JP2012160682A - Substrate processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate processing method capable of drying and processing a substrate successfully without damaging a pattern on the substrate.SOLUTION: An intrusion prevention liquid is supplied to a surface Wf of a substrate, then a liquid to be frozen is supplied to the surface Wf of the substrate to allow a HFE to remain in a patten gap and in the vicinity of the pattern. The HFE maintains its liquid state, the liquid to be frozen is frozen and the surface Wf of the substrate is frozen except the inside of the pattern gap and the neighbor region. Next a frozen film is sublimed and dried to expose a surface of the intrusion prevention liquid and remove the intrusion prevention liquid, simultaneously. The surface Wf of the substrate can be dried without damaging the pattern by removing the frozen film in the removing step.

Description

  The present invention includes a semiconductor substrate, a glass substrate for photomask, a glass substrate for liquid crystal display, a glass substrate for plasma display, a substrate for FED (Field Emission Display), a substrate for optical disk, a substrate for magnetic disk, a substrate for magneto-optical disk, etc. The present invention relates to a substrate processing method and a substrate processing apparatus for performing a cleaning process on various substrates (hereinafter simply referred to as “substrates”).

  The manufacturing process of electronic components such as a semiconductor device and a liquid crystal display device includes a process of forming a fine pattern by repeatedly performing processes such as film formation and etching on the surface of the substrate. Here, in order to perform fine processing satisfactorily, it is necessary to keep the substrate surface clean, and a cleaning process is performed on the substrate surface as necessary.

  For example, in the apparatus described in Patent Document 1, a liquid such as deionized water (hereinafter referred to as “DIW”) is supplied to the substrate surface, and after freezing it, it is thawed and removed with a rinse solution. As a result, contaminants such as particles on the substrate surface (hereinafter referred to as “particles”) are removed and cleaning is performed.

  After the cleaning process, it is necessary to remove the liquid such as DIW adhering to the substrate surface and dry the substrate. One of the important issues during drying is to dry the substrate without collapsing the pattern formed on the substrate surface.

  Patterns made of fine irregularities formed on electronic components such as semiconductor devices and liquid crystal display devices are further refined, and the structure itself is made three-dimensional and so minute and complicated. Has a shape. This tendency is particularly remarkable for patterns used for individual semiconductors such as transistors and capacitors.

  As the pattern becomes finer and the structure becomes more complex in this way, the area where the bottom surface of the convex portion of the pattern comes into contact with the substrate is reduced, and the adhesive force between the convex portion of the pattern and the substrate is reduced. . Accordingly, there is a high possibility that the convex portion of the pattern collapses and peels even with a small external force, and the shape of the concave portion is deformed (hereinafter, these are collectively referred to as “damage” to the pattern).

  When the conventional cleaning method disclosed in Patent Document 1 is applied to a substrate on which such a fine pattern is formed, further improvement is required for pattern collapse when the substrate is dried after the cleaning process. It is done. Sublimation drying techniques are attracting attention as a method for solving this problem. In this sublimation drying technique, as described in, for example, Patent Document 2 and Patent Document 3, after a liquid such as DIW adhering to the substrate surface is frozen in the processing chamber, the processing chamber is decompressed to freeze the frozen body. Is sublimated.

JP 2008-71875 A (FIG. 7) JP-A-4-242930 (FIG. 2) Japanese Laid-Open Patent Publication No. 4-331195 (FIG. 1)

  In the prior art disclosed in Patent Document 2 and Patent Document 3, decompression processing in the processing chamber is essential, and substrate drying cannot be performed in an atmospheric pressure state, and other substrate processing is continuously performed in the same apparatus. Can not do. For example, after cleaning a substrate using pure water such as DIW, it is difficult to dry the substrate immediately after cleaning the substrate. In addition, since it is necessary to reduce the pressure in the processing chamber, it is necessary to ensure airtightness in the processing chamber and to provide a vacuum pump or a valve for reducing the pressure in the processing chamber. As a result, the substrate drying apparatus is increased in size and cost.

  On the other hand, although the freezing process is performed in sublimation drying, when the conventional freezing method is applied to a substrate on which such a fine pattern is formed, adjacent convex portions separated by a minute interval due to the fluidity of DIW. And the inside of a three-dimensional cylindrical shape (hereinafter referred to as “pattern gap”) and the vicinity of the outer edge of the pattern (hereinafter referred to as “pattern gap excluding the upper surface of the pattern protrusion and the vicinity of the outer edge of the pattern” It also enters (in the vicinity of the pattern)) and the DIW including that portion is frozen.

  In this prior art, a force is generated when DIW becomes ice and expands, but this force works equally on the pattern. That is, a force acting in a direction parallel to the main surface of the substrate is applied to the entire pattern, and a force to push the pattern gap outward is applied to the pattern gap. This force may cause damage such as collapse or peeling of the convex portion of the pattern and deformation of the concave portion.

  This invention is made in view of the said subject, The board | substrate process which can remove the liquid adhering to a substrate surface and dry a board | substrate satisfactorily without giving a damage with respect to the pattern of a fine and complicated shape It aims to provide a method.

  In order to solve the above problems, a substrate processing method according to a first aspect includes an intrusion prevention liquid supply step for supplying an intrusion prevention liquid to a substrate on which a pattern is formed, and a substrate to which the intrusion prevention liquid is supplied. A coagulation target liquid supply step for supplying a coagulation target liquid capable of forming a coagulation body, and a coagulation step for generating a coagulation body of the coagulation target liquid, and the intrusion prevention liquid has a freezing point lower than the freezing point of the coagulation target liquid. It is a substance that prevents the liquid to be solidified from entering the pattern and remains in the vicinity of the pattern, and the solidification process cools the substrate below the freezing point of the liquid to be solidified and above the freezing point of the intrusion prevention liquid. And a removal step of removing the intrusion prevention liquid by supplying the removal gas toward the solidified body formed in the step at a temperature lower than the solidification point of the solidification target liquid.

  In the substrate processing method according to the second aspect, in the solidification target liquid supply step, the solidification target liquid is supplied to the substrate to which the intrusion prevention liquid has adhered, and the intrusion prevention liquid other than the vicinity of the pattern is removed.

  In the substrate processing method according to the third aspect, the intrusion prevention liquid is a substance that is insoluble in the liquid to be solidified.

  In the substrate processing method according to the first aspect configured as described above, the intrusion prevention liquid is left in the vicinity of the pattern on the substrate on which the pattern is formed to form a region where the solidification target liquid does not enter, and only the solidification target liquid is solidified. Then, the substrate is dried by supplying the removing gas. As a result, the substrate is dried while preventing damage to the pattern.

  That is, an intrusion prevention liquid having a freezing point lower than the freezing point of the liquid to be solidified is used, and is cooled below the freezing point of the liquid to be solidified and above the freezing point of the intrusion prevention liquid to solidify only the liquid to be solidified. To be left. Thereby, it is possible to prevent the external force from being directly transmitted to the pattern by receiving the force generated by the solidification target liquid being solidified and volume expansion, thereby preventing damage to the pattern. Next, the gas for removal is supplied to the solidified body formed in the solidification step at a temperature lower than the solidification point of the solidification target liquid to remove the solidified body. Here, the solidified body is removed by sublimation drying. Then, in the removal process by sublimation drying, the intrusion prevention liquid is removed in parallel with the removal of the frozen film, thereby making it possible to prevent the pattern from being damaged.

  In the substrate processing method according to the second aspect, in the solidification target liquid supply step, the solidification target liquid can be supplied to the substrate to which the intrusion prevention liquid has adhered, and the intrusion prevention liquid other than the vicinity of the pattern can be removed. That is, by only supplying the liquid to be solidified on the substrate, the intrusion prevention liquid attached to the substrate can be left only in the vicinity of the pattern, and other portions can be removed by being pushed away by the flow of the liquid to be solidified.

  In the substrate processing method according to the third aspect, the intrusion prevention liquid can be made an insoluble substance with respect to the coagulation target liquid. Therefore, after the intrusion prevention liquid existing outside the pattern is removed by the coagulation target liquid and before the coagulation target liquid is solidified, the intrusion prevention liquid is mixed with the coagulation target liquid and is present in the vicinity of the pattern. The freezing point of the region is not increased by reducing the region or mixing with the liquid to be solidified. Accordingly, the area where the liquid state should be originally maintained is reduced or does not coagulate to that area, and the pattern is protected from the external force due to the coagulation target liquid coagulating and volume expanding.

  According to this invention, the substrate can be sublimated and dried without damaging the pattern by the invasion preventing liquid having a freezing point different from the freezing point of the liquid to be solidified remaining in the vicinity of the pattern. That is, by allowing the intrusion prevention liquid to remain in the vicinity of the pattern and coagulating only the liquid to be solidified, the force generated by the solidification of the liquid to be solidified and volume expansion is received by the liquid intrusion prevention liquid, and the external force is directly applied to the pattern. Prevent transmission. Further, since the intrusion prevention liquid is removed in parallel in the solidified body removing step, the substrate can be dried while preventing damage to the pattern.

It is a front view which shows schematic structure of the substrate processing apparatus which concerns on this invention. It is arrow sectional drawing along the B1-B1 line | wire of FIG. It is the side view seen from arrow B2 of FIG. It is a figure which shows the whole structure of the processing unit concerning 1st embodiment. It is a figure which shows the structure of the board | substrate holding means in the processing unit of FIG. It is a figure which shows the structure of the coagulation object liquid supply means in the processing unit of FIG. It is a figure which shows the structure of the 1st DIW supply part in FIG. It is a figure which shows the structure of the intrusion prevention liquid supply means in the processing unit of FIG. It is a figure which shows the structure of the intrusion prevention liquid supply part in FIG. It is a figure which shows the structure of the solidification means in the processing unit of FIG. It is a figure which shows the structure of the nitrogen gas supply part for solidification in FIG. It is a figure which shows the structure of the rinse means and drying gas supply means in the processing unit of FIG. It is a flowchart which shows operation | movement of the substrate processing apparatus of 1st embodiment. FIG. 4A is a schematic diagram showing the state of the intrusion prevention liquid. FIG. 4A shows a state after the intrusion prevention liquid supplying process is completed, and FIG. It is a vapor pressure curve of water and ice. FIG. 6 is a schematic diagram showing the state of the substrate surface Wf in the intrusion prevention liquid removing step, where (a) shows the state of the substrate surface Wf after the start of the intrusion prevention liquid removing step, and (b) shows the state after the end of the intrusion prevention liquid removing step. The state of the substrate surface Wf is shown. FIG. 6 is a schematic diagram showing the state of the substrate surface Wf in the removal step and the intrusion prevention liquid removal step, where (a) shows the state of the substrate surface Wf after the start of the removal step, and (b) after the start of the intrusion prevention liquid removal step. The state of the substrate surface Wf is shown, and (c) shows the state of the substrate surface Wf after completion of the intrusion prevention liquid removing step.

  In the following description, a substrate means a semiconductor substrate, a glass substrate for photomask, a glass substrate for liquid crystal display, a glass substrate for plasma display, a substrate for FED (Field Emission Display), a substrate for optical disk, a substrate for magnetic disk, and a magneto-optical substrate. Various substrates such as disk substrates.

  In the following description, a substrate on which a circuit pattern or the like (hereinafter referred to as “pattern”) is formed only on one main surface will be used as an example. Here, the main surface on which the circuit pattern or the like is formed is referred to as “front surface”, and the main surface on which the circuit pattern or the like on the opposite side is not formed is referred to as “back surface”. Further, the surface of the substrate directed downward is referred to as “lower surface”, and the surface of the substrate directed upward is referred to as “upper surface”. In the following description, the upper surface is the surface.

  In addition, the influence of the convex portion of the pattern having a fine concavo-convex shape collapsing / peeling or the shape of the concave portion being deformed is collectively referred to as “damage” to the pattern. In addition, between adjacent convex portions spaced apart by a minute interval, the inside of a three-dimensional cylindrical shape, or the like is referred to as “pattern gap”, and the vicinity of the pattern gap and the outer edge of the pattern are collectively referred to as “pattern vicinity”. However, the upper surface of the convex portion of the pattern is not included in the vicinity of the pattern. Further, a region other than the vicinity of the pattern and where no pattern is formed (for example, a portion between individual semiconductors) is referred to as an “outside pattern region”.

  Embodiments of the present invention will be described below with reference to the drawings, taking as an example a substrate processing apparatus used for processing semiconductor wafers. The present invention can be applied not only to processing of semiconductor wafers but also to processing of various substrates such as glass substrates for liquid crystal displays.

