is transported by the factory transport mechanism to apparatus 213, but the wait time in apparatus 212 may vary. If the hydrolysis reaction described above progresses due to the ambient atmosphere around the cassette C during this wait time, the CD of the pattern formed after the second development process may vary among wafers W stored in different cassettes C due to the variation in the degree of progress of this reaction.

[0129] Therefore, in the apparatus 212, as described in the second embodiment and its modifications, a development processing module DEV configured to supply acidic gas or acidic mist to the entire semiconductor device formation area W0 is provided for processing. This processing saturates the hydrolysis reaction throughout the entire semiconductor device formation area W0, preventing further hydrolysis reaction during the waiting time, thereby suppressing CD variations between wafers W stored in different cassettes C. Note that CD variations can also be suppressed by performing similar processing in the wafer processing system 230 shown in FIG. 25, which transports the cassette C to a subsequent apparatus after the first development, similar to the wafer processing system 210.

[0130] The wafer processing system of the present disclosure is not limited to the configuration and operation described above. While some of the processes and transfers are illustrated as using an MOR resist film R, similar processes and transfers may be performed using other resist films R. Furthermore, while bubbling is exemplified as a method for vaporizing various liquids, any vaporization method may be used. Furthermore, the configuration of the apparatus may be modified as appropriate. For example, in the gas-based development and cleaning apparatus shown in FIGS. 4 and 10 , a gap is formed between the wafer mounting unit 81 constituting the processing vessel 82 and the lifting body 91 serving as the lid during processing of the wafer W. However, the apparatus may be configured such that these are in close contact with each other and the processing vessel is sealed while the wafer W is processed. In this case, the exhaust port 88 may be appropriately formed on the inner wall surface of the processing vessel.

[0131] Furthermore, the substrates processed in each substrate processing system are not limited to wafers W, but may also be FPD (flat panel display) substrates or mask substrates for manufacturing exposure masks. The embodiments disclosed herein should be considered to be illustrative and not restrictive in all respects. The above-described embodiments may be omitted, substituted, modified, and combined in various ways without departing from the scope and spirit of the appended claims.

[0132] W: Wafer D: Developer R: Resist film 1: Wafer processing system

Claims

1. A substrate processing system that supplies a processing fluid, which is a gas or mist composed of an acid or an organic solvent, to a substrate on which a resist film exposed to a developing fluid is formed.

2. The substrate processing system according to claim 1, wherein the processing fluid composed of the organic solvent is supplied to the substrate in a state where the resist film that forms irregularities by being exposed to the developing fluid is exposed.

3. The substrate processing system according to claim 1, wherein the processing fluid composed of an acid is supplied to the substrate on which the resist film is exposed to an alkaline developing fluid.

4. The substrate processing system according to claim 2, wherein the molecules constituting the organic solvent forming the processing fluid are one of polar molecules and non-polar molecules, and the molecules constituting the developing fluid are the other of the polar molecules and non-polar molecules.

5. The substrate processing system according to claim 2, comprising a second processing space for supplying the processing fluid to the substrate, which is distinguished from a first processing space for supplying the developing fluid to the substrate.

6. The substrate processing system according to claim 2, wherein the processing fluid is supplied to the substrate in a processing space for supplying the developing fluid to the substrate.

7. The substrate processing system according to claim 3, wherein the processing fluid is supplied to a part of the region where the irregularities are formed on the substrate.

8. A substrate processing method including a step of supplying a processing fluid, which is a gas or mist composed of an acid or an organic solvent, to a substrate on which a resist film exposed to a developing fluid is formed.

9. The substrate processing method according to claim 8, wherein the step of supplying the processing fluid is a step of supplying the processing fluid composed of the organic solvent to the substrate in a state where the resist film that forms irregularities by being exposed to the developing fluid is exposed.

10. The substrate processing method according to claim 8, wherein the step of supplying the processing fluid is a step of supplying the processing fluid composed of an acid to the substrate on which the resist film is exposed to an alkaline developing fluid.

11. The substrate processing method according to claim 9, wherein the molecules constituting the organic solvent forming the processing fluid are one of polar molecules and non-polar molecules, and the molecules constituting the developing fluid are the other of the polar molecules and non-polar molecules.

12. The substrate processing method according to claim 9, wherein the step of supplying the processing fluid includes a step of supplying the processing fluid to the substrate in a second processing space that is distinguished from a first processing space for supplying the developing fluid to the substrate.

13. The method for processing a substrate according to claim 9, wherein the step of supplying the processing fluid includes a step of supplying the processing fluid to the substrate in a processing space for supplying the developing fluid to the substrate.

14. The method for processing a substrate according to claim 10, wherein the step of supplying the processing fluid includes a step of supplying the processing fluid to a part of the uneven formation region on the substrate.

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