<First embodiment>
1, FIG. 2 and FIG. 3 are diagrams showing a schematic configuration of a substrate processing apparatus 9 according to the present invention. 1 is a front view of the substrate processing apparatus 9, and FIG. 2 is a cross-sectional view taken along line B1-B1 of the substrate processing apparatus 9 of FIG. FIG. 3 is a side view of the substrate processing apparatus 9 of FIG. 1 viewed from the arrow B2 side. This apparatus has a cleaning process for removing contaminants such as particles (hereinafter referred to as “particles”) adhering to a substrate W such as a semiconductor substrate (hereinafter simply referred to as “substrate W”). This is a single-wafer type substrate processing apparatus used for drying processing.

  In each figure, in order to clarify the directional relationship, a coordinate system in which the Z axis is the vertical direction and the XY plane is the horizontal plane is appropriately attached. Also, in each coordinate system, the direction in which the tip of the arrow faces is the + (plus) direction, and the opposite direction is the-(minus) direction.

  The substrate processing apparatus 9 takes out an unprocessed substrate W from the opener 94 on which a FOUP (Front Open Unified Pod) 949 containing, for example, 25 substrates W is placed, and the FOUP 949 on the opener 94, and after the processing is completed An indexer unit 93 for storing W in the FOUP 949, a shuttle 95 for transferring the substrate W between the indexer unit 93 and the center robot 96, and a processing for storing the substrate W in the center robot 96 for cleaning. The unit 91 includes a fluid box 92 that accommodates a pipe for liquid or gas supplied to the processing unit 91, an on-off valve, and the like.

  First, these planar arrangements will be described with reference to FIG. A plurality of (three in this embodiment) openers 94 are arranged at one end (left end in FIG. 2) of the substrate processing apparatus 9. An indexer unit 93 is arranged adjacent to the right side (+ Y side) of the opener 94 in FIG. A shuttle 95 is arranged near the center of the indexer unit 93 in the X direction and adjacent to the right side (+ Y side) of the indexer unit in FIG. 2, and on the right side (+ Y side) of the shuttle 95 in FIG. Center robot 96 is arranged so as to line up in the + Y direction. Thus, the indexer unit 93, the shuttle 95, and the center robot 96 are arranged in two orthogonal lines.

  A processing unit 91 and a fluid box 92 are arranged on the upper side (−X side) and the lower side (+ X side) in FIG. 2 of the shuttle 95 and the center robot 96 arranged in the + Y direction. That is, the fluid box 92 and the processing unit are adjacent to the upper side (−X side) or the lower side (+ X side) of the shuttle 95 and the center robot 96 in FIG. 2 and adjacent to the right side (+ Y side) of the indexer unit 93 in FIG. 91, the processing unit 91, and the fluid box 92 are arranged in this order.

  An operation unit 971 of a control unit 97 described later is installed on the side surface of the indexer unit 93 on the + X side (lower side in FIG. 2) (see FIG. 1).

  Next, the opener 94 will be described. The opener 94 is disposed so as to face the mounting surface 941 on which the FOUP 949 is mounted, and the front surface of the FOUP 949 (the right side (+ Y side) surface of the FOUP 949 in FIGS. 1 and 2). And an opening / closing mechanism 943 (see FIG. 3) for opening and closing a portion (not shown).

  The FOUP 949 carried in from the outside of the substrate processing apparatus 9 by an automatic conveyance vehicle or the like is placed on the placement surface 941 of the opener 94, and the lid is released by the opening / closing mechanism 943. As a result, an indexer robot 931 of the indexer unit 93 described later can carry out the substrate W in the FOUP 949, and conversely, carry in the substrate W into the FOUP 949.

  Next, the indexer unit 93 will be described. In the indexer unit 93, the substrates W before the processing step are taken out one by one from the FOUP 949, the substrates W after the processing step are accommodated one by one in the FOUP 949, and the substrates W are transferred to the shuttle 95 in the Z-axis direction. An indexer robot 931 having two sets of hands 933 arranged above and below is provided. The indexer robot 931 can move horizontally in the X-axis direction, can move up and down in the Z-axis direction, and can rotate about the Z-axis.

  Next, the shuttle 95 will be described. The shuttle 95 is in the vicinity of the peripheral edge on the upper side (−X side) and the lower side (+ X side) in FIG. 2 of the substrate W and does not interfere with the hand 933 of the indexer robot 931 and the hand 961 of the center robot 96 described later. Two sets of hands 951 arranged vertically in the Z-axis direction and a horizontal movement mechanism (not shown) for horizontally moving the two sets of hands 951 in the Y-axis direction are provided.

  The shuttle 95 is configured such that the substrate W can be transferred between both the indexer robot 931 and the center robot 96. That is, when the hand 951 is moved to the left side (−Y side) in FIG. 2 by a horizontal movement mechanism (not shown), the substrate W can be transferred to and from the hand 951 of the indexer robot 931. When moving to the right side (+ Y side), the substrate W can be delivered to and from the hand 961 of the center robot 96.

  Next, the center robot 96 will be described. The center robot 96 holds the substrates W one by one, and transfers the substrates W to and from the shuttle 95 or the processing unit 91. Two sets of hands 961 arranged vertically in the Z-axis direction and the vertical direction A lifting shaft 963 that extends in the (Z-axis direction) and serves as a vertical movement axis of the hand 961, a lifting mechanism 965 that moves the hand 961 up and down, and a rotating mechanism 967 that rotates the hand 961 around the Z axis. Is provided. The center robot 96 is movable up and down along the lifting shaft 963 in the Z-axis direction, and the hand can be rotated around the Z-axis by a rotating mechanism 967.

  Note that an opening through which the hand 961 of the center robot 96 is extended and the substrate W is carried into or out of the processing unit 91 is formed on a side wall, which will be described later, of the processing unit 91 facing the center robot 96. Is provided. In addition, when the center robot 96 does not deliver the processing unit 91 and the substrate W, a shutter 911 is provided for closing the opening and maintaining the cleanliness of the atmosphere inside the processing unit 91.

  As shown in FIG. 1, the processing unit 91 and the fluid box 92 are stacked in two upper and lower stages. Therefore, the substrate processing apparatus 9 in this embodiment includes eight processing units 91 and eight fluid boxes 92, respectively.

  Next, a procedure for transporting the substrate W by the indexer robot 931, the shuttle 95, and the center robot 96 will be described. The FOUP 949 carried in from the outside of the substrate processing apparatus 9 by an automatic conveyance vehicle or the like is placed on the placement surface 941 of the opener 94, and the lid is released by the opening / closing mechanism 943. The indexer robot 931 takes out one substrate W from the predetermined position of the FOUP 949 with the lower hand 933. Thereafter, the indexer robot 931 moves in front of the shuttle 95 (near the center in the X-axis direction of the indexer unit 93 in FIG. 2). At the same time, the shuttle 95 moves the lower hand 951 to the indexer unit 93 side (left side (-Y side in FIG. 2)).

  The indexer robot 931 that has moved in front of the shuttle 95 transfers the substrate W held by the lower hand 933 to the lower hand 951 of the shuttle 95. Thereafter, the shuttle 95 moves the lower hand 951 to the center robot 96 side (the right side (+ Y side in FIG. 2)). Further, the center robot 96 moves to a position where the hand 961 is directed to the shuttle 95.

  Thereafter, the center robot 96 takes out the substrate W held by the lower hand 951 of the shuttle 95 by the lower hand 961 and moves the hand 961 to one of the shutters 911 of the eight processing units 91. To do. Thereafter, the shutter 911 is released, the center robot 96 extends the lower hand 961 and carries the substrate W into the processing unit 91, and the drying process of the substrate W in the processing unit 91 is started.

  The substrate W that has been processed in the processing unit 91 is unloaded by the upper hand 961 of the center robot 96, and then the upper hand 961 of the center robot 96, contrary to the case of transporting the unprocessed substrate W, The upper hand 951 of the shuttle 95 and the upper hand 933 of the indexer robot 931 are transferred in this order, and are finally accommodated in a predetermined position of the FOUP 949.

  Next, the configuration of the processing unit 91 will be described with reference to FIG. FIG. 4 is a schematic diagram showing the configuration of the processing unit 91. Here, since the eight processing units 91 in the present embodiment have the same configuration, the processing unit 91 indicated by the arrow B3 in FIG. 2 (the processing unit 91 on the lower left side in FIG. 1) will be described as a representative. The processing unit 91 dries the substrate W using a drying process that follows the surface Wf of the substrate W after the rinsing process. Any one of the processing units 91 may be a unit for cleaning processing.

  The processing unit 91 holds the substrate W having a pattern formed on the surface thereof substantially horizontally, accommodates the rotating substrate holding means 11 and the substrate holding means 11 therein, and scatters from the substrate holding means 11 and the substrate W. A waste liquid collecting means 21 that receives and exhausts an object and the like and a surface Wf of the substrate W held by the substrate holding means 11 are arranged to face each other, and a space above the substrate surface Wf is blocked from the outside air. Atmosphere blocking means 23.

  Further, the processing unit 91 includes an intrusion prevention liquid supply means 31 for supplying an intrusion prevention liquid for remaining in the vicinity of the pattern formed on the surface Wf of the substrate W, and a solidification target for supplying the solidification target liquid to the surface of the substrate W. Liquid supply means 43, coagulation means 35 for supplying and solidifying a low-temperature coagulation gas to the liquid to be solidified on the surface Wf of the substrate W, and rinsing means for supplying a rinsing liquid toward the substrate surface Wf and the substrate back surface Wb 51, a drying gas supply means 55 for supplying a drying gas toward the substrate surface Wf and the substrate back surface Wb to block the substrate surface Wf and the substrate back surface Wb from outside air, and a substrate processing apparatus based on a cleaning program to be described later 9 and a control unit 97 that controls the operation of each unit. The solidifying means 35 also functions as a removing means for removing the solidified body by supplying a solidifying gas as a sublimation drying removal gas to the solidified liquid to be solidified on the substrate surface Wf.

  In this embodiment, HFE is used as the intrusion prevention liquid, and deionized water (hereinafter referred to as “DIW”) is used as the coagulation target liquid and the rinse liquid. In the present embodiment, nitrogen gas is used as the coagulation gas, the removal gas, and the drying gas.

Here, HFE refers to a liquid mainly composed of hydrofluoroether. As “HFE”, for example, HFE of the brand name Novec (registered trademark) manufactured by Sumitomo 3M Limited can be used. Specifically, as HFE, for example, chemical formula: C ₄ F ₉ OCH ₃ , chemical formula: C ₄ F ₉ OC ₂ H ₅ , chemical formula: C ₆ F ₁₃ OCH ₃ , chemical formula: C ₃ HF ₆ —CH (CH ₃ ) O—C ₃ HF ₆ , chemical formula: C ₂ HF ₄ OCH ₃ (freezing point: − (minus) 38 ° C. (Celsius) or lower) and the like can be used. These HFEs may be diluted.

  Further, the processing unit 91 includes a hollow side wall 901 having a substantially prismatic shape, an upper base member 902 and a lower base member 903 that are fixed substantially horizontally to the side wall 901 and partition the space in the processing unit 91, and the side wall 901. An upper space 905 above the upper base member 902, a processing space 904 inside the side wall 901, below the upper base member 902, and above the lower base member 903; A lower space 906 inside the side wall 901 and below the lower base member 903. In the present embodiment, the side wall 901 has a substantially prismatic shape, but the shape of the side wall is not limited thereto, and may be a substantially cylindrical shape or other shapes.

  On the side of the side wall 901 facing the center robot 96, an opening through which the center robot can load or unload the substrate W into the processing unit 91 and the opening inside the processing unit 91 are closed. A shutter 911 for maintaining cleanliness is provided.

  The upper base member 902 is fixed substantially horizontally above the side wall 901 (upper side in FIG. 4), and partitions the upper space 905 and the processing space 904 that are internal spaces of the processing unit 91. Near the center of the upper base member 902, an atmosphere introduction path 907 that communicates from the lower surface of the upper base member 902 to the upper end of the processing unit 91 is provided. A fan filter unit 908 that supplies a clean atmosphere to the processing space 904 is provided near the upper end of the atmosphere introduction path 907. The fan filter unit 908 installed in the atmosphere introduction path 907 in the upper space 905 takes in the atmosphere from above the processing unit 91 and collects particulates and the like in the atmosphere with a built-in HEPA filter or the like, and then performs processing below. A cleaned atmosphere is supplied into the space 904.

  The lower base member 903 is fixed substantially horizontally in the middle of the side wall 901 (lower side in FIG. 4), and partitions the processing space 904 that is the space inside the processing unit 91 and the lower space 906. . The lower base member 903 is provided with a plurality of exhaust ports 909, and each exhaust port 909 is connected to an exhaust system (not shown) and exhausts the atmosphere in the processing space 904 to the outside.

  Here, a clean atmosphere is maintained in the processing space 904, and the substrate W is cleaned. The upper space 905 and the lower space 906 are spaces in which drive sources and the like for driving each member installed in the processing space 904 are disposed.

  The atmosphere supplied into the processing space 904 through the fan filter unit 908 flows from the upper side to the lower side of the processing space 904, and is finally discharged out of the processing space 904 from the exhaust port 909. As a result, fine liquid fine particles and the like generated in each process of processing the substrate W to be described later are moved downward by the airflow flowing from the top to the bottom in the processing space 904 and discharged from the exhaust port 909. Therefore, these fine particles can be prevented from adhering to each member in the substrate W and the processing space 904.

  Next, the configuration of the substrate holding means 11, the drainage collecting means 21, and the atmosphere blocking means 23 will be described with reference to FIG. FIG. 5 is a schematic diagram showing the configuration of the substrate holding means 11, the drainage collecting means 21, and the atmosphere blocking means 23.

  First, the substrate holding means 11 will be described. The base unit 111 of the substrate holding means 11 is fixed on the lower base member 903, and a disk-shaped spin base 113 having an opening at the center is provided substantially horizontally above the base unit 111 so as to be rotatable. It is supported. At the center of the lower surface of the spin base 113, the upper end of the central shaft 117 is fixed by a fastening component such as a screw. In addition, a plurality of substrate holding members 115 for holding the periphery of the substrate W are erected in the vicinity of the periphery of the spin base 113. Three or more substrate holding members 115 may be provided in order to securely hold the circular substrate W, and are arranged at equiangular intervals along the periphery of the spin base 113. Each of the substrate holding members 115 includes a substrate support portion that supports the peripheral portion of the substrate W from below, and a substrate holding portion that holds the substrate W by pressing the outer peripheral end surface of the substrate W supported by the substrate support portion. I have.

  Each substrate holding member 115 is connected to an air cylinder in the substrate holding member driving mechanism 119 via a known link mechanism, a swinging member, or the like. The substrate holding member driving mechanism 119 is installed below the spin base 113 and inside the base unit 111. The substrate holding member drive mechanism 119 is electrically connected to the control unit 97. In response to an operation command from the control unit 97 to the substrate holding unit 11, the air cylinder of the substrate holding member driving mechanism 119 expands and contracts, so that each substrate holding member 115 presses the outer peripheral end surface of the substrate W. The “closed state” is switched between the “closed state” and the “open state” in which the substrate holding portion is separated from the outer peripheral end surface of the substrate W. In addition to the air cylinder, a known drive source such as a motor or a solenoid can be used as a drive source for the substrate holding member 115.

  When the substrate W is delivered to the spin base 113, each substrate holding member 115 is opened, and when performing a cleaning process or the like on the substrate W, each substrate holding member 115 is closed. And When each substrate holding member 115 is in the closed state, each substrate holding member 115 holds the peripheral edge of the substrate W, and the substrate W is held in a substantially horizontal posture at a predetermined interval from the spin base 113. As a result, the substrate W is held with the front surface Wf facing upward and the back surface Wb facing downward. In this embodiment, a fine pattern is formed on the surface Wf of the substrate W, and the surface Wf is a pattern formation surface.

  In addition, a rotation shaft of a substrate rotation mechanism 121 including a motor is connected to the central shaft 117 of the substrate holding means 11. The substrate rotation mechanism 121 is installed on the lower base member 903 and inside the base unit 111. The substrate rotation mechanism 121 is electrically connected to the control unit 97. When the substrate rotation mechanism 121 is driven by an operation command from the control unit 97 to the substrate holding unit 11, the spin base 113 fixed to the central shaft 117 rotates about the rotation central axis A1.

  From the upper surface of the spin base 113 to the lower space 906 through the central axis 117, a communicating hollow portion is formed so that a lower first supply pipe and a lower second supply pipe described later can be inserted. Yes.

  Next, the drainage collecting means 21 will be described. A substantially annular cup 210 is provided around the substrate holding means 11 and above the lower base member 903 so as to surround the periphery of the substrate W held by the substrate holding means 11. The cup 210 has a substantially rotationally symmetric shape with respect to the rotation center axis A1 so as to be able to collect the liquid scattered from the substrate holding means 11 and the substrate W. In the drawing, the cup 210 has a cross-sectional shape for explanation.

  The cup 210 includes an inner component member 211, an intermediate component member 213, and an outer component member 215 that can be moved up and down independently of each other. As shown in FIG. 5, the intermediate component member 213 and the outer component member 215 are stacked on the inner component member 211. The inner component member 211, the middle component member 213, and the outer component member 215 are respectively connected to a guard lifting mechanism 217 that is provided in the lower space 906 and is configured by a known drive mechanism such as a motor and a ball screw. Further, the guard lifting mechanism 217 is electrically connected to the control unit 97. When the guard elevating mechanism 217 is driven by an operation command from the control unit 97 to the drainage collecting means 21, the inner component member 211, the middle component member 213, and the outer component member 215 are each independently or a plurality of members. Move in the vertical direction along the rotation center axis A1.

  The inner component member 211 is provided with three collection grooves for guiding the liquid collected by the inner component member 211, the middle component member 213, and the outer component member 215 to the drainage treatment system through different paths. Yes. Each collection groove is provided in a substantially concentric shape with the rotation center axis A1 as the center, and a pipe connected to a drainage treatment system (not shown) is connected to each collection groove.

  The cup 210 is used by combining the positions of the inner component member 211, the middle component member 213, and the outer component member 215 in the vertical direction. For example, the home position in which all of the inner component member 211, the middle component member 213, and the outer component member 215 are in the lower position, and the inner component member 211 and the middle component member 213 are in the lower position, and only the outer component member 215 is in the upper position. Outer collection position, middle collection position in which inner component member 211 is in the lower position and middle component member 213 and outer component member 215 are in the upper position, and inner component member 211, middle component member 213, and outer component member 215 It is an internal collection position where everything is in the upper position.

  The home position is a position taken when the center robot 96 carries the substrate W into and out of the processing unit 91. The outer collection position is a position where the liquid received by the outer component member 215 is collected and guided to the outer collection groove, and the intermediate collection position is a position where the liquid received by the middle component member 213 is guided to the intermediate collection groove. In addition, the internal collection position is a position for guiding the liquid received by the internal component 211 to the internal collection groove.

  By using the drainage collecting means 21 having such a configuration, the respective positions of the inner component member 211, the middle component member 213, and the outer component member 215 are changed according to the liquid used in the process, and collected separately. By separating each liquid and discharging it to a corresponding drainage processing system, it becomes possible to separate and process a plurality of liquids that are dangerous to reuse or mix.

  Next, the atmosphere blocking means 23 will be described. A blocking member 231 that is a substrate facing member of the atmosphere blocking means 23 is formed in a disk shape having an opening at the center. The lower surface of the blocking member 231 is a substrate facing surface that faces the surface Wf of the substrate W substantially in parallel, and is formed to have a size equal to or larger than the diameter of the substrate W. The blocking member 231 is supported substantially horizontally so as to be rotatable below a support shaft 233 having a hollow inside and a substantially cylindrical shape.

  The upper end portion of the support shaft 233 is fixed to the lower surface of the blocking member rotating mechanism 235 that rotates the blocking member 231. The blocking member rotation mechanism 235 includes, for example, a hollow motor 237 and a hollow shaft 239. One end (the upper end in FIG. 5) of the hollow shaft 239 is connected to the rotating shaft of the hollow motor 237, and the other end (the lower end in FIG. 5) is connected to the upper surface of the blocking member 231 through the support shaft 233. The blocking member rotating mechanism 235 is electrically connected to the control unit 97. When the blocking member rotation mechanism 235 is driven by an operation command from the control unit 97 to the atmosphere blocking means 23, the blocking member 231 is rotated around the vertical axis passing through the center of the support shaft 233. The blocking member rotating mechanism 235 is configured to rotate the blocking member 231 in the same rotational direction as the substrate W and at substantially the same rotational speed in accordance with the rotation of the substrate W held by the substrate holding unit 11.

  The hollow motor 237 and the hollow shaft 239 are inserted so that an upper first supply pipe and an upper second supply pipe, which will be described later, can be inserted from the upper surface of the blocking member rotating mechanism 235 to the opening of the central portion of the blocking member 231. A communicating hollow portion including the internal space is formed.

  One end of the arm 241 is connected to one side surface (left side surface in FIG. 5) of the blocking member rotation mechanism 235, and the other end of the arm 241 is connected to the vicinity of the upper end of the vertical shaft 243 in FIG. The vertical shaft 243 is outside the circumferential direction of the cup 210 of the drainage collecting means 21 and is attached to a cylindrical base member 245 fixed on the lower base member 903 so as to be movable up and down. A blocking member elevating mechanism 247 configured by a known drive mechanism such as a motor and a ball screw is connected to the vertical shaft 243 through the base member 245.

  The blocking member elevating mechanism 247 is provided in the lower space 906. Further, the blocking member lifting mechanism 247 is electrically connected to the control unit 97. When the blocking member elevating mechanism 247 is driven by an operation command from the control unit 97 to the atmosphere blocking means 23, the blocking member 231 approaches the spin base 113 and is separated away.

  That is, the control unit 97 controls the operation of the blocking member elevating mechanism 247 to raise the blocking member 231 to a separation position above the substrate holding means 11 when the substrate W is loaded into and unloaded from the processing unit 91. On the other hand, when performing the rinsing process described later on the substrate W, drying the substrate W, or the like, the blocking position 231 is set to a position close to the surface Wf of the substrate W held by the substrate holding unit 11. To lower.

  Next, the configuration of the coagulation target liquid supply means 43 will be described with reference to FIG. FIG. 6 is a schematic diagram showing the configuration of the coagulation target liquid supply means 43. The nozzle 411 for supplying the liquid to be solidified to the surface Wf of the substrate W is supported by a nozzle drive mechanism 413 installed on the lower surface of the upper base member 902 so as to be able to move up and down. The base member 415 of the nozzle driving mechanism 413 is fixed so as to extend downward on the lower surface of the upper base member 902 and outside the atmosphere introduction path 907.

  Below the base member 415, a turning vertical shaft 417 is held vertically and rotatably. Note that the base member 415 is formed in a hollow, substantially cylindrical shape for connecting the swing vertical shaft 417 to the vertical drive unit 421 and the swing drive unit 419 described later. One end of an arm 423 is coupled to the lower surface of the turning vertical axis 417, and a nozzle 411 is attached to the other end of the arm 423.

  The swivel vertical axis 417 is connected through the base member 415 to a vertical drive unit 421 configured with a known drive mechanism such as a motor and a ball screw, and a swing drive unit 419 configured with a known drive mechanism such as a motor and a gear. Has been. Further, the vertical drive unit 421 and the turning drive unit 419 are electrically connected to the control unit 97. The vertical drive unit 421 and the turning drive unit 419 are disposed in the upper space 905.

  When the vertical drive unit 421 is driven by an operation command from the control unit 97 to the nozzle drive mechanism 413, the turning vertical axis 417 moves up and down, and the nozzle 411 attached to the arm 423 moves up and down. Further, when the turning drive unit 419 is driven by an operation command from the control unit 97 to the nozzle drive mechanism 413, the turning vertical axis 417 rotates around the rotation center axis A4, and the arm 423 is turned, thereby turning the arm 423. The nozzle 411 attached to is swung.

  The nozzle 411 is connected to the first DIW supply unit 433 via a pipe 449. An opening / closing valve 437 is inserted in the pipe 449, and the opening / closing valve 437 is normally closed. The on-off valve 437 is electrically connected to the control unit 97. Then, when the on-off valve 437 is opened by an operation command from the control unit 97 to the coagulation target liquid supply means 43, the coagulation target liquid is pumped from the first DIW supply unit 433 to the nozzle 411 through the pipe 449. The first DIW supply unit 433 may be provided inside the substrate processing apparatus 9 or may be provided outside.

  FIG. 7 shows the configuration of the first DIW supply unit 433. The first DIW supply unit 433 includes a DIW tank 441 that stores DIW, a pump 443 that pumps DIW from the DIW tank 441, and a temperature adjustment unit 445 that adjusts the temperature of the DIW. The pump 443 connected to the DIW tank 441 is pressurized to supply DIW to the temperature adjustment unit 445. The DIW supplied to the temperature adjustment unit 445 via the pump 443 is adjusted to a predetermined temperature by the temperature adjustment unit 445 and supplied to the nozzle 411 via the pipe 449.

  Here, the temperature adjustment unit 445 may use a known temperature adjustment means such as a temperature adjustment device using a Peltier element or a heat exchanger using a refrigerant. Alternatively, the DIW tank 441 may not be provided in the first DIW supply unit 433, and DIW may be directly supplied from the factory utility side. Note that the pump 443 of the first DIW supply unit 433 always operates from the time when the substrate processing apparatus 9 is activated.

  The first DIW supply unit 433, the pipe 449, the collective pipe 449, the on-off valve 437, the nozzle 411, and the nozzle drive mechanism 413 constitute the coagulation target liquid supply means 43.

  Next, the configuration of the intrusion prevention liquid supply means 31 will be described with reference to FIG. FIG. 8 is a schematic diagram showing the configuration of the intrusion prevention liquid supply means 31. The nozzle 311 for supplying the intrusion prevention liquid to the substrate W is supported by a nozzle drive mechanism 313 installed on the lower surface of the upper base member 902 so as to be able to move up and down. The base member 315 of the nozzle drive mechanism 313 is fixed so as to extend downward on the lower surface of the upper base member 902 and outside the atmosphere introduction path 907.

  Below the base member 315, a turning vertical shaft 317 is held vertically and rotatably. Note that the base member 315 is formed in a hollow, substantially cylindrical shape for connecting a swing vertical shaft 317, a vertical drive unit 321 and a swing drive unit 319 described later. One end of an arm 323 is coupled to the lower surface of the turning vertical axis 317, and a nozzle 311 is attached to the other end of the arm 323.

  The swing vertical shaft 317 is connected through the base member 315 to a vertical drive unit 321 configured with a known drive mechanism such as a motor and a ball screw, and a swing drive unit 319 configured with a known drive mechanism such as a motor and a gear. Has been. Further, the vertical drive unit 321 and the turning drive unit 319 are electrically connected to the control unit 97. The vertical drive unit 321 and the turning drive unit 319 are disposed in the upper space 905.

  When the vertical drive unit 321 is driven by an operation command from the control unit 97 to the intrusion prevention liquid supply means 31, the turning vertical shaft 317 moves up and down, and the nozzle 311 attached to the arm 323 moves up and down. Further, when the turning drive unit 319 is driven by an operation command from the control unit 97 to the intrusion prevention liquid supply means 31, the turning vertical shaft 317 rotates around the rotation center axis A2, and the arm 323 turns, The nozzle 311 attached to the arm 323 is swung.

  The nozzle 311 is connected to the intrusion prevention liquid supply unit 333 via a pipe 335. The intrusion prevention liquid supply unit 333 may be provided inside the substrate processing apparatus 9 or may be provided outside.

  FIG. 9 shows the configuration of the intrusion prevention liquid supply unit 333. The intrusion prevention liquid supply unit 333 includes an intrusion prevention liquid tank 341 that stores the intrusion prevention liquid, a pump 343 that pumps intrusion prevention liquid from the intrusion prevention liquid tank 341, and a temperature adjustment unit 345 that adjusts the temperature of the intrusion prevention liquid. Is done.

  The pump 343 connected to the intrusion prevention liquid tank 341 by pressure connects the intrusion prevention liquid and sends it out through the pipe 335. A pipe 336 is further connected to the side where the pump 343 inserted in the pipe 335 sends out the intrusion prevention liquid, and the path through which the intrusion prevention liquid is sent is branched into two. The pipe 335 is connected to the nozzle 311, and the other pipe 336 is connected to the intrusion prevention liquid tank 341. An open / close valve 337 is inserted in the pipe 335, and an open / close valve 338 is inserted in the pipe 336. The open / close valve 337 is normally closed and the open / close valve 338 is always open.

  The on-off valves 337 and 338 are electrically connected to the control unit 97. Then, when the on-off valve 337 is opened and the on-off valve 338 is closed by an operation command from the control unit 97 to the intrusion prevention liquid supply means 31, the intrusion prevention liquid adjusted to a predetermined temperature is supplied from the intrusion prevention liquid supply unit 333. It is supplied to the nozzle 311 via the pipe 335.

  Further, when the on-off valve 337 is closed and the on-off valve 338 is opened by an operation command from the control unit 97 to the intrusion prevention liquid supply means 31, the intrusion prevention liquid sent from the pump 343 passes through the pipe 336 again and the intrusion prevention liquid tank. Return to 341. Thereby, the intrusion prevention liquid in the intrusion prevention liquid tank 341 is agitated, and the temperature of the intrusion prevention liquid in the intrusion prevention liquid tank 341 is made uniform. The pump 343 always operates from the time when the substrate processing apparatus 9 is activated.

  The intrusion prevention liquid tank 341 is provided with a temperature adjustment unit 345, and the heat exchange pipe 347 extending from the temperature adjustment unit 345 is immersed in the intrusion prevention liquid in the intrusion prevention liquid tank 341. Water is circulated inside the heat exchange pipe 347, and the temperature of the water circulating inside the heat exchange pipe 347 is adjusted by the temperature adjustment unit 345. The water flowing inside the heat exchange pipe 347 exchanges heat with the intrusion prevention liquid in the intrusion prevention liquid tank 341 to adjust the temperature of the intrusion prevention liquid.

  Here, the on-off valves 337 and 338 are configured such that the opened and closed states are opposite to each other. That is, when the intrusion prevention liquid is discharged from the nozzle 311 to the substrate surface Wf, the on-off valve 337 is opened, and the on-off valve 338 is closed. On the other hand, when the intrusion prevention liquid is not discharged from the nozzle 311 to the substrate surface Wf, the on-off valve 337 is closed, and sometimes the on-off valve 338 is opened.

  When the intrusion prevention liquid is not discharged from the nozzle 311 to the substrate surface Wf, the intrusion prevention liquid sent from the intrusion prevention liquid tank 341 by the pump 343 is returned to the intrusion prevention liquid tank 341 through the pipe 336, thereby entering. The intrusion prevention liquid in the prevention liquid tank 341 is agitated. Thereby, the temperature of the intrusion prevention liquid in the intrusion prevention liquid tank 341 can be made uniform.

  The method of adjusting the temperature of the intrusion prevention liquid is not limited to the above-described method, and a method of adjusting the temperature of the wall surface of the intrusion prevention liquid tank 341 itself or a unit of a Peltier element is immersed in place of the heat exchange pipe 347. A known temperature adjusting method such as a temperature adjusting method can be used.

  Further, the method for making the temperature of the intrusion prevention liquid in the intrusion prevention liquid tank 341 uniform is not limited to the above-described method, and a method of circulating an intrusion prevention liquid by providing a separate circulation pump, or an intrusion prevention liquid tank A known method such as a method of providing a propeller for stirring in 341 can be used.

  Next, the configuration of the coagulation means 35 will be described with reference to FIG. FIG. 10 is a schematic diagram showing the configuration of the solidifying means 35. The nozzle 351 that supplies the gas for solidification to the substrate W is supported by a nozzle drive mechanism 353 installed on the lower surface of the upper base member 902 so as to be able to move up and down and turn. The base member 355 of the nozzle drive mechanism 353 is fixed so as to extend to the lower surface of the upper base member 902 and to the outside of the atmosphere introduction path 907.

  Below the base member 355, a turning vertical shaft 357 is held vertically and rotatably. The base member 355 is formed in a hollow, substantially cylindrical shape for connecting a swing vertical shaft 357, a vertical drive unit 361 and a swing drive unit 359, which will be described later. The turning vertical axis 357 is supported so as to be movable up and down and rotatable with respect to the base member 355. One end of an arm 363 is coupled to the lower surface of the turning vertical axis 357, and a nozzle 351 is attached to the other end of the arm 363.

  The swing vertical shaft 357 is connected through the base member 355 to a vertical drive unit 361 configured with a known drive mechanism such as a motor and a ball screw, and a swing drive unit 359 configured with a known drive mechanism such as a motor and a gear. Has been. Further, the vertical drive unit 361 and the turning drive unit 359 are electrically connected to the control unit 97. The vertical drive unit 361 and the turning drive unit 359 are disposed in the upper space 905.

  When the vertical drive unit 361 is driven by an operation command from the control unit 97 to the solidifying means 35, the turning vertical shaft 357 moves up and down, and the nozzle 351 attached to the arm 363 moves up and down. Further, when the turning drive unit 359 is driven by an operation command from the control unit 97 to the solidifying means 35, the turning vertical shaft 357 rotates around the central axis A3, and the arm 363 turns to attach to the arm 363. The nozzle 351 is swung.

  The nozzle 351 is connected to a solidification nitrogen gas supply unit 373 via a pipe 375. The solidification nitrogen gas supply unit 373 is electrically connected to the control unit 97. The coagulation nitrogen gas supply unit 373 supplies nitrogen gas having a temperature lower than the solidification point of the coagulation target liquid to the nozzle 351 via the pipe 375 in accordance with an operation command from the control unit 97. Further, the solidification nitrogen gas supply unit 373 may be provided inside or outside the substrate processing apparatus 9.

  FIG. 11 shows the configuration of the solidification nitrogen gas supply unit 373. The solidification nitrogen gas supply unit 373 supplies the nitrogen gas to the gas cooling unit 611 from the gas cooling unit 611 that cools the nitrogen gas using the cold heat of liquid nitrogen, the liquid nitrogen tank 613 that stores liquid nitrogen, and the liquid nitrogen tank 613. A pump 615 that stores nitrogen gas, a pump 621 that supplies nitrogen gas from the nitrogen gas tank 619 to the gas cooling unit 611, and a mass flow that controls the flow rate of nitrogen gas supplied from the nitrogen gas tank 619 to the gas cooling unit 611 The controller 625 is configured. Note that the nitrogen gas in the nitrogen gas tank 619 is a gas that does not contain moisture such as water vapor in a dry state.

  The container 627 of the gas cooling unit 611 has a tank shape so that liquid nitrogen can be stored therein, and a material that can withstand the temperature of liquid nitrogen (− (minus) 195.8 ° C. (Celsius)), for example, It is made of glass, quartz or HDPE (High Density Polyethylene). In addition, you may employ | adopt the double structure which covers the container 627 with a heat insulation container. In this case, the heat insulating container is formed of a highly heat insulating material such as a foamable resin or PVC (Polyvinyl Chloride) in order to suppress heat transfer between the external atmosphere and the container 627. It is preferable to do this.

  The container 627 is connected to the liquid nitrogen tank 613 via a pipe 617, and a pump 615 is inserted in the pipe 617. The pump 615 is electrically connected to the control unit 97. A liquid level sensor (not shown) is provided in the container 627 and is electrically connected to the control unit 97. The control unit 97 keeps the amount of liquid nitrogen stored in the container 627 constant by controlling the operation of the pump 615 based on the value detected by the liquid level sensor.

  Inside the container 627, a coiled heat exchange pipe 629 formed of a metal tube such as stainless steel or copper is provided as a gas transmission path, and is immersed in liquid nitrogen stored in the container 627. One end of the heat exchange pipe 629 (the side protruding to the right from the upper side of the side wall of the container 627 in FIG. 13) is connected to a nitrogen gas tank 619 via a pipe 623, and a pump 621 is connected to the pipe 623. The mass flow controller 625 is inserted between the pump 621 and the container 627.

  The mass flow controller 625 is electrically connected to the control unit 97. The other end of the heat exchange pipe 629 (the side protruding above the container 627 in FIG. 13) is connected to the nozzle 351 through a pipe 375. The pump 621 always operates from the time when the substrate processing apparatus 9 is activated.

  When the mass flow controller 625 is opened to a predetermined flow rate by an operation command from the control unit 97 to the solidifying means 35, nitrogen gas is supplied from the nitrogen gas tank 619 to the heat exchange pipe 629 in the gas cooling unit 611, and nitrogen is supplied. While the gas passes through the heat exchange pipe 629, it is cooled by the cold heat of liquid nitrogen stored in the container 627. Nitrogen gas cooled while passing through the heat exchange pipe 629 is supplied to the nozzle 351 through the pipe 375.

  Note that a minute space is provided between the other end of the heat exchange pipe 629 (the side protruding above the container 627 in FIG. 11) and the container 627, and the space inside the container 627 is connected to the exhaust pipe 631. It forms a continuous distribution channel. The liquid nitrogen stored in the container 627 is vaporized by cooling the nitrogen gas flowing in the heat exchange pipe 629, and the vaporized nitrogen gas passes through this flow path and is exhausted through an exhaust pipe 631 (not shown). Discharged into the grid.

  In this embodiment, nitrogen gas is used as the coagulation gas. However, the coagulation gas is not limited to nitrogen gas, and other gases such as dry air, ozone gas, and argon gas can be used. The means for cooling the coagulation gas is not limited to liquid nitrogen, and a low-temperature liquid such as liquid helium can be used, and it is also possible to electrically cool using a Peltier element. .

  Further, the liquid nitrogen tank 613 and the nitrogen gas tank 619 may not be provided in the solidification nitrogen gas supply unit 373, and liquid nitrogen and nitrogen gas may be supplied from the factory utility side. The solidification nitrogen gas supply unit 373 may be provided inside or outside the substrate processing apparatus 9.

  As will be described later, the solidifying means 35 also functions as a removing means by discharging nitrogen gas cooled from the nozzle 351 to the substrate W continuously in the removing process following the solidifying process. The coagulating gas also functions as a removing gas in the removing step.

  Next, the structure of the rinse means 51 and the gas supply means 55 for drying is demonstrated using FIG. FIG. 12 is a schematic diagram showing the configuration of the rinsing means 51 and the drying gas supply means 55. The rinsing means 51 supplies a rinsing liquid toward the substrate surface Wf and the substrate back surface Wb, and the drying gas supply means 55 supplies a drying gas toward the substrate surface Wf and the substrate back surface Wb.

  First, the pipeline configuration on the substrate surface Wf side will be described. The upper first supply pipe 271 is inserted into the hollow portion that communicates from the upper surface of the blocking member rotating mechanism 235 of the atmosphere blocking means 23 to the opening of the central portion of the blocking member 231, and the upper first supply pipe The upper second supply pipe 273 is inserted into the 271 to form a so-called double pipe structure. The lower ends of the upper first supply pipe 271 and the upper second supply pipe 273 are extended to the opening of the blocking member 231, and a nozzle 275 is provided at the tip of the upper second supply pipe 273.

  Next, the pipe line configuration on the substrate rear surface Wb side will be described. The lower first supply pipe 281 is inserted into the communication space from the upper surface of the spin base 113 of the substrate holding means 11 to the lower space 906 through the central axis 117 and the lower first supply pipe. A lower second supply pipe 283 is inserted through 281 to form a so-called double pipe structure. Upper ends of the lower first supply pipe 281 and the lower second supply pipe 283 are extended to the opening of the spin base 113, and a nozzle 291 is provided at the tip of the lower second supply pipe 283. .

  Next, the rinsing means 51 will be described. The rinsing means 51 supplies DIW as a rinsing liquid from the second DIW supply unit 513, which is a supply source of the rinsing liquid, to the substrate surface Wf and the substrate back surface Wb, respectively. One end of a main pipe 515 is connected to a second DIW supply unit 513 having a DIW tank, a temperature adjustment unit, and a pump (not shown). The other end of the main pipe 515 branches to an upper branch pipe 517 and a lower branch pipe 521, the upper branch pipe 517 is connected to the upper second supply pipe 273, and the lower branch pipe 521 is connected to the lower second supply pipe 283, respectively. The pipeline is connected. The pump of the second DIW supply unit 513 is always operating from the time when the substrate processing apparatus 9 is activated.

  Next, the rinsing means 51 will be described. The rinsing means 51 supplies DIW as a rinsing liquid from the second DIW supply unit 513, which is a supply source of the rinsing liquid, to the substrate surface Wf and the substrate back surface Wb, respectively. One end of a main pipe 515 is connected to a second DIW supply unit 513 having a DIW tank, a temperature adjustment unit, and a pump (not shown). The other end of the main pipe 515 branches to an upper branch pipe 517 and a lower branch pipe 521, the upper branch pipe 517 is connected to the upper second supply pipe 273, and the lower branch pipe 521 is connected to the lower second supply pipe 283, respectively. The pipeline is connected. The pump of the second DIW supply unit 513 is always operating from the time when the substrate processing apparatus 9 is activated.

  The rinse liquid is not limited to DIW, and may be pure water, carbonated water in which carbonic acid is dissolved, or a mixed liquid in which isopropyl alcohol is added to DIW. Those which can be used for removing pretreatment chemicals and the like can be used.

  An open / close valve 523 is inserted in the lower branch pipe 521. The on-off valve 523 is always closed. The on-off valve 523 is electrically connected to the control unit 97. When the opening / closing valve 523 is opened by an operation command from the control unit 97 to the rinsing means 51, the rinsing liquid is supplied from the second DIW supply unit 513 to the nozzle through the main pipe 515, the lower branch pipe 521 and the lower second supply pipe 283. 291 to the substrate back surface Wb.

  The second DIW supply unit 513, main pipe 515, upper branch pipe 517, lower branch pipe 521, on-off valve 519, on-off valve 523, upper second supply pipe 273, lower second supply pipe 283, nozzle 275, and The nozzle 291 constitutes the rinsing means 51. The second DIW supply unit 513 may be provided inside the substrate processing apparatus 9 or may be provided outside.

  Next, the drying gas supply means 55 will be described. The drying gas supply means 55 supplies the drying nitrogen gas to the substrate front surface Wf and the substrate back surface Wb from the drying nitrogen gas supply unit 553 that is a supply source of the drying gas. One end of a main pipe 555 is connected to a drying nitrogen gas supply unit 553 having a nitrogen gas tank and a pump (not shown). The other end of the main pipe 555 branches into an upper branch pipe 557 and a lower branch pipe 561, the upper branch pipe 557 is connected to the upper first supply pipe 271 and the lower branch pipe is connected to the lower first supply pipe 281. Road connection. Further, the pump of the drying nitrogen gas supply unit 553 is always operating from the time when the substrate processing apparatus 9 is activated.

  A mass flow controller 559 is inserted in the upper branch pipe 557. The mass flow controller 559 is electrically connected to the control unit 97. Then, when the mass flow controller 559 is opened by the operation command from the control unit 97 to the drying gas supply means 55 so that the flow rate becomes a predetermined flow rate, normal temperature nitrogen gas is supplied to the main pipe 555, the upper branch pipe 557, and the upper first supply. It is supplied to the substrate surface Wf via the tube 271.

  A mass flow controller 563 is inserted in the lower branch pipe 561. The mass flow controller 563 is electrically connected to the control unit 97. Then, when the mass flow controller 563 is opened by the operation command from the control unit 97 to the drying gas supply means 55 so that the flow rate becomes a predetermined flow rate, nitrogen gas at room temperature is supplied to the main pipe 555, the lower branch pipe 561, and the lower side It is supplied to the substrate back surface Wb through one supply pipe 281.

  The drying nitrogen gas supply unit 553, the main pipe 555, the upper branch pipe 557, the lower branch pipe 561, the mass flow controller 559, the mass flow controller 563, the upper first supply pipe 271 and the lower first supply pipe 281 are for drying. The gas supply means 55 is comprised. Note that the drying nitrogen gas supply unit 553 may be provided inside or outside the substrate processing apparatus 9.

  The control unit 97 is a CPU that performs various arithmetic processes, a ROM that is a read-only memory that stores basic programs, a RAM that is a readable and writable memory that stores various information, and a magnet that stores control software and data. Have a disc. In the magnetic disk, drying (processing) conditions corresponding to the substrate W are stored in advance as a drying program (also called a recipe), and the CPU reads the contents into the RAM, and according to the contents of the drying program read into the RAM. The CPU controls each part of the substrate processing apparatus 9. The control unit 97 is connected to an operation unit 971 (see FIG. 1) used for creating / changing a drying program and selecting a desired one from a plurality of drying programs.

  Next, the drying processing operation in the substrate processing apparatus 9 configured as described above will be described with reference to FIG. FIG. 13 is a flowchart showing the overall operation of the substrate processing apparatus 9. Unless otherwise specified in the following description, the atmosphere blocking unit 23 is configured to rotate at substantially the same rotational speed in the direction in which the substrate rotating mechanism 121 of the substrate holding unit 11 rotates the spin base 113 when the blocking member 231 is in the facing position. It is assumed that the blocking member 231 is rotated.

  First, a drying program corresponding to a predetermined substrate W is selected by the operation unit 971 and executed. Thereafter, in preparation for carrying the substrate W into the processing unit 91, the following operation is performed according to an operation command from the control unit 97.

  That is, the atmosphere blocking unit 23 stops the rotation of the blocking member 231, and the substrate holding unit 11 stops the rotation of the spin base 113. The atmosphere blocking unit 23 moves the blocking member 231 to the separated position, and the substrate holding unit 11 positions the spin base 113 to a position suitable for delivery of the substrate W. Further, the drainage collecting means 21 positions the cup 210 at the home position. After the spin base 113 is positioned at a position suitable for delivery of the substrate W, the substrate holding means 11 is brought into the substrate holding member 115 open state.

  Further, the intrusion prevention liquid supply means 31 is the retreat position of the nozzle 311, the coagulation means 35 is the nozzle 351, and the coagulation target liquid supply means 43 is the retreat position (position where each nozzle is outside the circumferential direction of the cup 210). Move to. Further, the on-off valves 337, 437, 519 and 523 are closed, and the on-off valve 338 is opened. Further, the mass flow controllers 559, 563, and 625 are set to a flow rate 0 (zero).

  After the preparation for carrying the substrate W into the processing unit 91 is completed, a substrate carrying-in step (step S101) for carrying the unprocessed substrate W into the processing unit 91 is performed. That is, the indexer robot 931 takes out the substrate W at a predetermined position of the FOUP 949 on the opener 94 with the lower hand 933 and places it on the lower hand 951 of the shuttle 95. Thereafter, the lower hand 951 of the shuttle 95 is moved toward the center robot 96, and the center robot 96 picks up the substrate W on the lower hand 951 of the shuttle 95 with the lower hand 961.

  Thereafter, the shutter 911 of the processing unit 91 is opened, the center robot 96 extends the lower hand 961 into the processing unit 91, and the substrate W is placed on the substrate support portion of the substrate holding member 115 of the substrate holding means 11. Put. When the loading of the substrate W into the processing unit 91 is completed, the center robot 96 contracts the lower hand 961 and puts it out of the processing unit 91, and the shutter 911 is closed.

  When an unprocessed substrate W is carried into the processing unit 91 and placed on the substrate support portion of the substrate holding member 115, a substrate holding member driving mechanism is operated by an operation command from the control unit 97 to the substrate holding means 11. 119 closes the substrate holding member 115. In the substrate processing apparatus 9, the substrate W on which the surface Wf has been subjected to a chemical treatment such as hydrofluoric acid with the substrate surface Wf facing upward is carried into the apparatus and held by the substrate holding means 11.

  When the substrate loading is completed, a rinsing process is performed next (step S102). The DIW discharge nozzle 3 is moved to the rotation center position above the rotation center A0 of the substrate W, and the rinse process is executed. In response to an operation instruction from the control unit 97 to the atmosphere blocking means 23, the blocking member lifting mechanism 247 moves the blocking member 231 to the opposite position. Further, according to an operation command from the control unit 97 to the substrate holding means 11, the substrate rotation mechanism 121 changes the rotation speed of the spin base 113 and maintains it during the rinsing process. Note that the cup 210 remains in the internal collection position.

  The number of rotations of the substrate W in the rinsing process is such that the rinsing liquid supplied to the substrate surface Wf and the substrate back surface Wb can be diffused over the entire surface of the substrate surface Wf and the substrate back surface Wb, and the substrate surface Wf is diffused. It is preferable to set it as 300-1000 rpm so that the chemical | medical solution which remains on the surface Wf can be removed. Below, the rotation speed of the board | substrate W in a rinse process is demonstrated as 800 rpm.

  After the blocking member 231 is positioned at the facing position, the opening / closing valve 519 and the opening / closing valve 523 are opened by an operation instruction from the control unit 97 to the rinsing means 51.

  As a result, the rinsing liquid from the second DIW supply unit 513 passes from the nozzle 275 to the substrate surface Wf via the main pipe 515, the upper branch pipe 517, and the upper second supply pipe 273, and the main pipe 515 and the lower branch pipe. 521 and the lower second supply pipe 283 to be supplied from the nozzle 291 to the substrate back surface Wb. The rinsing liquid supplied near the center of each of the substrate front surface Wf and the substrate back surface Wb flows in the direction of the substrate periphery due to the centrifugal force generated by the rotation of the substrate W, and finally scatters from the substrate periphery to the outside of the substrate W. It is collected and drained by the drainage collecting means 21.

  In this rinsing step, the control unit 97 drives the chuck rotating mechanism 22 to rotate the substrate W together with the spin chuck 2 at, for example, 300 rpm, and the DIW from the nozzle 275 and the nozzle 291 to the substrate surface Wf and the back surface Wb for 10 seconds, for example. Supply. The DIW supplied to the substrate surface Wf is subjected to a centrifugal force accompanying the rotation of the substrate W, and is uniformly spread outward in the radial direction of the substrate W, so that a rinsing process is performed on the substrate surface Wf. The rinsing liquid also plays a role of removing DIW and the like scattered on the back surface Wb portion of the substrate W in each of the preceding steps, and particles adhering to the substrate W attached to the substrate W. .

  After the rinsing process, the on / off valve 519 and the on / off valve 523 are closed by an operation command from the control unit 97 to the rinsing means 51.

  Next, an intrusion prevention liquid supply step (step S103) for supplying an intrusion prevention liquid is performed on the substrate surface Wf. First, in response to an operation command from the control unit 97 to the substrate holding means 11, the substrate rotation mechanism 121 starts rotation of the spin base 113 and maintains it during the intrusion prevention liquid supply process. Further, the cup 210 is positioned at the middle collection position by an operation command from the control unit 97 to the drainage collecting means 21. Note that the blocking member 231 of the atmosphere blocking means 23 remains in the separated position.

  The number of rotations of the substrate W in the intrusion prevention liquid supply step is preferably 300 to 500 rpm so that the intrusion prevention liquid supplied to the substrate surface Wf can diffuse over the entire surface of the substrate surface Wf. In the following description, it is assumed that the rotation speed of the substrate W in the intrusion prevention liquid supply step is 300 rpm.

  Further, the nozzle drive mechanism 313 positions the nozzle 311 above the center of the substrate surface Wf according to an operation command from the control unit 97 to the intrusion prevention liquid supply unit 31. After the positioning of the nozzle 311 is completed, the on-off valve 337 is opened and the on-off valve 338 is closed by an operation command from the control unit 97 to the intrusion prevention liquid supply means 31. As a result, HFE is supplied from the intrusion prevention liquid supply unit 333 as an intrusion prevention liquid from the nozzle 311 to the vicinity of the center of the substrate surface Wf via the pipe 335.

  The intrusion prevention liquid is cooled to − (minus) 10 ° C. (degrees Celsius) to 5 ° C. (degrees Celsius) in order to cool the substrate W and reduce the time required for the solidification of the liquid to be solidified in the solidification step described later. It is preferable. In the following description, it is assumed that the temperature of the intrusion prevention liquid is 0.5 ° C. (Celsius). HFE has a freezing point between −38 ° C. and −135 ° C., and is used as −38 ° C. in this embodiment, so that it is supplied as a liquid even if the temperature is adjusted to the above range.

  The intrusion prevention liquid supplied near the center of the substrate surface Wf flows from the center of the substrate W toward the peripheral edge of the substrate W by the centrifugal force generated by the rotation of the substrate W, and diffuses over the entire surface of the substrate surface Wf. . As the intrusion prevention liquid flows, the rinsing liquid is removed and DIW is insoluble in HFE, so the intrusion prevention liquid is used until the intrusion prevention liquid penetrates into the gaps of the pattern formed on the substrate surface Wf. Supply. As a result, the DIW on the substrate surface Wf is replaced by HFE.

  After the intrusion prevention liquid diffuses over the entire surface Wf of the substrate, the on / off valve 337 is closed and the on / off valve 338 is opened by an operation command from the control unit 97 to the intrusion prevention liquid supply means 31. Further, according to an operation command from the control unit 97 to the intrusion prevention liquid supply means 31, the nozzle drive mechanism 313 positions the nozzle 311 to a retracted position (a position where the nozzle 311 is outside the circumferential direction of the cup 210).

  Next, a coagulation target liquid supply step (step S104) for supplying the coagulation target liquid to the substrate surface Wf to which the intrusion prevention liquid is attached is performed. First, the cup 210 is positioned at the external collection position by an operation command from the control unit 97 to the drainage collecting means 21. The rotation of the substrate W is maintained at the same rotational speed as that in the intrusion prevention liquid supplying process. Note that the blocking member 231 of the atmosphere blocking means 23 remains in the separated position.

  Further, the nozzle drive mechanism 413 positions the nozzle 411 above the center of the substrate surface Wf by an operation command from the control unit 97 to the coagulation target liquid supply means 43. After the positioning of the nozzle 411 is completed, the on-off valve 437 is opened by an operation command from the control unit 97 to the coagulation target liquid supply means 43. Thereby, DIW is supplied from the first DIW supply unit 433 as the liquid to be solidified from the nozzle 411 to the vicinity of the center of the substrate surface Wf via the pipe 449.

  It should be noted that the liquid to be coagulated is 0 ° C. (Celsius) so as to shorten the time required for coagulation in the coagulation process described later, and to prevent evaporation and collapse of the pattern before being coagulated in the coagulation process due to the high temperature. ) To 5 ° C. (degrees Celsius). In the following description, it is assumed that the temperature of the coagulation target liquid is 0.5 ° C. (Celsius).

  The liquid to be solidified supplied to the vicinity of the center of the substrate surface Wf is the intrusion prevention liquid attached to the substrate surface Wf from the center of the substrate W toward the peripheral edge of the substrate W due to the centrifugal force generated by the rotation of the substrate W. It flows while eliminating. However, since the pattern formed on the substrate surface Wf is fine, and DIW has a large surface tension, the liquid to be solidified has a small area in the vicinity of the pattern including the inside of the pattern gap (hereinafter referred to as “pattern vicinity”). It cannot be easily penetrated. Moreover, since HFE is insoluble in DIW, it becomes more difficult to enter. Therefore, in the solidification target liquid supply step, a liquid layer of the solidification target liquid is formed on the substrate surface Wf while the intrusion prevention liquid remains in the vicinity of the pattern formed on the substrate surface Wf.

  Here, the state of the substrate surface Wf in the solidification target liquid supplying step will be described with reference to FIGS. FIG. 14A is a schematic view showing the state of the substrate surface Wf after the end of the intrusion prevention liquid supplying step, and FIG. 14B is a schematic view showing the state of the substrate surface Wf after the end of the solidification target liquid supplying step. FIG.

  In the intrusion prevention liquid supply step, the intrusion prevention liquid 983 supplied to the substrate surface Wf is, as shown in FIG. 14A, the gap between the pattern 981 and the pattern 981 and the pattern 981 having a group of fine irregularities. It penetrates into the pattern gap between adjacent convex portions.

  Thereafter, the intrusion prevention liquid 983 on the substrate surface Wf is swept away by the solidification target liquid 985 supplied on the substrate surface Wf in the solidification target liquid supply step. However, since the intrusion prevention liquid 983 remains in the vicinity of the pattern 981 as described above, the state shown in FIG. 14B is obtained when the coagulation target liquid supply process is completed.

  That is, the intrusion prevention liquid 983 remains inside the gap of the pattern 981 formed on the substrate surface Wf and in the vicinity of the side wall of the outermost convex portion, and other portions (the substrate surface where the pattern is not formed or the convexity of the pattern). A liquid film of the coagulation target liquid 985 is formed on the part upper surface and the like. Here, “in the vicinity of the pattern” in the present embodiment indicates an area where the intrusion prevention liquid 983 indicated by reference numeral 987 in FIG. 14B remains, and the “outside pattern area” indicates in FIG. 14B. An intrusion prevention liquid 983 indicated by reference numeral 989 is removed by the coagulation target liquid 985, and indicates an area where the coagulation target liquid 985 is in contact with the substrate surface Wf.

  The boundary between the pattern vicinity 987 and the non-pattern area 989 is determined by the supply time and flow rate of the coagulation target liquid 985 supplied in the coagulation target liquid supply step, the number of rotations of the substrate W, and the like. By changing, the pattern vicinity 987 can be widened and the pattern outside area 989 can be narrowed, or the pattern vicinity 987 can be narrowed and the pattern outside area 989 can be widened. The width of these areas is appropriately determined based on the strength of the pattern, the range of the non-pattern area 989 to be cleaned, and the like.

  Returning to FIG. After the liquid layer of the coagulation target liquid is formed on the substrate surface Wf, the on-off valve 437 is closed by an operation command from the control unit 97 to the coagulation target liquid supply means 43. Further, according to an operation command from the control unit 97 to the coagulation target liquid supply means 43, the nozzle drive mechanism 413 positions the nozzle 411 to the retracted position (position where the nozzle 411 is disengaged in the circumferential direction outside the cup 210).

  Next, a coagulation step (step S105) for coagulating the liquid film of the liquid to be coagulated formed on the substrate surface Wf is performed. First, according to an operation command from the control unit 97 to the substrate holding means 11, the substrate rotation mechanism 121 changes the rotation speed of the spin base 113 and maintains it during the solidification process. The rotation speed of the substrate W in the coagulation step is desirably rotated at a rotation speed of 30 to 100 rpm so that the liquid film of the liquid to be solidified formed on the substrate surface Wf can be uniformly solidified. In the following description, it is assumed that the rotation speed of the substrate W in the solidification process is 60 rpm. Further, the cup 210 is positioned at the internal collection position by an operation command from the control unit 97 to the drainage collecting means 21. Note that the blocking member 231 of the atmosphere blocking means 23 remains in the separated position.

  Further, the nozzle drive mechanism 353 positions the nozzle 351 above the center of the substrate surface Wf in accordance with an operation command from the control unit 97 to the solidifying means 35. After the positioning of the nozzle 353 is completed, the control unit 97 adjusts the temperature to be lower than the freezing point of the liquid to be solidified (DIW freezing point 0 ° C. (degrees Celsius)) from the solidification nitrogen gas supply unit 373 by an operation command from the solidification means 35. The solidified gas is supplied from the nozzle 351 to the vicinity of the center of the substrate surface Wf via the pipe 375.

  The temperature of the coagulation gas is preferably as low as possible in order to reduce the temperature of the solidification target liquid as much as possible to improve the removal rate of particles and the like. However, in order to perform freezing and cleaning while maintaining the intrusion prevention liquid as a liquid, the temperature of the coagulation target liquid and the intrusion prevention liquid is set to the freezing point of HFE (the one with the highest freezing point, − (minus) 38 ° C. (Celsius). ) Do not cool to lower temperatures.

  However, as will be described later, the coagulation gas is discharged from the nozzle 351 moving on the surface Wf of the rotating substrate W from above the vicinity of the center of the substrate W to above the end thereof, and solidifies on the substrate W and the substrate surface Wf. In order to cool the target liquid and the intrusion prevention liquid, the amount of cooling heat supplied per unit area on the substrate W is limited. Moreover, it is preferable that the temperature is adjusted to −50 ° C. to − (minus) 190 ° C. (degrees Celsius) in consideration of the efficiency of cooling the liquid and solid with gas and the endothermic heat from the atmosphere. In the following description, it is assumed that the temperature of the coagulation gas is adjusted to − (minus) 190 ° C. (Celsius).

  After the discharge of the coagulation gas from the nozzle 351, the nozzle drive mechanism 353 causes the nozzle 351 to move from the vicinity of the center of the substrate surface Wf to the vicinity of the peripheral portion of the substrate surface Wf by an operation command from the control unit 97 to the coagulation means 35. Turn to the sky. In this way, by rotating the nozzle 351 from the vicinity of the center of the substrate surface Wf to the vicinity of the peripheral edge while rotating the substrate W, it becomes possible to blow the coagulation gas over the entire surface of the substrate surface Wf. It is possible to form a solidified body of the liquid to be solidified uniformly over the entire surface of Wf.

  The volume of DIW, which is the coagulation target liquid, increases in volume by solidifying into ice (when water at 0 ° C (degrees Celsius) becomes ice at 0 ° C (degrees Celsius), the volume increases approximately 1.1 times. To do). Accordingly, the DIW that has entered between the substrate surface Wf and the particles or the like solidifies and expands, whereby the particles or the like are separated from the substrate surface Wf by a minute distance. As a result, the adhesion force between the substrate surface Wf and the particles or the like is reduced, and further, the particles or the like are detached from the substrate W. Further, by expanding in a direction parallel to the substrate surface Wf, particles and the like fixed to the substrate are peeled off. As a result, the solidified body of the liquid to be solidified is removed by a removal step described later, and particles and the like are also easily removed.

  Note that the expansion of the volume due to the solidification of the liquid to be solidified occurs over the entire surface of the substrate surface Wf, but the intrusion prevention liquid remains in the liquid state in the vicinity of the pattern as shown in FIG. The pattern is prevented from being damaged without being affected by the force due to the solidification of the liquid to be solidified and the volume expanding. That is, the force due to volume expansion is received by the liquid and does not directly affect the pattern itself. Therefore, damage such as collapse or peeling of the pattern convex portion that becomes finer due to the solidification process does not occur.

  The swiveling movement of the nozzle 351 not only moves from the sky near the center of the substrate surface Wf to the sky near the peripheral edge of the substrate surface Wf, but also repeatedly moves from the sky near the center to the sky near the peripheral edge a plurality of times. Alternatively, it may be reciprocated between the sky near the center and the sky near the periphery.

  Next, a removal process (step S106) is performed to remove the solidified body of the liquid to be solidified formed on the substrate surface Wf. First, according to an operation command from the control unit 97 to the substrate holding means 11, the substrate rotation mechanism 121 maintains the rotation speed of the spin base 113 during the removal process. On the other hand, after the liquid to be solidified has solidified, the temperature of the solidifying gas is adjusted from −190 ° C. to −60 ° C.

Even after the formation of the frozen film in which DIW is solidified to become ice, the coagulation gas is continuously supplied to the substrate surface Wf. Then, the frozen film sublimates with time. This is the same phenomenon as the ice in the freezer gets smaller and smaller. That is, in this embodiment, the temperature of the nitrogen gas is adjusted by the gas cooling unit 611, and the temperature at which the water vapor in the solidifying nitrogen gas begins to condense, that is, the dew point is about −60 ° C. As shown in FIG. 15, the pressure is reduced to about 1 Pa (7.5 × 10 ⁻³ Torr).

  On the other hand, the temperature of the frozen film is higher than the temperature of the solidifying nitrogen gas, and is about −20 ° C. according to actual measurement. This is presumably because the back surface Wb of the substrate W faces a normal temperature atmosphere, and the temperature drop of the frozen film is suppressed by heat transfer from the substrate back surface Wd to the substrate surface Wf. However, since the solidification nitrogen gas is continuously supplied to the substrate surface Wf, the frozen film does not change to the liquid phase, and the solidification nitrogen gas temperature Tg (−60 ° C. in this embodiment) and DIW The temperature Ts (−20 ° C. in this embodiment) between the freezing point of

  Therefore, the vapor pressure (sublimation pressure) of the frozen film at the temperature Ts, for example, about 100 Pa at −20 ° C., the partial pressure of water vapor in the coagulation nitrogen gas is as low as about 1 Pa as described above. Sublimation evaporation of the frozen film occurs to fill the pressure difference. In addition, in this embodiment, since the coagulation nitrogen gas is continuously supplied, the situation where the partial pressure of water vapor in the coagulation nitrogen gas is lower than the vapor pressure of the frozen film is maintained, and sublimation drying proceeds. To go.

  Moreover, since the water vapor component generated by sublimation is removed from the substrate surface Wf by riding on the flow of nitrogen gas for solidification, the water vapor component generated by sublimation from the frozen film returns to the liquid phase or solid phase and reattaches to the substrate surface Wf. Can be surely prevented. As described above, in the present embodiment, the frozen film is sublimated into the gas phase without causing the liquid phase in the atmospheric pressure atmosphere, and is removed from the substrate surface Wf together with the nitrogen gas for solidification, and the substrate W is dried. The Therefore, the coagulation gas supplied from the coagulation process in the removal process functions as a gas for removal in the removal process.

  As the sublimation drying proceeds, an intrusion prevention liquid removing step (step S107) is performed next. Here, the state of the substrate surface Wf in the intrusion prevention liquid removing step will be described with reference to FIGS. FIG. 16A is a schematic view showing the state of the substrate surface Wf after the start of the intrusion prevention liquid removing step, and FIG. 16B is a schematic view showing the state of the substrate surface Wf after the end of the intrusion prevention liquid removing step. FIG.

  In the removing step, the frozen film 985a on the substrate surface Wf is continuously supplied with nitrogen gas for solidification, and sublimation evaporation occurs from the surface. As a result, as shown in FIG. 16A, the thickness of the frozen film 985a is reduced, and the tip of the pattern 981 is exposed. At the same time, the liquid surface of the intrusion prevention liquid 983 that is liquid HFE remaining in the pattern vicinity 987 is exposed. For this reason, the coagulation nitrogen gas is supplied to the liquid surface of the intrusion prevention liquid 983.

  Here, similarly to the frozen film 985a, the intrusion prevention liquid 983 has a vapor pressure (sublimation pressure) of HFE as the intrusion prevention liquid 983 at the temperature Ts of about 20 kPa at −20 ° C. The partial pressure of the vapor is as low as about 0 Pa when the solidification nitrogen gas is generated in a dry state gas so as not to contain HFE vapor, and HFE is evaporated to fill this vapor pressure difference. As described above, evaporation of the intrusion prevention liquid 983 occurs in parallel with the sublimation drying of the frozen film 985a, whereby the removal of the frozen film by sublimation drying and the intrusion prevention liquid removal process are started.

  Then, as shown in FIG. 16B, the end of the intrusion prevention liquid removing step, the intrusion prevention liquid 983 is completely evaporated during the sublimation drying of the frozen film 985a. That is, the pattern 981 is prevented from being damaged by the intrusion prevention liquid 983 in the solidification process.

  Furthermore, the coagulation gas is continuously supplied to the substrate surface Wf even after the intrusion prevention liquid removing step is completed. The removal process is completed when the frozen film 985a is sublimated into the gas phase without causing a liquid phase in an atmospheric pressure atmosphere and is completely removed from the substrate surface Wf together with the solidifying nitrogen gas. Thus, in this embodiment, the coagulation means 35 also functions as a removal means that performs the removal process and the intrusion prevention liquid removal process, and the coagulation gas also functions as a removal gas in the removal process.

  After the solidified body of the liquid to be solidified is formed on the entire surface of the substrate surface Wf, the solidified body of the liquid to be solidified is removed from the substrate surface Wf, and then the solidification nitrogen gas is generated by an operation command from the control unit 97 to the solidifying means 35. The supply of nitrogen gas from the supply unit 373 is stopped. Further, according to an operation command from the control unit 97 to the coagulation means 35, the nozzle drive mechanism 353 positions the nozzle 351 to the retracted position (position where the nozzle 351 is disengaged in the circumferential direction outside the cup 210).

  Next, an atmosphere replacement process for replacing the atmosphere on the surface of the substrate surface Wf is performed (step S108). In response to an operation command from the control unit 97 to the drying gas supply means 55, the mass flow controller 559 and the mass flow controller 563 are opened so as to have a predetermined flow rate. Note that the blocking member 231 of the atmosphere blocking means 23 remains at the facing position, and the cup 210 remains at the internal collection position.

  As a result, room temperature drying nitrogen gas from the drying nitrogen gas supply unit 553 is supplied to the substrate surface Wf via the main pipe 555, the upper branch pipe 557, and the upper first supply pipe 271, and also to the main pipe 555, It is supplied to the substrate back surface Wb through the side branch pipe 561 and the lower first supply pipe 281. The drying nitrogen gas fills the space between the lower surface of the blocking member 231 positioned at the opposite position and the substrate surface Wf, and also fills the space between the upper surface of the spin base 113 and the substrate back surface Wb. This prevents the substrate front surface Wf and the substrate back surface Wb from coming into contact with the outside air.

  After the substrate W is shut off from the outside air, the substrate rotation mechanism 121 changes the rotation speed of the spin base 113 according to an operation command from the control unit 97 to the substrate holding means 11 and maintains it during the atmosphere replacement process. The rotation speed of the substrate W in the atmosphere replacement process is set to 1500 to 3000 rpm so that the nitrogen gas for solidification remaining on the substrate front surface Wf and the substrate back surface Wb can be shaken out of the substrate W by centrifugal force. preferable. Below, the rotation speed of the board | substrate W in an atmosphere substitution process is demonstrated as 2000 rpm.

  After the atmosphere replacement of the substrate W is completed, the mass flow controller 559 and the mass flow controller 563 are set to 0 (zero) in accordance with an operation command from the control unit 97 to the drying gas supply means 55. Further, the substrate rotation mechanism 121 stops the rotation of the spin base 113 in accordance with an operation command from the control unit 97. Further, the blocking member rotating mechanism 235 stops the rotation of the blocking member 231 according to an operation command from the control unit 97 to the atmosphere blocking means 23. Further, the cup 210 is positioned at the home position by an operation command from the control unit 97 to the drainage collecting means 21. After the rotation of the spin base 113 is stopped, the substrate rotation mechanism 121 positions the spin base 113 at a position suitable for delivery of the substrate W by an operation command from the control unit 97. Further, in response to an operation command from the control unit 97 to the atmosphere blocking means 23, the blocking member elevating mechanism 247 moves the blocking member 231 to the separated position.

  When the freezing film 985a is completely removed from the substrate surface Wf and the removal process is completed, the temperature of the substrate W is equal to or lower than the freezing point of DIW. If the substrate W is carried out at a low temperature, dew condensation occurs on the substrate surface Wf. Will occur. Therefore, in the present embodiment, the atmosphere replacement process is performed for the purpose of preventing condensation after the removal process is completed.

  In this atmosphere replacement step, the supply of the room temperature nitrogen gas is started in place of the supply of the solidification nitrogen gas from the gas cooling unit 611 being stopped. In this way, the room temperature nitrogen gas is supplied to the substrate surface Wf, whereby the temperature of the substrate W is returned to near the room temperature. For this reason, it is possible to reliably prevent dew condensation on the substrate W.

  Finally, a substrate unloading process for unloading the substrate W from the processing unit 91 is performed (step S109). After the substrate holding unit 11 is positioned at a position suitable for delivery of the substrate W, the substrate holding member drive mechanism 119 opens the substrate holding member 115 and supports the substrate in response to an operation command from the control unit 97 to the substrate holding unit 11. Place on top of the part.

  Thereafter, the shutter 911 is opened, and the center robot 96 extends the upper hand 961 into the processing unit 91, carries the substrate W out of the processing unit 91, and transfers it to the upper hand 951 of the shuttle 95. Thereafter, the shuttle 95 moves the upper hand 951 toward the indexer unit 93. Then, the indexer robot 931 takes out the substrate W held by the upper hand 951 of the shuttle 95 with the upper hand 933 and carries it into a predetermined position of the FOUP 949, and a series of processing ends.

  As described above, in this embodiment, since the intrusion prevention liquid remains in the vicinity of the pattern in a liquid state, the force due to the solidification of the liquid to be solidified and the expansion of the volume is reduced, and the pattern is damaged. Is prevented. That is, the force due to volume expansion is received by the liquid and does not directly affect the pattern itself. Accordingly, since no force is applied to the pattern itself, damage such as collapse or peeling of the pattern convex portion does not occur.

  Then, nitrogen gas for solidification at a temperature lower than the freezing point of DIW constituting the frozen film is supplied to the substrate surface Wf to prevent the frozen film from returning to the liquid phase, and the dew point of the solidified nitrogen gas is set to the temperature of the frozen film. Sublimation drying is performed by setting the pressure lower than the vapor pressure (sublimation pressure) of the frozen film by lowering the partial pressure of water vapor in the solidifying nitrogen gas.

  Further, although the partial pressure of water vapor in the coagulation nitrogen gas may increase instantaneously due to sublimation drying, since the fresh coagulation nitrogen gas is continuously supplied to the substrate surface Wf, the frozen film is covered. The partial pressure of water vapor in the coagulating nitrogen gas is always low, and sublimation drying proceeds. Moreover, since the water vapor component generated by sublimation is removed from the substrate surface Wf by riding on the flow of nitrogen gas for solidification, the water vapor component can be reliably prevented from returning to the liquid phase or solid phase and reattaching to the substrate surface Wf. Can do. In this way, the rinse liquid (DIW) adhering to the substrate surface Wf in the atmospheric pressure atmosphere is removed well after being replaced with HEF, and a DIW frozen film is formed with HFE remaining in the vicinity of the pattern by supplying DIW. Then, the frozen film can be sublimated and dried to dry the substrate W. Therefore, damage to the pattern by the frozen film is prevented by the intrusion prevention liquid. Then, since the liquid surface of the intrusion prevention liquid is exposed during the process of removing the frozen film by sublimation drying, the intrusion prevention liquid is simultaneously removed by evaporation.

In the first embodiment, HFE is used as the intrusion prevention liquid. However, other liquids may be used as long as the liquid is insoluble in the liquid to be solidified and has a freezing point lower than the freezing point of the liquid to be solidified. Can also be used. For example, o-xylene (1,2-dimethylbenzene) (chemical formula: C ₈ H ₁₀ , freezing point:-(minus) 25.2 ° C. (Celsius)), m-xylene (1,3-dimethylbenzene) (chemical formula: C ₈ H ₁₀ , freezing point: − (minus) 48.9 ° C. (Celsius)), trichloromethane (chemical formula: CHCl ₃ , freezing point: − (minus) 63.5 ° C. (Celsius)), tetrachlorethylene (chemical formula: CCl ₂ = CCl , Freezing point: − (minus) 22.2 ° C. (Celsius)) and the like. These substances may be diluted.

Moreover, it is also possible to use a liquid that is soluble in the coagulation target liquid and has a freezing point lower than the freezing point of the coagulation target liquid as the intrusion prevention liquid. For example, isopropyl alcohol (chemical formula: C ₃ H ₈ O, freezing point: − (minus) 90 ° C. (Celsius)), ethyl alcohol (chemical formula: C ₂ H ₅ OH, freezing point: − (minus) 114 ° C. (Celsius)), Methyl alcohol (chemical formula: CH ₃ OH, freezing point:-(minus) 98 ° C. (Celsius)). These substances may be diluted.

  When a substance soluble in the coagulation target liquid is used as the intrusion prevention liquid, the time required for the coagulation target liquid supply process is shortened and the next coagulation process is performed before the liquid is completely removed from the vicinity of the pattern. It is only necessary to proceed and solidify the liquid to be coagulated. In addition, when the coagulation target liquid and the intrusion prevention liquid are mixed in the vicinity of the pattern, the solidification point of the coagulation target liquid is lowered, and the mixture of the coagulation target liquid and the intrusion prevention liquid in the vicinity of the pattern remains after the coagulation process is completed. The liquid state is maintained, and damage to the pattern can be prevented.

  In addition, when an intrusion prevention liquid that is soluble in the coagulation target liquid is used, the replacement with the intrusion prevention liquid is performed smoothly after the rinsing process when the coagulation target liquid and the rinse liquid are the same DIW, so the processing time is shortened. preferable.

  Furthermore, a replacement process may be interposed after the rinsing process, and an intrusion prevention liquid supply process may be performed after the replacement process. The substitution liquid supplied near the center of the substrate surface Wf flows from the center of the substrate surface Wf toward the peripheral edge of the substrate surface Wf by the centrifugal force accompanying the rotation of the substrate W, and diffuses over the entire surface of the substrate surface Wf. The replacement liquid diffused on the substrate surface Wf is replaced with the rinse liquid remaining in the vicinity of the pattern or mixed with the rinse liquid. Since the substitution liquid or the mixture of the substitution liquid and the rinse liquid is easy to mix with the intrusion prevention liquid, the substitution liquid near the pattern or the mixture of the rinse liquid and the substitution liquid is removed by the intrusion prevention liquid in the intrusion prevention liquid supply process. Become.

  Specifically, in the first embodiment, when a rinse liquid and insoluble HFE are used as the intrusion prevention liquid, IPA may be used as a replacement liquid for the rinse liquid. Furthermore, other substances can be used as long as they are soluble in the rinsing liquid and can be replaced with the intrusion prevention liquid or mixed with the intrusion prevention liquid to facilitate mixing with the rinsing liquid. For example, ethyl alcohol or methyl alcohol can be used. These liquids may be diluted.

  Further, the substrate processing apparatus 9 may be an apparatus that performs a chemical treatment process before the rinsing process. That is, a chemical processing mechanism may be provided in the substrate processing apparatus 9. Further, the substrate processing apparatus 9 may carry in the above-mentioned processing by carrying the substrate after the rinsing process.

<Second embodiment>
Further, the coagulation gas may be generated and supplied as a dry state gas. By doing so, the partial pressure of water vapor in the solidifying nitrogen gas is reduced to about 0 Pa. And the temperature Tg of nitrogen gas for solidification shall be -20 degreeC. Therefore, the vapor pressure (sublimation pressure) of the frozen film is about 100 Pa at −20 ° C., whereas the partial pressure of water vapor in the coagulation nitrogen gas is about 0 Pa as described above because the dry state gas does not contain water vapor. Low, sublimation evaporation occurs to fill this vapor pressure difference. Since the coagulation nitrogen gas is continuously supplied, the state that the partial pressure of water vapor in the coagulation nitrogen gas is lower than the vapor pressure of the frozen film is maintained, and the sublimation drying proceeds.

  As the sublimation drying proceeds, an intrusion prevention liquid removing step is performed next. In the removing step, the frozen film on the substrate surface Wf undergoes sublimation evaporation from the surface to which the solidification nitrogen gas is continuously supplied. As a result, the coagulation nitrogen gas is supplied to the liquid surface of the intrusion prevention liquid. Here, the vapor pressure (sublimation pressure) of HFE as an intrusion prevention liquid is about 20 kPa at −20 ° C., whereas the partial pressure of HFE vapor in the nitrogen gas for solidification is as low as about 0 Pa as described above. Evaporation occurs to fill the vapor pressure difference.

  In the second embodiment, since the freezing point of HFE is −38 ° C. and the temperature Tg of the solidifying nitrogen gas is −20 ° C., the HFE is directly exposed to the solidifying nitrogen gas in the intrusion prevention liquid removing step. Even if it becomes, it can prevent that HFE solidifies. That is, by using the solidifying nitrogen gas in a dry state gas, sublimation drying and removal of the intrusion preventing liquid can be performed using the solidifying nitrogen gas at a temperature not lower than the freezing point of the intrusion preventing liquid.

<Third embodiment>
Moreover, in the said embodiment, although the coagulation object liquid and the rinse liquid are made into the same DIW, it is also possible to set it as a respectively different liquid. Specifically, in the above embodiment, HFE is used as the intrusion prevention liquid, and DIW is used as the coagulation target liquid and the rinse liquid. Instead, isopropyl alcohol (hereinafter referred to as “IPA”) is used as the coagulation target liquid. A mixture of DIW and DIW may be used. In this way, the removal process can be performed in a shorter time. The removal process will be described in detail below.

  The state of the substrate surface Wf in the removal step and the intrusion prevention liquid removal step will be described with reference to FIGS. FIG. 17A is a schematic diagram showing the state of the substrate surface Wf after the start of the removing process, and FIG. 17B is a schematic diagram showing the state of the substrate surface Wf after the start of the intrusion prevention liquid removing process. FIG. 17C is a schematic diagram showing the state of the substrate surface Wf after the intrusion prevention liquid removing step is completed.

  In the solidification target liquid supply process, a mixed liquid of DIW and IPA in a ratio of 5: 2 (mixed liquid having a solidification point of −10 ° C.) is supplied, and the solidification process is performed in a state where the intrusion prevention liquid remains in the vicinity of the pattern. As a result, when the frozen film is formed, as shown in FIG. 17A, the frozen film 985b is formed with DIW as ice and the IPA as liquid. Since the freezing point of IPA is −90 ° C., even when the frozen film 985b becomes −20 ° C., it remains in a liquid state and is dispersed in a granular form.

  In addition, what is necessary is just to set a mixing ratio of the coagulation | solidification object liquid so that the freezing point of a liquid mixture may be set to -20 degreeC or more. In this way, when the coagulation process is performed so that a frozen film at −20 ° C. is generated, DIW forms a frozen film in the coagulation target liquid.

  Even after the DIW component is completely iced, the frozen film 985a on the substrate surface Wf undergoes sublimation evaporation from the surface to which the nitrogen gas for solidification is continuously supplied. That is, the removal process is started as in the first embodiment. As a result, as shown in FIG. 17B, the thickness of the frozen film 985b is reduced, the tip of the pattern 981 is exposed, and the liquid IPA is evaporated. At the same time, the liquid surface of the intrusion prevention liquid 983 that is liquid HFE remaining in the pattern vicinity 987 is exposed. Therefore, the frozen film 985b has a porous surface in which a plurality of pores are formed, and the coagulation nitrogen gas is supplied to the liquid surface of the intrusion prevention liquid 983.

  As described above, when the IPA is exposed in the process of removing the frozen film 985b because the IPA does not solidify and remains in a liquid state, the exposed IPA evaporates to form pores in the frozen film 985b. It becomes. Therefore, the remaining amount of the frozen film 985b is reduced, and the removal time of the frozen film 985b can be shortened in the subsequent removal process. Further, when a part of the liquid surface of the intrusion prevention liquid 983 is exposed through the holes, the intrusion prevention liquid removing process is also started from the exposed surface. In this way, the IPA and intrusion prevention liquid 983 evaporate in parallel with the sublimation drying of the frozen film 985b, so that the intrusion prevention liquid removing process is started. Further, since the frozen film 985b on the top surface of the pattern 981 forms a bridge between the patterns, it functions as a pattern reinforcement when the intrusion prevention liquid 983 is removed by evaporation from the holes.

  Then, as shown in FIG. 17C, the end of the intrusion prevention liquid removing step, the intrusion prevention liquid 983 is completely evaporated during the sublimation drying of the frozen film 985b. That is, the pattern 981 is prevented from being damaged by the intrusion prevention liquid 983 in the coagulation process, and in the intrusion prevention liquid removal process of the intrusion prevention liquid 983 by the evaporation of the intrusion prevention liquid 983 in a state where the pattern is reinforced by the frozen film 985b. Removal is performed, and damage such as collapse of the pattern 981 is prevented by surface tension due to evaporation of the intrusion prevention liquid 983.

  Furthermore, the coagulation gas is continuously supplied to the substrate surface Wf even after the intrusion prevention liquid removing step is completed. When the frozen film 985b is sublimated into the gas phase without causing the liquid phase in the atmospheric pressure atmosphere, the IPA is evaporated, and the removal process is completed when all of the frozen film 985b is removed from the substrate surface Wf together with the solidification nitrogen gas. To do. As described above, in this embodiment, the frozen membrane is composed of two component liquids having different freezing points, and the IPA is evaporated faster than the frozen membrane during sublimation drying, so that the frozen membrane can be sublimated and dried in a shorter time. That is, the vapor pressure (sublimation pressure) of the frozen film is about 100 Pa at −20 ° C., whereas the vapor pressure of IPA is about 133 Pa at −20 ° C., and the amount of IPA vapor contained in the coagulation nitrogen gas is Since it is close to zero, IPA evaporates faster than the frozen membrane.

<Others>
The present invention is not limited to the above-described embodiment, and various modifications other than those described above can be made without departing from the spirit of the present invention. For example, in each of the above embodiments, DIW is supplied to the substrate surface Wf as the coagulation target liquid, but the coagulation target liquid is not limited to DIW, and pure water, ultrapure water, hydrogen water, carbonated water Etc., and even liquids such as SC1 can be used. A gas solution obtained by dissolving nitrogen gas in DIW can also be used.

DESCRIPTION OF SYMBOLS 9 Substrate processing apparatus 11 Substrate holding means 21 Drainage collecting means 23 Atmosphere blocking means 31 Intrusion prevention liquid supply means 35 Coagulation means 43 Coagulation target liquid supply means 51 Rinse means 55 Drying gas supply means 91 Processing unit 97 Control unit 313 Nozzle Drive mechanism 331 Intrusion prevention liquid supply means 353 Nozzle drive mechanism 371 Coagulation nitrogen gas supply means 413 Nozzle drive mechanism 553 Nitrogen gas supply section for drying 738 Substrate holding member drive mechanism W substrate Wb Substrate back surface Wf Substrate surface

Claims (3)

An intrusion prevention liquid supply step for supplying an intrusion prevention liquid to the substrate on which the pattern is formed;
A coagulation target liquid supply step for supplying a coagulation target liquid capable of forming a solidified body to the substrate supplied with the intrusion prevention liquid;
A solidification step for producing a solidified body of the liquid to be solidified;
With
The intrusion prevention liquid is a substance having a freezing point lower than the freezing point of the coagulation target liquid, and prevents the coagulation target liquid from entering the pattern vicinity by remaining in the vicinity of the pattern;
In the solidification step, the substrate is cooled below the solidification point of the liquid to be solidified and above the solidification point of the intrusion prevention liquid.
Further, a removal step of removing the intrusion prevention liquid by supplying a gas for removal at a temperature lower than the freezing point of the solidification target liquid toward the solidified body formed in the solidification step;
The substrate processing method characterized by comprising. The substrate processing method according to claim 1,
The solidification target liquid supply step is a substrate processing method in which the solidification target liquid is supplied to the substrate to which the intrusion prevention liquid is attached, and the intrusion prevention liquid other than the vicinity of the pattern is removed. A substrate processing method according to claim 2, wherein
The substrate processing method, wherein the intrusion prevention liquid is a substance insoluble in the coagulation target liquid.

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